WorldWideScience

Sample records for chemically reactive non-isothermal

  1. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    Energy Technology Data Exchange (ETDEWEB)

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.

    1997-07-01

    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  2. Typical parameters of the plasma chemical similarity in non-isothermal reactive plasmas

    International Nuclear Information System (INIS)

    Gundermann, S.; Jacobs, H.; Miethke, F.; Rutsher, A.; Wagner, H.E.

    1996-01-01

    The substance of physical similarity principles is contained in parameters which govern the comparison of different realizations of a model device. Because similarity parameters for non-isothermal plasma chemical reactors are unknown to a great extent, an analysis of relevant equations is given together with some experimental results. Modelling of the reactor and experimental results for the ozone synthesis are presented

  3. Quasi-equilibria and plasma chemical similarity in non-isothermal reactive plasmas

    International Nuclear Information System (INIS)

    Miethke, F.; Rutscher, A.; Wagner, H.E.

    2000-01-01

    With regard to the output of stable products the mode of operation of non-isothermal plasma chemical reactors shows physical and chemical well defined states, which represent limiting cases and may be interpreted as quasi-equilibrium states. The occurrence and the characteristics of these states, meanwhile more than once observed and described, are demonstrated by an instructive model reaction. Within the frame of the so-called Macroscopic Kinetics a central parameter is dominating the reactor operation. This result may be generalized and is linked up to the application of similarity principles for the reactor operation. After the general formulation of such principles, starting from the balance equations of particles and energy, a dimensionless similarity parameter is formulated, characterizing the composition of the effluent gas of the reactor. The applicability of this parameter is demonstrated by experimental examples. (Authors)

  4. TOURGHREACT: A Simulation Program for Non-isothermal Multiphase Reactive Geochemical Transport in Variably Saturated Geologic Media

    OpenAIRE

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2004-01-01

    TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media. The program was written in Fortran 77 and developed by introducing reactive geochemistry into the multiphase fluid and heat flow simulator TOUGH2. A variety of subsurface thermo-physical-chemical processes are considered under a wide range of conditions of pressure, temperature, water saturation, ionic strength, and pH and Eh. Interactions between ...

  5. TOUGHREACT Version 2.0: A simulator for subsurface reactive transport under non-isothermal multiphase flow conditions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, T.; Spycher, N.; Sonnenthal, E.; Zhang, G.; Zheng, L.; Pruess, K.

    2010-08-01

    TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media, and was developed by introducing reactive chemistry into the multiphase fluid and heat flow simulator TOUGH2 V2. The first version of TOUGHREACT was released to the public through the U.S. Department of Energy's Energy Science and Technology Software Center (ESTSC) in August 2004. It is among the most frequently requested of ESTSC's codes. The code has been widely used for studies in CO{sub 2} geological sequestration, nuclear waste isolation, geothermal energy development, environmental remediation, and increasingly for petroleum applications. Over the past several years, many new capabilities have been developed, which were incorporated into Version 2 of TOUGHREACT. Major additions and improvements in Version 2 are discussed here, and two application examples are presented: (1) long-term fate of injected CO{sub 2} in a storage reservoir and (2) biogeochemical cycling of metals in mining-impacted lake sediments.

  6. TOUGHREACT User's Guide: A Simulation Program for Non-isothermal Multiphase Reactive geochemical Transport in Variably Saturated Geologic Media

    International Nuclear Information System (INIS)

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2004-01-01

    Coupled modeling of subsurface multiphase fluid and heat flow, solute transport and chemical reactions can be used for the assessment of mineral alteration in hydrothermal systems, waste disposal sites, acid mine drainage remediation, contaminant transport, and groundwater quality. A comprehensive non-isothermal multi-component reactive fluid flow and geochemical transport simulator, TOUGHREACT, has been developed. A wide range of subsurface thermo-physical-chemical processes is considered under various thermohydrological and geochemical conditions of pressure, temperature, water saturation, and ionic strength. The program can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity. The model can accommodate any number of chemical species present in liquid, gas and solid phases. A variety of equilibrium chemical reactions are considered, such as aqueous complexation, gas dissolution/exsolution, and cation exchange. Mineral dissolution/precipitation can proceed either subject to local equilibrium or kinetic conditions. Changes in porosity and permeability due to mineral dissolution and precipitation can be considered. Linear adsorption and decay can be included. For the purpose of future extensions, surface complexation by double layer model is coded in the program. Xu and Pruess (1998) developed a first version of a non-isothermal reactive geochemical transport model, TOUGHREACT, by introducing reactive geochemistry into the framework of the existing multi-phase fluid and heat flow code TOUGH2 (Pruess, 1991). Xu, Pruess, and their colleagues have applied the program to a variety of problems such as: (1) supergene copper enrichment (Xu et al, 2001), (2) caprock mineral alteration in a hydrothermal system (Xu and Pruess, 2001a), and (3) mineral trapping for CO 2 disposal in deep saline aquifers (Xu et al, 2003b and 2004a). For modeling the coupled thermal, hydrological, and chemical processes during heater

  7. Isothermal and non-isothermal conditions of isotope separation by chemical exchange method

    International Nuclear Information System (INIS)

    Khoroshilov, A.V.; Andreev, B.M.; Katalnikov, S.G.

    1992-01-01

    The published data about the effect of temperature on thermodynamic and mass transfer parameters of isotope separation by the chemical exchange method were used to examine the influence of iso- and non-isothermal conditions on the effectiveness of the separation process. It has been shown that simultaneous fulfillment of several optimization criteria is impossible in optimization of the isothermal process. If the limitation that temperature must be constant in the whole range of concentrational changes for an isolated isotope is removed, then it is possible to solve the problem of optimization with simultaneous fulfillment of several optimization criteria. When the separation process is carried out with non-isothermal conditions, that is, in temperature cascade, then the maximum concentration change takes place at every theoretical separation plate, and whole cascade is characterised by maximum throughput, minimum height and volume, and minimum cost for the stream reflux. From the results of our study, it was concluded that in the optimum temperature cascade, the cost of production of unity quantity of isotope can be decreased at least by a factor of two as compared with the optimal isothermal version of the separation process. (author)

  8. Dual continuum models of fully coupled non-isothermal multiphase flow and reactive transport in porous media

    International Nuclear Information System (INIS)

    Zheng, L.; Samper, J.

    2005-01-01

    Full text of publication follows: Double porosity, double permeability and dual continuum models (DCM) are widely used for modeling preferential water flow and mass transport in unsaturated and fractured media. Here we present a DCM of fully coupled non-isothermal multiphase flow and reactive transport model for the FEBEX compacted bentonite, a material which exhibits a double porosity behavior.. FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project dealing with the bentonite engineered barrier designed for sealing and containment of a high level radioactive waste repository. Our DCM considers inter-aggregate macro-pores, and intra-aggregate and interlayer micro-pores. Two types of DCMs are tested: the dual continuum connected matrix (DCCM) and the dual continuum dis connected matrix (DCDM). Liquid flow in macro-pores is described with a mass conservation equation accounting for Darcian flow, chemical and thermal osmosis. In DCCM, water flux in micropores is calculated with a modified Darcy's law by adding a chemical osmosis term. A simple mass balance equation is used for DCDM which contains a storage and a water exchange term for water in micropores. A mixed type of water exchange term is adopted which includes a second order term accounting for water transfer due to the difference in liquid pressure and a first order term accounting for the gradient in chemical osmosis pressure. Equations of mass conservation for liquid, gas and heat in macro-pores and liquid mass conservation in micropores are solved by using a Newton-Raphson method. Two transport equations with a coupling interaction term are used to describe solute transport in macro- and micro-pores. The coupling term contains a first order diffusion term and a convection term (solute exchange due to water exchange). Transport equations as well as chemical reactions in the two domains are solved by means of a sequential iteration method. All these feature have been

  9. A Non-Isothermal Chemical Lattice Boltzmann Model Incorporating Thermal Reaction Kinetics and Enthalpy Changes

    Directory of Open Access Journals (Sweden)

    Stuart Bartlett

    2017-08-01

    Full Text Available The lattice Boltzmann method is an efficient computational fluid dynamics technique that can accurately model a broad range of complex systems. As well as single-phase fluids, it can simulate thermohydrodynamic systems and passive scalar advection. In recent years, it also gained attention as a means of simulating chemical phenomena, as interest in self-organization processes increased. This paper will present a widely-used and versatile lattice Boltzmann model that can simultaneously incorporate fluid dynamics, heat transfer, buoyancy-driven convection, passive scalar advection, chemical reactions and enthalpy changes. All of these effects interact in a physically accurate framework that is simple to code and readily parallelizable. As well as a complete description of the model equations, several example systems will be presented in order to demonstrate the accuracy and versatility of the method. New simulations, which analyzed the effect of a reversible reaction on the transport properties of a convecting fluid, will also be described in detail. This extra chemical degree of freedom was utilized by the system to augment its net heat flux. The numerical method outlined in this paper can be readily deployed for a vast range of complex flow problems, spanning a variety of scientific disciplines.

  10. TOUGHREACT User's Guide: A Simulation Program for Non-isothermal Multiphase Reactive Geochemical Transport in Variably Saturated Geologic Media, V1.2.1

    International Nuclear Information System (INIS)

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2008-01-01

    Coupled modeling of subsurface multiphase fluid and heat flow, solute transport, and chemical reactions can be applied to many geologic systems and environmental problems, including geothermal systems, diagenetic and weathering processes, subsurface waste disposal, acid mine drainage remediation, contaminant transport, and groundwater quality. TOUGHREACT has been developed as a comprehensive non-isothermal multi-component reactive fluid flow and geochemical transport simulator to investigate these and other problems. A number of subsurface thermo-physical-chemical processes are considered under various thermohydrological and geochemical conditions of pressure, temperature, water saturation, and ionic strength. TOUGHREACT can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity. The code can accommodate any number of chemical species present in liquid, gas and solid phases. A variety of equilibrium chemical reactions are considered, such as aqueous complexation, gas dissolution/exsolution, and cation exchange. Mineral dissolution/precipitation can take place subject to either local equilibrium or kinetic controls, with coupling to changes in porosity and permeability and capillary pressure in unsaturated systems. Chemical components can also be treated by linear adsorption and radioactive decay. The first version of the non-isothermal reactive geochemical transport code TOUGHREACT was developed (Xu and Pruess, 1998) by introducing reactive geochemistry into the framework of the existing multi-phase fluid and heat flow code TOUGH2 (Pruess, 1991). TOUGHREACT was further enhanced with the addition of (1) treatment of mineral-water-gas reactive-transport under boiling conditions, (2) an improved HKF activity model for aqueous species, (3) gas species diffusion coefficients calculated as a function of pressure, temperature, and molecular properties, (4) mineral reactive surface area formulations for fractured

  11. TOUGHREACT User's Guide: A Simulation Program for Non-isothermal Multiphase Reactive Geochemical Transport in Variably Saturated Geologic Media, V1.2.1

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2008-09-29

    Coupled modeling of subsurface multiphase fluid and heat flow, solute transport, and chemical reactions can be applied to many geologic systems and environmental problems, including geothermal systems, diagenetic and weathering processes, subsurface waste disposal, acid mine drainage remediation, contaminant transport, and groundwater quality. TOUGHREACT has been developed as a comprehensive non-isothermal multi-component reactive fluid flow and geochemical transport simulator to investigate these and other problems. A number of subsurface thermo-physical-chemical processes are considered under various thermohydrological and geochemical conditions of pressure, temperature, water saturation, and ionic strength. TOUGHREACT can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity. The code can accommodate any number of chemical species present in liquid, gas and solid phases. A variety of equilibrium chemical reactions are considered, such as aqueous complexation, gas dissolution/exsolution, and cation exchange. Mineral dissolution/precipitation can take place subject to either local equilibrium or kinetic controls, with coupling to changes in porosity and permeability and capillary pressure in unsaturated systems. Chemical components can also be treated by linear adsorption and radioactive decay. The first version of the non-isothermal reactive geochemical transport code TOUGHREACT was developed (Xu and Pruess, 1998) by introducing reactive geochemistry into the framework of the existing multi-phase fluid and heat flow code TOUGH2 (Pruess, 1991). TOUGHREACT was further enhanced with the addition of (1) treatment of mineral-water-gas reactive-transport under boiling conditions, (2) an improved HKF activity model for aqueous species, (3) gas species diffusion coefficients calculated as a function of pressure, temperature, and molecular properties, (4) mineral reactive surface area formulations for fractured

  12. Core2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

    International Nuclear Information System (INIS)

    Samper, J.; Juncosa, R.; Delgado, J.; Montenegro, L.

    2000-01-01

    Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

  13. Core 2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

    Energy Technology Data Exchange (ETDEWEB)

    Samper, J; Juncosa, R; Delgado, J; Montenegro, L [Universidad de A Coruna (Spain)

    2000-07-01

    Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

  14. Core 2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

    Energy Technology Data Exchange (ETDEWEB)

    Samper, J.; Juncosa, R.; Delgado, J.; Montenegro, L. [Universidad de A Coruna (Spain)

    2000-07-01

    Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

  15. Simultaneous resolution of reactive radioactive decay, non-isothermal flow, and migration with application to the performance assessment for HLW repositories

    International Nuclear Information System (INIS)

    Juncosa, R.; Delgado, J.; Font, I.

    2010-01-01

    Radioactive decay is an important subject to take into account when studying the thermo-hydro-dynamic behavior of the buffer clay material used in the containment of radioactive waste. The modern concepts for the multibarrier design of a repository of high level waste in deep geologic formations consider that once canisters have failed, the buffer clay material must ensure the retention and/or delay of radionuclides within the time framework given in the assessment studies. Within the clay buffer, different chemical species are retarded/fixed according to several physicochemical processes (ion exchange, surface complexation, precipitation, matrix diffusion,..) but typical approaches do not consider the eventuality that radioactive species change their chemical nature (i.e. phase) thereby affecting their reactive behavior. The radioactive decay of an element takes place independently of the phase (aqueous, solid or gaseous) to which it belongs. This means that, in terms of radionuclide fixation, some geochemical processes will be effective scavengers (for instance mineral precipitation of crystal growth) while others will not (for instance ion exchange and/or sorption). In this contribution we present a reactive radioactive decay model of any number of chemical components including those that belong to decay series. The model, which is named FLOW-DECAY, also takes into account flow and isotopic migration and it has been applied considering a hypothetical model scenario provided by the project ENRESA 2000 and direct comparison with the results generated by the probabilistic code GoldSim. Results indicate that FLOW-DECAY may simulate the decay processes in a similar way that GoldSim, being the differences related to factors associated to code architecture. (orig.)

  16. Characterization, non-isothermal decomposition kinetics and photocatalytic water splitting of green chemically synthesized polyoxoanions of molybdenum containing phosphorus as hetero atom

    International Nuclear Information System (INIS)

    D’Cruz, Bessy; Samuel, Jadu; George, Leena

    2014-01-01

    Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H 2 evolution and was found to be 1.514 mmol/g/h

  17. Characterization, non-isothermal decomposition kinetics and photocatalytic water splitting of green chemically synthesized polyoxoanions of molybdenum containing phosphorus as hetero atom

    Energy Technology Data Exchange (ETDEWEB)

    D’Cruz, Bessy [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); Samuel, Jadu, E-mail: jadu_samuel@yahoo.co.in [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); George, Leena [Catalysis and Inorganic Chemistry Division, National Chemical Laboratory, Pune 411008 (India)

    2014-11-20

    Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H{sub 2} evolution and was found to be 1.514 mmol/g/h.

  18. Chemical Reactivity Test (CRT)

    Energy Technology Data Exchange (ETDEWEB)

    Zaka, F. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-13

    The Chemical Reactivity Test (CRT) is used to determine the thermal stability of High Explosives (HEs) and chemical compatibility between (HEs) and alien materials. The CRT is one of the small-scale safety tests performed on HE at the High Explosives Applications Facility (HEAF).

  19. Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory II. Non-isothermal study

    NARCIS (Netherlands)

    Frank, M.J.W.; Kuipers, J.A.M.; Krishna, R.; van Swaaij, W.P.M.

    1995-01-01

    In Part I a general applicable model has been developed which calculates mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to

  20. Model-fitting approach to kinetic analysis of non-isothermal oxidation of molybdenite

    International Nuclear Information System (INIS)

    Ebrahimi Kahrizsangi, R.; Abbasi, M. H.; Saidi, A.

    2007-01-01

    The kinetics of molybdenite oxidation was studied by non-isothermal TGA-DTA with heating rate 5 d eg C .min -1 . The model-fitting kinetic approach applied to TGA data. The Coats-Redfern method used of model fitting. The popular model-fitting gives excellent fit non-isothermal data in chemically controlled regime. The apparent activation energy was determined to be about 34.2 kcalmol -1 With pre-exponential factor about 10 8 sec -1 for extent of reaction less than 0.5

  1. Reactive chemicals and process hazards

    International Nuclear Information System (INIS)

    Surianarayanan, M.

    2016-01-01

    Exothermic chemical reactions are often accompanied by significant heat release, and therefore, need a thorough investigation before they are taken to a plant scale. Sudden thermal energy releases from exothermic decompositions and runaway reactions have contributed to serious fire and explosions in several chemical process plants. Similarly, thermal runaway had also occurred in storage and transportation of reactive chemicals. The secondary events of thermal runaway reactions can be rupture of process vessel, toxic spills and release of explosive vapor clouds or combination of these also. The explosion hazards are governed by the system thermodynamics and kinetics of the thermal process. Theoretical prediction of limiting temperature is difficult due to process complexities. Further, the kinetic data obtained through classical techniques, at conditions far away from runaway situation, is often not valid for assessing the runaway behavior of exothermic processes. The main focus of this lecture is to discuss the causes and several contributing factors for thermal runaway and instability and present analyses of the methodologies of the new instrumental techniques for assessing the thermal hazards of reactive chemicals during processing, storage and transportation. (author)

  2. Analysis of form deviation in non-isothermal glass molding

    Science.gov (United States)

    Kreilkamp, H.; Grunwald, T.; Dambon, O.; Klocke, F.

    2018-02-01

    Especially in the market of sensors, LED lighting and medical technologies, there is a growing demand for precise yet low-cost glass optics. This demand poses a major challenge for glass manufacturers who are confronted with the challenge arising from the trend towards ever-higher levels of precision combined with immense pressure on market prices. Since current manufacturing technologies especially grinding and polishing as well as Precision Glass Molding (PGM) are not able to achieve the desired production costs, glass manufacturers are looking for alternative technologies. Non-isothermal Glass Molding (NGM) has been shown to have a big potential for low-cost mass manufacturing of complex glass optics. However, the biggest drawback of this technology at the moment is the limited accuracy of the manufactured glass optics. This research is addressing the specific challenges of non-isothermal glass molding with respect to form deviation of molded glass optics. Based on empirical models, the influencing factors on form deviation in particular form accuracy, waviness and surface roughness will be discussed. A comparison with traditional isothermal glass molding processes (PGM) will point out the specific challenges of non-isothermal process conditions. Furthermore, the underlying physical principle leading to the formation of form deviations will be analyzed in detail with the help of numerical simulation. In this way, this research contributes to a better understanding of form deviations in non-isothermal glass molding and is an important step towards new applications demanding precise yet low-cost glass optics.

  3. Non-isothermal Moisture Transport Through Insulation Materials

    DEFF Research Database (Denmark)

    Peuhkuri, Ruut Hannele; Rode, Carsten; Hansen, Kurt Kielsgaard

    2008-01-01

    An experimental investigation was conducted in order to draw some conclusions on the magnitude of moisture transport due to temperature gradient on a range of porous light-weight building materials. A special constructed non-isothermal set-up allowed the creation of a temperature gradient of 10K...... and given humidity gradient over the sample. The resulting moisture ux as well as the hygrothermal states around and within the material were monitored. The hypothesis of relative humidity being a driving force for non-isothermal moisture transport already in the hygroscopic range could not be confirmed....... On the contrary, indications exist that the temperature gradient itself is driving the moisture from the warm side towards the cold side. An attempt to identify and quantify the single contributions of the different transport forms involved is also presented. The diferent results gave, however, diverging...

  4. Steam-chemical reactivity for irradiated beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Anderl, R.A.; McCarthy, K.A.; Oates, M.A.; Petti, D.A.; Pawelko, R.J.; Smolik, G.R. [Idaho National Engineering and Environmental Lab., Idaho Falls, ID (United States)

    1998-01-01

    This paper reports the results of an experimental investigation to determine the influence of neutron irradiation effects and annealing on the chemical reactivity of beryllium exposed to steam. The work entailed measurements of the H{sub 2} generation rates for unirradiated and irradiated Be and for irradiated Be that had been previously annealed at different temperatures ranging from 450degC to 1200degC. H{sub 2} generation rates were similar for irradiated and unirradiated Be in steam-chemical reactivity experiments at temperatures between 450degC and 600degC. For irradiated Be exposed to steam at 700degC, the chemical reactivity accelerated rapidly and the specimen experienced a temperature excursion. Enhanced chemical reactivity at temperatures between 400degC and 600degC was observed for irradiated Be annealed at temperatures of 700degC and higher. This reactivity enhancement could be accounted for by the increased specific surface area resulting from development of a surface-connected porosity in the irradiated-annealed Be. (author)

  5. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  6. Mathematical modelling of non-isothermal venturi scrubbers

    Energy Technology Data Exchange (ETDEWEB)

    Rahimi, A. [Isfahan Univ., Isfahan (Iran, Islamic Republic of). Dept. of Chemical Engineering; Taheri, M.; Fathikakajahi, J. [Shiraz Univ., Shiraz (Iran, Islamic Republic of). Dept. of Chemical Engineering

    2005-06-01

    Venturi scrubbers collect gaseous pollutants and particulate matter from industrial exhaust. This air pollution control device is highly efficient, easy to maintain and has a low initial cost. However, the high pressure drop through the device results in a high running cost. The main mechanism for collecting particulates is the inertial impaction of the particles on the droplets, which occurs due to high velocity between the gas stream and droplets. Droplet acceleration and irreversible drag-force which results from this high relative velocity are responsible for the high pressure drop in this type of scrubber. While several attempts have been made to mathematically model particulate removal in Venturi scrubbers, most models do not consider simultaneous heat and mass transfer. This factor is important because most Venturi scrubbers operate under non-isothermal conditions where the inlet gas is humidified in order to cool it before entering the scrubber. For that reason, the authors developed a more realistic model to determine the effects of heat and mass transfer on the particulate removal efficiency of a non-isothermal Venturi type scrubber. The model considers the effect of droplet size distribution and liquid film flow on the walls. It consists of differential equations for energy, momentum and material exchange. Model results were compared with data from experimental studies and industrial facilities. It was concluded that the removal efficiency of the scrubber is influenced by the inlet humidity temperature of the inlet gas. 26 refs., 1 tab., 10 figs.

  7. Nonequilibrium steady state of biochemical cycle kinetics under non-isothermal conditions

    Science.gov (United States)

    Jin, Xiao; Ge, Hao

    2018-04-01

    The nonequilibrium steady state of isothermal biochemical cycle kinetics has been extensively studied, but that under non-isothermal conditions has been much less extensively investigated. When the heat exchange between subsystems is slow, the isothermal assumption of the whole system breaks down, as is true for many types of living organisms. Here, starting with a four-state model of molecular transporter across the cell membrane, we generalize the nonequilibrium steady-state theory of isothermal biochemical cycle kinetics to the circumstances with non-uniform temperatures of subsystems in terms of general master equation models. We obtain a new thermodynamic relationship between the chemical reaction rates and thermodynamic potentials in non-isothermal circumstances, based on the overdamped dynamics along the continuous reaction coordinate. We show that the entropy production can vary up to 3% in real cells, even when the temperature difference across the cell membrane is only approximately 1 K. We then decompose the total thermodynamic driving force into its thermal and chemical components and predict that the net flux of molecules transported by the molecular transporter can potentially go against the temperature gradient in the absence of a chemical driving force. Furthermore, we demonstrate that the simple application of the isothermal transition-state rate formula for each chemical reaction in terms of only the reactant’ temperature is not thermodynamically consistent. Therefore, we mathematically derive several revised reaction rate formulas that are not only consistent with the new thermodynamic relationship but also approximate the exact reaction rate better than Kramers’ rate formula under isothermal conditions.

  8. Rock fracture processes in chemically reactive environments

    Science.gov (United States)

    Eichhubl, P.

    2015-12-01

    Rock fracture is traditionally viewed as a brittle process involving damage nucleation and growth in a zone ahead of a larger fracture, resulting in fracture propagation once a threshold loading stress is exceeded. It is now increasingly recognized that coupled chemical-mechanical processes influence fracture growth in wide range of subsurface conditions that include igneous, metamorphic, and geothermal systems, and diagenetically reactive sedimentary systems with possible applications to hydrocarbon extraction and CO2 sequestration. Fracture processes aided or driven by chemical change can affect the onset of fracture, fracture shape and branching characteristics, and fracture network geometry, thus influencing mechanical strength and flow properties of rock systems. We are investigating two fundamental modes of chemical-mechanical interactions associated with fracture growth: 1. Fracture propagation may be aided by chemical dissolution or hydration reactions at the fracture tip allowing fracture propagation under subcritical stress loading conditions. We are evaluating effects of environmental conditions on critical (fracture toughness KIc) and subcritical (subcritical index) fracture properties using double torsion fracture mechanics tests on shale and sandstone. Depending on rock composition, the presence of reactive aqueous fluids can increase or decrease KIc and/or subcritical index. 2. Fracture may be concurrent with distributed dissolution-precipitation reactions in the hostrock beyond the immediate vicinity of the fracture tip. Reconstructing the fracture opening history recorded in crack-seal fracture cement of deeply buried sandstone we find that fracture length growth and fracture opening can be decoupled, with a phase of initial length growth followed by a phase of dominant fracture opening. This suggests that mechanical crack-tip failure processes, possibly aided by chemical crack-tip weakening, and distributed solution-precipitation creep in the

  9. Phase equilibria in chemical reactive fluid mixtures

    International Nuclear Information System (INIS)

    Maurer, Gerd

    2011-01-01

    Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author's group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the 'chilled ammonia process'. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of 'counter ion condensation' and methods to model the Gibbs free energy of such solutions.

  10. A numerical study of non-isothermal turbulent coaxial jets

    Energy Technology Data Exchange (ETDEWEB)

    Kriaa, Wassim; Abderrazak, Kamel; Mhiri, Hatem [Ecole Nationale d' Ingenieurs de Monastir, Laboratoire de Mecanique des Fluides et Thermique, Monastir (Tunisia); Palec, Georges le; Bournot, Philippe [Institut de Mecanique de Marseille, Marseille (France)

    2008-07-15

    In this work, we propose to study non isothermal air-air coaxial jets with two different approaches: parabolic and elliptic approaches. The standard k-{epsilon} model and the RSM model were applied in this study. The numerical resolution of the equations governing this flow type was carried out for: the parabolic approach, by a ''home-made'' CFD code based on a finite difference method, and the elliptic approach by an industrial code (FLUENT) based on a finite volume method. In forced convection mode (Fr={infinity}), the two turbulence models are valid for the prediction of the mean flow. But for turbulent sizes, k-{epsilon} model gives results closer to those achieved in experiments compared to RSM Model. Concerning the limit of validity of the parabolic and elliptic approaches, we showed that for velocities ratio r lower than 1, the results of the two approaches were satisfactory. On the other hand, for r>1, the difference between the results became increasingly significant. In mixed convection mode (Fr{approx_equal}20), the results obtained by the two turbulence models for the mean axial velocity were very different even in the plume region. For the temperature and the turbulent sizes the two models give satisfactory results which agree well with the correlations suggested by the experimenters for X{>=}20. Thus, the second order model with {sigma}{sub t}=0.85 is more effective for a coaxial jet study in a mixed convection mode. (orig.)

  11. Modeling of Non-isothermal Austenite Formation in Spring Steel

    Science.gov (United States)

    Huang, He; Wang, Baoyu; Tang, Xuefeng; Li, Junling

    2017-12-01

    The austenitization kinetics description of spring steel 60Si2CrA plays an important role in providing guidelines for industrial production. The dilatometric curves of 60Si2CrA steel were measured using a dilatometer DIL805A at heating rates of 0.3 K to 50 K/s (0.3 °C/s to 50 °C/s). Based on the dilatometric curves, a unified kinetics model using the internal state variable (ISV) method was derived to describe the non-isothermal austenitization kinetics of 60Si2CrA, and the abovementioned model models the incubation and transition periods. The material constants in the model were determined using a genetic algorithm-based optimization technique. Additionally, good agreement between predicted and experimental volume fractions of transformed austenite was obtained, indicating that the model is effective for describing the austenitization kinetics of 60Si2CrA steel. Compared with other modeling methods of austenitization kinetics, this model, which uses the ISV method, has some advantages, such as a simple formula and explicit physics meaning, and can be probably used in engineering practice.

  12. Non-isothermal crystallization of PET/PLA blends

    International Nuclear Information System (INIS)

    Chen, Huipeng; Pyda, Marek; Cebe, Peggy

    2009-01-01

    Binary blends of poly(ethylene terephthalate) with poly(lactic acid), PET/PLA, were studied by differential scanning calorimetry and X-ray scattering. The PET/PLA blends, prepared by solution casting, were found to be miscible in the melt over the entire composition range. Both quenched amorphous and semicrystalline blends exhibit a single, composition dependent glass transition temperature. We report the non-isothermal crystallization of (a) PET, with and without the presence of PLA crystals and (b) PLA, with and without the presence of PET crystals. PET can crystallize in all blends, regardless of whether PLA is amorphous or crystalline, and degree of crystallinity of PET decreases as PLA content increases. In contrast, PLA crystallization is strongly affected by the mobility of the PET fraction. When PET is wholly amorphous, PLA can crystallize even in 70/30 blends, albeit weakly. But when PET is crystalline, PLA cannot crystallize when its own content drops below 0.90. These different behaviors may possibly be related to the tendency of each polymer to form constrained chains, i.e., to form the rigid amorphous fraction, or RAF. PET is capable of forming a large amount of RAF, whereas relatively smaller amount of RAF forms in PLA. Like the crystals, the rigid amorphous fraction of one polymer component may inhibit the growth of crystals of the other blend partner.

  13. Pre-eruptive magmatic processes re-timed using a non-isothermal approach to magma chamber dynamics.

    Science.gov (United States)

    Petrone, Chiara Maria; Bugatti, Giuseppe; Braschi, Eleonora; Tommasini, Simone

    2016-10-05

    Constraining the timescales of pre-eruptive magmatic processes in active volcanic systems is paramount to understand magma chamber dynamics and the triggers for volcanic eruptions. Temporal information of magmatic processes is locked within the chemical zoning profiles of crystals but can be accessed by means of elemental diffusion chronometry. Mineral compositional zoning testifies to the occurrence of substantial temperature differences within magma chambers, which often bias the estimated timescales in the case of multi-stage zoned minerals. Here we propose a new Non-Isothermal Diffusion Incremental Step model to take into account the non-isothermal nature of pre-eruptive processes, deconstructing the main core-rim diffusion profiles of multi-zoned crystals into different isothermal steps. The Non-Isothermal Diffusion Incremental Step model represents a significant improvement in the reconstruction of crystal lifetime histories. Unravelling stepwise timescales at contrasting temperatures provides a novel approach to constraining pre-eruptive magmatic processes and greatly increases our understanding of magma chamber dynamics.

  14. Negative Saturation Approach for Non-Isothermal Compositional Two-Phase Flow Simulations

    NARCIS (Netherlands)

    Salimi, H.; Wolf, K.H.; Bruining, J.

    2011-01-01

    This article deals with developing a solution approach, called the non-isothermal negative saturation (NegSat) solution approach. The NegSat solution approach solves efficiently any non-isothermal compositional flow problem that involves phase disappearance, phase appearance, and phase transition.

  15. An autonomous organic reaction search engine for chemical reactivity

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

    2017-06-01

    The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

  16. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft

    2002-04-01

    Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

  17. Multiple stable isotope fronts during non-isothermal fluid flow

    Science.gov (United States)

    Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

    2018-02-01

    Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

  18. Isothermal and non-isothermal cure of a tri-functional epoxy resin (TGAP): A stochastic TMDSC study

    International Nuclear Information System (INIS)

    Hutchinson, John M.; Shiravand, Fatemeh; Calventus, Yolanda; Fraga, Iria

    2012-01-01

    Highlights: ► First evaluation of T g of tri-functional epoxy resin TGAP by DSC. ► Clearly shows advantages of TOPEM for isothermal and non-isothermal cure analysis. ► Evidence of highly non-linear enthalpy relaxation in partially cured TGAP system. - Abstract: The isothermal cure of a highly reactive tri-functional epoxy resin, tri-glycidyl para-amino phenol (TGAP), with diamino diphenyl sulphone (DDS), at two different cure temperatures T c has been studied by both conventional differential scanning calorimetry (DSC) and by a stochastic temperature modulated DSC technique, TOPEM. From a series of isothermal cure experiments for increasing cure times, the glass transition temperature T g as a function of isothermal cure time is determined by conventional DSC from a second (non-isothermal) scan, and the vitrification time t v is obtained as the time at which T g = T c . In parallel, TOPEM experiments at the same T c lead directly to the determination of t v from the sigmoidal change in the quasi-static heat capacity. It is not possible to identify the glass transition temperature of the fully cured system, T g∞ , in a third scan by conventional DSC. In contrast, with TOPEM a second (non-isothermal) scan at 2 K/min after the isothermal cure gives rise to three separate transitions: devitrification of the partially cured and vitrified material; almost immediate vitrification as the T g of the system again rises; finally another devitrification, at a temperature approximating closely to T g∞ . Thus with TOPEM it is possible to obtain a calorimetric measure of the glass transition temperature of this fully cured system.

  19. Model-free method for isothermal and non-isothermal decomposition kinetics analysis of PET sample

    International Nuclear Information System (INIS)

    Saha, B.; Maiti, A.K.; Ghoshal, A.K.

    2006-01-01

    Pyrolysis, one possible alternative to recover valuable products from waste plastics, has recently been the subject of renewed interest. In the present study, the isoconversion methods, i.e., Vyazovkin model-free approach is applied to study non-isothermal decomposition kinetics of waste PET samples using various temperature integral approximations such as Coats and Redfern, Gorbachev, and Agrawal and Sivasubramanian approximation and direct integration (recursive adaptive Simpson quadrature scheme) to analyze the decomposition kinetics. The results show that activation energy (E α ) is a weak but increasing function of conversion (α) in case of non-isothermal decomposition and strong and decreasing function of conversion in case of isothermal decomposition. This indicates possible existence of nucleation, nuclei growth and gas diffusion mechanism during non-isothermal pyrolysis and nucleation and gas diffusion mechanism during isothermal pyrolysis. Optimum E α dependencies on α obtained for non-isothermal data showed similar nature for all the types of temperature integral approximations

  20. Reactivity of Dual-Use Decontaminants with Chemical Warfare Agents

    Science.gov (United States)

    2016-07-01

    REACTIVITY OF DUAL-USE DECONTAMINANTS WITH CHEMICAL WARFARE AGENTS ECBC-TR-1384... Decontaminants with Chemical Warfare Agents 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Willis, Matthew P...extraction) of chemical warfare agents from materials. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent Liquid-phase

  1. Kinetic Model of LiFePO4 Formation Using Non-Isothermal Thermogravimetric Analysis

    Directory of Open Access Journals (Sweden)

    Abdul Halim

    2014-03-01

    Full Text Available The formation reaction of LiFePO4 from decomposition of precursors LiOH, FeSO4.7H2O and (NH42HPO4 with mol ratio of Li:Fe:P=1:1:1 was investigated. The experiment was carried out by thermogravimetric differential thermal analysis (TG-DTA method using nitrogen as atmosfer at a constant heating rate to obtain kinetic constant parameters. Several heating rates were selected, there are 5, 7, 10, 15, 17.5, 22.5 and 25 °C/min. Activation energy, pre-exponential factor and reaction order were taken using Kissinger method and obtained respectively 56.086 kJ/mol, 6.95×108 min-1, and 1.058. Based on fitting result between reaction model and experiment were obtained that reaction obeyed the three dimension diffusion model. © 2014 BCREC UNDIP. All rights reservedReceived: 19th September 2013; Revised: 9th December 2013; Accepted: 23rd January 2014 [How to Cite: Halim, A., Widiyastuti, W., Setyawan, H., Winardi, S. (2014. Kinetic of LiFePO4 For-mation Using Non-isothermal Thermogravimetric Analysis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 60-65. (doi:10.9767/bcrec.9.1.5508.60-65][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5508.60-65] 

  2. Nondestructive Reactivation of Chemical Protective Garments

    National Research Council Canada - National Science Library

    Chang, Kuo

    1995-01-01

    .... Complete reactivation was achieved when the aqueous/ i-propanol/ iodine displacement method of Manes, which removed all but pure hydrocarbon oil soils from the current overgarment Type III foam...

  3. Fluxes of chemically reactive species inferred from mean concentration measurements

    NARCIS (Netherlands)

    Galmarini, S.; Vilà-Guerau De Arellano, J.; Duyzer, J.H.

    1997-01-01

    A method is presented for the calculation of the fluxes of chemically reactive species on the basis of routine measurements of meteorological variables and chemical species. The method takes explicity into account the influence of chemical reactions on the fluxes of the species. As a demonstration

  4. Hardness of H13 Tool Steel After Non-isothermal Tempering

    Science.gov (United States)

    Nelson, E.; Kohli, A.; Poirier, D. R.

    2018-04-01

    A direct method to calculate the tempering response of a tool steel (H13) that exhibits secondary hardening is presented. Based on the traditional method of presenting tempering response in terms of isothermal tempering, we show that the tempering response for a steel undergoing a non-isothermal tempering schedule can be predicted. Experiments comprised (1) isothermal tempering, (2) non-isothermal tempering pertaining to a relatively slow heating to process-temperature and (3) fast-heating cycles that are relevant to tempering by induction heating. After establishing the tempering response of the steel under simple isothermal conditions, the tempering response can be applied to non-isothermal tempering by using a numerical method to calculate the tempering parameter. Calculated results are verified by the experiments.

  5. Chemical reactor modeling multiphase reactive flows

    CERN Document Server

    Jakobsen, Hugo A

    2014-01-01

    Chemical Reactor Modeling closes the gap between Chemical Reaction Engineering and Fluid Mechanics.  The second edition consists of two volumes: Volume 1: Fundamentals. Volume 2: Chemical Engineering Applications In volume 1 most of the fundamental theory is presented. A few numerical model simulation application examples are given to elucidate the link between theory and applications. In volume 2 the chemical reactor equipment to be modeled are described. Several engineering models are introduced and discussed. A survey of the frequently used numerical methods, algorithms and schemes is provided. A few practical engineering applications of the modeling tools are presented and discussed. The working principles of several experimental techniques employed in order to get data for model validation are outlined. The monograph is based on lectures regularly taught in the fourth and fifth years graduate courses in transport phenomena and chemical reactor modeling, and in a post graduate course in modern reactor m...

  6. Non-isothermal effects on multi-phase flow in porous medium

    DEFF Research Database (Denmark)

    Singh, Ashok; Wang, W; Park, C. H.

    2010-01-01

    In this paper a ppT -formulation for non-isothermal multi-phase flow is given including diffusion and latent heat effects. Temperature and pressure dependencies of governing parameters are considered, in particular surface tension variation on phase interfaces along with temperature changes. A we...

  7. A simple method of evaluating non-isothermal crystallization kinetics in multicomponent polymer systems

    Czech Academy of Sciences Publication Activity Database

    Kratochvíl, Jaroslav; Kelnar, Ivan

    2015-01-01

    Roč. 47, October (2015), s. 79-86 ISSN 0142-9418 R&D Projects: GA ČR(CZ) GA13-15255S Institutional support: RVO:61389013 Keywords : non-isothermal crystallization kinetics * cumulative curves * inflection point Subject RIV: JI - Composite Materials Impact factor: 2.350, year: 2015

  8. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  9. Chemical reactivities of some interstellar molecules

    Energy Technology Data Exchange (ETDEWEB)

    Chadha, M S

    1980-01-01

    Work in the area of chemical evolution during the last 25 years has revealed the formation of a large number of biologically important molecules produced from simple starting materials under relatively simple experimental conditions. Much of this work has resulted from studies under atmospheres simulating that of the primitive earth or other planets. During the last decade, progress has also been made in the identification of chemical constituents of interstellar medium. A number of these molecules are the same as those identified in laboratory experiments. Even though the conditions of the laboratory experiments are vastly different from those of the cool, low-density interstellar medium, some of the similarities in composition are too obvious to go unnoticed. The present paper highlights some of the similarities in the composition of prebiotic molecules and those discovered in the interstellar medium. Also the chemical reactions which some of the common molecules e.g., NH3, HCN, H2CO, HC(triple bond)-C-CN etc. can undergo are surveyed.

  10. Non-isothermal kinetics model to predict accurate phase transformation and hardness of 22MnB5 boron steel

    Energy Technology Data Exchange (ETDEWEB)

    Bok, H.-H.; Kim, S.N.; Suh, D.W. [Graduate Institute of Ferrous Technology, POSTECH, San 31, Hyoja-dong, Nam-gu, Pohang, Gyeongsangbuk-do (Korea, Republic of); Barlat, F., E-mail: f.barlat@postech.ac.kr [Graduate Institute of Ferrous Technology, POSTECH, San 31, Hyoja-dong, Nam-gu, Pohang, Gyeongsangbuk-do (Korea, Republic of); Lee, M.-G., E-mail: myounglee@korea.ac.kr [Department of Materials Science and Engineering, Korea University, Anam-dong, Seongbuk-gu, Seoul (Korea, Republic of)

    2015-02-25

    A non-isothermal phase transformation kinetics model obtained by modifying the well-known JMAK approach is proposed for application to a low carbon boron steel (22MnB5) sheet. In the modified kinetics model, the parameters are functions of both temperature and cooling rate, and can be identified by a numerical optimization method. Moreover, in this approach the transformation start and finish temperatures are variable instead of the constants that depend on chemical composition. These variable reference temperatures are determined from the measured CCT diagram using dilatation experiments. The kinetics model developed in this work captures the complex transformation behavior of the boron steel sheet sample accurately. In particular, the predicted hardness and phase fractions in the specimens subjected to a wide range of cooling rates were validated by experiments.

  11. Modeling food matrix effects on chemical reactivity: Challenges and perspectives.

    Science.gov (United States)

    Capuano, Edoardo; Oliviero, Teresa; van Boekel, Martinus A J S

    2017-06-29

    The same chemical reaction may be different in terms of its position of the equilibrium (i.e., thermodynamics) and its kinetics when studied in different foods. The diversity in the chemical composition of food and in its structural organization at macro-, meso-, and microscopic levels, that is, the food matrix, is responsible for this difference. In this viewpoint paper, the multiple, and interconnected ways the food matrix can affect chemical reactivity are summarized. Moreover, mechanistic and empirical approaches to explain and predict the effect of food matrix on chemical reactivity are described. Mechanistic models aim to quantify the effect of food matrix based on a detailed understanding of the chemical and physical phenomena occurring in food. Their applicability is limited at the moment to very simple food systems. Empirical modeling based on machine learning combined with data-mining techniques may represent an alternative, useful option to predict the effect of the food matrix on chemical reactivity and to identify chemical and physical properties to be further tested. In such a way the mechanistic understanding of the effect of the food matrix on chemical reactions can be improved.

  12. Slow Invariant Manifolds in Chemically Reactive Systems

    Science.gov (United States)

    Paolucci, Samuel; Powers, Joseph M.

    2006-11-01

    The scientific design of practical gas phase combustion devices has come to rely on the use of mathematical models which include detailed chemical kinetics. Such models intrinsically admit a wide range of scales which renders their accurate numerical approximation difficult. Over the past decade, rational strategies, such as Intrinsic Low Dimensional Manifolds (ILDM) or Computational Singular Perturbations (CSP), for equilibrating fast time scale events have been successfully developed, though their computation can be challenging and their accuracy in most cases uncertain. Both are approximations to the preferable slow invariant manifold which best describes how the system evolves in the long time limit. Strategies for computing the slow invariant manifold are examined, and results are presented for practical combustion systems.

  13. Study on chemical reactivity control of liquid sodium. Research program

    International Nuclear Information System (INIS)

    Saito, Jun-ichi; Ara, Kuniaki; Sugiyama, Ken-ichiro; Kitagawa, Hiroshi; Oka, Nobuki; Yoshioka, Naoki

    2007-01-01

    Liquid sodium has the excellent properties as coolant of the fast breeder reactor (FBR). On the other hand, it reacts high with water and oxygen. So an innovative technology to suppress the reactivity is desired. The purpose of this study is to control the chemical reactivity of liquid sodium by dispersing the nanometer-size metallic particles (we call them Nano-particles) into liquid sodium. We focus on the atomic interaction between Nano-particles and sodium atoms. And we try to apply it to suppress the chemical reactivity of liquid sodium. Liquid sodium dispersing Nano-particles is named 'Nano-fluid'. Research programs of this study are the Nano-particles production, the evaluation of reactivity suppression of liquid sodium and the feasibility study to FBR plant. In this paper, the research programs and status are described. The important factors for particle production were understood. In order to evaluate the chemical reactivity of Nano-fluid the research programs were planned. The feasibility of the application of Nano-fluid to the coolant of FBR plant was evaluated preliminarily from the viewpoint of design and operation. (author)

  14. Local Chemical Reactivity of a Metal Alloy Surface

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Scheffler, Matthias

    1995-01-01

    The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

  15. In Situ Study of Phase Transformations during Non-Isothermal Tempering of Bainitic and Martensitic Microstructures

    Directory of Open Access Journals (Sweden)

    S. Hesamodin Talebi

    2017-09-01

    Full Text Available Phase transformations during non-isothermal tempering of bainitic or martensitic microstructures obtained after quenching of a medium-carbon low-alloy steel was studied. The microstructures correspond to different locations of an as-quenched large-sized forged ingot used as a die material in the automotive industry. High-resolution dilatometry experiments were conducted to simulate the heat treatment process, as well as to investigate different phenomena occurring during non-isothermal tempering. The microstructures were characterized using optical and scanning electron microscopy. Dilatometry analyses demonstrated that tempering behavior varied significantly from bainitic to martensitic microstructures. Retained austenite, which exists between bainitic ferrite sheaves, decomposes to lower bainite causing a remarkable volume increase. It was found that this decomposition finishes below 386 °C. By contrast, martensite tempering was accompanied with a volume decrease due to the decomposition of medium-carbon martensite to low carbon martensite and carbides.

  16. Oscillations of non-isothermal N/S boundary with a high frequency and large amplitude

    International Nuclear Information System (INIS)

    Bezuglyj, A.I.; Shklovskij, V.A.

    2016-01-01

    Within the framework of the phenomenological approach based on the heat balance equation and the dependence of the critical temperature of the superconductor on the current value theoretically investigated the impact of high-frequency current of high amplitude and arbitrary shape on the non-isothermal balance of the oscillating N/S interface in a long superconductor. We introduce a self-consistent average temperature field of rapidly oscillating non-isothermal N/S boundary (heat kink), which allows to go beyond the well-known concept of mean-square heating and consider the impact of current waveform. With regard to experiments on the effects of microwave high-power radiation on the current-voltage characteristics (CVC) of superconducting films, we give the classification of the families of the CVC for inhomogeneous superconductors which carry a current containing a high frequency component of large amplitude. Several characteristics have hysteresis of thermal nature.

  17. Modelling for Temperature Non-Isothermal Continuous Stirred Tank Reactor Using Fuzzy Logic

    OpenAIRE

    Nasser Mohamed Ramli; Mohamad Syafiq Mohamad

    2017-01-01

    Many types of controllers were applied on the continuous stirred tank reactor (CSTR) unit to control the temperature. In this research paper, Proportional-Integral-Derivative (PID) controller are compared with Fuzzy Logic controller for temperature control of CSTR. The control system for temperature non-isothermal of a CSTR will produce a stable response curve to its set point temperature. A mathematical model of a CSTR using the most general operating condition was developed through a set of...

  18. A new approach to non-isothermal models for nematic liquid crystals

    Czech Academy of Sciences Publication Activity Database

    Feireisl, Eduard; Frémond, M.; Rocca, E.; Schimperna, G.

    2012-01-01

    Roč. 205, č. 2 (2012), s. 651-672 ISSN 0003-9527 R&D Projects: GA ČR GA201/09/0917 Institutional research plan: CEZ:AV0Z10190503 Keywords : liquid crystals * non-isothermal model * flows Subject RIV: BA - General Mathematics Impact factor: 2.292, year: 2012 http://www.springerlink.com/content/cl205h73077jr810/

  19. Method to Predict Tempering of Steels Under Non-isothermal Conditions

    Science.gov (United States)

    Poirier, D. R.; Kohli, A.

    2017-05-01

    A common way of representing the tempering responses of steels is with a "tempering parameter" that includes the effect of temperature and time on hardness after hardening. Such functions, usually in graphical form, are available for many steels and have been applied for isothermal tempering. In this article, we demonstrate that the method can be extended to non-isothermal conditions. Controlled heating experiments were done on three grades in order to verify the method.

  20. Ion-sound oscillations in strongly non-isotherm weakly ionized nonuniform hydrogen plasma

    International Nuclear Information System (INIS)

    Leleko, Ya.F.; Stepanov, K.N.

    2010-01-01

    A stationary distribution of strongly non-isotherm weakly ionized hydrogen plasma parameters is obtained in the hydrodynamic approximation in a quasi neutrality region in the transient layer between the plasma and dielectric taking the ionization, charge exchange, diffusion, viscosity, and a self-consistent field potential distribution. The ion-sound oscillation frequency and the collisional damping decrement as functions of the wave vector in the plasma with the obtained parameters are found in the local approximation.

  1. Dispersive kinetic model for the non-isothermal reduction of nickel oxide by hydrogen

    International Nuclear Information System (INIS)

    Adnadevic, Borivoj; Jankovic, Bojan

    2008-01-01

    The kinetics of the non-isothermal reduction process of powder nickel oxide samples using hydrogen was investigated by temperature-programmed experiments at the different constant heating rates. The new procedure for the determination of density distribution function of activation energies (ddfE a ), evaluated from the experimentally obtained non-isothermal conversion curves, was developed. The analytical relationships between the corresponding thermo-kinetic parameters for the investigated reduction process were established. From the influence of heating rate on the basic characteristics of ddfE a 's, it was concluded that the evaluated ddfE a 's are completely independent of the heating rate (v h ). It was found that the value of activation energy at the peak of the distribution curve (E a,max ), at all considered heating rates, is in good agreement with the value of E a,0 (96.6 kJ mol -1 ) calculated from the isoconversional dependence of activation energy, in the conversion range of 0.20≤α≤0.60. From the appearances of the true compensation effect, it was concluded that the factor that produces the changes of kinetic parameter values is a conversion fraction (α). Using the model prediction, the experimentally obtained conversion curves are completely described by the evaluated distribution curves (g(E a ) vhj ) at all considered heating rates. It was concluded that the assumption about the distribution of potential energies of oxygen vacancies presented in NiO samples leads to the distribution of activation energies, which determine the kinetics of non-isothermal reduction processes

  2. The impact of non-isothermal soil moisture transport on evaporation fluxes in a maize cropland

    Science.gov (United States)

    Shao, Wei; Coenders-Gerrits, Miriam; Judge, Jasmeet; Zeng, Yijian; Su, Ye

    2018-06-01

    The process of evaporation interacts with the soil, which has various comprehensive mechanisms. Multiphase flow models solve air, vapour, water, and heat transport equations to simulate non-isothermal soil moisture transport of both liquid water and vapor flow, but are only applied in non-vegetated soils. For (sparsely) vegetated soils often energy balance models are used, however these lack the detailed information on non-isothermal soil moisture transport. In this study we coupled a multiphase flow model with a two-layer energy balance model to study the impact of non-isothermal soil moisture transport on evaporation fluxes (i.e., interception, transpiration, and soil evaporation) for vegetated soils. The proposed model was implemented at an experimental agricultural site in Florida, US, covering an entire maize-growing season (67 days). As the crops grew, transpiration and interception became gradually dominated, while the fraction of soil evaporation dropped from 100% to less than 20%. The mechanisms of soil evaporation vary depending on the soil moisture content. After precipitation the soil moisture content increased, exfiltration of the liquid water flow could transport sufficient water to sustain evaporation from soil, and the soil vapor transport was not significant. However, after a sufficient dry-down period, the soil moisture content significantly reduced, and the soil vapour flow significantly contributed to the upward moisture transport in topmost soil. A sensitivity analysis found that the simulations of moisture content and temperature at the soil surface varied substantially when including the advective (i.e., advection and mechanical dispersion) vapour transport in simulation, including the mechanism of advective vapour transport decreased soil evaporation rate under wet condition, while vice versa under dry condition. The results showed that the formulation of advective soil vapor transport in a soil-vegetation-atmosphere transfer continuum can

  3. The non-isothermal kinetics of decomposition of manganese carbonate ore

    Directory of Open Access Journals (Sweden)

    Kenan Yıldız

    2012-06-01

    Full Text Available The non-isothermal kinetics of decomposition of manganese carbonate ore from Denizli – Tavas region was studied. The ore decomposed according to a serie of reaction, MnCO3 ;#8594;(400-600°C MnO2 ;#8594;(;600 Mn2O3. By using of Kissenger equation, the activation energies for the decomposition of MnCO3 to MnO2 and the transformation of MnO2 to Mn2O3 were calculated as 185,7 kJ/mol and 217,3 kJ/mol, respectively.

  4. Non-isothermal compositional gas flow during carbon dioxide storage and enhanced gas recovery

    DEFF Research Database (Denmark)

    Singh, Ashok; Böettcher, N.; Wang, W.

    2011-01-01

    In this work we present the conceptual modeling and the numerical scheme for carbon dioxide storage into nearly depleted gas reservoirs for enhanced gas recovery reasons. For this we develop non-isothermal compositional gas flow model. We used a combined monolithic / staggered coupling scheme...... to solve mass balance equation for the gaseous mixture with heat and fractional mass transport equations. Temperature change resulting from fluid expansion and viscous heat dissipation is included in heat transport in addition to advection and conduction. We have used a modified version of the Peng...

  5. Asymptotic solution of the non-isothermal Cahn-Hilliard system

    International Nuclear Information System (INIS)

    Omel'yanov, G.A.

    1995-05-01

    The non-isothermal Cahn-Hillard questions with a small parameter in the n-dimensional case (n = 2.3) are considered. The small parameter is proportional both to the relaxation time and to the linear scale of transition zone, so the large time process is examined. The asymptotic solution describing the free interface dynamics is constructed. As the small parameter tends to zero, the limiting solution satisfies the modified Stefan problem with corrected Gibbs-Thomson law. The justification of the asymptotic solution is proved. (author). 26 refs

  6. Wall modeling for the simulation of highly non-isothermal unsteady flows; Modelisation de paroi pour la simulation d'ecoulements instationnaires non-isothermes

    Energy Technology Data Exchange (ETDEWEB)

    Devesa, A

    2006-12-15

    Nuclear industry flows are most of the time characterized by their high Reynolds number, density variations (at low Mach numbers) and a highly unsteady behaviour (low to moderate frequencies). High Reynolds numbers are un-affordable by direct simulation (DNS), and simulations must either be performed by solving averaged equations (RANS), or by solving only the large eddies (LES), both using a wall model. A first investigation of this thesis dealt with the derivation and test of two variable density wall models: an algebraic law (CWM) and a zonal approach dedicated to LES (TBLE-{rho}). These models were validated in quasi-isothermal cases, before being used in academic and industrial non-isothermal flows with satisfactory results. Then, a numerical experiment of pulsed passive scalars was performed by DNS, were two forcing conditions were considered: oscillations are imposed in the outer flow; oscillations come from the wall. Several frequencies and amplitudes of oscillations were taken into account in order to gain insights in unsteady effects in the boundary layer, and to create a database for validating wall models in such context. The temporal behaviour of two wall models (algebraic and zonal wall models) were studied and showed that a zonal model produced better results when used in the simulation of unsteady flows. (author)

  7. Non-isothermal cure and exfoliation of tri-functional epoxy-clay nanocomposites

    Directory of Open Access Journals (Sweden)

    F. Shiravand

    2015-08-01

    Full Text Available The non-isothermal cure kinetics of polymer silicate layered nanocomposites based on a tri-functional epoxy resin has been investigated by differential scanning calorimetry. From an analysis of the kinetics as a function of the clay content, it can be concluded that the non-isothermal cure reaction can be considered to consist of four different processes: the reaction of epoxy groups with the diamine curing agent; an intra-gallery homopolymerisation reaction which occurs concurrently with the epoxy-amine reaction; and two extra-gallery homopolymerisation reactions, catalysed by the onium ion of the organically modified clay and by the tertiary amines resulting from the epoxy-amine reaction. The final nanostructure displays a similar quality of exfoliation as that observed for the isothermal cure of the same nanocomposite system. This implies that the intra-gallery reaction, which is responsible for the exfoliation, is not significantly inhibited by the extra-gallery epoxy-amine cross-linking reaction.

  8. Asymptotic Approximations to the Non-Isothermal Distributed Activation Energy Model for Bio-Mass Pyrolysis

    Directory of Open Access Journals (Sweden)

    Dhaundiyal Alok

    2017-12-01

    Full Text Available This paper describes the influence of some parameters significant to biomass pyrolysis on the numerical solutions of the non-isothermal nth order distributed activation energy model (DAEM using the Gamma distribution and discusses the special case for the positive integer value of the scale parameter (λ, i.e. the Erlang distribution. Investigated parameters are the integral upper limit, the frequency factor, the heating rate, the reaction order, and the shape and rate parameters of the Gamma distribution. Influence of these parameters has been considered for the determination of the kinetic parameters of the non-isothermal nth order Gamma distribution from the experimentally derived thermoanalytical data of biomass pyrolysis. Mathematically, the effect of parameters on numerical solution is also used for predicting the behaviour of the unpyrolysized fraction of biomass with respect to temperature. Analysis of the mathematical model is based upon asymptotic expansions, which leads to the systematic methods for efficient way to determine the accurate approximations. The proposed method, therefore, provides a rapid and highly effective way for estimating the kinetic parameters and the distribution of activation energies.

  9. Non-isothermal cold crystallization kinetics of poly(3-hydoxybutyrate) filled with zinc oxide

    Energy Technology Data Exchange (ETDEWEB)

    Ries, Andreas, E-mail: ries750@yahoo.com.br [Electrical Engineering Department, Federal University of Paraíba, João Pessoa, PB 58051-900 (Brazil); Canedo, Eduardo L. [Materials Engineering Department, Federal University of Campina Grande, Campina Grande, PB 58429-900 (Brazil); Souto, Cícero R. [Electrical Engineering Department, Federal University of Paraíba, João Pessoa, PB 58051-900 (Brazil); Wellen, Renate M.R. [Materials Engineering Department, Federal University of Paraíba, João Pessoa, PB 58051-900 (Brazil)

    2016-08-10

    Highlights: • Non-isothermal cold crystallization kinetics of PHB filled with ZnO is presented. • Pseudo-Avrami model is best for describing an individual crystallization condition. • Mo model is allows to judge the kinetics of a condition untested in this work. • ZnO affects the kinetics irregularly. - Abstract: The non-isothermal cold crystallization kinetics of poly(3-hydroxybutyrate) (PHB) and PHB-ZnO composites, with ZnO content of 1%, 5% and 10% per weight, was investigated at different heating rates (5, 7.5, 10, 15, 20 and 30 °C/min) using differential scanning calorimetry. Both, Kissinger and Friedman activation energies predict correctly the slowest and fastest crystallizing composition. It was further found, that ZnO can neither be classified as a crystallization accelerator, nor as a crystallization inhibitor; its action is strongly concentration dependent. The empirical Pseudo-Avrami model has the best overall capability for fitting the experimental kinetic data. However, since the Pseudo-Avrami exponent was found to vary irregularly with heating rate and filler content, this model should not be applied for kinetic predictions of an arbitrary composition or an untested heating rate. In such cases, Mo's model should be used.

  10. The non-isothermal DSC kinetics of polyethylene tereftalate–epoxy compatible blends

    International Nuclear Information System (INIS)

    Zvetkov, V.L.; Djoumaliisky, S.; Simeonova-Ivanova, E.

    2013-01-01

    Highlights: ► The non-isothermal DSC kinetics of the reaction of DGEBA with DDS, in particular in the presence of phase separating PET, has been studied. ► The specific features in the kinetics of PET formulations in comparison to the pure system have been discussed. ► The fast pre-curing of the epoxy phase allows supposing sub-micro phase separation of PET and efficient toughening of the epoxy matrix. - Abstract: Polyethylene tereftalate has been dissolved in an epoxy resin based on diglycidyl ether of bisphenol-A, DGEBA, and the epoxy component has been cross-linked with the aid of two diamine hardeners. Two series of samples have been tested at the epoxy-amine stoichiometry applying the differential scanning calorimetry, DSC, in scanning mode. One of the series of samples was pre-cured at low temperatures with the aid of an aliphatic diamine hardener near the gel point and post-cured with diaminodiphenyl sulfone, DDS. The other series of samples contained the higher temperature hardener only. Consequently, the experimental data obtained in this study on both systems relate to the non-isothermal curing of DGEBA with DDS. The kinetics has been estimated applying preferably isoconversional (model free) methods. It has been established that the fast pre-curing allows performing a sub-micro phase separation and efficient toughening of the epoxy matrix

  11. The non-isothermal DSC kinetics of polyethylene tereftalate–epoxy compatible blends

    Energy Technology Data Exchange (ETDEWEB)

    Zvetkov, V.L., E-mail: zvetval@yahoo.com [Institute of Mechanics, Bulgarian Academy of Sciences, bl. I, Sofia 1113 (Bulgaria); Djoumaliisky, S.; Simeonova-Ivanova, E. [Institute of Mechanics, Bulgarian Academy of Sciences, bl. I, Sofia 1113 (Bulgaria)

    2013-02-10

    Highlights: ► The non-isothermal DSC kinetics of the reaction of DGEBA with DDS, in particular in the presence of phase separating PET, has been studied. ► The specific features in the kinetics of PET formulations in comparison to the pure system have been discussed. ► The fast pre-curing of the epoxy phase allows supposing sub-micro phase separation of PET and efficient toughening of the epoxy matrix. - Abstract: Polyethylene tereftalate has been dissolved in an epoxy resin based on diglycidyl ether of bisphenol-A, DGEBA, and the epoxy component has been cross-linked with the aid of two diamine hardeners. Two series of samples have been tested at the epoxy-amine stoichiometry applying the differential scanning calorimetry, DSC, in scanning mode. One of the series of samples was pre-cured at low temperatures with the aid of an aliphatic diamine hardener near the gel point and post-cured with diaminodiphenyl sulfone, DDS. The other series of samples contained the higher temperature hardener only. Consequently, the experimental data obtained in this study on both systems relate to the non-isothermal curing of DGEBA with DDS. The kinetics has been estimated applying preferably isoconversional (model free) methods. It has been established that the fast pre-curing allows performing a sub-micro phase separation and efficient toughening of the epoxy matrix.

  12. Kink Waves in Non-isothermal Stratified Solar Waveguides: Effect of the External Magnetic Field

    Energy Technology Data Exchange (ETDEWEB)

    Lopin, I. [Ussuriisk Astrophysical Observatory, Russian Academy of Sciences (Russian Federation); Nagorny, I., E-mail: lopin78@mail.ru [Institute of Automation and Control Processes FEB RAS, Vladivostok (Russian Federation)

    2017-10-01

    We study the effect of an external magnetic field on the properties of kink waves, propagating along a thin non-isothermal stratified and diverging magnetic flux tube. A wave equation, governing the propagation of kink waves under the adopted model is derived. It is shown that the vertical gradient of temperature introduces a spatially local cut-off frequency ω {sub c}. The vertical distribution of the cut-off frequency is calculated for the reference VAL-C model of the solar atmosphere and for different values of a ratio of external to internal magnetic fields. The results show that the cut-off frequency is negative below the temperature minimum due to the negative temperature gradient. In the chromosphere the cut-off frequency at a given height is smaller for a stronger external magnetic field. For the appropriate range of a ratio B{sub e} / B{sub i}  ≈ 0–0.8, the cutoff lies in the range ω{sub c}  ≈ 0.003–0.010 s{sup −1} (periods 600 < P{sub c} < 2000 s). The estimate of the cut-off frequency in the transition region is provided as well. In the propagating wave regime, the effective wave energy flux in the non-isothermal diverging flux tubes is the same as in the straight and homogeneous cylindrical waveguides. The obtained wave equation in the limit β  = 0 is used to study the kink oscillations of non-isothermal coronal loops. It is found that the gradient of temperature along the coronal loops reduces the frequency ratio of the first overtone to the fundamental mode, i.e., ω{sub 2}/ ω{sub 1} < 2. This reduction grows for a larger ratio of temperature at the loop top to the temperature at the footpoints. Moreover, the effect of reduction is most pronounced for the steeper temperature profiles.

  13. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

    Energy Technology Data Exchange (ETDEWEB)

    Malek, Ali; Balawender, Robert, E-mail: rbalawender@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, PL-01-224 Warsaw (Poland)

    2015-02-07

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor.

  14. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

    International Nuclear Information System (INIS)

    Malek, Ali; Balawender, Robert

    2015-01-01

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor

  15. Non-isothermal Crystallization, Thermal Stability, and Mechanical Performance of Poly(L-lactic acid/Barium Phenylphosphonate Systems

    Directory of Open Access Journals (Sweden)

    Cai Yan-Hua

    2017-11-01

    Full Text Available The introduction of a nucleating agent in semi-crystalline polymers is a frequently utilized way to improve the crystallization performance, and the use of a nucleating agent has a very great effect on the performance of the polymer in other areas including thermal stability and mechanical properties. In this investigation, barium phenylphosphonate (BaP was prepared as a crystallization accelerator for Poly(L-lactic acid (PLLA, and the non-isothermal crystallization behavior, thermal stability, and mechanical properties of PLLA modified by BaP were investigated using differential scanning calorimetry (DSC, X-ray diffraction (XRD, thermogravimetric analysis (TGA, and electronic tensile testing. Non-isothermal crystallization analysis showed that the BaP could significantly accelerate the crystallization of PLLA, and the non-isothermal crystallization peak shifted to a higher temperature with increasing concentration of BaP, however, the corresponding crystallization peak became wider. XRD results after non-isothermal crystallization confirmed the non-isothermal crystallization DSC results. Additionally, the addition of BaP did not change the crystal form of PLLA. A comparative study on thermal stability indicated that BaP decreased the onset decomposition temperature of PLLA, resulting from the formation of more tiny and imperfect crystals. Whereas the influence of BaP on the thermal decomposition profile of PLLA was negligible. In terms of mechanical properties, the tensile strength and elastic modulus of PLLA/BaP increased compared to the virgin PLLA, unfortunately, the elongation at break decreased.

  16. To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

    Science.gov (United States)

    Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad

    2015-08-25

    Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with

  17. Synthesis and kinetics of non-isothermal degradation of acetylene terminated silazane

    Institute of Scientific and Technical Information of China (English)

    Wei Jian Han; Li Ye; Ji Dong Hu; Tong Zhao

    2011-01-01

    Novel acetylene terminated silazane compounds, with three types of substituent, were synthesized by the aminolysis of dichlorosilane with 3-aminophenylacetylene (3-APA). Thermal property of the compounds is studied by thermogravimetry analysis (TGA). It shows that the acetylene terminated silazane has high temperature resistance. The char yield at 1000℃ is 77.6, 81.9 and 68.7 wt% for methyl, vinyl, and phenyl substituted silazane, respectively. The pyrolysis kinetics of the silazane is investigated by non-isothermal thermogravimetric measurement. The pyrolysis undergoes three stages, which is resolved by PEAKFIT. The kinetic parameters are calculated by the Kissinger method. The role of functionalities on the thermal resistance is discussed. The vinyl-silazane exhibits higher thermal stability because of higher cross-linking density.

  18. Simulation of competitive Cu precipitation in steel during non-isothermal aging

    International Nuclear Information System (INIS)

    Yang, J.B.; Yamashita, T.; Sano, N.; Enomoto, M.

    2008-01-01

    A numerical model has been developed to simulate Cu precipitation in dilute bcc Fe-Cu alloys during non-isothermal aging taking into account competitive nucleation at grain boundaries, dislocations and in the matrix, and structural transformation of Cu particles that occurs during growth. The temporal evolution of number density, mean particle size and size distribution during continuous cooling is simulated and is compared with experimental observations under transmission electron microscope and three-dimensional atom probe field ion microscope. With decreasing temperature the growth and coarsening rates diminishes rapidly whereas nucleation continues to occur down to lower temperatures due to the decrease in the activation energy of nucleation and thus, distributions of fine particles can be obtained relatively easily after cooling. Precipitation and dissolution during continuous heating are simulated and are compared with experimental observations in the literature

  19. Non-isothermal modelling of the all-vanadium redox flow battery

    International Nuclear Information System (INIS)

    Al-Fetlawi, H.; Shah, A.A.; Walsh, F.C.

    2009-01-01

    An non-isothermal model for the all-vanadium redox flow battery (RFB) is presented. The two-dimensional model is based on a comprehensive description of mass, charge, energy and momentum transport and conservation, and is combined with a global kinetic model for reactions involving vanadium species. Heat is generated as a result of activation losses, electrochemical reaction and ohmic resistance. Numerical simulations demonstrate the effects of changes in the operating temperature on performance. It is shown that variations in the electrolyte flow rate and the magnitude of the applied current substantially alter the charge/discharge characteristics, the temperature rise and the distribution of temperature. The influence of heat losses on the charge/discharge behaviour and temperature distribution is investigated. Conditions for localised heating and membrane degradation are discussed.

  20. Non-isothermal curing kinetics and physical properties of MMT-reinforced unsaturated polyester (UP) resins

    Energy Technology Data Exchange (ETDEWEB)

    Vargas, María A., E-mail: angelesvh@yahoo.com [Tecnológico de Estudios Superiores de Ecatepec, Av. Tecnológico S/N, Valle de Anáhuac, 55210 Ecatepec de Morelos (Mexico); Vázquez, H. [Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Física, Av. San Rafael Atlixco 186, col. Vicentina, Mexico, D.F. 09340 (Mexico); Guthausen, G. [KIT, Pro2NMR at MVM and IBG, Karlsruhe (Germany)

    2015-07-10

    Highlights: • Non-isothermal DSC analysis results have shown that the addition of MMT to a UP resin produces a delay in the cure reaction. • The shape of experimental heat-flow DSC curves showed two exothermic peaks for all the samples at different heating rates. • The overall kinetic analysis was performed by isoconversional methods. • It was found that the dependence of the activation energy (E{sub a}) on degree of reaction (α) is complex. - Abstract: Cure behavior of unsaturated polyester (UP)/montmorillonite (MMT)/methyl ethyl ketone peroxide (MEKP)/cobalt octoate intercalated nanocomposites with various MMT loadings was investigated by dynamic differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). UP/MMT nanocomposites were prepared by sequential mixing. Non-isothermal DSC curves were obtained by applying heating rates ranging from 5 to 20 °C/min. They presented two exothermic peaks, which should correspond to two independent cure reactions. The effective activation energy E{sub a}, was determined by applying both the Kissinger’s and Starink’s methods. The results showed slightly higher activation energy for nanocomposites, except for UP/10-MMT. It was found that the dependence of E{sub a} on α is complex. All the systems in this study fitted Sesták–Berggren (SB) model in overall reaction controlled kinetics and the corresponding model parameters, n, m, A were obtained, but it was insufficient in depicting the complex reaction kinetics. Transmission electron microscopy data support the formation of a partially delaminated nanocomposite material. UP and nanocomposites showed similar behavior on thermal stability.

  1. Non-isothermal processes during the drying of bare soil: Model Development and Validation

    Science.gov (United States)

    Sleep, B.; Talebi, A.; O'Carrol, D. M.

    2017-12-01

    Several coupled liquid water, water vapor, and heat transfer models have been developed either to study non-isothermal processes in the subsurface immediately below the ground surface, or to predict the evaporative flux from the ground surface. Equilibrium phase change between water and gas phases is typically assumed in these models. Recently, a few studies have questioned this assumption and proposed a coupled model considering kinetic phase change. However, none of these models were validated against real field data. In this study, a non-isothermal coupled model incorporating kinetic phase change was developed and examined against the measured data from a green roof test module. The model also incorporated a new surface boundary condition for water vapor transport at the ground surface. The measured field data included soil moisture content and temperature at different depths up to the depth of 15 cm below the ground surface. Lysimeter data were collected to determine the evaporation rates. Short and long wave radiation, wind velocity, air ambient temperature and relative humidity were measured and used as model input. Field data were collected for a period of three months during the warm seasons in south eastern Canada. The model was calibrated using one drying period and then several other drying periods were simulated. In general, the model underestimated the evaporation rates in the early stage of the drying period, however, the cumulative evaporation was in good agreement with the field data. The model predicted the trends in temperature and moisture content at the different depths in the green roof module. The simulated temperature was lower than the measured temperature for most of the simulation time with the maximum difference of 5 ° C. The simulated moisture content changes had the same temporal trend as the lysimeter data for the events simulated.

  2. Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory.

    Science.gov (United States)

    Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2017-05-31

    In this work we establish a new temperature dependent procedure within the grand canonical ensemble, to avoid the Dirac delta function exhibited by some of the second order chemical reactivity descriptors based on density functional theory, at a temperature of 0 K. Through the definition of a local chemical potential designed to integrate to the global temperature dependent electronic chemical potential, the local chemical hardness is expressed in terms of the derivative of this local chemical potential with respect to the average number of electrons. For the three-ground-states ensemble model, this local hardness contains a term that is equal to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba, which integrates to the global hardness given by the difference in the first ionization potential, I, and the electron affinity, A, at any temperature. However, in the present approach one finds an additional temperature-dependent term that introduces changes at the local level and integrates to zero. Additionally, a τ-hard dual descriptor and a τ-soft dual descriptor given in terms of the product of the global hardness and the global softness multiplied by the dual descriptor, respectively, are derived. Since all these reactivity indices are given by expressions composed of terms that correspond to products of the global properties multiplied by the electrophilic or nucleophilic Fukui functions, they may be useful for studying and comparing equivalent sites in different chemical environments.

  3. Rarefied gas flow in a rectangular enclosure induced by non-isothermal walls

    Energy Technology Data Exchange (ETDEWEB)

    Vargas, Manuel; Tatsios, Giorgos; Valougeorgis, Dimitris, E-mail: diva@mie.uth.gr [Department of Mechanical Engineering, University of Thessaly, 38334 Volos (Greece); Stefanov, Stefan [Institute of Mechanics, Bulgarian Academy of Sciences, Sofia (Bulgaria)

    2014-05-15

    The flow of a rarefied gas in a rectangular enclosure due to the non-isothermal walls with no synergetic contributions from external force fields is investigated. The top and bottom walls are maintained at constant but different temperatures and along the lateral walls a linear temperature profile is assumed. Modeling is based on the direct numerical solution of the Shakhov kinetic equation and the Direct Simulation Monte Carlo (DSMC) method. Solving the problem both deterministically and stochastically allows a systematic comparison and verification of the results as well as the exploitation of the numerical advantages of each approach in the investigation of the involved flow and heat transfer phenomena. The thermally induced flow is simulated in terms of three dimensionless parameters characterizing the problem, namely, the reference Knudsen number, the temperature ratio of the bottom over the top plates, and the enclosure aspect ratio. Their effect on the flow configuration and bulk quantities is thoroughly examined. Along the side walls, the gas flows at small Knudsen numbers from cold-to-hot, while as the Knudsen number is increased the gas flows from hot-to-cold and the thermally induced flow configuration becomes more complex. These flow patterns with the hot-to-cold flow to be extended to the whole length of the non-isothermal side walls may exist even at small temperature differences and then, they are enhanced as the temperature difference between the top and bottom plates is increased. The cavity aspect ratio also influences this flow configuration and the hot-to-cold flow is becoming more dominant as the depth compared to the width of the cavity is increased. To further analyze the flow patterns a novel solution decomposition into ballistic and collision parts is introduced. This is achieved by accordingly modifying the indexing process of the typical DSMC algorithm. The contribution of each part of the solution is separately examined and a physical

  4. Non-isothermal kinetics of phase transformations in magnetron sputtered alumina films with metastable structure

    International Nuclear Information System (INIS)

    Zuzjaková, Š.; Zeman, P.; Kos, Š.

    2013-01-01

    Highlights: • Non-isothermal kinetics of phase transformations in alumina films was investigated. • The structure of alumina films affects kinetics of the transformation processes. • Kinetic triplets of all transformation processes were determined. • The KAS, FWO, FR and IKP methods for determination of E a and A were used. • The Málek method for determination of the kinetic model was used. - Abstract: The paper reports on non-isothermal kinetics of transformation processes in magnetron sputtered alumina thin films with an amorphous and γ-phase structure leading ultimately to the formation of the thermodynamically stable α-Al 2 O 3 phase. Phase transformation sequences in the alumina films were investigated using differential scanning calorimetry (DSC) at four different heating rates (10, 20, 30, 40 °C/min). Three isoconversional methods (Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO) and Friedman (FR) method) as well as the invariant kinetic parameters (IKP) method were used to determine the activation energies for transformation processes. Moreover, the pre-exponential factors were determined using the IKP method. The kinetic models of the transformation processes were determined using the Málek method. It was found that the as-deposited structure of alumina films affects kinetics of the transformation processes. The film with the amorphous as-deposited structure heated at 40 °C/min transforms to the crystalline γ phase at a temperature of ∼930 °C (E a,IKP = 463 ± 10 kJ/mol) and subsequently to the crystalline α phase at a temperature of ∼1200 °C (E a,IKP = 589 ± 10 kJ/mol). The film with the crystalline γ-phase structure heated at 40 °C/min is thermally stable up to ∼1100 °C and transforms to the crystalline α phase (E a,IKP = 511 ± 16 kJ/mol) at a temperature of ∼1195 °C. The empirical two-parameter Šesták–Berggren kinetic model was found to be the most adequate one to describe all transformation processes

  5. Hydrodynamic boundary conditions for one-component liquid-gas flows on non-isothermal solid substrates

    KAUST Repository

    Xu, Xinpeng; Liu, Chun; Qian, Tiezheng

    2012-01-01

    profiles of liquid-gas flows on non-isothermal, heterogeneous solid substrates is still absent. The purpose of this work is to construct a continuum model for simulating the liquid-gas flows on solid surfaces that are flat and rigid, and may involve

  6. Studies of non-isothermal flow in saturated and partially saturated porous media

    International Nuclear Information System (INIS)

    Ho, C.K.; Maki, K.S.; Glass, R.J.

    1993-01-01

    Physical and numerical experiments have been performed to investigate the behavior of nonisothermal flow in two-dimensional saturated and partially saturated porous media. The physical experiments were performed to identify non-isothermal flow fields and temperature distributions in fully saturated, half-saturated, and residually saturated two-dimensional porous media with bottom heating and top cooling. Two counter-rotating liquid-phase convective cells were observed to develop in the saturated regions of all three cases. Gas-phase convection was also evidenced in the unsaturated regions of the partially saturated experiments. TOUGH2 numerical simulations of the saturated case were found to be strongly dependent on the assumed boundary conditions of the physical system. Models including heat losses through the boundaries of the test cell produced temperature and flow fields that were in better agreement with the observed temperature and flow fields than models that assumed insulated boundary conditions. A sensitivity analysis also showed that a reduction of the bulk permeability of the porous media in the numerical simulations depressed the effects of convection, flattening the temperature profiles across the test cell

  7. Pyrolysis kinetics investigation of Malaysian based biomass with non-isothermal thermogravimetric analysis (TGA)

    International Nuclear Information System (INIS)

    Seyed Shahabeddin Nehzati; Dayang Radiah Awang Biak; Wan Azlina Wan Abdul Karim Ghani; Mohd Amran Mohd Salleh

    2010-01-01

    Full text: Biomass is currently being used as a sustainable energy source. Otherwise the scarceness of fossil fuel sources and the demand for environmental responsibility force the industries to use biomass as an alternate source of energy. Pyrolysis is the first step of biomass conversion and well understanding of this process can develop the biomass conversion such as gasification, liquefaction, carbonization and combustion .TGA studies of Malaysian based biomass have been carried out. TGA studies provide important insight on the thermochemical behavior of specific solid waste. The results of non-isothermal thermogravimetric analysis of palm kernel shell, coconut shell and bagasse, carried out at heating rates of 10 degree Celsius/ min, 20 degree Celsius/ min and 50 degree Celsius/ min, to ramp the temperature from 30 to 1000 were analysed. The TGA studies were carried out in an inert atmosphere of nitrogen. Arrhenius parameters were estimated by 3 different models namely Kissinger model, three-pseudo component and DEAM model the estimated values and the models were compared. The results show that the three-pseudo component model has a good agreement with the experimental results, indicating that ligno celluloses components in the mixture behave in the same way as they do separately. Also it is seen that the decomposition process shifts to higher temperatures at higher heating rates as a result of the competing effects of heat and mass transfer to the material. (Author)

  8. Non-isothermal electrochemical model for lithium-ion cells with composite cathodes

    Science.gov (United States)

    Basu, Suman; Patil, Rajkumar S.; Ramachandran, Sanoop; Hariharan, Krishnan S.; Kolake, Subramanya Mayya; Song, Taewon; Oh, Dukjin; Yeo, Taejung; Doo, Seokgwang

    2015-06-01

    Transition metal oxide cathodes for Li-ion batteries offer high energy density and high voltage. Composites of these materials have shown excellent life expectancy and improved thermal performance. In the present work, a comprehensive non-isothermal electrochemical model for a Lithium ion cell with a composite cathode is developed. The present work builds on lithium concentration-dependent diffusivity and thermal gradient of cathode potential, obtained from experiments. The model validation is performed for a wide range of temperature and discharge rates. Excellent agreement is found for high and room temperature with moderate success at low temperatures, which can be attributed to the low fidelity of material properties at low temperature. Although the cell operation is limited by electronic conductivity of NCA at room temperature, at low temperatures a shift in controlling process is seen, and operation is limited by electrolyte transport. At room temperature, the lithium transport in Cathode appears to be the main source of heat generation with entropic heat as the primary contributor at low discharge rates and ohmic heat at high discharge rates respectively. Improvement in electronic conductivity of the cathode is expected to improve the performance of these composite cathodes and pave way for its wider commercialization.

  9. A NON-ISOTHERMAL THEORY FOR INTERPRETING SODIUM LINES IN TRANSMISSION SPECTRA OF EXOPLANETS

    Energy Technology Data Exchange (ETDEWEB)

    Heng, Kevin; Lavie, Baptiste [University of Bern, Physics Institute, Center for Space and Habitability, Sidlerstrasse 5, CH-3012 Bern (Switzerland); Wyttenbach, Aurélien; Ehrenreich, David; Lovis, Christophe [Observatoire de l’Université de Genève, 51 chemin des Maillettes, CH-1290 Sauverny (Switzerland); Sing, David K., E-mail: kevin.heng@csh.unibe.ch [Astrophysics Group, School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)

    2015-04-10

    We present a theory for interpreting the sodium lines detected in transmission spectra of exoplanetary atmospheres. Previous analyses employed the isothermal approximation and dealt only with the transit radius. By recognizing the absorption depth and the transit radius as being independent observables, we develop a theory for jointly interpreting both quantities, which allows us to infer the temperatures and number densities associated with the sodium lines. We are able to treat a non-isothermal situation with a constant temperature gradient. Our novel diagnostics take the form of simple-to-use algebraic formulae and require measurements of the transit radii (and their corresponding absorption depths) at line center and in the line wing for both sodium lines. We apply our diagnostics to the HARPS data of HD 189733b, confirm the upper atmospheric heating reported by Huitson et al., derive a temperature gradient of 0.4376 ± 0.0154 K km{sup −1}, and find densities ∼1–10{sup 4} cm{sup −3}.

  10. Heat transfer analysis for unsteady MHD flow past a non-isothermal stretching surface

    International Nuclear Information System (INIS)

    Mukhopadhyay, Swati

    2011-01-01

    Highlights: ► Unsteady boundary layer flow and heat transfer over a non-isothermal stretching sheet in a magnetic field are studied. ► Fluid velocity and temperature decrease for increasing unsteadiness parameter. ► Fluid velocity decreases but temperature increases with the increasing values of the Hartman number. ► The sheet temperature in respect of distance and time has analogous effects on the heat transfer. - Abstract: An analysis is made for the unsteady two-dimensional magneto-hydrodynamic flow of an incompressible viscous and electrically conducting fluid over a stretching surface having a variable and general form of surface temperature which removes the restrictions of the particular forms of prescribed surface temperature. Similarity solutions for the transformed governing equations are obtained. The transformed boundary layer equations are solved numerically for some values of the involved parameters, namely the unsteadiness parameter, magnetic parameter, the temperature exponent parameters. The features of the flow and heat transfer characteristics for different values of the governing parameters are analysed and discussed. It is found that the fluid velocity and temperature decrease for increasing unsteadiness parameter. Fluid velocity decreases with the increasing values of the Hartman number resulting an increase in the temperature field in steady as well in unsteady case. It is observed that the variation of the sheet temperature in respect of distance and time has analogous effects both on the free surface temperature and on the heat transfer rate (Nusselt number) at the sheet.

  11. Non-isothermal degradation kinetics of filled with rise husk ash polypropene composites

    Directory of Open Access Journals (Sweden)

    2008-02-01

    Full Text Available The thermal stability and kinetics of non-isothermal degradation of polypropene and polypropene composites filled with 20 mass% vigorously grounded and mixed raw rice husks (RRH, black rice husks ash (BRHA, white rice husks ash (WRHA and Aerosil Degussa (AR were studied. The calculation procedures of Coats – Redfern, Madhysudanan et al., Tang et al., Wanjun et al. and 27 model kinetic equations were used. The kinetics of thermal degradation were found to be best described by kinetic equations of n-th order (Fn mechanism. The kinetic parameters E, A, ΔS≠, ΔH≠and ΔG≠for all the samples studied were calculated. The highest values of n, E and A were obtained for the composites filled with WRHA and AR. A linear dependence between lnA and E was observed, known also as kinetic compensation effect. The results obtained were considered enough to conclude that the cheap RRH and the products of its thermal degradation BRHA and WRHA, after vigorously grounding and mixing, could successfully be used as fillers for polypropene instead of the much more expensive synthetic material Aerosil to prepare various polypropene composites.

  12. Transient non-isothermal model of a polymer electrolyte fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Shah, A.A. [Queen' s-RMC Fuel Cell Research Centre, 945 Princess Street, Kingston, Ont. K7L 5L9 (Canada); Kim, G.-S.; Harvey, D. [Ballard Power Systems, 4343 North Fraser Way, Burnaby, BC V5J 5J9 (Canada); Sui, P.C. [Institute for Integrated Energy Systems, University of Victoria, Victoria, BC V8W 3P6 (Canada)

    2007-01-01

    In this paper we present a one-dimensional transient model for the membrane electrode assembly of a polymer-electrolyte fuel cell. In earlier work we established a framework to describe the water balance in a steady-state, non-isothermal cathode model that explicitly included an agglomerate catalyst layer component. This paper extends that work in several directions, explicitly incorporating components of the anode, including a micro-porous layer, and accounting for electronic potential variations, gas convection and time dependance. The inclusion of temperature effects, which are vital to the correct description of condensation and evaporation, is new to transient modelling. Several examples of the modelling results are given in the form of potentiostatic sweeps and compared to experimental results. Excellent qualitative agreement is demonstrated, particularly in regard to the phenomenon of hysteresis, a manifestation of the sensitive response of the system to the presence of water. Results pertaining to pore size, contact angle and the presence of a micro-porous layer are presented and future work is discussed. (author)

  13. Replicative manufacturing of complex lighting optics by non-isothermal glass molding

    Science.gov (United States)

    Kreilkamp, Holger; Vu, Anh Tuan; Dambon, Olaf; Klocke, Fritz

    2016-09-01

    The advantages of LED lighting, especially its energy efficiency and the long service life have led to a wide distribution of LED technology in the world. However, in order to make fully use of the great potential that LED lighting offers, complex optics are required to distribute the emitted light from the LED efficiently. Nowadays, many applications use polymer optics which can be manufactured at low costs. However, due to ever increasing luminous power, polymer optics reach their technological limits. Due to its outstanding properties, especially its temperature resistance, resistance against UV radiation and its long term stability, glass is the alternative material of choice for the use in LED optics. This research is introducing a new replicative glass manufacturing approach, namely non-isothermal glass molding (NGM) which is able to manufacture complex lighting optics in high volumes at competitive prices. The integration of FEM simulation at the early stage of the process development is presented and helps to guarantee a fast development cycle. A coupled thermo-mechanical model is used to define the geometry of the glass preform as well as to define the mold surface geometry. Furthermore, simulation is used to predict main process outcomes, especially in terms of resulting form accuracy of the molded optics. Experiments conducted on a commercially available molding machine are presented to validate the developed simulation model. Finally, the influence of distinct parameters on important process outcomes like form accuracy, surface roughness, birefringence, etc. is discussed.

  14. Wall modeling for the simulation of highly non-isothermal unsteady flows

    International Nuclear Information System (INIS)

    Devesa, A.

    2006-12-01

    Nuclear industry flows are most of the time characterized by their high Reynolds number, density variations (at low Mach numbers) and a highly unsteady behaviour (low to moderate frequencies). High Reynolds numbers are un-affordable by direct simulation (DNS), and simulations must either be performed by solving averaged equations (RANS), or by solving only the large eddies (LES), both using a wall model. A first investigation of this thesis dealt with the derivation and test of two variable density wall models: an algebraic law (CWM) and a zonal approach dedicated to LES (TBLE-ρ). These models were validated in quasi-isothermal cases, before being used in academic and industrial non-isothermal flows with satisfactory results. Then, a numerical experiment of pulsed passive scalars was performed by DNS, were two forcing conditions were considered: oscillations are imposed in the outer flow; oscillations come from the wall. Several frequencies and amplitudes of oscillations were taken into account in order to gain insights in unsteady effects in the boundary layer, and to create a database for validating wall models in such context. The temporal behaviour of two wall models (algebraic and zonal wall models) were studied and showed that a zonal model produced better results when used in the simulation of unsteady flows. (author)

  15. Electron temperature measurement in Maxwellian non-isothermal beam plasma of an ion thruster

    International Nuclear Information System (INIS)

    Zhang, Zun; Tang, Haibin; Kong, Mengdi; Zhang, Zhe; Ren, Junxue

    2015-01-01

    Published electron temperature profiles of the beam plasma from ion thrusters reveal many divergences both in magnitude and radial variation. In order to know exactly the radial distributions of electron temperature and understand the beam plasma characteristics, we applied five different experimental approaches to measure the spatial profiles of electron temperature and compared the agreement and disagreement of the electron temperature profiles obtained from these techniques. Experimental results show that the triple Langmuir probe and adiabatic poly-tropic law methods could provide more accurate space-resolved electron temperature of the beam plasma than other techniques. Radial electron temperature profiles indicate that the electrons in the beam plasma are non-isothermal, which is supported by a radial decrease (∼2 eV) of electron temperature as the plume plasma expands outward. Therefore, the adiabatic “poly-tropic law” is more appropriate than the isothermal “barometric law” to be used in electron temperature calculations. Moreover, the calculation results show that the electron temperature profiles derived from the “poly-tropic law” are in better agreement with the experimental data when the specific heat ratio (γ) lies in the range of 1.2-1.4 instead of 5/3

  16. Non-isothermal precipitation behaviors of Al-Mg-Si-Cu alloys with different Zn contents

    International Nuclear Information System (INIS)

    Guo, M.X.; Zhang, Y.; Zhang, X.K.; Zhang, J.S.; Zhuang, L.Z.

    2016-01-01

    The non-isothermal precipitation behaviors of Al–Mg–Si–Cu alloys with different Zn contents were investigated by differential scanning calorimetry (DSC) analysis, hardness measurement and high resolution transmission electron microscope characterization. The results show that Zn addition has a significant effect on the GP zone dissolution and precipitation of Al-Mg-Si-Cu alloys. And their activation energies change with the changes of Zn content and aging conditions. Precipitation kinetics can be improved by adding 0.5 wt% or 3.0 wt%Zn, while be suppressed after adding 1.5 wt%Zn. The Mg-Si precipitates (GP zones and β″) are still the main precipitates in the Al-Mg-Si-Cu alloys after heated up to 250 °C, and no Mg-Zn precipitates are observed in the Zn-added alloy due to the occurrence of Mg-Zn precipitates reversion. The measured age-hardening responses of the alloys are corresponding to the predicted results by the established precipitation kinetic equations. Additionally, a double-hump phenomenon of hardness appears in the artificial aging of pre-aged alloy with 3.0 wt% Zn addition, which resulted from the formation of pre-β″ and β″ precipitates. Finally, the precipitation mechanism of Al-Mg-Si-Cu alloys with different Zn contents was proposed based on the microstructure evolution and interaction forces between Mg, Si and Zn atoms.

  17. Reactive solute transport in physically and chemically heterogeneous porous media with multimodal reactive mineral facies: the Lagrangian approach.

    Science.gov (United States)

    Soltanian, Mohamad Reza; Ritzi, Robert W; Dai, Zhenxue; Huang, Chao Cheng

    2015-03-01

    Physical and chemical heterogeneities have a large impact on reactive transport in porous media. Examples of heterogeneous attributes affecting reactive mass transport are the hydraulic conductivity (K), and the equilibrium sorption distribution coefficient (Kd). This paper uses the Deng et al. (2013) conceptual model for multimodal reactive mineral facies and a Lagrangian-based stochastic theory in order to analyze the reactive solute dispersion in three-dimensional anisotropic heterogeneous porous media with hierarchical organization of reactive minerals. An example based on real field data is used to illustrate the time evolution trends of reactive solute dispersion. The results show that the correlation between the hydraulic conductivity and the equilibrium sorption distribution coefficient does have a significant effect on reactive solute dispersion. The anisotropy ratio does not have a significant effect on reactive solute dispersion. Furthermore, through a sensitivity analysis we investigate the impact of changing the mean, variance, and integral scale of K and Kd on reactive solute dispersion. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Attenuation of Chemical Reactivity of Shale Matrixes following Scale Precipitation

    Science.gov (United States)

    Li, Q.; Jew, A. D.; Kohli, A. H.; Alalli, G.; Kiss, A. M.; Kovscek, A. R.; Zoback, M. D.; Brown, G. E.; Maher, K.; Bargar, J.

    2017-12-01

    Introduction of fracture fluids into shales initiates a myriad of fluid-rock reactions that can strongly influence migration of fluid and hydrocarbon through shale/fracture interfaces. Due to the extremely low permeability of shale matrixes, studies on chemical reactivity of shales have mostly focused on shale surfaces. Shale-fluid interactions inside within shale matrixes have not been examined, yet the matrix is the primary conduit through which hydrocarbons and potential contaminants are transmitted. To characterize changes in matrix mineralogy, porosity, diffusivity, and permeability during hydraulic stimulation, we reacted Marcellus (high clay and low carbonate) and Eagle Ford (low clay and high carbonate) shale cores with fracture fluids for 3 weeks at elevated pressure and temperature (80 oC, and 77 bars). In the carbonate-poor Marcellus system, fluid pH increased from 2 to 4, and secondary Fe(OH)3 precipitates were observed in the fluid. Sulfur X-ray fluorescence maps show that fluids had saturated and reacted with the entire 1-cm-diameter core. In the carbonate-rich Eagle Ford system, pH increased from 2 to 6 due to calcite dissolution. When additional Ba2+ and SO42- were present (log10(Q/K)=1.3), extensive barite precipitation was observed in the matrix of the Eagle Ford core (and on the surface). Barite precipitation was also observed on the surface of the Marcellus core, although to a lesser extent. In the Marcellus system, the presence of barite scale attenuated diffusivity in the matrix, as demonstrated by sharply reduced Fe leaching and much less sulfide oxidation. Systematic studies in homogeneous solution show that barite scale precipitation rates are highly sensitive to pH, salinity, and the presence of organic compounds. These findings imply that chemical reactions are not confined to shale/fluid interfaces but can penetrate into shale matrices, and that barite scale formation can clog diffusion pathways for both fluid and hydrocarbon.

  19. Chemical stability of reactive skin decontamination lotion (RSDL®).

    Science.gov (United States)

    Bogan, R; Maas, H J; Zimmermann, T

    2018-09-01

    Reactive Skin Decontamination Lotion (RSDL ® ) is used for the decontamination of Chemical Warfare Agents and Toxic Industrial Compounds after dermal exposure. It has to be stockpiled over a long period and is handled in all climatic zones. Therefore stability is an essential matter of concern. In this work we describe a study to the chemical stability of RSDL ® as basis for an estimation of shelf life. We analysed RSDL ® for the active ingredient 2,3-butandione monoxime (diacetylmonooxime, DAM), the putative degradation product dimethylglyoxime (DMG) and unknown degradation products by means of a reversed phase high pressure liquid chromatography (HPLC). Calculations were done according to the Arrhenius equation. Based on the temperature dependent rate constants, the time span was calculated, until defined threshold values for DAM and DMG subject to specification and valid regulations were exceeded. The calculated data were compared to the ones gathered from stockpiled samples and samples exposed during foreign mission. The decline of DAM followed first order kinetics, while formation of DMG could be described by zero order kinetics. The rate constants were distinctively temperature dependent. Calculated data were in good accordance to the measured ones from stockpile and mission. Based on a specified acceptable DAM-content of 90% and a valid threshold value of 0.1% (w/w) for the degradation product DMG, RSDL ® proved to be stable for at least four years if stored at the recommended conditions of 15°C-30°C. If continuously stored at higher temperatures shelf life will decrease markedly. Therefore RSDL ® is an object for risk orientated quality monitoring during storage. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

    Science.gov (United States)

    Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

    2015-12-17

    Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

  1. Encoding of Fundamental Chemical Entities of Organic Reactivity Interest using chemical ontology and XML.

    Science.gov (United States)

    Durairaj, Vijayasarathi; Punnaivanam, Sankar

    2015-09-01

    Fundamental chemical entities are identified in the context of organic reactivity and classified as appropriate concept classes namely ElectronEntity, AtomEntity, AtomGroupEntity, FunctionalGroupEntity and MolecularEntity. The entity classes and their subclasses are organized into a chemical ontology named "ChemEnt" for the purpose of assertion, restriction and modification of properties through entity relations. Individual instances of entity classes are defined and encoded as a library of chemical entities in XML. The instances of entity classes are distinguished with a unique notation and identification values in order to map them with the ontology definitions. A model GUI named Entity Table is created to view graphical representations of all the entity instances. The detection of chemical entities in chemical structures is achieved through suitable algorithms. The possibility of asserting properties to the entities at different levels and the mechanism of property flow within the hierarchical entity levels is outlined. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Simulation of non-isothermal gas-water processes in complex fracture-matrix systems

    International Nuclear Information System (INIS)

    Jakobs, H.

    2004-01-01

    Degassing effects may occur in fractures in the vicinity of deep radioactive-waste-disposal sites as a result of a pressure drop. These effects play an important role in the investigation of the hydraulic conditions in the near field of the disposal sites. The assumption of single-phase conditions may lead to the misinterpretation of experimental data as degassing leads to two-phase conditions and to a reduction of the effective permeability. The aim of this work is to contribute to the simulation of non-isothermal behaviour of water-gas systems in the near field of atomic waste disposal sites in fractured porous media. We distinguish between sub-REV effects within single fractures and effects due to super-REV heterogeneities which result from the fracture matrix system. We assume to have undisturbed physical conditions as report from the AespoeHard Rock Laboratory in Sweden, i.e.: - a fully water saturated system - a hydrostatic pressure of 5 million Pa. For the simulation on the laboratory scale we use a percolation model. To transfer the information from the laboratory scale to the field scale we use a renormalisation scheme. On the field scale we use a numerical simulator which solves the multiphase flow equations based on the extended form of Darcy's law. In order to investigate the limits of our models we analyse the importance of the forces taken into account, i.e., capillary forces, gravity forces, and viscous forces. This method allows us to quantify the constraints of our models. Furthermore, we investigate the influence of strong parameter heterogeneities caused by the fracture-matrix system on the flow behaviour of gas and water. We consider in particular the influence of the large difference between the entry pressures of matrix and fracture on the migration of the gas phase from the fracture system into the matrix system. (orig.)

  3. Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

    International Nuclear Information System (INIS)

    Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.; Monteiro, Regina C. C.

    2014-01-01

    The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B 2 O 3 -10SiO 2 were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T g ) and of the maximum crystallization temperature (T p ) on the heating rate was used to determine the activation energy associated with the glass transition (E g ), the activation energy for crystallization (E c ), and the Avrami exponent (n). X-ray diffraction (XRD) revealed that barium borate (β-BaB 2 O 4 ) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba 5 Si 8 O 21 ). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E c (χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures

  4. Thermal explosion analysis of methyl ethyl ketone peroxide by non-isothermal and isothermal calorimetric applications

    International Nuclear Information System (INIS)

    Chi, Jen-Hao; Wu, Sheng-Hung; Shu, Chi-Min

    2009-01-01

    In the past, process incidents attributed to organic peroxides (OPs) that involved near misses, over-pressures, runaway reactions, and thermal explosions occurred because of poor training, human error, incorrect kinetic assumptions, insufficient change management, and inadequate chemical knowledge in the manufacturing process. Calorimetric applications were employed broadly to test organic peroxides on a small-scale because of their thermal hazards, such as exothermic behavior and self-accelerating decomposition in the laboratory. In essence, methyl ethyl ketone peroxide (MEKPO) is highly reactive and exothermically unstable. In recent years, it has undergone many thermal explosions and runaway reaction incidents in the manufacturing process. Differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and thermal activity monitor (TAM) were employed to analyze thermokinetic parameters and safety index. The intent of the analyses was to facilitate the use of various auto-alarm equipments to detect over-pressure, over-temperature, and hazardous materials leaks for a wide spectrum of operations. Results indicated that MEKPO decomposition is detected at low temperatures (30-40 deg. C), and the rate of decomposition was shown to exponentially increase with temperature and pressure. Determining time to maximum rate (TMR), self-accelerating decomposition temperature (SADT), maximum temperature (T max ), exothermic onset temperature (T 0 ), and heat of decomposition (ΔH d ) was essential for identifying early-stage runaway reactions effectively for industries.

  5. Non-linear frequency response of non-isothermal adsorption controlled by micropore diffusion with variable diffusivity

    Directory of Open Access Journals (Sweden)

    MENKA PETKOVSKA

    2000-12-01

    Full Text Available The concept of higher order frequency response functions (FRFs is used for the analysis of non-linear adsorption kinetics on a particle scale, for the case of non-isothermal micropore diffusion with variable diffusivity. Six series of FRFs are defined for the general non-isothermal case. A non-linerar mathematical model is postulated and the first and second order FRFs derived and simulated. A variable diffusivity influences the shapes of the second order FRFs relating the sorbate concentration in the solid phase and t he gas pressure significantly, but they still keep their characteristics which can be used for discrimination of this from other kinetic mechanisms. It is also shown that first and second order particle FRFs offter sufficient information for an easy and fast estimation of all model parameters, including those defining the system non-linearity.

  6. Non-isothermal crystallization kinetics and characterization of biodegradable poly(butylene succinate-co-neopentyl glycol succinate) copolyesters.

    Science.gov (United States)

    Xie, Wen-Jie; Zhou, Xiao-Ming

    2015-01-01

    Both biodegradable aliphatic neat poly(butylene succinate) (PBS) and poly(butylene succinate-co-neopentyl glycol succinate) (P(BS-co-NPGS)) copolyesters with different 1,4-butanediol/neopentyl glycol ratios were synthesized through a two-step process of transesterification and polycondensation using stannous chloride and 4-Methylbenzenesulfonic acid as the co-catalysts. The structure, non-isothermal crystallization behavior, crystalline morphology and crystal structure of neat PBS and P(BS-co-NPGS) copolyesters were characterized by (1)H NMR, differential scanning calorimetry (DSC), polarized optical microscope (POM) and wide angle X-ray diffraction (WAXD), respectively. The Avrami equation modified by Jeziorny and Mo's method was employed to describe the non-isothermal crystallization kinetics of the neat PBS and its copolyesters. The modified Avrami equation could adequately describe the primary stage of non-isothermal crystallization kinetics of the neat PBS and its copolyesters. Mo's method provided a fairly satisfactory description of the non-isothermal crystallization of neat PBS and its copolyesters. Interestingly, the values of 1/t1/2, Zc and F(T) obtained by the modified Avrami equation and Mo's method analysis indicated that the crystallization rate increased first and then decreased with an increase of NPGS content compared that of neat PBS, whereas the crystallization mechanism almost kept unchanged. The results of tensile testing showed that the ductility of PBS was largely improved by incorporating NPGS units. The elongation at break increased remarkably with increasing NPGS content. In particular, the sample with 20% NPGS content showed around 548% elongation at break. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Non-isothermal crystallization kinetics and characterization of biodegradable poly(butylene succinate-co-neopentyl glycol succinate) copolyesters

    International Nuclear Information System (INIS)

    Xie, Wen-Jie; Zhou, Xiao-Ming

    2015-01-01

    Both biodegradable aliphatic neat poly(butylene succinate) (PBS) and poly(butylene succinate-co-neopentyl glycol succinate) (P(BS-co-NPGS)) copolyesters with different 1,4-butanediol/neopentyl glycol ratios were synthesized through a two-step process of transesterification and polycondensation using stannous chloride and 4-Methylbenzenesulfonic acid as the co-catalysts. The structure, non-isothermal crystallization behavior, crystalline morphology and crystal structure of neat PBS and P(BS-co-NPGS) copolyesters were characterized by 1 H NMR, differential scanning calorimetry (DSC), polarized optical microscope (POM) and wide angle X-ray diffraction (WAXD), respectively. The Avrami equation modified by Jeziorny and Mo's method was employed to describe the non-isothermal crystallization kinetics of the neat PBS and its copolyesters. The modified Avrami equation could adequately describe the primary stage of non-isothermal crystallization kinetics of the neat PBS and its copolyesters. Mo's method provided a fairly satisfactory description of the non-isothermal crystallization of neat PBS and its copolyesters. Interestingly, the values of 1/t 1/2 , Z c and F(T) obtained by the modified Avrami equation and Mo's method analysis indicated that the crystallization rate increased first and then decreased with an increase of NPGS content compared that of neat PBS, whereas the crystallization mechanism almost kept unchanged. The results of tensile testing showed that the ductility of PBS was largely improved by incorporating NPGS units. The elongation at break increased remarkably with increasing NPGS content. In particular, the sample with 20% NPGS content showed around 548% elongation at break. - Highlights: • The incorporation of NPGS units reduced the spherulite size of BS unit. • The existence of NPGS units did not change the crystal structure of BS unit. • The NPGS units incorporated in PBS could significantly improve the ductility of PBS. • The

  8. Isothermal and non-isothermal infiltration and deuterium transport: a case study in a soil column from a headwater catchment

    Czech Academy of Sciences Publication Activity Database

    Sobotková, M.; Sněhota, M.; Budínová, E.; Tesař, Miroslav

    2017-01-01

    Roč. 65, č. 3 (2017), s. 234-243 ISSN 0042-790X Grant - others:GA ČR(CZ) GA14-03691S Institutional support: RVO:67985874 Keywords : isothermal infiltration * non-isothermal infiltration * column leaching * breakthrough curve * deuterium * viscosity * capillary trapping * entrapped air * permeability Subject RIV: DA - Hydrology ; Limnology OBOR OECD: Environmental sciences (social aspects to be 5.7) Impact factor: 1.654, year: 2016

  9. The Reduced Rank of Ensemble Kalman Filter to Estimate the Temperature of Non Isothermal Continue Stirred Tank Reactor

    OpenAIRE

    Erna Apriliani; Dieky Adzkiya; Arief Baihaqi

    2011-01-01

    Kalman filter is an algorithm to estimate the state variable of dynamical stochastic system. The square root ensemble Kalman filter is an modification of Kalman filter. The square root ensemble Kalman filter is proposed to keep the computational stability and reduce the computational time. In this paper we study the efficiency of the reduced rank ensemble Kalman filter. We apply this algorithm to the non isothermal continue stirred tank reactor problem. We decompose the covariance of the ense...

  10. Production of valuable pyrolytic oils from mixed Municipal Solid Waste (MSW in Indonesia using non-isothermal and isothermal experimental

    Directory of Open Access Journals (Sweden)

    Indra Mamad Gandidi

    2017-09-01

    Full Text Available Municipal solid waste (MSW, disposed of at open dumping sites, poses health risks, contaminates surface water, and releases greenhouse gasses such as methane. However, pyrolysis offers the opportunity to convert MSW into Bio-Oil (BO for clean energy resource. In this paper, an MSW sample consisting of plastic, paper and cardboard, rubber and textiles, and vegetable waste is pyrolysed on a laboratory scale in a fixed-bed vacuum reactor. In the non-isothermal process, the sample was fed into the reactor and then heated. In the isothermal process, the reactor is first heated and then the sample is added. The non-isothermal process created greater BO in both quality and quantity. The BO had a larger amount of gasoline species than diesel-48 fuel, with at 33.44%the BO produced by isothermal pyrolysis and 36.42% in non-isothermal pyrolysis. However the product of isothermal pyrolysis had a higher acid content that reduced its heating value.

  11. Chemical reactivity of alkali lignin modified with laccase

    International Nuclear Information System (INIS)

    Sun, Yong; Qiu, Xueqing; Liu, Yunquan

    2013-01-01

    The modification of alkali lignin with laccase was investigated. The structural change of lignin was analyzed. The sulfonation reactivity was measured by the content of sulfonic group. The results showed the sulfonation reactivity increased to some extent under the condition of atmosphere pressure, but decreased under the condition of 0.3 MPa oxygen pressure. The analysis of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) showed the cleavage of various ether linkages and demethylation took place in the structure of lignin to certain extent during modification with laccase, which contributed to the improvement of sulfonation reactivity. Under the condition of 0.3 MPa oxygen pressure, the ratio of s/g (guaiacyl/syringyl) increased after modification, which reduced the sulfonation reactivity of lignin. Simultaneously partial polymerization reaction, such as 4-O-5′, β-5, 5-5 and other reaction in the aromatic ring decreased the activity sites of C 2 , C 5 and C 6 . Abundant polymerization reaction of α-O increased steric hindrance of C 2 and C 6 in aromatic ring, resulting in low sulfonation reactivity of lignin. -- Highlights: ► The modification of alkali lignin with laccase was investigated. ► The sulfonation reactivity increased under the condition of atmosphere pressure. ► More content of guaiacyl and hydroxy, the less content of methoxyl, syringyl can enhance the sulfonation reactivity of lignin. ► Partial moieties polymerized each other with α-O linkgages during treatment with laccase under oxygen pressure. ► The steric hindrance on C 2 and C 6 in aromatic ring resulted in low sulfonation reaction reactivity of lignin

  12. Non-isothermal kinetics of the thermal desorption of mercury from a contaminated soil

    Directory of Open Access Journals (Sweden)

    López, Félix A.

    2014-03-01

    Full Text Available The Almadén mining district (Ciudad Real, Spain was the largest cinnabar (mercury sulphide mine in the world. Its soils have high levels of mercury a consequence of its natural lithology, but often made much worse by its mining history. The present work examines the thermal desorption of two contaminated soils from the Almadén area under non-isothermal conditions in a N2 atmosphere, using differential scanning calorimetry (DSC. DSC was performed at different heating rates between room temperature and 600 °C. Desorption temperatures for different mercury species were determined. The Friedman, Flynn-Wall-Ozawa and Coasts–Redfern methods were employed to determine the reaction kinetics from the DSC data. The activation energy and pre-exponential factor for mercury desorption were calculated.El distrito minero de Almadén (Ciudad Real, España tiene la mayor mina de cinabrio (sulfuro de mercurio del mundo. Sus suelos tienen altos niveles de mercurio como consecuencia de su litología natural, pero a menudo su contenido en mercurio es mucho más alto debido a la historia minera de la zona. Este trabajo examina la desorción térmica de dos suelos contaminados procedentes de Almadén bajo condiciones isotérmicas en atmósfera de N2, empleando calorimetría diferencial de barrido (DSC. La calorimetría se llevó a cabo a diferentes velocidades de calentamiento desde temperatura ambiente hasta 600 °C. Se determinaron las diferentes temperaturas de desorción de las especies de mercurio presentes en los suelos. Para determinar la cinética de reacción a partir de los datos de DSC se utilizaron los métodos de Friedman, Flynn-Wall-Ozawa y Coasts–Redfern. Además se calcularon las energías de activación y los factores pre-exponenciales para la desorción del mercurio.

  13. Numerical studies of pulsating buoyant plume in isothermal and non isothermal situations

    International Nuclear Information System (INIS)

    Sharma, Pavan K.; Singh, R.K.; Mohanty, Ananya; Das, D.

    2014-01-01

    A computational study has been carried out for predicting the behaviour of buoyant plume in isothermal and non isothermal configuration. General simulation objectives of any buoyant flow simulation are macroscopic in nature and deals with the grass data in respect of buoyancy induced scalar transport. However, the accuracy of predicting such macroscopic parameters is a strong function of several other microscopic parameters which govern the overall macroscopic behaviour. Some of the microscopic parameters for analysis could be buoyancy induced stable/unstable flows, relative plume behaviour, baroclinic velocity distribution etc. Only the CFD based flow modelling approach is capable of calculating several of these aspects. LES based modelling scores over the conventional RANS based computational modelling. The primary objective of the present study was to model buoyant plume simulation of different types in order to explore the details regarding plume and flow structure, instabilities and puffing behaviour. One of the influencing parameters on the overall plume behaviour is the buoyancy resolution index i.e. fineness of chosen grid in relation to the buoyancy intensity and other hydrodynamic parameters. The grid sensitivity studies have been carried out to find out the optimum value grid size by way of buoyant pool fire simulations. Comparative simulation has also been made for a square and round pool fire and it was found that for engineering simulations equivalent area square pool modeling is sufficient. Using the optimum value of grid size and square pool shape simulations have been carried out for different value of fire intensity. The flame puffing frequency as calculated by the reported correlation was compared against the computationally observed puffing frequency and the agreement was generally found to be excellent. Besides these results the comparisons of predicted peak flames temperatures data for various case studies with the available experimental data

  14. Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials

    Science.gov (United States)

    2016-06-01

    2013 4. TITLE AND SUBTITLE Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials 5a...directions for future decontamination formulation approaches. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent... DECONTAMINANTS TO PROVIDE HAZARD MITIGATION OF CHEMICAL WARFARE AGENTS FROM MATERIALS 1. INTRODUCTION Decontamination of materials is the

  15. Material characterization and finite element simulations of aluminum alloy sheets during non-isothermal forming process

    Science.gov (United States)

    Zhang, Nan

    The utilization of more non-ferrous materials is one of the key factors to succeed out of the constantly increasing demand for lightweight vehicles in automotive sector. Aluminum-magnesium alloys have been identified as the most promising substitutions to the conventional steel without significant compromise in structural stiffness and strength. However, the conventional forming methods to deform the aluminum alloy sheets are either costly or insufficient in formability which limit the wide applications of aluminum alloy sheets. A recently proposed non-isothermal hot stamping approach, which is also referred as Hot Blank - Cold Die (HB-CD) stamping, aims at fitting the commercial grade aluminum alloy sheets, such as AA5XXX and AA7XXX, into high-volume and cost-effective production for automotive sector. In essence, HB-CD is a mutation of the conventional hot stamping approach for boron steel (22MnB5) which deforms the hot blank within the cold tool set. By elevating the operation temperature, the formability of aluminum alloy sheets can be significantly improved. Meanwhile, heating the blank only and deforming within the cold tool sets allow to reduce the energy and time consumed. This research work aims at conducting a comprehensive investigation of HB-CD with particular focuses on material characterization, constitutive modeling and coupled thermo-mechanical finite element simulations with validation. The material properties of AA5182-O, a popular commercial grade of aluminum alloy sheet in automotive sector, are obtained through isothermal tensile testing at temperatures from 25° to 300°, covering a quasi-static strain-rate range (0.001--0.1s-1). As the state-of-the-art non-contact strain measurement technique, digital image correlation (DIC) system is utilized to evaluate the stress-strain curves as well as to reveal the details of material deformation with full-field and multi-axis strain measurement. Material anisotropy is characterized by extracting the

  16. Modeling of the non isothermal and non isobaric transformations kinetics. Application to the kaolinite de-hydroxylation and to the tri-uranium octo-oxide reduction by hydrogen; Modelisation de la cinetique de transformations non isothermes et (ou) non isobares. Application a la deshydroxylation de la kaolinite et a la reduction de l'octooxyde de triuranium par l'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Perrin, St

    2002-12-15

    The aim of this work is to be able to describe transformations, occurring when solids and gases are in non isothermal and non isobaric conditions, with kinetic models. A methodology has been used. Two essential processes have to be taken into account: the germination and the growth. The germs are supposed to be formed (at constant temperature and pressure) in the grains surface with a constant velocity by surface unit, (gamma), called germination surface frequency (number of germs.m{sup -2}.s{sup -1}. The growth velocity is characterized by a growth surface reactivity, (phi) (in mol.m{sup -2}.s{sup -1}). With an appropriate transformation model, it is possible to obtain the variations of (gamma) and (phi) in terms of the temperature and pressure which are then used in the calculation of the velocity in non isothermal and non isobaric conditions. In order to validate the developed method, two reactions have been studied. For the first one, the kaolinite de-hydroxylation, an anisotropic germination-growth model, where the step limiting the growth is a diffusion step, has been developed in order to explain the experimental kinetic curves. Nevertheless the velocity curves calculated from this model do not allow to describe the reaction for some temperature variations. This result shows the difficulty to precisely determine the germination surface frequency what induces an important approximation on the kinetic curves. The second reaction is the tri-uranium octo-oxide reduction by hydrogen. It has been shown that this reaction occurs according to three successive transformations. A kinetic model has been developed for each of these reactions considering germination as instantaneous. At last, in comparing this model with the experimental velocity curves, a very good agreement has been verified as well as for a temperature variation than for a hydrogen partial pressure change during the reaction. (O.M.)

  17. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    NARCIS (Netherlands)

    Scheeren, H.A.

    2003-01-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large

  18. Chemical reactivity of the compressed noble gas atoms and their ...

    Indian Academy of Sciences (India)

    Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study ...

  19. Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

    Science.gov (United States)

    Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

    2016-12-01

    In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ( 1 H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Models for risk assessment of reactive chemicals in aquatic toxicology

    NARCIS (Netherlands)

    Freidig, Andreas Peter

    2000-01-01

    A quantitative structure property relationship (QSPR) for a,b-unsaturated carboxylates (mainly acrylates and methacrylates) was established in chapter 2. Chemical reaction rate constants were measured for 12 different chemicals with three different nucleophiles, namely H 2 O, OH - and glutathione

  1. Reactive skin decontamination lotion (RSDL) for the decontamination of chemical warfare agent (CWA) dermal exposure.

    Science.gov (United States)

    Schwartz, M D; Hurst, C G; Kirk, M A; Reedy, S J D; Braue, E H

    2012-08-01

    Rapid decontamination of the skin is the single most important action to prevent dermal absorption of chemical contaminants in persons exposed to chemical warfare agents (CWA) and toxic industrial chemicals (TICs) as a result of accidental or intentional release. Chemicals on the skin may be removed by mechanical means through the use of dry sorbents or water. Recent interest in decontamination systems which both partition contaminants away from the skin and actively neutralize the chemical has led to the development of several reactive decontamination solutions. This article will review the recently FDA-approved Reactive Skin Decontamination Lotion (RSDL) and will summarize the toxicity and efficacy studies conducted to date. Evidence of RSDL's superior performance against vesicant and organophosphorus chemical warfare agents compared to water, bleach, and dry sorbents, suggests that RSDL may have a role in mass human exposure chemical decontamination in both the military and civilian arenas.

  2. Entropy stable modeling of non-isothermal multi-component diffuse-interface two-phase flows with realistic equations of state

    KAUST Repository

    Kou, Jisheng; Sun, Shuyu

    2018-01-01

    In this paper, we consider mathematical modeling and numerical simulation of non-isothermal compressible multi-component diffuse-interface two-phase flows with realistic equations of state. A general model with general reference velocity is derived rigorously through thermodynamical laws and Onsager's reciprocal principle, and it is capable of characterizing compressibility and partial miscibility between multiple fluids. We prove a novel relation among the pressure, temperature and chemical potentials, which results in a new formulation of the momentum conservation equation indicating that the gradients of chemical potentials and temperature become the primary driving force of the fluid motion except for the external forces. A key challenge in numerical simulation is to develop entropy stable numerical schemes preserving the laws of thermodynamics. Based on the convex-concave splitting of Helmholtz free energy density with respect to molar densities and temperature, we propose an entropy stable numerical method, which solves the total energy balance equation directly, and thus, naturally satisfies the first law of thermodynamics. Unconditional entropy stability (the second law of thermodynamics) of the proposed method is proved by estimating the variations of Helmholtz free energy and kinetic energy with time steps. Numerical results validate the proposed method.

  3. Entropy stable modeling of non-isothermal multi-component diffuse-interface two-phase flows with realistic equations of state

    KAUST Repository

    Kou, Jisheng

    2018-02-25

    In this paper, we consider mathematical modeling and numerical simulation of non-isothermal compressible multi-component diffuse-interface two-phase flows with realistic equations of state. A general model with general reference velocity is derived rigorously through thermodynamical laws and Onsager\\'s reciprocal principle, and it is capable of characterizing compressibility and partial miscibility between multiple fluids. We prove a novel relation among the pressure, temperature and chemical potentials, which results in a new formulation of the momentum conservation equation indicating that the gradients of chemical potentials and temperature become the primary driving force of the fluid motion except for the external forces. A key challenge in numerical simulation is to develop entropy stable numerical schemes preserving the laws of thermodynamics. Based on the convex-concave splitting of Helmholtz free energy density with respect to molar densities and temperature, we propose an entropy stable numerical method, which solves the total energy balance equation directly, and thus, naturally satisfies the first law of thermodynamics. Unconditional entropy stability (the second law of thermodynamics) of the proposed method is proved by estimating the variations of Helmholtz free energy and kinetic energy with time steps. Numerical results validate the proposed method.

  4. Approximations to the Non-Isothermal Distributed Activation Energy Model for Biomass Pyrolysis Using the Rayleigh Distribution

    Directory of Open Access Journals (Sweden)

    Dhaundiyal Alok

    2017-09-01

    Full Text Available This paper deals with the influence of some parameters relevant to biomass pyrolysis on the numerical solutions of the nonisothermal nth order distributed activation energy model using the Rayleigh distribution. Investigated parameters are the integral upper limit, the frequency factor, the heating rate, the reaction order and the scale parameters of the Rayleigh distribution. The influence of these parameters has been considered for the determination of the kinetic parameters of the non-isothermal nth order Rayleigh distribution from the experimentally derived thermoanalytical data of biomass pyrolysis.

  5. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity

    Science.gov (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  6. Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

    Energy Technology Data Exchange (ETDEWEB)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi [Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I–35131 Padova, Italy and DEMOCRITOS National Simulation Center of the Italian Istituto Officina dei Materiali (IOM) of the Italian National Research Council (CNR), Trieste (Italy)

    2016-03-21

    Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

  7. Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

    International Nuclear Information System (INIS)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi

    2016-01-01

    Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp 2 hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

  8. Phase rule calculations and the thermodynamics of reactive systems under chemical equilibrium

    Directory of Open Access Journals (Sweden)

    PLATT G. M.

    1999-01-01

    Full Text Available In this paper, we examine the resolution of some phase rule problems within the context of multiple chemical equilibrium reactions, using cubic equations of state and an activity coefficient model. Bubble and dew reactive surfaces, reactive azeotropic loci and reactive critical loci are generated and presented in graphical form. Also isobaric bubble and dew reactive enthalpy loci, which may be useful in the modeling of reactive distillation operations, are depicted. All the formalism here employed is developed within the coordinate transformation of Ung and Doherty, which is appropriate for equilibrium reactive or multireactive systems. The major contribution of this work is the determination of critical loci for reactive or multireactive equilibrium systems. Since it is known that for some class of chemical reactions the kinetics and product distribution exhibit high sensitivity to pressure near criticality, the present study may be useful as a predicting tool in these cases if the chemical equilibrium condition is not too far from the real phenomenon.

  9. The effects of non-isothermal deformation on martensitic transformation in 22MnB5 steel

    International Nuclear Information System (INIS)

    Naderi, M.; Saeed-Akbari, A.; Bleck, W.

    2008-01-01

    In the present paper, the effects of process parameters on phase transformations during non-isothermal deformations are described and discussed. Non-isothermal high temperature compressive deformations were conducted on 22MnB5 boron steel by using deformation dilatometry. Cylindrical samples were uniaxially deformed at different strain rates ranging from 0.05 to 1.0 s -1 to a maximum compressive strain of 50%. Qualitative and quantitative investigations were carried out using surface hardness mapping data as well as dilatation curves. It was observed that a higher initial deformation temperatures resulted in a higher martensite fraction of the microstructure, while a variation in the martensite start temperature was negligible. Another conclusion was that by applying larger amounts of strain as well as higher force levels, not only the martensite start temperature, but also the amount of martensite was reduced. Moreover, it was concluded that using surface hardness mapping technique and dilatometry experiments were very reliable methods to quantify and qualify the coexisting phases

  10. The effects of non-isothermal deformation on martensitic transformation in 22MnB5 steel

    Energy Technology Data Exchange (ETDEWEB)

    Naderi, M. [Department of Materials Science and Engineering, Faculty of Engineering, Arak University, Shariati Street, Arak (Iran, Islamic Republic of)], E-mail: malek.naderi@iehk.rwth-aachen.de; Saeed-Akbari, A.; Bleck, W. [Department of Ferrous Metallurgy, RWTH Aachen University, Aachen (Germany)

    2008-07-25

    In the present paper, the effects of process parameters on phase transformations during non-isothermal deformations are described and discussed. Non-isothermal high temperature compressive deformations were conducted on 22MnB5 boron steel by using deformation dilatometry. Cylindrical samples were uniaxially deformed at different strain rates ranging from 0.05 to 1.0 s{sup -1} to a maximum compressive strain of 50%. Qualitative and quantitative investigations were carried out using surface hardness mapping data as well as dilatation curves. It was observed that a higher initial deformation temperatures resulted in a higher martensite fraction of the microstructure, while a variation in the martensite start temperature was negligible. Another conclusion was that by applying larger amounts of strain as well as higher force levels, not only the martensite start temperature, but also the amount of martensite was reduced. Moreover, it was concluded that using surface hardness mapping technique and dilatometry experiments were very reliable methods to quantify and qualify the coexisting phases.

  11. Experimental and Numerical Studies on Isothermal and Non-isothermal Deep Drawing of IS 513 CR3 Steel Sheets

    Science.gov (United States)

    Mayavan, T.; Karthikeyan, L.; Senthilkumar, V. S.

    2016-11-01

    The present work aims to investigate the effects of the temperature gradient developed within the tool profiles on the formability of IS 513 CR3-grade steel sheets using the cup drawing test. The deformation characteristics of steel sheets were analyzed by comparing the thicknesses in various regions of the formed cup and also the limiting drawing ratios (LDR). Finite element simulations were carried out to predict the behavior of the steel sheets in isothermal and non-isothermal forming using Abaqus/Standard 6.12-1. An analytical model created by Kim was used to validate the experimental and finite element analysis (FEA) results on identical process parameters. Both the FEA and analytical modeling results showed that formability improvement is possible in warm forming; the findings are in good agreement with the experimental results in determining the locations and values of excessive thinning. The results also indicated that formability improvement cannot be achieved by keeping the tooling temperature at the same level. The LDR increased by around 9.5% in isothermal forming and by 19% in non-isothermal forming (with the punch maintained at a lower temperature compared with the die and blank holder). In addition, the fractured surfaces of unsuccessfully formed samples were analyzed using scanning electron microscopy. Metallographic investigations confirmed that the fracture mechanism during the forming of IS 513 CR3-grade steel sheets depends on the brittleness, strain hardening value, forming temperature, and magnitude of stresses developed.

  12. Non-isothermal crystallization kinetics of As{sub 30}Te{sub 60}Ga{sub 10} glass

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Mansour; Abd-Elnaiem, Alaa M.; Abdel-Rahim, M.A.; Hafiz, M.M. [Assiut University, Physics Department, Faculty of Science, Assiut (Egypt); Hassan, R.M. [Assiut University, Physics Department, Faculty of Science, Assiut (Egypt); Aden University, Physics Department, Faculty of Education-Zingiber, Aden (Yemen)

    2017-08-15

    The crystallization study under non-isothermal conditions of As{sub 30}Te{sub 60}Ga{sub 10} glass was investigated. The studied composition was synthesized by melt-quenching technique and characterized by different techniques such as X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The XRD analysis revealed that the as-prepared and annealed bulk glass of As{sub 30}Te{sub 60}Ga{sub 10} exhibit the amorphous, and polycrystalline nature, respectively. The DSC results showed that the heating rate affects the characteristic temperatures, for instance, the glass transition, onset, and peak crystallization temperatures. Furthermore, some thermal analysis methods such as the Kissinger and Matusita et al., approximations were employed to determine the crystallization parameters: for example Avrami exponent and the activation energies for glass transition and crystallization process. In addition, we have compared the experimental DSC data with the calculated ones based on the Johnson-Mehl-Avrami (JMA) and Sestak-Berggren SB(M,N) models. The results indicated that the SB(M,N) model is more suitable for describing the non-isothermal crystallization kinetics of the investigated composition. (orig.)

  13. Evaluation of the chemical reactivity in lignin precursors using the Fukui function.

    Science.gov (United States)

    Martinez, Carmen; Rivera, José L; Herrera, Rafael; Rico, José L; Flores, Nelly; Rutiaga, José G; López, Pablo

    2008-02-01

    The hydroxycinnamyl alcohols: p-coumarol, coniferol and sinapol are considered the basic units and precursors of lignins models. In this work, the specific reactivity of these molecules was studied. We investigate their intrinsic chemical reactivity in terms of the Fukui function, applying the principle of hard and soft acids and bases (HSAB) in the framework of the density functional theory (DFT). Comparisons of their nucleophilic, electrophilic and free radical reactivity show their most probably sites to form linkages among them. It is found that the most reactive sites, for reactions involving free radicals, are the carbons at the beta-position in the p-coumarol and sinapol molecules, whilst the regions around the carbon-oxygen bond of the phenoxyl group are the most reactive in coniferol.

  14. Reactive formulations for a neutralization of toxic industrial chemicals

    Science.gov (United States)

    Tucker, Mark D [Albuqueruqe, NM; Betty, Rita G [Rio Rancho, NM

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  15. Chemical and Photochemical Reactivity in Microemulsions and Waterless Microemulsions.

    Science.gov (United States)

    1988-02-10

    virtually the same as that found in the alcohol rich microemulsion A. This value is also close to that found in pure butanol (= 5.0 - table I). It would...formamide or alcohol rich). RESEARCH PATTERN -Supplementing the physical chemical study of the microemulsion medium involving ionic surfactants with density...SAMII (1/02/1988) Ii&N 3 Part II - OXYDATIONS BY HYDROPEROXIDES IN MICROEMULSIONS E. OLIVEROS and M.T. MAURETTE During the past six months, the financial

  16. Importance of asparagine on the conformational stability and chemical reactivity of selected anti-inflammatory peptides

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: csorico@comunidad.unam.mx [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz-Boca del Río, Universidad Veracruzana, C.P. 91700 Veracruz (Mexico); Campos-Fernández, Linda; Alvarado-Salazar, Andres [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), C.P. 09340 México, D.F. (Mexico)

    2015-08-18

    Highlights: • Asparagine plays an important role to anti-inflammatory effect of peptides. • The electron-donor substituent groups favor the formation of the hydrogen bonds, which contribute in the structural stability of peptides. • Chemical reactivity and the physicochemical features are crucial in the biological functions of peptides. - Abstract: Inflammatory response events are initiated by a complex series of molecular reactions that generate chemical intermediaries. The structure and properties of peptides and proteins are determined by the charge distribution of their side chains, which play an essential role in its electronic structure and physicochemical properties, hence on its biological functionality. The aim of this study was to analyze the effect of changing one central amino acid, such as substituting asparagine for aspartic acid, from Cys–Asn–Ser in aqueous solution, by assessing the conformational stability, physicochemical properties, chemical reactivity and their relationship with anti-inflammatory activity; employing quantum-chemical descriptors at the M06-2X/6-311+G(d,p) level. Our results suggest that asparagine plays a more critical role than aspartic acid in the structural stability, physicochemical features, and chemical reactivity of these tripeptides. Substituent groups in the side chain cause significant changes on the conformational stability and chemical reactivity, and consequently on their anti-inflammatory activity.

  17. Large-Eddy Simulation of Chemically Reactive Pollutant Transport from a Point Source in Urban Area

    Science.gov (United States)

    Du, Tangzheng; Liu, Chun-Ho

    2013-04-01

    Most air pollutants are chemically reactive so using inert scalar as the tracer in pollutant dispersion modelling would often overlook their impact on urban inhabitants. In this study, large-eddy simulation (LES) is used to examine the plume dispersion of chemically reactive pollutants in a hypothetical atmospheric boundary layer (ABL) in neutral stratification. The irreversible chemistry mechanism of ozone (O3) titration is integrated into the LES model. Nitric oxide (NO) is emitted from an elevated point source in a rectangular spatial domain doped with O3. The LES results are compared well with the wind tunnel results available in literature. Afterwards, the LES model is applied to idealized two-dimensional (2D) street canyons of unity aspect ratio to study the behaviours of chemically reactive plume over idealized urban roughness. The relation among various time scales of reaction/turbulence and dimensionless number are analysed.

  18. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B F [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1998-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  20. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1997-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  1. An experimental study of steam explosions involving chemically reactive metal

    International Nuclear Information System (INIS)

    Cho, D.H.; Armstrong, D.R.; Gunther, W.H.; Basu, S.

    1997-01-01

    An experimental study of molten zirconium-water explosions was conducted. A 1-kg mass of zirconium melt was dropped into a column of water. Explosions took place only when an external trigger was used. In the triggered tests, the extent of oxidation of the zirconium melt was very extensive. However, the explosion energetics estimated were found to be very small compared to the potential chemical energy available from the oxidation reaction. Zirconium is of particular interest, since it is a component of the core materials of the current nuclear power reactors. This paper describes the test apparatus and summarizes the results of four tests conducted using pure zirconium melt

  2. Chemical stability and in chemico reactivity of 24 fragrance ingredients of concern for skin sensitization risk assessment.

    Science.gov (United States)

    Avonto, Cristina; Wang, Mei; Chittiboyina, Amar G; Vukmanovic, Stanislav; Khan, Ikhlas A

    2018-02-01

    Twenty-four pure fragrance ingredients have been identified as potential concern for skin sensitization. Several of these compounds are chemically unstable and convert into reactive species upon exposure to air or light. In the present work, a systematic investigation of the correlation between chemical stability and reactivity has been undertaken. The compounds were subjected to forced photodegradation for three months and the chemical changes were studied with GC-MS. At the end of the stability study, two-thirds of the samples were found to be unstable. The generation of chemically reactive species was investigated using the in chemico HTS-DCYA assay. Eleven and fourteen compounds were chemically reactive before and after three months, respectively. A significant increase in reactivity upon degradation was found for isoeugenol, linalool, limonene, lyral, citronellol and geraniol; in the same conditions, the reactivity of hydroxycitronellal decreased. The non-reactive compounds α-isomethyl ionone, benzyl alcohol, amyl cinnamal and farnesol became reactive after photo-oxidative degradation. Overall, forced degradation resulted in four non-reactive fragrance compounds to display in chemico thiol reactivity, while ten out of 24 compounds remained inactive. Chemical degradation does not necessarily occur with generation of reactive species. Non-chemical activation may be involved for the 10 stable unreactive compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. A model for non-isothermal flow and mineral precipitation and dissolution in a thin strip

    NARCIS (Netherlands)

    Bringedal, C.; Berre, I.; Pop, I.S.; Radu, F.A.

    2015-01-01

    Sixth International Conference on Advanced Computational Methods in Engineering (ACOMEN 2014) Motivated by porosity changes due to chemical reactions caused by injection of cold water in a geothermal reservoir, we propose a two-dimensional pore scale model of a thin strip. The pore scale model

  4. Morphology, melting behavior, and non-isothermal crystallization of poly(butylene terephthalate)/poly(ethylene-co-methacrylic acid) blends

    International Nuclear Information System (INIS)

    Huang, J.-W.; Wen, Y.-L.; Kang, C.-C.; Yeh, M.-Y.; Wen, S.-B.

    2007-01-01

    The morphology, melting behavior, and non-isothermal crystallization of poly(butylene terephthalate) (PBT) and poly(ethylene-co-methacrylic acid) (PEMA) blends were studied with scanning electron microscopy, X-ray diffraction and differential scanning calorimetry (DSC). PEMA forms immiscible, yet compatible, blends with PBT. Subsequent DSC scans on melt-crystallized samples exhibited two melting endotherms (T mI and T mII ). The presence of PEMA would facilitate the recrystallization during heating scan and retard PBT molecular chains to form a perfect crystal in cooling crystallization. The dispersion phases of molten PEMA acts as nucleating agents to enhance the crystallization rate of PBT. The solidified PBT could act as nucleating agents to enhance the crystallization of PEMA, but also retard the molecular mobility to reduce crystallization rate. The U* and K g of Hoffman-Lauritzen theory were also determined by Vyazovkin's methods to support the interpretation

  5. Prediction of as-cast grain size of inoculated aluminum alloys melt solidified under non-isothermal conditions

    International Nuclear Information System (INIS)

    Du, Qiang; Li, Yanjun

    2015-01-01

    In this paper, a multi-scale as-cast grain size prediction model is proposed to predict as-cast grain size of inoculated aluminum alloys melt solidified under non-isothermal condition, i.e., the existence of temperature gradient. Given melt composition, inoculation and heat extraction boundary conditions, the model is able to predict maximum nucleation undercooling, cooling curve, primary phase solidification path and final as-cast grain size of binary alloys. The proposed model has been applied to two Al-Mg alloys, and comparison with laboratory and industrial solidification experimental results have been carried out. The preliminary conclusion is that the proposed model is a promising suitable microscopic model used within the multi-scale casting simulation modelling framework. (paper)

  6. A study by non-isothermal thermal methods of spruce wood bark materialss after their application for dye removal

    Directory of Open Access Journals (Sweden)

    VIORICA DULMAN

    2005-11-01

    Full Text Available This paper deals with a study of some materials obtained from spruce bark (Picea abies, Romania, after retention of some dyes frequently used in dyeing processes in the textile industry and waste water treatment. These materials obtained by dye retention exhibit a particular thermal behavior which is different from that of the blank sample (spruce bark. The characteristic temperatures, weight losses, the residue remaining after thermo-oxidative degradation, as well as the activation energies of the significant thermo-destruction stages, estimated from non-isothermal thermogravimetric data, together with the thermal quantities calculated from DTAdata support the conclusion presented in a previous study on dye retention from aqueous solution. The obtained results made evident that, under optimal retention conditions, spruce bark shows the highest retention capacity for the Basic Blue dye, followed by Direct Brown 95 and Direct Brown 2.

  7. Study of Non-Isothermal Crystallization Kinetics of Biodegradable Poly(ethylene adipate/SiO2 Nanocomposites

    Directory of Open Access Journals (Sweden)

    M. R. Memarzadeh

    2013-09-01

    Full Text Available Poly(ethylene adipte and poly(ethylene adipate/silica nanocomposite (PEAd/SiO2 containing 3 wt. % SiO2  were prepared by an in situ method. The examinations on the non-isothermal crystallization kinetic behavior have been conducted by means of differential scanning calorimeter (DSC. The Avrami, Ozawa, and combined Avrami and Ozawa equations were applied to describe the crystallization kinetics and to determine the crystallization parameters of the prepared PEAd/SiO2 nanocomposites. It is found that the inclusion of the silica nanoparticles can accelerate the nucleation rate due to heterogeneous nucleation effect of silica on the polymer matrix. According to the obtained results, the combined Avrami and Ozawa equation shown that the better model for examination of this system.

  8. On the integrability of a Hamiltonian reduction of a 2+1-dimensional non-isothermal rotating gas cloud system

    International Nuclear Information System (INIS)

    Rogers, C; Schief, W K

    2011-01-01

    A 2+1-dimensional version of a non-isothermal gas dynamic system with origins in the work of Ovsiannikov and Dyson on spinning gas clouds is shown to admit a Hamiltonian reduction which is completely integrable when the adiabatic index γ = 2. This nonlinear dynamical subsystem is obtained via an elliptic vortex ansatz which is intimately related to the construction of a Lax pair in the integrable case. The general solution of the gas dynamic system is derived in terms of Weierstrass (elliptic) functions. The latter derivation makes use of a connection with a stationary nonlinear Schrödinger equation and a Steen–Ermakov–Pinney equation, the superposition principle of which is based on the classical Lamé equation

  9. Wave propagation in a non-isothermal atmosphere and the solar five-minute oscillations. [Acoustic waves

    Energy Technology Data Exchange (ETDEWEB)

    Chiuderi, C; Giovanardi, C [Florence Univ. (Italy). Istituto di Astronomia

    1979-11-01

    This paper presents a detailed discussion of the properties of linear, periodic acoustic waves that propagate vertically in a non-isothermal atmosphere. In order to retain the basic feature of the solar atmosphere we have chosen a temperature profile presenting a minimum. An analytical solution of the problem is possible if T/..mu.., ..mu.. being the mean molecular weight, varies parabolically with height. The purpose of this study is to point out the qualitative differences existing between the case treated here and the customary analysis based on a locally isothermal treatment. The computed velocity amplitude and the temperature-perturbation as functions of the wave period exhibit a sharp peak in the region between 180 and 300 s, thus showing the possibility of interpreting the five-minute oscillations as a resonant phenomenon. The propagating or stationary nature of the waves is investigated by a study of the phase of the proposed analytical solution.

  10. Chemical and physical characteristics of phosphate rock materials of varying reactivity

    International Nuclear Information System (INIS)

    Syers, J.K.; Currie, L.D.

    1986-01-01

    Several chemical and physical properties of 10 phosphate rock (PR) materials of varying reactivity were evaluated. The highest concentrations of As and Cd were noted. Because Cd and U can accumulate in biological systems, it may be necessary to direct more attention towards the likely implications of Cd and U concentrations when evaluating a PR for direct application. Three sequential extractions with 2% citric acid may be more useful for comparing the chemical solubility of PR materials, particularly for those containing appreciable CaC0 3 . The poor relationship obtained between surface area and the solubility of the PR materials suggests that surface area plays a secondary role to chemical reactivity in controlling the solubility of a PR in a chemical extractant. A Promesh plot provided an effective method for describing the particle-size characteristics of those PR materials which occurred as sands. Fundamental characteristics, such as mean particle size and uniformity, can readily be determined from a Promesh plot. (author)

  11. Coal structure and reactivity changes induced by chemical demineralisation

    Energy Technology Data Exchange (ETDEWEB)

    Rubiera, F.; Arenillas, A.; Pevida, C.; Garcia, R.; Pis, J.J. [Department of Energy and Environment, Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain); Steel, K.M.; Patrick, J.W. [Fuel Technology Group, School of Chemical, Environmental and Mining Engineering, Nottingham University, University Park, NG7 2RD Nottingham (United Kingdom)

    2002-12-01

    The aim of this work was to determine the influence that an advanced demineralisation procedure has on the combustion characteristics of coal. A high-volatile bituminous coal with 6.2% ash content was treated in a mixture of hydrofluoric and fluorosilicic acids (HF/H{sub 2}SiF{sub 6}). Nitric acid was used either as a pretreatment, or as a washing stage after HF/H{sub 2}SiF{sub 6} demineralisation, with an ash content as low as 0.3% being attained in the latter case. The structural changes produced by the chemical treatment were evaluated by comparison of the FTIR spectra of the raw and treated coal samples. The devolatilisation and combustibility behaviour of the samples was studied by using a thermobalance coupled to a mass spectrometer (TGA-MS) for evolved gas analysis. The combustibility characteristics of the cleaned samples were clearly improved, there being a decrease in SO{sub 2} emissions.

  12. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  13. A two-phase flow and non-isothermal agglomerate model for a proton exchange membrane (PEM) fuel cell

    International Nuclear Information System (INIS)

    Xing, Lei; Liu, Xiaoteng; Alaje, Taiwo; Kumar, Ravi; Mamlouk, Mohamed; Scott, Keith

    2014-01-01

    A two dimensional, across the channel, steady-state model for a proton exchange membrane fuel cell (PEMFC) is presented in which the non-isothermal model for temperature distribution, the two-phase flow model for liquid water transport and the agglomerate model for oxygen reduction reaction are fully coupled. This model is used to investigate thermal transport within the membrane electrode assembly (MEA) associated with the combinational water phase-transfer and transport mechanisms. Effective temperature distribution strategies are established aim to enhance the cell performance. Agglomerate assumption is adopted in which the ionomer and liquid water in turn cover the agglomerate to form the ionomer and liquid water films. Ionomer swelling is associated with the non-uniform distribution of the water content. The modelling results show that heat accumulates within the cathode catalyst layer under the channel. Higher operating temperature improves the cell performance by increasing the kinetics, reducing the liquid water saturation on the cathode and increasing the water carrying capacity of the anode gas. Applying higher temperature on the anode and enlarging the width ratio of the channel/rib could improve the cell performance. Higher cathode temperature decreases the oxygen mole fraction, resulting in an insufficient oxygen supply and a limitation of the cell performance. - Highlights: • The two-phase flow and non-isothermal model couple with the agglomerate model. • Oxygen diffusivity and solubility in Nafion ® relate to water content and temperature. • Higher anode operating temperature improves the fuel cell performance. • Insufficient oxygen supply limits cell performance at higher current densities

  14. Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application.

    Science.gov (United States)

    Vabbilisetty, Pratima; Boron, Mallorie; Nie, Huan; Ozhegov, Evgeny; Sun, Xue-Long

    2018-02-28

    Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell's functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine-poly(ethylene glycol)-dibenzocyclooctyne (DSPE-PEG 2000 -DBCO) and cholesterol-PEG-dibenzocyclooctyne (CHOL-PEG 2000 -DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids.

  15. Deposition of chemically reactive and repellent sites on biosensor chips for reduced non-specific binding.

    Science.gov (United States)

    Gandhiraman, R P; Gubala, V; Le, N C H; Nam, Le Cao Hoai; Volcke, C; Doyle, C; James, B; Daniels, S; Williams, D E

    2010-08-01

    The performances of new polymeric materials with excellent optical properties and good machinability have led the biomedical diagnostics industry to develop cheap disposable biosensor platforms appropriate for point of care applications. Zeonor, a type of cycloolefin polymer (COP), is one such polymer that presents an excellent platform for biosensor chips. These polymer substrates have to be modified to have suitable physico-chemical properties for immobilizing proteins. In this work, we have demonstrated the amine functionalization of COP substrates, by plasma enhanced chemical vapour deposition (PECVD), through codeposition of ethylene diamine and 3-aminopropyltriethoxysilane precursors, for building chemistries on the plastic chip. The elemental composition, adhesion, ageing and reactivity of the plasma polymerized film were examined. The Si-O functionality present in amino silane contributed for a good interfacial adhesion of the coating to COP substrates and also acted as a network building layer for plasma polymerization. Wet chemical modification was then carried out on the amine functionalized chips to create chemically reactive isothiocyanate sites and protein repellent fluorinated sites on the same chip. The density of the reactive and repellent sites was altered by choosing appropriate mixtures of homofunctional phenyldiisothiocyanate (PDITC), pentafluoroisothiocyanate (5FITC) and phenylisothiocyanate (PITC) compounds. By tailoring the density of reactive binding sites and protein repellent sites, the non-specific binding of ssDNA has been decreased to a significant extent. Copyright 2010 Elsevier B.V. All rights reserved.

  16. Unifying principles of irreversibility minimization for efficiency maximization in steady-flow chemically-reactive engines

    International Nuclear Information System (INIS)

    Ramakrishnan, Sankaran; Edwards, Christopher F.

    2014-01-01

    Systems research has led to the conception and development of various steady-flow, chemically-reactive, engine cycles for stationary power generation and propulsion. However, the question that remains unanswered is: What is the maximum-efficiency steady-flow chemically-reactive engine architecture permitted by physics? On the one hand the search for higher-efficiency cycles continues, often involving newer processes and devices (fuel cells, carbon separation, etc.); on the other hand the design parameters for existing cycles are continually optimized in response to improvements in device engineering. In this paper we establish that any variation in engine architecture—parametric change or process-sequence change—contributes to an efficiency increase via one of only two possible ways to minimize total irreversibility. These two principles help us unify our understanding from a large number of parametric analyses and cycle-optimization studies for any steady-flow chemically-reactive engine, and set a framework to systematically identify maximum-efficiency engine architectures. - Highlights: • A unified thermodynamic model to study chemically-reactive engine architectures is developed. • All parametric analyses of efficiency are unified by two irreversibility-minimization principles. • Variations in internal energy transfers yield a net work increase that is greater than engine irreversibility reduced. • Variations in external energy transfers yield a net work increase that is lesser than engine irreversibility reduced

  17. Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application

    Science.gov (United States)

    2018-01-01

    Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell’s functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine–poly(ethylene glycol)–dibenzocyclooctyne (DSPE–PEG2000–DBCO) and cholesterol–PEG–dibenzocyclooctyne (CHOL–PEG2000–DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids. PMID:29503972

  18. Non-isothermal Kinetics of Pyrolysis of Three Kinds of Fresh Biomass

    Institute of Scientific and Technical Information of China (English)

    MIN Fan-fei; ZHANG Ming-xu; CHEN Qing-ru

    2007-01-01

    The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, com straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic parameters of the pyrolysis process were calculated using the method of Ozawa-Flynn-Wall and the mechanism of reactions were investigated using the method of Popescu. It was found that the values of activation energy varied in different temperature ranges. The pyrolysis processes are well described by the models of Zhuravlev (Zh) and valid for diffusion-controlled between 200℃ and 280℃, by Ginstling-Brounshtein (G-B), valid for diffusion-control between 280℃ and 310℃, for first-order chemical reaction between 310℃ and 350℃, by Zhuravlev (Zh) valid for diffusion-control between 350℃ and 430℃ and by the one-way transport model when temperatures are over 430℃.

  19. Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

    Science.gov (United States)

    Zhang, Wei; Huang, Guangming

    2015-11-15

    Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

  20. Chemical reactivity of analogous technetium(V) and rhenium(V) dioxo complexes

    International Nuclear Information System (INIS)

    Kremer, C.; Kremer, E.; Leon, A.

    1993-01-01

    All complexes of the series [MO 2 L 2 ] + (M = Tc, Re, L = ethylenediamine (en), 1,3-diaminopropane (1,3-dap)) have been synthesized and their chemical reactivities investigated. The following properties were studied: stability of the aqueous solutions at different pH values, substitution kinetics, lipophilicity and protein binding. The complexes show very similar reactivity in aqueous solution. From a radiopharmaceutical point of view, no significant difference in their in vivo behavior is expected. (author) 12 refs.; 1 fig.; 3 tabs

  1. Chemical reactivity of potential ferrocyanide precipitates in Hanford tanks with nitrates and nitrites

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.; Tingey, J.M.; Hallen, R.T.; Lilga, M.A.

    1992-01-01

    Ferrocyanide-bearing wastes were produced at the Hanford Site during the 1950s. Safe storage of these wastes has recently drawn increased attention. As a result of these concerns, the Pacific Northwest Laboratory was chartered to investigate the chemical reactivity and explosivity of the ferrocyanide-bearing wastes. We have investigated the thermal sensitivity of synthetic wastes and ferrocyanides and observed oxidation at 130 deg. C and explosions down to 295 deg. C. Coupled with thermodynamic calculations, these thermal studies have also shown a dependence of the reactivity on the synthetic waste composition, which is dependent on the solids settling behavior. (author)

  2. Self-organised synthesis of Rh nanostructures with tunable chemical reactivity

    Directory of Open Access Journals (Sweden)

    Lizzit S

    2007-01-01

    Full Text Available AbstractNonequilibrium periodic nanostructures such as nanoscale ripples, mounds and rhomboidal pyramids formed on Rh(110 are particularly interesting as candidate model systems with enhanced catalytic reactivity, since they are endowed with steep facets running along nonequilibrium low-symmetry directions, exposing a high density of undercoordinated atoms. In this review we report on the formation of these novel nanostructured surfaces, a kinetic process which can be controlled by changing parameters such as temperature, sputtering ion flux and energy. The role of surface morphology with respect to chemical reactivity is investigated by analysing the carbon monoxide dissociation probability on the different nanostructured surfaces.

  3. Non isothermal kinetic study of the aluminium titanate formation in alumina-titania mixtures

    Directory of Open Access Journals (Sweden)

    N. M. Rendtorff

    2014-09-01

    Full Text Available Aluminum titanate (Al2TiO5 is a high refractoriness material with excellent thermal shock resistance. Hence it is suitable for several applications at elevated temperatures where insulation and thermal shock resistance are required. Such as components of internal combustion engines, exhaust port liners, metallurgy, and thermal barriers. The thermal instability of Al2TiO5 at high temperature is another characteristic of this material that has been studied and controlled by the incorporation of several additives. The Al2TiO5 formation from pure oxides presents an endothermic peak in the differential thermal analysis (DTA. The thermodynamic temperature is 1280 ºC. But experimentally, as in every other DTA experiment, these peaks strongly depend on the heating rate: this fact has been extensively employed for the kinetic study of transformation processes and the mechanism determination of chemical reactions. Both activation energies (Ea and nucleation rates can be obtained from these experiments. The present work reports the formation Ea of Al2TiO5 prepared from pure oxides at air atmosphere by the Kissinger DTA based methods. Previously the particle size distribution of the starting powders together with X-ray diffraction analysis of the starting powders and the resulting materials was carried out. The properties of the Al2TiO5 formation were grouped into two groups corresponding to the low and high heating rates, below and over 5 K/min. Ea values were obtained after the Avrami (n constant evidenced that the crystallization mechanism is strongly related to the heating rate, even in the wide range studied which includes the technological ones(0.5-40 K/min.

  4. Fluid Creep Effects on Near-Wall Solute Transport for Non-Isothermal Ampoules

    Science.gov (United States)

    Papadopoulos, Dimitrios; Rosner, Daniel E.

    1996-01-01

    There is a growing practical and theoretical interest in developing accurate macroscopic modelling for flows arising in chemical or physical vapor transport (VT) crystal growth experiments, including those conducted in reduced gravity environments. Rosner was the first person to point out that previously neglected rarefield gas dynamics phenomena (Stefan and bouyancy-driven flows) become rather important sources of convection. In particular, the combination of rarefaction and strong gradients of temperature (and/or concentration) tangential to the side-walls of the ampoule induces convective flows known as thermal (and concentration) 'creep' respectively. His order-of-magnitude estimates revealed that thermal creep effects can be non-negligible even at normal gravitational levels. On the macroscopic level, the bulk fluid mechanics can be adequately described by the familiar macroscopic equations as long as the boundary conditions are modified to account for the integrated effect of kinetic boundary layers adjacent to solid boundaries. Motivated by the growing importance of these phenomena, we have embarked on a series of computational studies to elucidate these fundamental creep-induced effects for a rarefied gas in simple, two-dimensional confined geometries. However, unlike previous related studies, we resort to a microscopic description of the gas, mathematically expressed by the Boltzmann integro-differential equation. We employ the direct simulation Monte Carlo (DSMC) method of Bird, the theoretical foundations and several practical applications. In the case of thermally induced flows, the no-time counter method of Bird is used, as implemented for a hard-sphere gas. The scheme has been also extended to account for realistic molecular interaction models, an extension necessary if the diffusion physics underlying concentration creep are to be captured.

  5. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

    Science.gov (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

    2015-07-23

    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  6. RICE: a computer program for multicomponent chemically reactive flows at all speeds

    International Nuclear Information System (INIS)

    Rivard, W.C.; Farmer, O.A.; Butler, T.D.

    1974-11-01

    The fluid dynamics of chemically reactive mixtures are calculated at arbitrary flow speeds with the RICE program. The dynamics are governed by the two-dimensional, time-dependent Navier-Stokes equations together with the species transport equations and the mass-action rate equations for the chemical reactions. The mass and momentum equations for the mixture are solved implicitly by the ICE technique. The equations for total energy and species transport are solved explicitly while the chemical rate equations are solved implicitly with a time step that may be a submultiple of the hydrodynamic time step. Application is made to continuous wave HF chemical lasers to compute the supersonic mixing and chemical reactions that take place in the lasing cavity. (U.S.)

  7. Enhancing the design of in situ chemical barriers with multicomponent reactive transport modeling

    International Nuclear Information System (INIS)

    Sevougian, S.D.; Steefel, C.I.; Yabusaki, S.B.

    1994-11-01

    This paper addresses the need for systematic control of field-scale performance in the emplacement and operation of in situ chemical treatment barriers; in particular, it addresses the issue of how the local coupling of reaction kinetics and material heterogeneities at the laboratory or bench scale can be accurately upscaled to the field. The authors have recently developed modeling analysis tools that can explicitly account for all relevant chemical reactions that accompany the transport of reagents and contaminants through a chemically and physically heterogeneous subsurface rock or soil matrix. These tools are incorporated into an enhanced design methodology for in situ chemical treatment technologies, and the new methodology is demonstrated in the ongoing design of a field experiment for the In Situ Redox Manipulation (ISRM) project at the U.S. Department of Energy (DOE) Hanford Site. The ISRM design approach, which systematically integrates bench-scale and site characterization information, provides an ideal test for the new reactive transport techniques. The need for the enhanced chemistry capability is demonstrated by an example that shows how intra-aqueous redox kinetics can affect the transport of reactive solutes. Simulations are carried out on massively parallel computer architectures to resolve the influence of multiscale heterogeneities on multicomponent, multidimensional reactive transport. The technology will soon be available to design larger-scale remediation schemes

  8. Modeling of the non isothermal and non isobaric transformations kinetics. Application to the kaolinite de-hydroxylation and to the tri-uranium octo-oxide reduction by hydrogen

    International Nuclear Information System (INIS)

    Perrin, St.

    2002-12-01

    The aim of this work is to be able to describe transformations, occurring when solids and gases are in non isothermal and non isobaric conditions, with kinetic models. A methodology has been used. Two essential processes have to be taken into account: the germination and the growth. The germs are supposed to be formed (at constant temperature and pressure) in the grains surface with a constant velocity by surface unit, (gamma), called germination surface frequency (number of germs.m -2 .s -1 . The growth velocity is characterized by a growth surface reactivity, (phi) (in mol.m -2 .s -1 ). With an appropriate transformation model, it is possible to obtain the variations of (gamma) and (phi) in terms of the temperature and pressure which are then used in the calculation of the velocity in non isothermal and non isobaric conditions. In order to validate the developed method, two reactions have been studied. For the first one, the kaolinite de-hydroxylation, an anisotropic germination-growth model, where the step limiting the growth is a diffusion step, has been developed in order to explain the experimental kinetic curves. Nevertheless the velocity curves calculated from this model do not allow to describe the reaction for some temperature variations. This result shows the difficulty to precisely determine the germination surface frequency what induces an important approximation on the kinetic curves. The second reaction is the tri-uranium octo-oxide reduction by hydrogen. It has been shown that this reaction occurs according to three successive transformations. A kinetic model has been developed for each of these reactions considering germination as instantaneous. At last, in comparing this model with the experimental velocity curves, a very good agreement has been verified as well as for a temperature variation than for a hydrogen partial pressure change during the reaction. (O.M.)

  9. Thermal chemical-mechanical reactive flow model of shock initiation in solid explosives

    International Nuclear Information System (INIS)

    Nicholls, A.L. III; Tarver, C.M.

    1998-01-01

    The three dimensional Arbitrary Lagrange Eulerian hydrodynamic computer code ALE3D with fully coupled thermal-chemical-mechanical material models provides the framework for the development of a physically realistic model of shock initiation and detonation of solid explosives. The processes of hot spot formation during shock compression, subsequent ignition of reaction or failure to react, growth of reaction in individual hot spots, and coalescence of reacting hot spots during the transition to detonation can now be modeled using Arrhenius chemical kinetic rate laws and heat transfer to propagate the reactive flow. This paper discusses the growth rates of reacting hot spots in HMX and TATB and their coalescence during shock to detonation transition. Hot spot deflagration rates are found to be fast enough to consume explosive particles less than 10 mm in diameter during typical shock duration times, but larger particles must fragment and create more reactive surface area in order to be rapidly consumed

  10. Effects of Covalent Functionalization of MWCNTs on the Thermal Properties and Non-Isothermal Crystallization Behaviors of PPS Composites

    Directory of Open Access Journals (Sweden)

    Myounguk Kim

    2017-09-01

    Full Text Available In this study, a PPS/MWCNTs composite was prepared with poly(phenylene sulfide (PPS, as well as pristine and covalent functionalized multi-walled carbon nanotubes (MWCNTs via melt-blending techniques. Moreover, the dispersion of the MWCNTs on the PPS matrix was improved by covalent functionalization as can be seen from a Field-Emission Scanning Electron Microscope (FE-SEM images. The thermal properties of the PPS/MWCNTs composites were characterized using a thermal conductivity analyzer, and a differential scanning calorimeter (DSC. To analyze the crystallization behavior of polymers under conditions similar with those in industry, the non-isothermal crystallization behaviors of the PPS/MWCNTs composites were confirmed using various kinetic equations, such as the modified Avrami equation and Avrami-Ozawa combined equation. The crystallization rate of PPS/1 wt % pristine MWCNTs composite (PPSP1 was faster because of the intrinsic nucleation effect of the MWCNTs. However, the crystallization rates of the composites containing covalently-functionalized MWCNTs were slower than PPSP1 because of the destruction of the MWCNTs graphitic structure via covalent functionalization. Furthermore, the activation energies calculated by Kissinger’s method were consistently decreased by covalent functionalization.

  11. Rapid analytical assessment of the mechanical perturbations induced by non-isothermal injection into a subsurface formation.

    Science.gov (United States)

    De Simone, Silvia; Carrera, Jesús; María Gómez Castro, Berta

    2016-04-01

    Fluid injection into geological formations is required for several engineering operations, e.g. geothermal energy production, hydrocarbon production and storage, CO2 storage, wastewater disposal, etc. Non-isothermal fluid injection causes alterations of the pressure and temperature fields, which affect the mechanical stability of the reservoir. This coupled thermo-hydro-mechanical behavior has become a matter of special interest because of public concern about induced seismicity. The response is complex and its evaluation often requires numerical modeling. Nevertheless, analytical solutions are useful in improving our understanding of interactions, identifying the controlling parameters, testing codes and in providing a rapid assessment of the system response to an alteration. We present an easy-to-use solution to the transient advection-conduction heat transfer problem for parallel and radial flow. The solution is then applied to derive analytical expressions for hydraulic and thermal driven displacements and stresses. The validity is verified by comparison with numerical simulations and yields fairly accurate results. The solution is then used to illustrate some features of the poroelastic and thermoelastic response and, in particular, the sensitivity to the external mechanical constraints and to the reservoir dimension.

  12. Thermodiffusion as a close-to-interface effect that matters in non-isothermal (dis)orderly protein aggregations

    Energy Technology Data Exchange (ETDEWEB)

    Gadomski, A., E-mail: agad@utp.edu.pl; Kruszewska, N., E-mail: nkruszewska@utp.edu.pl

    2014-08-01

    The goal of this discussion letter is to argue how and why an inherent nanoscale thermodiffusion (Soret-type) effect can be relevant in (dis)orderly protein aggregation. We propose a model in which the aggregation of proteins, in the presence of temperature gradient, is described in terms of Smoluchowski dynamics in the phase space of nuclei sizes. The Soret coefficient of the aggregation is proportional to the variations of the aggregation free energy over temperature. The free energy is related to the (interface) boundary condition of the system. When boundary condition is of equilibrium Gibbs–Thomson type, with a well-stated surface tension of the nucleus, to the system can be assigned a negative Soret effect. On the contrary, when a non-equilibrium perturbing (salting-out) term enters the boundary condition, a positive Soret effect may manifest. A zero-value Soret regime is expected to occur in between, yielding very soft (“fragile”) non-Kossel protein-type crystals. - Highlights: • Comprehension for non-isothermal formation of (dis)orderly protein aggregation. • Classification of temperature-sensitive morphologies in colloid-type aggregation. • Morphologies split into near-equilibrium and nonequilibrium structural outcomes. • Classification on mesoscopic nonequilibrium thermodynamics near local equilibrium.

  13. Parallel numerical modeling of hybrid-dimensional compositional non-isothermal Darcy flows in fractured porous media

    Science.gov (United States)

    Xing, F.; Masson, R.; Lopez, S.

    2017-09-01

    This paper introduces a new discrete fracture model accounting for non-isothermal compositional multiphase Darcy flows and complex networks of fractures with intersecting, immersed and non-immersed fractures. The so called hybrid-dimensional model using a 2D model in the fractures coupled with a 3D model in the matrix is first derived rigorously starting from the equi-dimensional matrix fracture model. Then, it is discretized using a fully implicit time integration combined with the Vertex Approximate Gradient (VAG) finite volume scheme which is adapted to polyhedral meshes and anisotropic heterogeneous media. The fully coupled systems are assembled and solved in parallel using the Single Program Multiple Data (SPMD) paradigm with one layer of ghost cells. This strategy allows for a local assembly of the discrete systems. An efficient preconditioner is implemented to solve the linear systems at each time step and each Newton type iteration of the simulation. The numerical efficiency of our approach is assessed on different meshes, fracture networks, and physical settings in terms of parallel scalability, nonlinear convergence and linear convergence.

  14. Modeling Coupled Water and Heat Transport in the Root Zone of Winter Wheat under Non-Isothermal Conditions

    Directory of Open Access Journals (Sweden)

    Rong Ren

    2017-04-01

    Full Text Available Temperature is an integral part of soil quality in terms of moisture content; coupling between water and heat can render a soil fertile, and plays a role in water conservation. Although it is widely recognized that both water and heat transport are fundamental factors in the quantification of soil mass and energy balance, their computation is still limited in most models or practical applications in the root zone under non-isothermal conditions. This research was conducted to: (a implement a fully coupled mathematical model that contains the full coupled process of soil water and heat transport with plants focused on the influence of temperature gradient on soil water redistribution and on the influence of change in soil water movement on soil heat flux transport; (b verify the mathematical model with detailed field monitoring data; and (c analyze the accuracy of the model. Results show the high accuracy of the model in predicting the actual changes in soil water content and temperature as a function of time and soil depth. Moreover, the model can accurately reflect changes in soil moisture and heat transfer in different periods. With only a few empirical parameters, the proposed model will serve as guide in the field of surface irrigation.

  15. The Reduced Rank of Ensemble Kalman Filter to Estimate the Temperature of Non Isothermal Continue Stirred Tank Reactor

    Directory of Open Access Journals (Sweden)

    Erna Apriliani

    2011-01-01

    Full Text Available Kalman filter is an algorithm to estimate the state variable of dynamical stochastic system. The square root ensemble Kalman filter is an modification of Kalman filter. The square root ensemble Kalman filter is proposed to keep the computational stability and reduce the computational time. In this paper we study the efficiency of the reduced rank ensemble Kalman filter. We apply this algorithm to the non isothermal continue stirred tank reactor problem. We decompose the covariance of the ensemble estimation by using the singular value decomposition (the SVD, and then we reduced the rank of the diagonal matrix of those singular values. We make a simulation by using Matlab program. We took some the number of ensemble such as 100, 200 and 500. We compared the computational time and the accuracy between the square root ensemble Kalman filter and the ensemble Kalman filter. The reduced rank ensemble Kalman filter can’t be applied in this problem because the dimension of state variable is too less.

  16. The chemical reactivity and structure of collagen studied by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wess, T.J.; Wess, L.; Miller, A. [Univ. of Stirling (United Kingdom)

    1994-12-31

    The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon.

  17. The chemical reactivity and structure of collagen studied by neutron diffraction

    International Nuclear Information System (INIS)

    Wess, T.J.; Wess, L.; Miller, A.

    1994-01-01

    The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon

  18. Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse: Chapter 12

    Science.gov (United States)

    Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

    2009-01-01

    Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

  19. Reactive chemically modified piezoelectric crystal detectors: A new class of high-selectivity sensors

    International Nuclear Information System (INIS)

    Fadeev, A.Yu.; Filatov, A.L.; Lisichkin, G.V.

    1994-01-01

    A great number of works have focused on the study of properties of modified piezoelectric quartz crystal detectors (PQCDs) coated with sorbing substrates and on applying sensors based on them for the analysis of diluted gas mixtures and solutions. This work offers a new class of gravemetric sensors characterized by a reversible chemical reaction that occurs on their surface. Silica films are proposed as a sorbing coating of quartz detectors, and a chemical modification of a surface is suggested for covalent fixation of the necessary compounds. PQCDs were chemically modified with reactive diene derivatives that can also act as dienophiles. Hexachlorocyclopentadiene (HCCPD, resonater I) and cyclopentadiene (CPD, resonator II) were fixed on a PQCD surface in several stages. After treatment with the resonaters, the PQCD in a CPD gas phase exhibited time dependent frequency shifts from 20-100 Hz. The results suggest that there is a reversible chemical reaction on the electrode surface of resonators I and II when they interact with CPD vapors. Therefore, PQCDs modified with reactive dienes were prepared for the first time and may be employed as selective sensors for CPD

  20. Automated chemical kinetic modeling via hybrid reactive molecular dynamics and quantum chemistry simulations.

    Science.gov (United States)

    Döntgen, Malte; Schmalz, Felix; Kopp, Wassja A; Kröger, Leif C; Leonhard, Kai

    2018-06-13

    An automated scheme for obtaining chemical kinetic models from scratch using reactive molecular dynamics and quantum chemistry simulations is presented. This methodology combines the phase space sampling of reactive molecular dynamics with the thermochemistry and kinetics prediction capabilities of quantum mechanics. This scheme provides the NASA polynomial and modified Arrhenius equation parameters for all species and reactions that are observed during the simulation and supplies them in the ChemKin format. The ab initio level of theory for predictions is easily exchangeable and the presently used G3MP2 level of theory is found to reliably reproduce hydrogen and methane oxidation thermochemistry and kinetics data. Chemical kinetic models obtained with this approach are ready-to-use for, e.g., ignition delay time simulations, as shown for hydrogen combustion. The presented extension of the ChemTraYzer approach can be used as a basis for methodologically advancing chemical kinetic modeling schemes and as a black-box approach to generate chemical kinetic models.

  1. Is the non-isothermal double β-model incompatible with no time evolution of galaxy cluster gas mass fraction?

    Science.gov (United States)

    Holanda, R. F. L.

    2018-05-01

    In this paper, we propose a new method to obtain the depletion factor γ(z), the ratio by which the measured baryon fraction in galaxy clusters is depleted with respect to the universal mean. We use exclusively galaxy cluster data, namely, X-ray gas mass fraction (fgas) and angular diameter distance measurements from Sunyaev-Zel'dovich effect plus X-ray observations. The galaxy clusters are the same in both data set and the non-isothermal spherical double β-model was used to describe their electron density and temperature profiles. In order to compare our results with those from recent cosmological hydrodynamical simulations, we suppose a possible time evolution for γ(z), such as, γ(z) =γ0(1 +γ1 z) . As main conclusions we found that: the γ0 value is in full agreement with the simulations. On the other hand, although the γ1 value found in our analysis is compatible with γ1 = 0 within 2σ c.l., our results show a non-negligible time evolution for the depletion factor, unlike the results of the simulations. However, we also put constraints on γ(z) by using the fgas measurements and angular diameter distances obtained from the flat ΛCDM model (Planck results) and from a sample of galaxy clusters described by an elliptical profile. For these cases no significant time evolution for γ(z) was found. Then, if a constant depletion factor is an inherent characteristic of these structures, our results show that the spherical double β-model used to describe the galaxy clusters considered does not affect the quality of their fgas measurements.

  2. Ultraviolet light photobiology of the protozoan Tetrahymena pyriformis and chemical reactivation of DNA damage

    International Nuclear Information System (INIS)

    Wheeler, J.S.

    1988-01-01

    The tunable dye laser was developed in order to perform UV-B and UV-C (254-320 nm) action spectra studies on several different organisms. Using the laser, action spectra studies have been performed for Escherichia coli, Saccharomyces, Chlamydomonas, Caenorhabditis elegans, Paramecium, and Tetrahymena pyriformis. Studies generally indicate increasing LD 50 values with increasing wavelength. Two notable findings were made: (1) The action spectra does not follow the DNA absorption spectra at 280, 290 and 295 nm; (2) The repair competent/repair defective sensitization factor does not remain constant throughout the wavelength region. In addition it was found that the repair defective strain of E. coli, Bs-1, showed an increase in survival with increasing UV irradiation, at certain dose levels. Further experiments were designed to better characterize the reactivation. Tetrahymena were exposed to UV-C and reactivated with methyl methanesulfonate (MMS) and 4-nitro quinoline oxide (4-NQO). In both cases survival was seen to increase after chemical exposure. Likewise, UV-C was found to reactivate chemical damage (MMS)

  3. Properties of amorphous silicon thin films synthesized by reactive particle beam assisted chemical vapor deposition

    International Nuclear Information System (INIS)

    Choi, Sun Gyu; Wang, Seok-Joo; Park, Hyeong-Ho; Jang, Jin-Nyoung; Hong, MunPyo; Kwon, Kwang-Ho; Park, Hyung-Ho

    2010-01-01

    Amorphous silicon thin films were formed by chemical vapor deposition of reactive particle beam assisted inductively coupled plasma type with various reflector bias voltages. During the deposition, the substrate was heated at 150 o C. The effects of reflector bias voltage on the physical and chemical properties of the films were systematically studied. X-ray diffraction and Raman spectroscopy results showed that the deposited films were amorphous and the films under higher reflector voltage had higher internal energy to be easily crystallized. The chemical state of amorphous silicon films was revealed as metallic bonding of Si atoms by using X-ray photoelectron spectroscopy. An increase in reflector voltage induced an increase of surface morphology of films and optical bandgap and a decrease of photoconductivity.

  4. THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

    Science.gov (United States)

    In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

  5. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  6. Feasibility Study for the Use of Green, Bio-Based, Efficient Reactive Sorbent Material to Neutralize Chemical Warfare Agents

    Science.gov (United States)

    2012-08-02

    REPORT Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents 14. ABSTRACT 16...way cellulose, lignin and hemicelluloses interact as well as whole wood dissolution occurs in ILs. The present project was conducted to 1. REPORT...Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents Report Title ABSTRACT Over the

  7. Microstructure Evolution and the Resulted Influence on Localized Corrosion in Al-Zn-Mg-Cu Alloy during Non-Isothermal Ageing

    Directory of Open Access Journals (Sweden)

    Jun-Zhou Chen

    2018-05-01

    Full Text Available A non-isothermal ageing process was proposed for an Al-Zn-Mg-Cu alloy aiming to accommodate the slow heating/cooling procedure during the ageing of large components. The evolution of microstructure and microchemistry was analyzed by using transmission electron microscopy, high-angle annular dark field imaging, and energy dispersive spectrometry. The age-hardening of the alloy was examined to evaluate the strengthening behavior during the non-isothermal process. The corrosion behavior was investigated via observing the specimens immersed in EXCO solution (solution for Exfoliation Corrosion Susceptibility test in 2xxx and 7xxx series aluminum alloys, referring ASTM G34-01. Secondary precipitation was observed during the cooling stage, leading to increased precipitate number density. The distribution of grain boundary precipitates transits from discontinuous to continuous at the cooling stage, due to the secondary precipitation’s linking-up effect. The solutes’ enrichment on grain boundary precipitates and the depletion in precipitate-free zones develops during the heating procedure, but remains invariable during the cooling procedure. The corrosion in NIA (Non-isothermal Ageing treated specimens initiates from pitting and then transits to intergranular corrosion and exfoliation corrosion. The transition from pitting to intergranular corrosion is very slow for specimens heated to 190 °C, but accelerates slightly as the cooling procedure proceeds. The transition to exfoliation corrosion is observed to be quite slow in all specimens in non-isothermal aged to over-aged condition, suggesting a corrosion resistance comparable to that of RRA condition.

  8. Microstructure Evolution and the Resulted Influence on Localized Corrosion in Al-Zn-Mg-Cu Alloy during Non-Isothermal Ageing.

    Science.gov (United States)

    Chen, Jun-Zhou; Li, Guo-Ai; Cai, Xin; Jiang, Jian-Tang; Shao, Wen-Zhu; Yang, Li; Zhen, Liang

    2018-05-03

    A non-isothermal ageing process was proposed for an Al-Zn-Mg-Cu alloy aiming to accommodate the slow heating/cooling procedure during the ageing of large components. The evolution of microstructure and microchemistry was analyzed by using transmission electron microscopy, high-angle annular dark field imaging, and energy dispersive spectrometry. The age-hardening of the alloy was examined to evaluate the strengthening behavior during the non-isothermal process. The corrosion behavior was investigated via observing the specimens immersed in EXCO solution (solution for Exfoliation Corrosion Susceptibility test in 2xxx and 7xxx series aluminum alloys, referring ASTM G34-01). Secondary precipitation was observed during the cooling stage, leading to increased precipitate number density. The distribution of grain boundary precipitates transits from discontinuous to continuous at the cooling stage, due to the secondary precipitation’s linking-up effect. The solutes’ enrichment on grain boundary precipitates and the depletion in precipitate-free zones develops during the heating procedure, but remains invariable during the cooling procedure. The corrosion in NIA (Non-isothermal Ageing) treated specimens initiates from pitting and then transits to intergranular corrosion and exfoliation corrosion. The transition from pitting to intergranular corrosion is very slow for specimens heated to 190 °C, but accelerates slightly as the cooling procedure proceeds. The transition to exfoliation corrosion is observed to be quite slow in all specimens in non-isothermal aged to over-aged condition, suggesting a corrosion resistance comparable to that of RRA condition.

  9. Chemical Reactivity Testing for the National Spent Nuclear Fuel Program. Quality Assurance Project Plan

    International Nuclear Information System (INIS)

    Newsom, H.C.

    1999-01-01

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of Work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, QA-101PD, revision 1, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted

  10. Chemical Reactivity and Spectroscopy Explored From QM/MM Molecular Dynamics Simulations Using the LIO Code

    Directory of Open Access Journals (Sweden)

    Juan P. Marcolongo

    2018-03-01

    Full Text Available In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU, that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  11. Chemical reactivity and spectroscopy explored from QM/MM molecular dynamics simulations using the LIO code

    Science.gov (United States)

    Marcolongo, Juan P.; Zeida, Ari; Semelak, Jonathan A.; Foglia, Nicolás O.; Morzan, Uriel N.; Estrin, Dario A.; González Lebrero, Mariano C.; Scherlis, Damián A.

    2018-03-01

    In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU), that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  12. A general approach for defining the macroscopic free energy density of saturated porous media at finite strains under non-isothermal conditions

    International Nuclear Information System (INIS)

    Gajo, A.

    2011-01-01

    A general approach is proposed for defining the macroscopic free energy density function (and its complement, the free enthalpy) of a saturated porous medium submitted to finite deformations under non-isothermal conditions, in the case of compressible fluid and solid constituents. Reference is made to an elementary volume treated as an 'open system', moving with the solid skeleton. The proposed free energy depends on the generalised strains (namely an appropriate measure of the strain of the solid skeleton and the variation in fluid mass content) and the absolute temperatures of the solid and fluid phases (which are assumed to differ from each other for the sake of generality). This macroscopic energy proves to be a potential for the generalised stresses (namely the associated measure of the total stress and the free enthalpy of the pore fluid per unit mass) and the entropies of the solid and fluid phases. In contrast with mixture theories, the resulting free energy is not the simple sum of the free energies of the single constituents. Two simplified cases are examined in detail, i.e. the semi-linear theory (originally proposed for isothermal conditions and extended here to non-isothermal problems) and the linear theory. The proposed approach paves the way to the consistent non-isothermal-hyper-elastic-plastic modelling of saturated porous media with a compressible fluid and solid constituents. (authors)

  13. Hydrodynamic boundary conditions for one-component liquid-gas flows on non-isothermal solid substrates

    KAUST Repository

    Xu, Xinpeng

    2012-01-01

    Recently, liquid-gas flows related to droplets, bubbles, and thin films on solid surfaces with thermal and wettability gradients have attracted widespread attention because of the many physical processes involved and their promising potential applications in biology, chemistry, and industry. Various new physical effects have been discovered at fluid-solid interfaces by experiments and molecular dynamics simulations, e.g., fluid velocity slip, temperature slip (Kapitza resistance), mechanical-thermal cross coupling, etc. There have been various models and theories proposed to explain these experimental and numerical observations. However, to the best of our knowledge,a continuum hydrodynamic model capable of predicting the temperature and velocity profiles of liquid-gas flows on non-isothermal, heterogeneous solid substrates is still absent. The purpose of this work is to construct a continuum model for simulating the liquid-gas flows on solid surfaces that are flat and rigid, and may involve wettability gradients and thermal gradients. This model is able to describe fluid velocity slip, temperature slip, and mechanical-thermal coupling that may occur at fluid-solid interfaces. For this purpose, we first employ the diffuse interface modeling to formulate the hydrodynamic equations for one-component liquid-gas flows in the bulk region. This reproduces the dynamic van der Waals theory of Onuki [Phys. Rev. Lett., 94: 054501, 2005]. We then extendWaldmann\\'s method [Z. Naturforsch. A, 22: 1269-1280, 1967] to formulate the boundary conditions at the fluid-solid interface that match the hydrodynamic equations in the bulk. The effects of the solid surface curvature are also briefly discussed in the appendix. The guiding principles of our model derivation are the conservation laws and the positive definiteness of entropy production together with the Onsager reciprocal relation. The derived model is self-consistent in the sense that the boundary conditions are

  14. The influence of condensed tannin structure on rate of microbial mineralization and reactivity to chemical assays.

    Science.gov (United States)

    Norris, Charlotte E; Preston, Caroline M; Hogg, Karen E; Titus, Brian D

    2011-03-01

    We examined how tannin structure influences reactivity in tannin assays and carbon and nitrogen mineralization. Condensed tannins from the foliage of ten tree and shrub species and from pecan shells (Carya illinoensis) had different proportions of: (a) epicatechin (cis) and catechin (trans) isomers, (b) procyanidin (PC) and prodelphinidin (PD) monomers, and (c) different chain lengths. The response of each tannin to several widely used tannin assays was determined. Although there was some variation in response to proanthocyanidin (butanol/HCl) and Folin Ciocalteu assays, we did not deduce any predictable relationship between tannin structure and response to either assay. There was little variation in protein precipitation among the different tannins. To assess biological activity, six of the tannins were incubated with forest humus for 22 days. We determined that, while PC-based tannins remained at least partly extractable for the duration of the incubation, tannins with a high proportion of PD subunits rapidly became unextractable from soil. There was a positive correlation between net nitrogen mineralization and cis chemical structure. Carbon mineralization was enhanced initially by the addition of tannins to humus, but after 22 days, a negative correlation between the proportion of cis subunits and respiration was determined. Overall, we were not able to demonstrate consistent effects of structure on either microbial mineralization or reactivity to chemical assays; such relationships remain elusive.

  15. Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition

    Science.gov (United States)

    2017-09-30

    Report: Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer ...Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition Report Term: 0-Other Email: pcappillino... Layer Electroless Deposition (ALED, Figure 1) is the ability to tune growth mechanism, hence growth morphology, by altering conditions. In this

  16. Efficient modeling of reactive transport phenomena by a multispecies random walk coupled to chemical equilibrium

    International Nuclear Information System (INIS)

    Pfingsten, W.

    1996-01-01

    Safety assessments for radioactive waste repositories require a detailed knowledge of physical, chemical, hydrological, and geological processes for long time spans. In the past, individual models for hydraulics, transport, or geochemical processes were developed more or less separately to great sophistication for the individual processes. Such processes are especially important in the near field of a waste repository. Attempts have been made to couple at least two individual processes to get a more adequate description of geochemical systems. These models are called coupled codes; they couple predominantly a multicomponent transport model with a chemical reaction model. Here reactive transport is modeled by the sequentially coupled code MCOTAC that couples one-dimensional advective, dispersive, and diffusive transport with chemical equilibrium complexation and precipitation/dissolution reactions in a porous medium. Transport, described by a random walk of multispecies particles, and chemical equilibrium calculations are solved separately, coupled only by an exchange term. The modular-structured code was applied to incongruent dissolution of hydrated silicate gels, to movement of multiple solid front systems, and to an artificial, numerically difficult heterogeneous redox problem. These applications show promising features with respect to applicability to relevant problems and possibilities of extensions

  17. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    T. F. Lyon

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  18. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    C. W. Spicer

    1994-08-01

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  19. New chemical-DSMC method in numerical simulation of axisymmetric rarefied reactive flow

    Science.gov (United States)

    Zakeri, Ramin; Kamali Moghadam, Ramin; Mani, Mahmoud

    2017-04-01

    The modified quantum kinetic (MQK) chemical reaction model introduced by Zakeri et al. is developed for applicable cases in axisymmetric reactive rarefied gas flows using the direct simulation Monte Carlo (DSMC) method. Although, the MQK chemical model uses some modifications in the quantum kinetic (QK) method, it also employs the general soft sphere collision model and Stockmayer potential function to properly select the collision pairs in the DSMC algorithm and capture both the attraction and repulsion intermolecular forces in rarefied gas flows. For assessment of the presented model in the simulation of more complex and applicable reacting flows, first, the air dissociation is studied in a single cell for equilibrium and non-equilibrium conditions. The MQK results agree well with the analytical and experimental data and they accurately predict the characteristics of the rarefied flowfield with chemical reaction. To investigate accuracy of the MQK chemical model in the simulation of the axisymmetric flow, air dissociation is also assessed in an axial hypersonic flow around two geometries, the sphere as a benchmark case and the blunt body (STS-2) as an applicable test case. The computed results including the transient, rotational and vibrational temperatures, species concentration in the stagnation line, and also the heat flux and pressure coefficient on the surface are compared with those of the other chemical methods like the QK and total collision energy (TCE) models and available analytical and experimental data. Generally, the MQK chemical model properly simulates the chemical reactions and predicts flowfield characteristics more accurate rather than the typical QK model. Although in some cases, results of the MQK approaches match with those of the TCE method, the main point is that the MQK does not need any experimental data or unrealistic assumption of specular boundary condition as used in the TCE method. Another advantage of the MQK model is the

  20. Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

    Science.gov (United States)

    Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R

    2006-04-15

    The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

  1. The chemical reactivity of the Martian soil and implications for future missions

    Science.gov (United States)

    Zent, Aaron P.; Mckay, Christopher P.

    1994-01-01

    Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

  2. Reactive Chemical Vapor Deposition Method as New Approach for Obtaining Electroluminescent Thin Film Materials

    Directory of Open Access Journals (Sweden)

    Valentina V. Utochnikova

    2012-01-01

    Full Text Available The new reactive chemical vapor deposition (RCVD method has been proposed for thin film deposition of luminescent nonvolatile lanthanide aromatic carboxylates. This method is based on metathesis reaction between the vapors of volatile lanthanide dipivaloylmethanate (Ln(dpm3 and carboxylic acid (HCarb orH2Carb′ and was successfully used in case of HCarb. Advantages of the method were demonstrated on example of terbium benzoate (Tb(bz3 and o-phenoxybenzoate thin films, and Tb(bz3 thin films were successfully examined in the OLED with the following structure glass/ITO/PEDOT:PSS/TPD/Tb(bz3/Ca/Al. Electroluminescence spectra of Tb(bz3 showed only typical luminescent bands, originated from transitions of the terbium ion. Method peculiarities for deposition of compounds of dibasic acids H2Carb′ are established on example of terbium and europium terephtalates and europium 2,6-naphtalenedicarboxylate.

  3. Reactive Ion Etching as Cleaning Method Post Chemical Mechanical Polishing for Phase Change Memory Device

    International Nuclear Information System (INIS)

    Min, Zhong; Zhi-Tang, Song; Bo, Liu; Song-Lin, Feng; Bomy, Chen

    2008-01-01

    In order to improve nano-scale phase change memory performance, a super-clean interface should be obtained after chemical mechanical polishing (CMP) of Ge 2 Sb 2 Te 5 phase change films. We use reactive ion etching (RIE) as the cleaning method. The cleaning effect is analysed by scanning electron microscopy and an energy dispersive spectrometer. The results show that particle residue on the surface has been removed. Meanwhile, Ge 2 Sb 2 Te 5 material stoichiometric content ratios are unchanged. After the top electrode is deposited, current-voltage characteristics test demonstrates that the set threshold voltage is reduced from 13 V to 2.7V and the threshold current from 0.1mA to 0.025mA. Furthermore, we analyse the RIE cleaning principle and compare it with the ultrasonic method

  4. Computer tool to evaluate the cue reactivity of chemically dependent individuals.

    Science.gov (United States)

    Silva, Meire Luci da; Frère, Annie France; Oliveira, Henrique Jesus Quintino de; Martucci Neto, Helio; Scardovelli, Terigi Augusto

    2017-03-01

    Anxiety is one of the major influences on the dropout of relapse and treatment of substance abuse treatment. Chemically dependent individuals need (CDI) to be aware of their emotional state in situations of risk during their treatment. Many patients do not agree with the diagnosis of the therapist when considering them vulnerable to environmental stimuli related to drugs. This research presents a cue reactivity detection tool based on a device acquiring physiological signals connected to personal computer. Depending on the variations of the emotional state of the drug addict, alteration of the physiological signals will be detected by the computer tool (CT) which will modify the displayed virtual sets without intervention of the therapist. Developed in 3ds Max® software, the CT is composed of scenarios and objects that are in the habit of marijuana and cocaine dependent individual's daily life. The interaction with the environment is accomplished using a Human-Computer Interface (HCI) that converts incoming physiological signals indicating anxiety state into commands that change the scenes. Anxiety was characterized by the average variability from cardiac and respiratory rate of 30 volunteers submitted stress environment situations. To evaluate the effectiveness of cue reactivity a total of 50 volunteers who were marijuana, cocaine or both dependent were accompanied. Prior to CT, the results demonstrated a poor correlation between the therapists' predictions and those of the chemically dependent individuals. After exposure to the CT, there was a significant increase of 73% in awareness of the risks of relapse. We confirmed the hypothesis that the CT, controlled only by physiological signals, increases the perception of vulnerability to risk situations of individuals with dependence on marijuana, cocaine or both. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  5. Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

    Science.gov (United States)

    Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

    2011-11-01

    Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

  6. The kinetic of mass loss of grades A and B of melted TNT by isothermal and non-isothermal gravimetric methods

    Directory of Open Access Journals (Sweden)

    Hamid Reza Pouretedal

    2018-04-01

    Full Text Available The kinetic and activation energy of mass loss of two grades of melted TNT explosive, grade A and grade B, with freezing points of 80.57 and 78.15 °C, respectively, were studied by isothermal and non-isothermal gravimetric methods. In isothermal method, the mass loss of samples in containers of glass and aluminum was followed in temperatures of 80, 90 and 100 °C. The kinetic of the mass loss of the samples in the aluminum container was higher than the kinetic of it in the glass container that can be related to the effects of heat transfer and catalytic of aluminum metal. Also, the presence of impurities in grade B was due to increasing of kinetic of mass loss of it versus grade A. The non-isothermal curves were obtained in range of 30–330 °C at heating rates of 10, 15 and 20 °C⋅min−1. The TG/DTG data were used for determination of activation energy (Ea of mass loss of TNT samples upon degradation by using Ozawa, Kissinger, Ozawa-Flynn-Wall (OFW and Kissinger-Akahira-Sunose (KAS methods as model free methods. The activation energies of grades of A and B of TNT was obtained 99–120 and 66–70 kJ mol−1, respectively. The lower values of activation energy of the degradation reaction of grade B confirm the effect of impurities in the kinetics of mass loss of this grade. Keywords: TNT, Isothermal, Non-isothermal, Kinetic, Mass loss

  7. Assessment of Salmonella spp. and Escherichia coli O157:H7 growth on lettuce exposed to isothermal and non-isothermal conditions.

    Science.gov (United States)

    de Oliveira Elias, Susana; Noronha, Tiago Baptista; Tondo, Eduardo Cesar

    2018-06-01

    This study aimed to assess the growth of Salmonella and Escherichia coli O157:H7 on lettuce exposed to isothermal and non-isothermal conditions. Pathogens were inoculated on lettuce separately and stored under isothermal condition at 5 °C, 10 °C, 25 °C, 37 °C for both bacteria, at 40 °C for Salmonella and 42 °C for E. coli O157:H7. Growth curves were built by fitting the data to the Baranyi's DMFit, generating R 2 values greater than 0.92 for primary models. Secondary models were fitted with Ratkowsky equations, generating R 2 values higher than 0.91 and RMSE lower than 0.1. Experimental data showed that both bacteria could grow at all temperatures. Also, the growth of both pathogens under non-isothermal conditions was studied simulating temperatures found from harvest to supermarkets in Brazil. Models were analysed by R 2 , RMSE, bias factor (Bf) and accuracy factor (Af). Salmonella and E. coli O157:H7 were able to grow in this temperature profile and the models could predict the behavior of these microorganisms on lettuce under isothermal and non-isothermal conditions. Based on the results, a negligible growth time (ς) was proposed to provide the time which lettuce could be exposed to a specific temperature and do not present an expressive growth of bacteria. The ς was developed based on Baranyi's primary model equation and on growth potential concept. ς is the value of lag phase added of the time necessary to population grow 0.5 log CFU/g. The ς of lettuce exposed to 37 °C was 1.3 h, while at 5 °C was 3.3 days. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

    Directory of Open Access Journals (Sweden)

    J. Rinne

    2012-06-01

    Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

  9. Non-Isothermal Gas-Based Direct Reduction Behavior of High Chromium Vanadium-Titanium Magnetite Pellets and the Melting Separation of Metallized Pellets

    Directory of Open Access Journals (Sweden)

    Jue Tang

    2017-04-01

    Full Text Available The non-isothermal reduction behavior of high chromium vanadium-titanium magnetite (HCVTM pellets by gas mixtures was investigated using different heating rates (4, 8, and 12 K/min and varied gas compositions (H2/CO = 2/5, H2/CO = 1/1, and H2/CO = 5/2 volume ratios; the pellets were then used for melting separation. It was observed that the temperature corresponding to the maximum reduction ratio increased with the increasing heating rate. The HCVTM pellets reached the same final reduction ratio under a given reducing gas composition, although the heating rates were different. Under the same heating rate, the gas mixture with more H2 was conducive for obtaining a higher reduction ratio. The phase transformations during the non-isothermal reduction were ordered as follows: Fe2O3 → Fe3O4 → FeO → Fe; Fe9TiO15 + Fe2Ti3O9 → Fe2.75Ti0.25O4 → FeTiO3 → TiO2; V1.7Cr0.3O3 → V2O3 → Fe2VO4; Fe1.2Cr0.8O3 → Cr2O3 → FeCr2O4. The non-isothermal reduction kinetic model was established based on the unreacted core model with multiple reaction interfaces. The correlation coefficients were greater than 0.99, revealing that this kinetic model could properly describe the non-isothermal reduction of the HCVTM pellets by gas mixtures. Iron containing V and Cr along with the Ti-rich slag was obtained through the melting separation of the metallized HCVTM pellets. The mass fractions and recovery rates of Fe, V, and Cr in the iron were 93.87% and 99.45%, 0.91% and 98.83%, and 0.72% and 95.02%, respectively. The mass fraction and recovery rate of TiO2 in the slag were 38.12% and 95.08%, respectively.

  10. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    Science.gov (United States)

    Scheeren, H. A.

    2003-09-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of

  11. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    International Nuclear Information System (INIS)

    Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L.; Vela, Alberto

    2015-01-01

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

  12. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Sudarjanto, Gatut [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller-Lehmann, Beatrice [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller, Jurg [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia)]. E-mail: j.keller@awmc.uq.edu.au

    2006-11-02

    The integrated chemical-biological degradation combining advanced oxidation by UV/H{sub 2}O{sub 2} followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H{sub 2}O{sub 2}/L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required.

  13. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    International Nuclear Information System (INIS)

    Sudarjanto, Gatut; Keller-Lehmann, Beatrice; Keller, Jurg

    2006-01-01

    The integrated chemical-biological degradation combining advanced oxidation by UV/H 2 O 2 followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H 2 O 2 /L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required

  14. Comparison of Electrocoagulation and Chemical Coagulation Processes in Removing Reactive red 196 from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Ali Assadi

    2016-06-01

    Full Text Available Background: Conventional chemical coagulation is considered as an old method to dye and COD removal in textile effluent. Electrocoagulation (EC process is a robust method to achieve maximum removal. Methods: This study was designed to compare the result of operational parameters including optimum pH and coagulant concentration for chemical coagulation with ferric chloride and alum also, voltage, electrolysis time, initial pH, and conductivity for EC with iron electrodes to remove reactive red 196 (RR 196. Results: The outcomes show that ferric chloride and alum at optimum concentration were capable of removing dye and COD by 79.63 % and 84.83% and 53% and 55%, respectively. In contrast, EC process removed the dye and COD by 99.98% and 90.4%, respectively. Conclusion: The highest treatment efficiency was obtained by increasing the voltage, electrolysis time, pH and conductivity. Increase initial dye concentration reduces removal efficiency. Ultimately, it could be concluded that EC technology is an efficient procedure for handling of colored industrial wastewaters.

  15. Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Sibener, Steven J. [Univ. of Chicago, IL (United States). James Franck Inst. and Dept. of Chemistry

    2014-03-11

    This research program explored the efficacy of using molecular-level manipulation, imaging and scanning tunneling spectroscopy in conjunction with supersonic molecular beam gas-surface scattering to significantly enhance our understanding of chemical processes occurring on well-characterized interfaces. One program focus was on the spatially-resolved emergent behavior of complex reaction systems as a function of the local geometry and density of adsorbate-substrate systems under reaction conditions. Another focus was on elucidating the emergent electronic and related reactivity characteristics of intentionally constructed single and multicomponent atom- and nanoparticle-based materials. We also examined emergent chirality and self-organization in adsorbed molecular systems where collective interactions between adsorbates and the supporting interface lead to spatial symmetry breaking. In many of these studies we combined the advantages of scanning tunneling (STM) and atomic force (AFM) imaging, scanning tunneling local electronic spectroscopy (STS), and reactive supersonic molecular beams to elucidate precise details of interfacial reactivity that had not been observed by more traditional surface science methods. Using these methods, it was possible to examine, for example, the differential reactivity of molecules adsorbed at different bonding sites in conjunction with how reactivity is modified by the local configuration of nearby adsorbates. At the core of this effort was the goal of significantly extending our understanding of interfacial atomic-scale interactions to create, with intent, molecular assemblies and materials with advanced chemical and physical properties. This ambitious program addressed several key topics in DOE Grand Challenge Science, including emergent chemical and physical properties in condensed phase systems, novel uses of chemical imaging, and the development of advanced reactivity concepts in combustion and catalysis including carbon

  16. The surface chemical reactivity of particles and its impact on human health

    Science.gov (United States)

    Setyan, A.; Sauvain, J. J.; Riediker, M.; Guillemin, M.; Rossi, M. J.

    2017-12-01

    The chemical composition of the particle-air interface is the gateway to chemical reactions of gases with condensed phase particles. It is of prime importance to understand the reactivity of particles and their interaction with surrounding gases, biological membranes, and solid supports. We used a Knudsen flow reactor to quantify functional groups on the surface of a few selected particle types. This technique is based on a heterogeneous titration reaction between a probe gas and a specific functional group on the particle surface. Six probe gases have been selected for the identification and quantification of important functional groups: N(CH3)3 for the titration of acidic sites, NH2OH for the detection of carbonyl functions (aldehydes and ketones) and/or oxidized sites owing to its strong reducing properties, CF3COOH and HCl for basic sites of different strength, O3 and NO2 for oxidizable groups. We also studied the kinetics of the reactions between particles and probe gases (uptake coefficient γ0). We tested the surface chemical composition and oxidation states of laboratory-generated aerosols (3 amorphous carbons, 2 flame soots, 2 Diesel particles, 2 secondary organic aerosols [SOA], 4 multiwall carbon nanotubes [MWCNT], 3 TiO2, and 2 metal salts) and of aerosols sampled in several bus depots. The sampling of particles in the bus depots was accompanied by the collection of urine samples of mechanics working full-time in these bus depots, and the quantification of 8-hydroxy-2'-deoxyguanosine, a biomarker of oxidative stress. The increase in oxidative stress biomarker levels over a working day was correlated (pcellular antioxidants.

  17. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  18. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  19. An attempt to model the probability of growth and aflatoxin B1 production of Aspergillus flavus under non-isothermal conditions in pistachio nuts.

    Science.gov (United States)

    Aldars-García, Laila; Ramos, Antonio J; Sanchis, Vicente; Marín, Sonia

    2015-10-01

    Human exposure to aflatoxins in foods is of great concern. The aim of this work was to use predictive mycology as a strategy to mitigate the aflatoxin burden in pistachio nuts postharvest. The probability of growth and aflatoxin B1 (AFB1) production of aflatoxigenic Aspergillus flavus, isolated from pistachio nuts, under static and non-isothermal conditions was studied. Four theoretical temperature scenarios, including temperature levels observed in pistachio nuts during shipping and storage, were used. Two types of inoculum were included: a cocktail of 25 A. flavus isolates and a single isolate inoculum. Initial water activity was adjusted to 0.87. Logistic models, with temperature and time as explanatory variables, were fitted to the probability of growth and AFB1 production under a constant temperature. Subsequently, they were used to predict probabilities under non-isothermal scenarios, with levels of concordance from 90 to 100% in most of the cases. Furthermore, the presence of AFB1 in pistachio nuts could be correctly predicted in 70-81 % of the cases from a growth model developed in pistachio nuts, and in 67-81% of the cases from an AFB1 model developed in pistachio agar. The information obtained in the present work could be used by producers and processors to predict the time for AFB1 production by A. flavus on pistachio nuts during transport and storage. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Analysis of a self-propelling sheet with heat transfer through non-isothermal fluid in an inclined human cervical canal.

    Science.gov (United States)

    Walait, Ahsan; Siddiqui, A M; Rana, M A

    2018-02-13

    The present theoretical analysis deals with biomechanics of the self-propulsion of a swimming sheet with heat transfer through non-isothermal fluid filling an inclined human cervical canal. Partial differential equations arising from the mathematical modeling of the proposed model are solved analytically. Flow variables like pressure gradient, propulsive velocity, fluid velocity, time mean flow rate, fluid temperature, and heat-transfer coefficients are analyzed for the pertinent parameters. Striking features of the pumping characteristics are explored. Propulsive velocity of the swimming sheet becomes faster for lower Froude number, higher Reynolds number, and for a vertical channel. Temperature and peak value of the heat-transfer coefficients below the swimming sheet showed an increase by the increment of Brinkmann number, inclination, pressure difference over wavelength, and Reynolds number whereas these quantities decrease with increasing Froude number. Aforesaid parameters have shown opposite effects on the peak value of the heat-transfer coefficients below and above the swimming sheet. Relevance of the current results to the spermatozoa transport with heat transfer through non-isothermal cervical mucus filling an inclined human cervical canal is also explored.

  1. Thermo-kinetic prediction of metastable and stable phase precipitation in Al–Zn–Mg series aluminium alloys during non-isothermal DSC analysis

    International Nuclear Information System (INIS)

    Lang, Peter; Wojcik, Tomasz; Povoden-Karadeniz, Erwin; Falahati, Ahmad; Kozeschnik, Ernst

    2014-01-01

    Highlights: • Comparison of laboratory Al–Zn–Mg alloy to industrial Al 7xxx series. • Heat flow evolution during non-isothermal DSC analysis is calculated. • TEM investigations of laboratory Al–Zn–Mg alloy at three pronounced temperatures. • Simulation and modelling of precipitation sequence. • Calculation and prediction of heat flow curves of Al 7xxx series. - Abstract: The technological properties of heat treatable Al–Zn–Mg alloys originate in the morphology and distribution of metastable particles. Starting from the solution-annealed condition, this paper describes the precipitate evolution during non-isothermal temperature changes, namely continuous heating differential scanning calorimetry (DSC) analysis. The distribution and the morphology of the metastable and stable precipitates and the heat flow accompanying the precipitation process is investigated experimentally and calculated by numerical thermo-kinetic simulations. The computer simulation results of the sizes and distributions are confirmed by transmission electron microscopy (TEM). The theoretical background and the results of the investigations are discussed

  2. Thermo-kinetic prediction of metastable and stable phase precipitation in Al–Zn–Mg series aluminium alloys during non-isothermal DSC analysis

    Energy Technology Data Exchange (ETDEWEB)

    Lang, Peter, E-mail: pl404@cam.ac.uk [Department of Materials Science and Metallurgy, University of Cambridge, Charles Babbage Road 27, Cambridge CB3 0FS (United Kingdom); Wojcik, Tomasz [Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria); Povoden-Karadeniz, Erwin [Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria); Christian Doppler Laboratory “Early Stages of Precipitation”, Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria); Falahati, Ahmad [Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria); Kozeschnik, Ernst [Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria); Christian Doppler Laboratory “Early Stages of Precipitation”, Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstraße 9-11, Vienna 1040 (Austria)

    2014-10-01

    Highlights: • Comparison of laboratory Al–Zn–Mg alloy to industrial Al 7xxx series. • Heat flow evolution during non-isothermal DSC analysis is calculated. • TEM investigations of laboratory Al–Zn–Mg alloy at three pronounced temperatures. • Simulation and modelling of precipitation sequence. • Calculation and prediction of heat flow curves of Al 7xxx series. - Abstract: The technological properties of heat treatable Al–Zn–Mg alloys originate in the morphology and distribution of metastable particles. Starting from the solution-annealed condition, this paper describes the precipitate evolution during non-isothermal temperature changes, namely continuous heating differential scanning calorimetry (DSC) analysis. The distribution and the morphology of the metastable and stable precipitates and the heat flow accompanying the precipitation process is investigated experimentally and calculated by numerical thermo-kinetic simulations. The computer simulation results of the sizes and distributions are confirmed by transmission electron microscopy (TEM). The theoretical background and the results of the investigations are discussed.

  3. A three-dimensional numerical investigation of trapezoid baffles effect on non-isothermal reactant transport and cell net power in a PEMFC

    International Nuclear Information System (INIS)

    Perng, Shiang-Wuu; Wu, Horng-Wen

    2015-01-01

    Highlights: • We study how angle and height of trapezoid baffle affect PEMFC net power. • The jet-type, trapping, and blockage effects augment non-isothermal transport in flow channel. • Greater angles and heights of trapezoid baffles provide more reactant to the catalyst layer. • Baffles of 1.5 mm and 90° fully block flow channel to show bad heat transfer and large pressure drop. • Maximum enhancement of cell net power is 90% with baffles of 60° angle and 1.125 mm height. - Abstract: The present study performed a three-dimensional numerical simulation to observe how trapezoid baffles affect non-isothermal reactant transports and cell net power in the proton exchange membrane fuel cell (PEMFC) by the SIMPLE-C method. The geometric parameters of trapezoid baffles installed in the gas channel employed in this study include the angle and height with the same gas diffusion and catalyst layers to realize the cell net power considering the effect of liquid water formation on the fluid flow field. The cell net power is adopted to evaluate the real enhancement of cell performance due to the additional pumping power induced by the pressure loss through the PEMFC. The results illustrated that compared with traditional gas channel without baffles, the novel gas channel with trapezoid baffles, whose angle is 60° and height is 1.125 mm, enhances the cell net power best by approximately 90% among all trapezoid baffle designs

  4. Isothermal and non-isothermal cure of a tri-functional epoxy resin (TGAP): a stochastic TMDSC study

    OpenAIRE

    Hutchinson, John M.; Shiravand, Fatemeh; Calventus Solé, Yolanda; Fraga Rivas, Iria

    2012-01-01

    The isothermal cure of a highly reactive tri-functional epoxy resin, tri-glycidyl para-amino phenol (TGAP), with diamino diphenyl sulphone (DDS), at two different cure temperatures Tc has been studied by both conventional differential scanning calorimetry (DSC) and by a stochastic temperature modulated DSC technique, TOPEM. From a series of isothermal cure experiments for increasing cure times, the glass transition temperature Tg as a function of isothermal cure time is determined by co...

  5. The synergistic effect of chemical carcinogens enhances Epstein-Barr virus reactivation and tumor progression of nasopharyngeal carcinoma cells.

    Science.gov (United States)

    Fang, Chih-Yeu; Huang, Sheng-Yen; Wu, Chung-Chun; Hsu, Hui-Yu; Chou, Sheng-Ping; Tsai, Ching-Hwa; Chang, Yao; Takada, Kenzo; Chen, Jen-Yang

    2012-01-01

    Seroepidemiological studies imply a correlation between Epstein-Barr virus (EBV) reactivation and the development of nasopharyngeal carcinoma (NPC). N-nitroso compounds, phorbols, and butyrates are chemicals found in food and herb samples collected from NPC high-risk areas. These chemicals have been reported to be risk factors contributing to the development of NPC, however, the underlying mechanism is not fully understood. We have demonstrated previously that low dose N-methyl-N'-nitro-N-nitrosoguanidine (MNNG, 0.1 µg/ml) had a synergistic effect with 12-O-tetradecanoylphorbol-13-acetate (TPA) and sodium butyrate (SB) in enhancing EBV reactivation and genome instability in NPC cells harboring EBV. Considering that residents in NPC high-risk areas may contact regularly with these chemical carcinogens, it is vital to elucidate the relation between chemicals and EBV and their contributions to the carcinogenesis of NPC. In this study, we constructed a cell culture model to show that genome instability, alterations of cancer hallmark gene expression, and tumorigenicity were increased after recurrent EBV reactivation in NPC cells following combined treatment of TPA/SB and MNNG. NPC cells latently infected with EBV, NA, and the corresponding EBV-negative cell, NPC-TW01, were periodically treated with MNNG, TPA/SB, or TPA/SB combined with MNNG. With chemically-induced recurrent reactivation of EBV, the degree of genome instability was significantly enhanced in NA cells treated with a combination of TPA/SB and MNNG than those treated individually. The Matrigel invasiveness, as well as the tumorigenicity in mouse, was also enhanced in NA cells after recurrent EBV reactivation. Expression profile analysis by microarray indicates that many carcinogenesis-related genes were altered after recurrent EBV reactivation, and several aberrations observed in cell lines correspond to alterations in NPC lesions. These results indicate that cooperation between chemical carcinogens can

  6. Chemical reactivation of resin-embedded pHuji adds red for simultaneous two-color imaging with EGFP

    Science.gov (United States)

    Guo, Wenyan; Liu, Xiuli; Liu, Yurong; Gang, Yadong; He, Xiaobin; Jia, Yao; Yin, Fangfang; Li, Pei; Huang, Fei; Zhou, Hongfu; Wang, Xiaojun; Gong, Hui; Luo, Qingming; Xu, Fuqiang; Zeng, Shaoqun

    2017-01-01

    The pH-sensitive fluorescent proteins enabling chemical reactivation in resin are useful tools for fluorescence microimaging. EGFP or EYFP is good for such applications. For simultaneous two-color imaging, a suitable red fluorescent protein is an urgent need. Here a pH-sensitive red fluorescent protein, pHuji, is selected and verified to remain pH-sensitive in HM20 resin. We observe 183% fluorescence intensity of pHuji in resin-embeded mouse brain and 29.08-fold fluorescence intensity of reactivated pHuji compared to the quenched state. pHuji and EGFP can be quenched and chemically reactivated simultaneously in resin, thus enabling simultaneous two-color micro-optical sectioning tomography of resin-embedded mouse brain. This method may greatly facilitate the visualization of neuronal morphology and neural circuits to promote understanding of the structure and function of the brain. PMID:28717566

  7. Investigation on reactivity of iron nickel oxides in chemical looping dry reforming

    International Nuclear Information System (INIS)

    Huang, Zhen; He, Fang; Chen, Dezhen; Zhao, Kun; Wei, Guoqiang; Zheng, Anqing; Zhao, Zengli; Li, Haibin

    2016-01-01

    Iron nickel oxides as oxygen carriers were investigated to clarify the reaction mechanism of NiFe_2O_4 material during the chemical looping dry reforming (CLDR) process. The thermodynamic analysis showed that metallic Fe can be oxidized into Fe_3O_4 by CO_2, but metallic Ni cannot. The oxidizability of the four oxygen carriers was in the order of NiO > synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3, and the reducibility sequence of their reduced products was synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3 > NiO. The NiO showed the best oxidizability but it was easy to cause CH_4 cracking and its reduced product (Ni) did not recover lattice oxygen under CO_2 atmosphere. It only produced 74 mL CO for 1 g Fe_2O_3 during the CO_2 reforming because of its weak oxidizability. The Redox ability of synthetic NiFe_2O_4 was obvious higher than that of NiO-Fe_2O_3 mixed oxides due to the synergistic effect of metallic Fe-Ni in the spinel structure. 1 g synthetic NiFe_2O_4 can produce 238 mL CO, which was twice higher than that of 1 g NiO-Fe_2O_3 mixed oxides (111 mL). A part of Fe element was divorced from the NiFe_2O_4 spinel structure after one cycle, which was the major reason for degradation of reactivity of NiFe_2O_4 oxygen carrier. - Highlights: • A synergistic effect of Fe/Ni can improve the reactivity of oxygen carrier (OC). • The oxidizability sequence of four OCs is NiO > NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3. • The reducibility sequence of four OCs is NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3 > NiO. • The formation of Fe (Ni) alloy phase facilitates more CO_2 reduced into CO. • Part of Fe is divorced from the spinel structure, leading to the degeneration of OC reactivity.

  8. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    Energy Technology Data Exchange (ETDEWEB)

    Hamaguchi, Satoshi [Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2013-07-11

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

  9. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    International Nuclear Information System (INIS)

    Hamaguchi, Satoshi

    2013-01-01

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed

  10. Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

    NARCIS (Netherlands)

    Duvigneau, Joost; Cornelissen, Stijn; Bardajı´Valls, Nuria; Schönherr, Holger; Vancso, Gyula J.

    2009-01-01

    Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at

  11. The comparative kinetic analysis of Acetocell and Lignoboost® lignin pyrolysis: the estimation of the distributed reactivity models.

    Science.gov (United States)

    Janković, Bojan

    2011-10-01

    The non-isothermal pyrolysis kinetics of Acetocell (the organosolv) and Lignoboost® (kraft) lignins, in an inert atmosphere, have been studied by thermogravimetric analysis. Using isoconversional analysis, it was concluded that the apparent activation energy for all lignins strongly depends on conversion, showing that the pyrolysis of lignins is not a single chemical process. It was identified that the pyrolysis process of Acetocell and Lignoboost® lignin takes place over three reaction steps, which was confirmed by appearance of the corresponding isokinetic relationships (IKR). It was found that major pyrolysis stage of both lignins is characterized by stilbene pyrolysis reactions, which were subsequently followed by decomposition reactions of products derived from the stilbene pyrolytic process. It was concluded that non-isothermal pyrolysis of Acetocell and Lignoboost® lignins can be best described by n-th (n>1) reaction order kinetics, using the Weibull mixture model (as distributed reactivity model) with alternating shape parameters. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Quick Look Report for Chemical Reactivity Modeling of Various Multi-Canister Overpack Breaches

    Energy Technology Data Exchange (ETDEWEB)

    Bratton, Robert Lawrence

    2002-04-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH_SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH_SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding. A

  13. Quick Look Report for Chemical Reactivity Modeling of Various Multi-Canister Overpack Breaches

    International Nuclear Information System (INIS)

    Bratton, Robert Lawrence

    2002-01-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH( ) SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH( ) SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding

  14. Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

    Directory of Open Access Journals (Sweden)

    Christelle Pau Ping Wong

    2015-10-01

    Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

  15. Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

    International Nuclear Information System (INIS)

    Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

    2014-01-01

    This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

  16. Le Châtelier's conjecture: Measurement of colloidal eigenstresses in chemically reactive materials

    Science.gov (United States)

    Abuhaikal, Muhannad; Ioannidou, Katerina; Petersen, Thomas; Pellenq, Roland J.-M.; Ulm, Franz-Josef

    2018-03-01

    Volume changes in chemically reactive materials, such as hydrating cement, play a critical role in many engineering applications that require precise estimates of stress and pressure developments. But a means to determine bulk volume changes in the absence of other deformation mechanisms related to thermal, pressure and load variations, is still missing. Herein, we present such a measuring devise, and a hybrid experimental-theoretical technique that permits the determination of colloidal eigenstresses. Applied to cementitious materials, it is found that bulk volume changes in saturated cement pastes at constant pressure and temperature conditions result from a competition of repulsive and attractive phenomena that originate from the relative distance of the solid particles - much as Henry Louis Le Châtelier, the father of modern cement science, had conjectured in the late 19th century. Precipitation of hydration products in confined spaces entails a repulsion, whereas the concurrent reduction in interparticle distance entails activation of attractive forces in charged colloidal particles. This cross-over from repulsion to attraction can be viewed as a phase transition between a liquid state (below the solid percolation) and the limit packing of hard spheres, separated by an energy barrier that defines the temperature-dependent eigenstress magnitude.

  17. Role of Chemical Reactivity and Transition State Modeling for Virtual Screening.

    Science.gov (United States)

    Karthikeyan, Muthukumarasamy; Vyas, Renu; Tambe, Sanjeev S; Radhamohan, Deepthi; Kulkarni, Bhaskar D

    2015-01-01

    Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product- like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

  18. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan

    2015-12-30

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  19. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  20. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Herng, Tun Seng; Aratani, Naoki; Goncalves, Theo; Qi, Qingbiao; Shi, Xueliang; Yamada, Hiroko; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2015-01-01

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  1. Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu [Nagoya University, Department of Mechanical Science and Engineering, Nagoya (Japan); Kubo, Takashi [Meijo University, Faculty of Science and Technology, Nagoya (Japan)

    2012-11-15

    This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction (A+B{yields}R), streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions. (orig.)

  2. Nano-patterning of perpendicular magnetic recording media by low-energy implantation of chemically reactive ions

    International Nuclear Information System (INIS)

    Martin-Gonzalez, M.S.; Briones, F.; Garcia-Martin, J.M.; Montserrat, J.; Vila, L.; Faini, G.; Testa, A.M.; Fiorani, D.; Rohrmann, H.

    2010-01-01

    Magnetic nano-patterning of perpendicular hard disk media with perpendicular anisotropy, but preserving disk surface planarity, is presented here. Reactive ion implantation is used to locally modify the chemical composition (hence the magnetization and magnetic anisotropy) of the Co/Pd multilayer in irradiated areas. The procedure involves low energy, chemically reactive ion irradiation through a resist mask. Among N, P and As ions, P are shown to be most adequate to obtain optimum bit density and topography flatness for industrial Co/Pd multilayer media. The effect of this ion contributes to isolate perpendicular bits by destroying both anisotropy and magnetic exchange in the irradiated areas. Low ion fluences are effective due to the stabilization of atomic displacement levels by the chemical effect of covalent impurities.

  3. Abiotic pyrite reactivity versus nitrate, selenate and selenite using chemical and electrochemical methods

    International Nuclear Information System (INIS)

    Ignatiadis, I.; Betelu, S.; Gaucher, E.; Tournassat, C.; Chainet, F.

    2010-01-01

    Document available in extended abstract form only. This work is part of ReCosy European project (www.recosy.eu), whose main objectives are the sound understanding of redox phenomena controlling the long-term release/retention of radionuclides in nuclear waste disposal and providing tools to apply the results to performance assessment/safety case. Redox is one of the main factor affecting speciation and mobility of redox-sensitive radionuclides. Thus, it is of a great importance to investigate the redox reactivity of the host radioactive waste formations, particularly when exposed to redox perturbations. Callovo-Oxfordian formation (COx), a clay rock known as an anoxic and reducing system, was selected in France as the most suitable location to store nuclear waste. Iron (II) sulfide, mostly constituted of pyrite (FeS 2 ), iron (II) carbonate, iron(II) bearing clays and organic matter are considered to account almost entirely for the total reducing capacity of the rock. We report here the redox reactivity of pyrite upon exposure to nitrate (N(V)), selenate (Se(VI)) and selenite (Se(IV)) that possibly occur in the nuclear storage. Both, chemical and electrochemical kinetic approaches were simultaneously conducted such as to (i) determine the kinetics parameters of the reactions and (ii) understand the kinetic mechanisms. In order to reach similar conditions that are encountered in the storage system, all experiments were realised in NaCl 0.1 M, near neutral pH solutions, and an abiotic glove box (O 2 less than 10 -8 M). Chemical approach has consisted to set in contact pyrite in grains with solutions containing respectively nitrate, selenate and selenite. Reactants and products chemical analyses, conducted at different contact times, allowed us to assess the kinetics of oxidant reduction. Electrochemical approach has consisted in the continuous or semi-continuous analysis of large surface pyrite electrodes immersed in solutions with or without oxidant (nitrate

  4. Advantages of using non-isothermal bioreactors for the enzymatic synthesis of antibiotics: the penicillin G acylase as enzyme model

    NARCIS (Netherlands)

    Travascio, P.; Zito, E.; Maio, de A.; Schroën, C.G.P.H.; Durante, D.; Luca, de P.; Bencivenga, U.

    2002-01-01

    A new hydrophobic and catalytic membrane was prepared by immobilizing Penicillin G acylase (PGA, EC.3.5.1.11) from E. coli on a nylon membrane, chemically grafted with butylmethacrylate (BMA). Hexamethylenediamine (HMDA) and glutaraldehyde (Glu) were used as a spacer and coupling agent,

  5. Theoretical study of some aspects of the nucleo-bases reactivity: definition of new theoretical tools for the study of chemical reactivity

    International Nuclear Information System (INIS)

    Labet, V.

    2009-09-01

    In this work, three kinds of nucleo-base damages were studied from a theoretical point of view with quantum chemistry methods based on the density-functional theory: the spontaneous deamination of cytosine and its derivatives, the formation of tandem lesion induced by hydroxyl radicals in anaerobic medium and the formation of pyrimidic dimers under exposition to an UV radiation. The complementary use of quantitative static methods allowing the exploration of the potential energy surface of a chemical reaction, and of 'conceptual DFT' principles, leads to information concerning the mechanisms involved and to the rationalization of the differences in the nucleo-bases reactivity towards the formation of a same kind of damage. At the same time, a reflexion was undertaken on the asynchronous concerted mechanism concept, in terms of physical meaning of the transition state, respect of the Maximum Hardness Principle, and determination of the number of primitive processes involved. Finally, a new local reactivity index was developed, relevant to understand the reactivity of a molecular system in an excited state. (author)

  6. Characterization of crystallization kinetics of a Ni- (Cr, Fe, Si, B, C, P) based amorphous brazing alloy by non-isothermal differential scanning calorimetry

    International Nuclear Information System (INIS)

    Raju, S.; Kumar, N.S. Arun; Jeyaganesh, B.; Mohandas, E.; Mudali, U. Kamachi

    2007-01-01

    The thermal stability and crystallization kinetics of a Ni- (Cr, Si, Fe, B, C, P) based amorphous brazing foil have been investigated by non-isothermal differential scanning calorimetry. The glass transition temperature T g , is found to be 720 ± 2 K. The amorphous alloy showed three distinct, yet considerably overlapping crystallization transformations with peak crystallization temperatures centered around 739, 778 and 853 ± 2 K, respectively. The solidus and liquidus temperatures are estimated to be 1250 and 1300 ± 2 K, respectively. The apparent activation energies for the three crystallization reactions have been determined using model free isoconversional methods. The typical values for the three crystallization reactions are: 334, 433 and 468 kJ mol -1 , respectively. The X-ray diffraction of the crystallized foil revealed the presence of following compounds Ni 3 B (Ni 4 B 3 ), CrB, B 2 Fe 15 Si 3 , CrSi 2 , and Ni 4.5 Si 2 B

  7. Kinetic Parameters of Non-Isothermal Thermogravimetric Non-Catalytic and Catalytic Pyrolysis of Empty Fruit Bunch with Alumina by Kissinger and Ozawa Methods

    Science.gov (United States)

    Rahayu Mohamed, Alina; Li, Nurfahani; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur; Munirah Rohaizad, Nor; Hamzah, Rosniza

    2018-03-01

    The non-isothermal thermogravimetric non-catalytic and catalytic empty fruit bunch (EFB) pyrolysis with alumina were performed at different heating rates of 10, 15, 20, 25, 30 and 40 K/min under nitrogen atmosphere at a flow rate of 100 ml/min under dynamic conditions from 301 K to 1273 K. The activation energy were calculated based on Kissinger and Ozawa methods. Both reactions followed first order reactions. By Kissinger method, the activation energy and Ln A values for non-catalytic and catalytic EFB pyrolysis with alumina were 188.69 kJ mol-1 and 201.67 kJ/mol respectively. By Ozawa method, the activation energy values for non-catalytic and catalytic EFB pyrolysis with alumina were 189.13 kJ/mol and 201.44 kJ/mol respectively. The presence of catalyst increased the activation energy values for EFB pyrolysis as calculated by Kissinger and Ozawa methods.

  8. Analysis of the non-isothermal austenite-martensite transformation in 13% Cr-type martensitic stainless steels

    International Nuclear Information System (INIS)

    Garcia-De-Andris, C.; Alvarez, L.F.

    1996-01-01

    In martensitic stainless steels, as in other alloyed containing carbide-forming elements, the carbide dissolution and precipitation processes that take place during heat treatment can cause modifications to the chemical composition of the austenite phase of these steels. The chemical composition of this phase is a fundamental factor for the evolution of the martensitic transformation. As a result of their influence on the dissolution and precipitation processes, the parameters of the quenching heat treatment exert a strong influence on the behavior of the martensitic transformation in these steels. In the present study, the effect of the heating temperature and the cooling rate on the martensitic transformation in two 13% Cr-type martensitic stainless steels with different carbon contents were properly evaluated. (author)

  9. Non-isothermal crystallization kinetics and fragility of (Cu46Zr47Al7)97Ti3 bulk metallic glass investigated by differential scanning calorimetry

    International Nuclear Information System (INIS)

    Zhu, Man; Li, Junjie; Yao, Lijuan; Jian, Zengyun; Chang, Fang’e; Yang, Gencang

    2013-01-01

    Highlights: • Non-isothermal crystallization kinetics of (Cu 46 Zr 47 Al 7 ) 97 Ti 3 BMGs was studied. • Two-stage of crystallization process is confirmed by DSC. • The nucleation process is difficult than growth process during crystallization. • The second crystallization process is the most sensitive to heating rate. • Kinetic fragility index is evaluated suggesting it is an intermediate glass. - Abstract: In this paper, bulk metallic glasses with the composition of (Cu 46 Zr 47 Al 7 ) 97 Ti 3 were prepared by copper mold casting technique. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were used to investigate its structure and non-isothermal crystallization kinetics. DSC traces revealed that it undergoes two-stage crystallization. The activation energies corresponding to the characteristic temperatures have been calculated, and the results reveal that the as-cast alloys have a good thermal stability in thermodynamics. Based on Kissinger equation, the activation energies for glass transition, the first and second crystallization processes were obtained as 485 ± 16 kJ/mol, 331 ± 7 kJ/mol and 210 ± 3 kJ/mol, respectively, suggesting that the nucleation process is more difficult than the grain growth process. The fitting curves using Lasocka's empirical relation show that the influence of the heating rate for crystallization is larger than glass transition. Furthermore, the kinetic fragility for (Cu 46 Zr 47 Al 7 ) 97 Ti 3 bulk metallic glasses is evaluated. Depending on the fragility index, (Cu 46 Zr 47 Al 7 ) 97 Ti 3 bulk metallic glasses should be considered as “intermediate glasses”

  10. Chemical Identity of Interaction of Protein with Reactive Metabolite of Diosbulbin B In Vitro and In Vivo

    Directory of Open Access Journals (Sweden)

    Kai Wang

    2017-08-01

    Full Text Available Diosbulbin B (DIOB, a hepatotoxic furan-containing compound, is a primary ingredient in Dioscorea bulbifera L., a common herbal medicine. Metabolic activation is required for DIOB-induced liver injury. Protein covalent binding of an electrophilic reactive intermediate of DIOB is considered to be one of the key mechanisms of cytotoxicity. A bromine-based analytical technique was developed to characterize the chemical identity of interaction of protein with reactive intermediate of DIOB. Cysteine (Cys and lysine (Lys residues were found to react with the reactive intermediate to form three types of protein modification, including Cys adduction, Schiff’s base, and Cys/Lys crosslink. The crosslink showed time- and dose-dependence in animals given DIOB. Ketoconazole pretreatment decreased the formation of the crosslink derived from DIOB, whereas pretreatment with dexamethasone or buthionine sulfoximine increased such protein modification. These data revealed that the levels of hepatic protein adductions were proportional to the severity of hepatotoxicity of DIOB.

  11. Drop drying on surfaces determines chemical reactivity - the specific case of immobilization of oligonucleotides on microarrays

    Science.gov (United States)

    2013-01-01

    Background Drop drying is a key factor in a wide range of technical applications, including spotted microarrays. The applied nL liquid volume provides specific reaction conditions for the immobilization of probe molecules to a chemically modified surface. Results We investigated the influence of nL and μL liquid drop volumes on the process of probe immobilization and compare the results obtained to the situation in liquid solution. In our data, we observe a strong relationship between drop drying effects on immobilization and surface chemistry. In this work, we present results on the immobilization of dye labeled 20mer oligonucleotides with and without an activating 5′-aminoheptyl linker onto a 2D epoxysilane and a 3D NHS activated hydrogel surface. Conclusions Our experiments identified two basic processes determining immobilization. First, the rate of drop drying that depends on the drop volume and the ambient relative humidity. Oligonucleotides in a dried spot react unspecifically with the surface and long reaction times are needed. 3D hydrogel surfaces allow for immobilization in a liquid environment under diffusive conditions. Here, oligonucleotide immobilization is much faster and a specific reaction with the reactive linker group is observed. Second, the effect of increasing probe concentration as a result of drop drying. On a 3D hydrogel, the increasing concentration of probe molecules in nL spotting volumes accelerates immobilization dramatically. In case of μL volumes, immobilization depends on whether the drop is allowed to dry completely. At non-drying conditions, very limited immobilization is observed due to the low oligonucleotide concentration used in microarray spotting solutions. The results of our study provide a general guideline for microarray assay development. They allow for the initial definition and further optimization of reaction conditions for the immobilization of oligonucleotides and other probe molecule classes to different

  12. Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

    Science.gov (United States)

    Hamers, Robert J.; Wang, Yajun; Shan, Jun

    1996-11-01

    We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

  13. Heterogeneously catalyzed reactive extraction for biomass valorization into chemicals and fuels

    NARCIS (Netherlands)

    Ordomskiy, V.; Khodakov, A.Y.; Nijhuis, T.A.; Schouten, J.C.

    2015-01-01

    This paper focuses on the heterogeneously catalyzed reactive extraction and separation in reaction steps in organic and aqueous phases during the transformation of biomass derived products. Two approaches are demonstrated for decomposing and preserving routes for biomass transformation into valuable

  14. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns.

    Science.gov (United States)

    Hartwig, Jan; Metternich, Jan B; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V

    2014-06-14

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  15. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns

    OpenAIRE

    Hartwig, Jan; Metternich, Jan B.; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V.

    2014-01-01

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  16. Kinetics of thermal decomposition of aluminium hydride: I-non-isothermal decomposition under vacuum and in inert atmosphere (argon)

    International Nuclear Information System (INIS)

    Ismail, I.M.K.; Hawkins, T.

    2005-01-01

    Recently, interest in aluminium hydride (alane) as a rocket propulsion ingredient has been renewed due to improvements in its manufacturing process and an increase in thermal stability. When alane is added to solid propellant formulations, rocket performance is enhanced and the specific impulse increases. Preliminary work was performed at AFRL on the characterization and evaluation of two alane samples. Decomposition kinetics were determined from gravimetric TGA data and volumetric vacuum thermal stability (VTS) results. Chemical analysis showed the samples had 88.30% (by weight) aluminium and 9.96% hydrogen. The average density, as measured by helium pycnometery, was 1.486 g/cc. Scanning electron microscopy showed that the particles were mostly composed of sharp edged crystallographic polyhedral such as simple cubes, cubic octahedrons and hexagonal prisms. Thermogravimetric analysis was utilized to investigate the decomposition kinetics of alane in argon atmosphere and to shed light on the mechanism of alane decomposition. Two kinetic models were successfully developed and used to propose a mechanism for the complete decomposition of alane and to predict its shelf-life during storage. Alane decomposes in two steps. The slowest (rate-determining) step is solely controlled by solid state nucleation of aluminium crystals; the fastest step is due to growth of the crystals. Thus, during decomposition, hydrogen gas is liberated and the initial polyhedral AlH 3 crystals yield a final mix of amorphous aluminium and aluminium crystals. After establishing the kinetic model, prediction calculations indicated that alane can be stored in inert atmosphere at temperatures below 10 deg. C for long periods of time (e.g., 15 years) without significant decomposition. After 15 years of storage, the kinetic model predicts ∼0.1% decomposition, but storage at higher temperatures (e.g. 30 deg. C) is not recommended

  17. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  18. Unravelling chemical priming machinery in plants: the role of reactive oxygen-nitrogen-sulfur species in abiotic stress tolerance enhancement.

    Science.gov (United States)

    Antoniou, Chrystalla; Savvides, Andreas; Christou, Anastasis; Fotopoulos, Vasileios

    2016-10-01

    Abiotic stresses severely limit crop yield and their detrimental effects are aggravated by climate change. Chemical priming is an emerging field in crop stress management. The exogenous application of specific chemical agents before stress events results in tolerance enhancement and reduction of stress impacts on plant physiology and growth. However, the molecular mechanisms underlying the remarkable effects of chemical priming on plant physiology remain to be elucidated. Reactive oxygen, nitrogen and sulfur species (RONSS) are molecules playing a vital role in the stress acclimation of plants. When applied as priming agents, RONSS improve stress tolerance. This review summarizes the recent knowledge on the role of RONSS in cell signalling and gene regulation contributing to abiotic stress tolerance enhancement. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Responses of human birch pollen allergen-reactive T cells to chemically modified allergens (allergoids).

    Science.gov (United States)

    Dormann, D; Ebner, C; Jarman, E R; Montermann, E; Kraft, D; Reske-Kunz, A B

    1998-11-01

    Allergoids are widely used in specific immunotherapy for the treatment of IgE-mediated allergic diseases. The aim of this study was to analyse whether a modification of birch pollen allergens with formaldehyde affects the availability of T-cell epitopes. Efficient modification of the allergens was verified by determining IgE and IgG binding activity using ELISA inhibition tests. T-cell responses to birch pollen allergoids were analysed in polyclonal systems, using peripheral blood mononuclear cells (PBMC) of five birch pollen-allergic individuals, as well as birch pollen extract-reactive T-cell lines (TCL), established from the peripheral blood of 14 birch pollen-allergic donors. To determine whether the modification of natural (n)Bet v 1 with formaldehyde or maleic anhydride results in epitope-specific changes in T-cell reactivities, 22 Bet v 1-specific T-cell clones (TCC), established from nine additional birch pollen-allergic individuals, were tested for their reactivity with these products. The majority of PBMC and TCL showed a reduced response to the birch pollen extract allergoid. Bet v 1-specific TCC could be divided into allergoid-reactive and -non-reactive TCC. No simple correlation between possible modification sites of formaldehyde in the respective T-cell epitopes and the stimulatory potential of the allergoid was observed. Mechanisms of suppression or of anergy induction were excluded as an explanation for the non-reactivity of representative TCC. All TCC could be stimulated by maleylated and unmodified nBet v 1 to a similar extent. These results demonstrate differences in the availability of T-cell epitopes between allergoids and unmodified allergens, which are most likely due to structural changes within the allergen molecule.

  20. Simulations of the dispersion of reactive pollutants in a street canyon, considering different chemical mechanisms and micromixing

    Science.gov (United States)

    Garmory, A.; Kim, I. S.; Britter, R. E.; Mastorakos, E.

    The Stochastic Fields (SF) or Field Monte Carlo method has been used to model the dispersion of reactive scalars in a street canyon, using a simple chemistry and the CBM-IV mechanism. SF is a Probability Density Function (PDF) method which allows both means and variances of the scalars to be calculated as well as considering the effect of segregation on reaction rates. It was found that the variance of reactive scalars such as NO 2 was very high in the mixing region at roof-top level with rms values of the order of the mean values. The effect of segregation on major species such as O 3 was found to be very small using either mechanism, however, some radical species in CBM-IV showed a significant difference. These were found to be the seven species with the fastest chemical timescales. The calculated photostationary state defect was also found to be in error when segregation is neglected.

  1. Evaluation of a high-throughput peptide reactivity format assay for assessment of the skin sensitization potential of chemicals

    Directory of Open Access Journals (Sweden)

    Chin Lin eWong

    2016-03-01

    Full Text Available The direct peptide reactivity assay (DPRA is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium and high concentrations and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme and non-sensitizers with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF, cysteine- (Ac-RFAACAA and lysine- (Ac-RFAAKAA containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7% and glass (47.3% vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2,4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further

  2. Introduction to chemical reaction engineering

    International Nuclear Information System (INIS)

    Kim, Yeong Geol

    1990-10-01

    This deals with chemical reaction engineering with thirteen chapters. The contents of this book are introduction on reaction engineering, chemical kinetics, thermodynamics and chemical reaction, abnormal reactor, non-isothermal reactor, nonideal reactor, catalysis in nonuniform system, diffusion and reaction in porosity catalyst, design catalyst heterogeneous reactor in solid bed, a high molecule polymerization, bio reaction engineering, reaction engineering in material process, control multi-variable reactor process using digital computer.

  3. A comparative study of changes in immunological reactivity during prolonged introduction of radioactive and chemical substances into the organism with drinking water

    International Nuclear Information System (INIS)

    Shubik, V.M.; Nevstrueva, M.A.; Kalnitskij, S.A.; Livshits, R.E.; Merkushev, G.N.; Pilshchik, E.M.; Ponomareva, T.V.

    1978-01-01

    A comparative study was conducted into the factors of non-specific protection and specific immunity, allergic and autoallergic reactivities during prolonged exposure of experimental animals to 6 different radioactive and 7 harmful chemical substances. Qualitative and quantitative peculiarities were found in the changes in immunological reactivity during the exposure of the organism to radionuclides and stable chemical compounds. Impairment of immunity plays an essential role in the course and the outcome of effects induced by chronic action of the substances examined. (author)

  4. Computational solutions for non-isothermal, nonlinear magneto-convection in porous media with hall/ionslip currents and ohmic dissipation

    Directory of Open Access Journals (Sweden)

    O. Anwar Bég

    2016-03-01

    Full Text Available A theoretical and numerical study is presented to analyze the nonlinear, non-isothermal, magnetohydrodynamic (MHD free convection boundary layer flow and heat transfer in a non-Darcian, isotropic, homogenous porous medium, in the presence of Hall currents, Ionslip currents, viscous heating and Joule heating. A power-law variation is used for the temperature at the wall. The governing nonlinear coupled partial differential equations for momentum conservation in the x and z directions and heat conservation, in the flow regime are transformed from an (x, y, z coordinate system to a (ξ,η coordinate system in terms of dimensionless x-direction velocity (∂F/∂η and z-direction velocity (G and dimensionless temperature function (H under appropriate boundary conditions. Both Darcian and Forchheimer porous impedances are incorporated in both momentum equations. Computations are also provided for the variation of the x and z direction shear stress components and also local Nusselt number. Excellent correlation is achieved with a Nakamura tridiagonal finite difference scheme (NTM. The model finds applications in magnetic materials processing, MHD power generators and purification of crude oils.

  5. Rheometric Non-Isothermal Gelatinization Kinetics of Chickpea Flour-Based Gluten-Free Muffin Batters with Added Biopolymers

    Directory of Open Access Journals (Sweden)

    María Dolores Alvarez

    2017-01-01

    Full Text Available An attempt was made to analyze the elastic modulus (G0 of chickpea flour (CF-based muffin batters made with CF alone and with added biopolymers (whey protein (WP, xanthan gum (XG, inulin (INL, and their blends in order to evaluate their suitability to be a wheat flour (WF substitute in muffins, and to model the heat-induced gelatinization of batters under non-isothermal heating condition from 25 ◦C to 90 ◦C. A rheological approach is proposed to determine the kinetic parameters (reaction order (n, frequency factor (k0, and activation energy (Ea using linearly-increasing temperature. Zero-order reaction kinetics adequately described batter gelatinization process, therefore assuming a constant rate independent of the initial G0 value. The change of the derivative of G0 with respect to time (dG0/dt versus temperature is described by one exponential function with activation energies ranging from 118 to 180 kJ·mol−1. Control wheat gluten batter, with higher and lower starch and protein contents, respectively, than CF-based batters, exhibited the highest Ea value. Formulation of CF-based gluten-free batters with starch and protein contents closer to the levels of WF-based batter could be a strategy to decrease differences in kinetic parameters of muffin batters and, therefore, in technological characteristics of baked muffins.

  6. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  7. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  8. CHMTRNS, Non-Equilibrium Chemical Transport Code

    International Nuclear Information System (INIS)

    Noorishad, J.; Carnahan, C.L.; Benson, L.V.

    1998-01-01

    1 - Description of program or function: CHMTRNS simulates solute transport for steady one-dimensional fluid flow by convection and diffusion or dispersion in a saturated porous medium based on the assumption of local chemical equilibrium. The chemical interactions included in the model are aqueous-phase complexation, solid-phase ion exchange of bare ions and complexes using the surface complexation model, and precipitation or dissolution of solids. The program can simulate the kinetic dissolution or precipitation for calcite and silica as well as irreversible dissolution of glass. Thermodynamic parameters are temperature dependent and are coupled to a companion heat transport simulator; thus, the effects of transient temperature conditions can be considered. Options for oxidation-reduction (redox) and C-13 fractionation as well as non-isothermal conditions are included. 2 - Method of solution: The governing equations for both reactive chemical and heat transport are discretized in time and space. For heat transport, the Crank-Nicolson approximation is used in conjunction with a LU decomposition and backward substitution solution procedure. To deal with the strong nonlinearity of the chemical transport equations, a generalized Newton-Raphson method is used

  9. Chemical conjugation of cowpea mosaic viruses with reactive HPMA-based polymers

    Czech Academy of Sciences Publication Activity Database

    Laga, Richard; Koňák, Čestmír; Šubr, Vladimír; Ulbrich, Karel; Suthiwangcharoen, N.; Niu, Q.; Wang, Q.

    2010-01-01

    Roč. 21, č. 12 (2010), s. 1669-1685 ISSN 0920-5063 R&D Projects: GA AV ČR KJB400500803; GA ČR GA202/09/2078; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40500505 Keywords : acylthiazolidine-2-thione reactive groups * bioconjugation * coating Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.842, year: 2010

  10. Thermogravimetric study on the influence of structural, textural and chemical properties of biomass chars on CO2 gasification reactivity

    International Nuclear Information System (INIS)

    Bouraoui, Zeineb; Jeguirim, Mejdi; Guizani, Chamseddine; Limousy, Lionel; Dupont, Capucine; Gadiou, Roger

    2015-01-01

    The present investigation aims to examine the influence of textural, structural and chemical properties of biomass chars on the CO 2 gasification rate. Various lignocellulosic biomass chars were prepared under the same conditions. Different analytical techniques were used to determine the char properties such as Scanning Electronic Microscopy, nitrogen adsorption manometry, Raman spectroscopy and X Ray Fluorescence. Gasification tests were carried out in a thermobalance under 20% CO 2 in nitrogen at 800 °C. Significant differences of the total average reactivity were observed with a factor of 2 between the prepared chars. Moreover, different behaviors of gasification rate profiles versus conversion were obtained. This difference of behavior appeared to be correlated with the biomass char properties. Hence, up to 70% of conversion, the gasification rate was shown to depend on the char external surface and the potassium content. At higher conversion ratio, a satisfactory correlation between the Catalytic Index and the average gasification rate was identified. The results highlight the importance of knowing both textural and structural properties and mineral contents of biomass chars to predict fuel reactivity during CO 2 gasification processes. Such behavior prediction is highly important in the gasifiers design for char conversion. - Highlights: • CO 2 gasification reactivity of various lignocellulosic chars were examined. • Chars properties affect strongly samples gasification behavior. • Initial gasification rate is affected by external surface, K content and D3/G ratio. • Gasification rate behavior depends on the Alkali index at high conversion

  11. The Atmospheric Tomography Mission (ATom): Comparing the Chemical Climatology of Reactive Species and Air Parcels from Measurements and Global Models

    Science.gov (United States)

    Prather, M. J.; Flynn, C.; Wennberg, P. O.; Kim, M. J.; Ryerson, T. B.; Hanisco, T. F.; Diskin, G. S.; Daube, B. C.; Commane, R.; McKain, K.; Apel, E. C.; Blake, N. J.; Blake, D. R.; Elkins, J. W.; Hall, S.; Steenrod, S.; Strahan, S. E.; Lamarque, J. F.; Fiore, A. M.; Horowitz, L. W.; Murray, L. T.; Mao, J.; Shindell, D. T.; Wofsy, S. C.

    2017-12-01

    The NASA Atmospheric Tomography Mission (ATom) is building a photochemical climatology of the remote troposphere based on objective sampling and profiling transects over the Pacific and Atlantic Oceans. These statistics provide direct tests of chemistry-climate models. The choice of species focuses on those controlling primary reactivity (a.k.a. oxidative state) of the troposphere, specifically chemical tendencies of O3 and CH4. These key species include, inter alia, O3, CH4, CO, C2H6, other alkanes, alkenes, aromatics, NOx, HNO3, HO2NO2, PAN, other organic nitrates, H2O, HCHO, H2O2, CH3OOH. Three of the four ATom deployments are now complete, and data from the first two (ATom-1 & -2) have been released as of this talk (see espoarchive.nasa.gov/archive/browse/atom). The statistical distributions of key species are presented as 1D and 2D probability densities (PDs) and we focus here on the tropical and mid-latitude regions of the Pacific during ATom-1 (Aug) and -2 (Feb). PDs are computed from ATom observations and 6 global chemistry models over the tropospheric depth (0-12 km) and longitudinal extent of the observations. All data are weighted to achieve equal mass-weighting by latitude regimes to account for spatial sampling biases. The models are used to calculate the reactivity in each ATom air parcel. Reweighting parcels with loss of CH4 or production of O3, for example, allows us to identify which air parcels are most influential, including assessment of the importance of fine pollution layers in the most remote troposphere. Another photochemical climatology developed from ATom, and used to test models, includes the effect of clouds on photolysis rates. The PDs and reactivity-weighted PDs reveal important seasonal differences and similarities between the two campaigns and also show which species may be most important in controlling reactivities. They clearly identify some very specific failings in the modeled climatologies and help us evaluate the chemical

  12. Acoustic sensors for the control of liquid-solid interface evolution and chemical reactivity

    International Nuclear Information System (INIS)

    Ferrandis, J.Y.; Tingry, S.; Attal, J.; Seta, P.

    2006-01-01

    Less classical than far-field acoustic investigations of solid materials and/or solid-liquid interfaces, near-field acoustic properties of an acoustic solid wave guide (tip), thin enough at its termination to present an external diameter smaller than the excitation acoustic wave wavelength, is shown to be able to probe interface properties. As a result of that, these near-field acoustic probes can play the role of chemical sensors, if chemical modifications or chemical reactions are concerned at their surface. In that context, a chemical sensor was realized by electrochemical deposition of an electron-conducting polymer (polypyrrole-biotin) on a metal tip, followed by enzyme attachment by molecular recognition process involving the biotin-avidin-specific interaction. Results from near-field acoustic showed that the enzyme modification of the polymer layer can be detected by this new acoustic sensor

  13. Evaluation of the Weibull and log normal distribution functions as survival models of Escherichia coli under isothermal and non isothermal conditions.

    Science.gov (United States)

    Aragao, Glaucia M F; Corradini, Maria G; Normand, Mark D; Peleg, Micha

    2007-11-01

    Published survival curves of Escherichia coli in two growth media, with and without the presence of salt, at various temperatures and in a Greek eggplant salad having various levels of essential oil, all had a characteristic downward concavity when plotted on semi logarithmic coordinates. Some also exhibited what appeared as a 'shoulder' of considerable length. Regardless of whether a shoulder was noticed, the survival pattern could be considered as a manifestation of an underlying unimodal distribution of the cells' death times. Mathematically, the data could be described equally well by the Weibull and log normal distribution functions, which had similar modes, means, standard deviations and coefficients of skewness. When plotted in their probability density function (PDF) form, the curves also appeared very similar visually. This enabled us to quantify and compare the effect of temperature or essential oil concentration on the organism's survival in terms of these temporal distributions' characteristics. Increased lethality was generally expressed in a shorter mean and mode, a smaller standard deviation and increased overall symmetry as judged by the distributions' degree of skewness. The 'shoulder', as expected, simply indicated that the distribution's standard deviation was much smaller than its mode. Rate models based on the two distribution functions could be used to predict non isothermal survival patterns. They were derived on the assumption that the momentary inactivation rate is the isothermal rate at the momentary temperature at a time that corresponds to the momentary survival ratio. In this application, however, the Weibullian model with a fixed power was not only simpler and more convenient mathematically than the one based on the log normal distribution, but it also provided more accurate estimates of the dynamic inactivation patterns.

  14. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  15. Establishment and intra-/inter-laboratory validation of a standard protocol of reactive oxygen species assay for chemical photosafety evaluation.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Matsuoka, Naoko; Nakamura, Kazuichi; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Seto, Yoshiki; Kato, Masashi; Yamada, Shizuo; Ohno, Yasuo; Kojima, Hajime

    2013-11-01

    A reactive oxygen species (ROS) assay was previously developed for photosafety evaluation of pharmaceuticals, and the present multi-center study aimed to establish and validate a standard protocol for ROS assay. In three participating laboratories, two standards and 42 coded chemicals, including 23 phototoxins and 19 nonphototoxic drugs/chemicals, were assessed by the ROS assay according to the standardized protocol. Most phototoxins tended to generate singlet oxygen and/or superoxide under UV-vis exposure, but nonphototoxic chemicals were less photoreactive. In the ROS assay on quinine (200 µm), a typical phototoxic drug, the intra- and inter-day precisions (coefficient of variation; CV) were found to be 1.5-7.4% and 1.7-9.3%, respectively. The inter-laboratory CV for quinine averaged 15.4% for singlet oxygen and 17.0% for superoxide. The ROS assay on 42 coded chemicals (200 µm) provided no false negative predictions upon previously defined criteria as compared with the in vitro/in vivo phototoxicity, although several false positives appeared. Outcomes from the validation study were indicative of satisfactory transferability, intra- and inter-laboratory variability, and predictive capacity of the ROS assay. Copyright © 2012 John Wiley & Sons, Ltd.

  16. Modeling the transport of chemical warfare agents and simulants in polymeric substrates for reactive decontamination

    Science.gov (United States)

    Pearl, Thomas; Mantooth, Brent; Varady, Mark; Willis, Matthew

    2014-03-01

    Chemical warfare agent simulants are often used for environmental testing in place of highly toxic agents. This work sets the foundation for modeling decontamination of absorbing polymeric materials with the focus on determining relationships between agents and simulants. The correlations of agents to simulants must consider the three way interactions in the chemical-material-decontaminant system where transport and reaction occur in polymer materials. To this end, diffusion modeling of the subsurface transport of simulants and live chemical warfare agents was conducted for various polymer systems (e.g., paint coatings) with and without reaction pathways with applied decontamination. The models utilized 1D and 2D finite difference diffusion and reaction models to simulate absorption and reaction in the polymers, and subsequent flux of the chemicals out of the polymers. Experimental data including vapor flux measurements and dynamic contact angle measurements were used to determine model input parameters. Through modeling, an understanding of the relationship of simulant to live chemical warfare agent was established, focusing on vapor emission of agents and simulants from materials.

  17. Topological analysis (BCP) of vibrational spectroscopic studies, docking, RDG, DSSC, Fukui functions and chemical reactivity of 2-methylphenylacetic acid

    Science.gov (United States)

    Kavimani, M.; Balachandran, V.; Narayana, B.; Vanasundari, K.; Revathi, B.

    2018-02-01

    Experimental FT-IR and FT-Raman spectra of 2-methylphenylacetic acid (MPA) were recorded and theoretical values are also analyzed. The non-linear optical (NLO) properties were evaluated by determination of first (5.5053 × 10- 30 e.s.u.) and second hyper-polarizabilities (7.6833 × 10- 36 e.s.u.) of the title compound. The Multiwfn package is used to find the weak non-covalent interaction (Van der Wall interaction) and strong repulsion (steric effect) of the molecule and examined by reduced density gradient. The molecular electrostatic potential (MEP) analysis used to find the most reactive sites for the electrophilic and nucleophilic attack. The chemical activity (electronegativity, hardness, chemical softness and chemical potential) of the title compound was predicted with the help of HOMO-LUMO energy values. The natural bond orbital (NBO) has been analyzed the stability of the molecule arising from the hyper-conjugative interaction. DSSCs were discussed in structural modifications that improve the electron injection efficiency of the title compound (MPA). The Fukui functions are calculated in order to get information associated with the local reactivity properties of the title compound. The binding sites of the two receptors were reported by molecular docking field and active site bond distance is same 1.9 Å. The inhibitor of the title compound forms a stable complex with 1QYV and 2H1K proteins at the binding energies are - 5.38 and - 5.85 (Δ G in kcal/mol).

  18. Electrochemical and Quantum Chemical Study of Reactivity of Orthophthalaldehyde with Aliphatic Primary Amines

    Czech Academy of Sciences Publication Activity Database

    Donkeng Dazie, Joel; Liška, Alan; Ludvík, Jiří

    2016-01-01

    Roč. 163, č. 9 (2016), G127-G132 ISSN 0013-4651 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : electrochemistry * quantum chemical study * amines Subject RIV: CG - Electrochemistry Impact factor: 3.259, year: 2016

  19. Development of a QSAR for worst case estimates of acute toxicity of chemically reactive compounds

    NARCIS (Netherlands)

    Freidig, A.P.; Dekkers, S.; Verwei, M.; Zvinavashe, E.; Bessems, J.G.M.; Sandt, van de J.J.M.

    2007-01-01

    Future EU legislations enforce a fast hazard and risk assessment of thousands of existing chemicals. If conducted by means of present data requirements, this assessment will use a huge number of test animals and will be neither cost nor time effective. The purpose of the current research was to

  20. Surface area and chemical reactivity characteristics of uranium metal corrosion products.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-02-17

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m{sup 2}/g. The reactivity of the products in Ar-9%O{sub 2} and Ar-20%O{sub 2} were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal.

  1. Quantum mechanical reactive scattering theory for simple chemical reactions: Recent developments in methodology and applications

    International Nuclear Information System (INIS)

    Miller, W.H.

    1989-08-01

    It has recently been discovered that the S-matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has made a major contribution to heavy particle reactive (and also to electron-atom/molecule) scattering which involve non-local (i.e., exchange) interactions that prevent solution of the coupled channel equations by propagation methods. This paper reviews the methodology briefly and presents a sample of integral and differential cross sections that have been obtained for the H + H 2 → H 2 +H and D + H 2 → HD + H reactions in the high energy region (up to 1.2 eV translational energy) relevant to resonance structures reported in recent experiments. 35 refs., 11 figs

  2. Surface area and chemical reactivity characteristics of uranium metal corrosion products

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m 2 /g. The reactivity of the products in Ar-9%O 2 and Ar-20%O 2 were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal

  3. Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k

    Science.gov (United States)

    Mcgee, H. A., Jr.

    1973-01-01

    The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.

  4. Attempts to identify a control system for chemical reactivity in the living state using virtual energy.

    Science.gov (United States)

    Reid, B L; Bourke, C

    2001-07-01

    This thesis explores the activation of chemicals in metabolic systems from the viewpoint that this activation is under the control of elements of the space-sea in which the chemicals are immersed. Themselves inert, the chemicals are theorised to exploit a force or action issuing from space (fluctuation) and characterized by the homogeneity (termed symmetry) of this medium. The fluctuation is heterogenized upon collision with matter from the intervention of well recognized fields of gravity and electromagnetism at the instant of its issue to form the near field of radiation. Fractions of original space waves and of their intrinsic spin are produced resulting in the activation of the orbitals (valency) in the chemical itself. The thesis continues: the disturbed fluctuation must return to space, obliging in turn, a prior return to the homogeneous state requiring special restorative wave rearrangements known as resonance. The success of the restorative resonance is signalled by a singularity of the fluctuation now propelled to infinity (space), and the contingent chemical reactions thereby terminated. Compromise to this return can occur from many causes and, in its presence, activation of the orbitals continues. They now effectively constitute autonomous reactions alienated from the system as a whole. The thesis is supported from evidence from diverse fields such as space theory, history of quantum field theory in attempts to derive its meaning, dielectrics and the near field of electromagnetic radiation, electron-space interactions at the Fermi surface during phase transitions and evolution of equilibrium conditions in resonance phenomena. The utility of the hypothesis rests on recognition of the resonance condition at various points in the system sufficiently macroscopic as to be available clinically as an abrupt interface between physiology and pathology. Copyright 2001 Harcourt Publishers Ltd.

  5. Role of Extracellular Polymeric Substances in the Surface Chemical Reactivity of Hymenobacter aerophilus, a Psychrotolerant Bacterium▿

    Science.gov (United States)

    Baker, M. G.; Lalonde, S. V.; Konhauser, K. O.; Foght, J. M.

    2010-01-01

    Bacterial surface layers, such as extracellular polymeric substances (EPS), are known to play an important role in metal sorption and biomineralization; however, there have been very few studies investigating how environmentally induced changes in EPS production affect the cell's surface chemistry and reactivity. Acid-base titrations, cadmium adsorption assays, and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the surface reactivities of Hymenobacter aerophilus cells with intact EPS (WC) or stripped of EPS (SC) and purified EPS alone. Linear programming modeling of titration data showed SC to possess functional groups corresponding to phosphoryl (pKa ∼6.5), phosphoryl/amine (pKa ∼7.9), and amine/hydroxyl (pKa ∼9.9). EPS and WC both possess carboxyl groups (pKa ∼5.1 to 5.8) in addition to phosphoryl and amine groups. FT-IR confirmed the presence of polysaccharides and protein in purified EPS that can account for the additional carboxyl groups. An increased ligand density was observed for WC relative to that for SC, leading to an increase in the amount of Cd adsorbed (0.53 to 1.73 mmol/liter per g [dry weight] and 0.53 to 0.59 mmol/liter per g [dry weight], respectively). Overall, the presence of EPS corresponds to an increase in the number and type of functional groups on the surface of H. aerophilus that is reflected by increased metal adsorption relative to that for EPS-free cells. PMID:19915039

  6. Role of extracellular polymeric substances in the surface chemical reactivity of Hymenobacter aerophilus, a psychrotolerant bacterium.

    Science.gov (United States)

    Baker, M G; Lalonde, S V; Konhauser, K O; Foght, J M

    2010-01-01

    Bacterial surface layers, such as extracellular polymeric substances (EPS), are known to play an important role in metal sorption and biomineralization; however, there have been very few studies investigating how environmentally induced changes in EPS production affect the cell's surface chemistry and reactivity. Acid-base titrations, cadmium adsorption assays, and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the surface reactivities of Hymenobacter aerophilus cells with intact EPS (WC) or stripped of EPS (SC) and purified EPS alone. Linear programming modeling of titration data showed SC to possess functional groups corresponding to phosphoryl (pKa approximately 6.5), phosphoryl/amine (pKa approximately 7.9), and amine/hydroxyl (pKa approximately 9.9). EPS and WC both possess carboxyl groups (pKa approximately 5.1 to 5.8) in addition to phosphoryl and amine groups. FT-IR confirmed the presence of polysaccharides and protein in purified EPS that can account for the additional carboxyl groups. An increased ligand density was observed for WC relative to that for SC, leading to an increase in the amount of Cd adsorbed (0.53 to 1.73 mmol/liter per g [dry weight] and 0.53 to 0.59 mmol/liter per g [dry weight], respectively). Overall, the presence of EPS corresponds to an increase in the number and type of functional groups on the surface of H. aerophilus that is reflected by increased metal adsorption relative to that for EPS-free cells.

  7. Physicochemical model for reactive sputtering of hot target

    Energy Technology Data Exchange (ETDEWEB)

    Shapovalov, Viktor I., E-mail: vishapovalov@mail.ru; Karzin, Vitaliy V.; Bondarenko, Anastasia S.

    2017-02-05

    A physicochemical model for reactive magnetron sputtering of a metal target is described in this paper. The target temperature in the model is defined as a function of the ion current density. Synthesis of the coating occurs due to the surface chemical reaction. The law of mass action, the Langmuir isotherm and the Arrhenius equation for non-isothermal conditions were used for mathematical description of the reaction. The model takes into consideration thermal electron emission and evaporation of the target surface. The system of eight algebraic equations, describing the model, was solved for the tantalum target sputtered in the oxygen environment. It was established that the hysteresis effect disappears with the increase of the ion current density. - Highlights: • When model is applied for a cold target, hysteresis width is proportional to the ion current density. • Two types of processes of hot target sputtering are possible, depending on the current density: with and without the hysteresis. • Sputtering process is dominant at current densities less than 50 A/m{sup 2} and evaporation can be neglected. • For current densities over 50 A/m{sup 2} the hysteresis width reaches its maximum and the role of evaporation increases.

  8. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. 3D imaging using X-Ray tomography and SEM combined FIB to study non isothermal creep damage of (111) oriented samples of γ / γ ′ nickel base single crystal superalloy MC2

    KAUST Repository

    Jouiad, Mustapha

    2012-01-01

    An unprecedented investigation consisting of the association of X-Ray tomography and Scanning Electron Microscopy combined with Focus Ion Beam (SEM-FIB) is conducted to perform a 3D reconstruction imaging. These techniques are applied to study the non-isothermal creep behavior of close (111) oriented samples of MC2 nickel base superalloys single crystal. The issue here is to develop a strategy to come out with the 3D rafting of γ\\' particles and its interaction whether with dislocation structures or/and with the preexisting voids. This characterization is uncommonly performed away from the conventional studied orientation [001] in order to feed the viscoplastic modeling leading to its improvement by taking into account the crystal anisotropy. The creep tests were performed at two different conditions: classical isothermal tests at 1050°C under 140 MPa and a non isothermal creep test consisting of one overheating at 1200°C and 30 seconds dwell time during the isothermal creep life. The X-Ray tomography shows a great deformation heterogeneity that is pronounced for the non-isothermal tested samples. This deformation localization seems to be linked to the preexisting voids. Nevertheless, for both tested samples, the voids coalescence is the precursor of the observed damage leading to failure. SEM-FIB investigation by means of slice and view technique gives 3D views of the rafted γ\\' particles and shows that γ corridors evolution seems to be the main creep rate controlling parameter. © 2012 Trans Tech Publications, Switzerland.

  10. Double stratification effects in chemically reactive squeezed Sutterby fluid flow with thermal radiation and mixed convection

    Science.gov (United States)

    Ahmad, S.; Farooq, M.; Javed, M.; Anjum, Aisha

    2018-03-01

    A current analysis is carried out to study theoretically the mixed convection characteristics in squeezing flow of Sutterby fluid in squeezed channel. The constitutive equation of Sutterby model is utilized to characterize the rheology of squeezing phenomenon. Flow characteristics are explored with dual stratification. In flowing fluid which contains heat and mass transport, the first order chemical reaction and radiative heat flux affect the transport phenomenon. The systems of non-linear governing equations have been modulating which then solved by mean of convergent approach (Homotopy Analysis Method). The graphs are reported and illustrated for emerging parameters. Through graphical explanations, drag force, rate of heat and mass transport are conversed for different pertinent parameters. It is found that heat and mass transport rate decays with dominant double stratified parameters and chemical reaction parameter. The present two-dimensional examination is applicable in some of the engineering processes and industrial fluid mechanics.

  11. Double stratification effects in chemically reactive squeezed Sutterby fluid flow with thermal radiation and mixed convection

    Directory of Open Access Journals (Sweden)

    S. Ahmad

    2018-03-01

    Full Text Available A current analysis is carried out to study theoretically the mixed convection characteristics in squeezing flow of Sutterby fluid in squeezed channel. The constitutive equation of Sutterby model is utilized to characterize the rheology of squeezing phenomenon. Flow characteristics are explored with dual stratification. In flowing fluid which contains heat and mass transport, the first order chemical reaction and radiative heat flux affect the transport phenomenon. The systems of non-linear governing equations have been modulating which then solved by mean of convergent approach (Homotopy Analysis Method. The graphs are reported and illustrated for emerging parameters. Through graphical explanations, drag force, rate of heat and mass transport are conversed for different pertinent parameters. It is found that heat and mass transport rate decays with dominant double stratified parameters and chemical reaction parameter. The present two-dimensional examination is applicable in some of the engineering processes and industrial fluid mechanics. Keywords: Squeezing flow, Sutterby fluid model, Mixed convection, Double stratification, Thermal radiation, Chemical reaction

  12. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan

    2016-03-11

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  13. A Model to Couple Flow, Thermal and Reactive Chemical Transport, and Geo-mechanics in Variably Saturated Media

    Science.gov (United States)

    Yeh, G. T.; Tsai, C. H.

    2015-12-01

    This paper presents the development of a THMC (thermal-hydrology-mechanics-chemistry) process model in variably saturated media. The governing equations for variably saturated flow and reactive chemical transport are obtained based on the mass conservation principle of species transport supplemented with Darcy's law, constraint of species concentration, equation of states, and constitutive law of K-S-P (Conductivity-Degree of Saturation-Capillary Pressure). The thermal transport equation is obtained based on the conservation of energy. The geo-mechanic displacement is obtained based on the assumption of equilibrium. Conventionally, these equations have been implicitly coupled via the calculations of secondary variables based on primary variables. The mechanisms of coupling have not been obvious. In this paper, governing equations are explicitly coupled for all primary variables. The coupling is accomplished via the storage coefficients, transporting velocities, and conduction-dispersion-diffusion coefficient tensor; one set each for every primary variable. With this new system of equations, the coupling mechanisms become clear. Physical interpretations of every term in the coupled equations will be discussed. Examples will be employed to demonstrate the intuition and superiority of these explicit coupling approaches. Keywords: Variably Saturated Flow, Thermal Transport, Geo-mechanics, Reactive Transport.

  14. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Goncalves, Theo; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2016-01-01

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  15. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    Science.gov (United States)

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation.

  16. Practical use of chemical probes for reactive oxygen species produced in biological systems by {gamma}-irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Min Hee; Moon, Yu Ran; Chung, Byung Yeoup; Kim, Jae-Sung [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Lee, Kang-Soo [Crop Production and Technology Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Cho, Jae-Young [Bio-environmental Science Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Kim, Jin-Hong [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)], E-mail: jhongkim@kaeri.re.kr

    2009-05-15

    Application of chemical probes, for detection of reactive oxygen species (ROS), was tested during {gamma}-irradiation. The ethanol/{alpha}-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) and 3,3'-diaminobenzidine (DAB) were structurally stable enough to detect {sup {center_dot}}OH and H{sub 2}O{sub 2}, increasingly generated by {gamma}-irradiation up to 1000 Gy. Interestingly, the production rate of H{sub 2}O{sub 2}, but not {sup {center_dot}}OH, during {gamma}-irradiation, was significantly different between in vitro systems of lettuce and spinach. These results suggest that 4-POBN and DAB could be utilized as a semi-quantitative probe to quantify {sup {center_dot}}OH and H{sub 2}O{sub 2}, produced by {gamma}-irradiation up to 1000 Gy.

  17. Laboratory Investigation of Rheology and Infiltration Process of Non-Newtonian Fluids through Porous Media in a Non-Isothermal Flow Regime for Effective Remediation of Contaminants

    Science.gov (United States)

    Naseer, F.

    2017-12-01

    Contamination of soil and groundwater by adsorbent (persistent) contaminants have been a major concern. Mine tailings, Acid mine drainage, waste disposal areas, active or abandoned surface and underground mines are some major causes of soil and water contamination. It is need of the hour to develop cost effective and efficient remediation techniques for clean-up of soil and aquifers. The objective of this research is to study a methodology of using non-Newtonian fluids for effective remediation of adsorbent contaminants in porous media under non-isothermal flow regimes. The research comprises of three components. Since, non-Newtonian fluid rheology has not been well studied in cold temperatures, the first component of the objective is to expose a non-Newtonian fluid (Guar gum solution) to different temperatures ranging from 30 °C through -5 °C to understand the change in viscosity, shear strength and contact angle of the fluid. Study of the flow characteristic of non-Newtonian fluids in complex porous media has been limited. Hence, the second component of this study will focus on a comparison of flow characteristics of a Newtonian fluid, non-Newtonian fluid and a combination of both fluids in a glass-tube-bundle setup that will act as a synthetic porous media. The study of flow characteristics will also be done for different thermal regimes ranging from -5 °C to 30 °C. The third component of the research will be to compare the effectiveness Guar gum to remediate a surrogate adsorbed contaminant at a certain temperature from the synthetic porous media. Guar gum is biodegradable and hence it is benign to the environment. Through these experiments, the mobility and behavior of Guar gum under varying temperature ranges will be characterized and its effectiveness in removing contaminants from soils will be understood. The impact of temperature change on the fluid and flow stability in the porous medium will be examined in this research. Guar gum is good suspension

  18. Chemical environment of iron atoms in iron oxynitride films synthesized by reactive magnetron sputtering

    International Nuclear Information System (INIS)

    Grafoute, M.; Petitjean, C.; Rousselot, C.; Pierson, J.F.; Greneche, J.M.

    2007-01-01

    An iron oxynitride film was deposited on silicon and glass substrates by magnetron sputtering in an Ar-N 2 -O 2 reactive mixture. Rutherford back-scattering spectrometry was used to determine the film composition (Fe 1.06 O 0.35 N 0.65 ). X-ray diffraction revealed the formation of a face-centred cubic (fcc) structure with a lattice parameter close to that of γ'''-FeN. X-ray photoelectron spectroscopy showed the occurrence of Fe-N and Fe-O bonds in the film. The local environment of iron atoms studied by 57 Fe Moessbauer spectrometry at both 300 and 77 K gives clear evidence that the Fe 1.06 O 0.35 N 0.65 is not a mixture of iron oxide and iron nitride phases. Despite a small amount of an iron nitride phase, the main sample consists of an iron oxynitride phase with an NaCl-type structure where oxygen atoms partially substitute for nitrogen atoms, thus indicating the formation of a iron oxynitride with an fcc structure

  19. Production of chemically reactive radioactive ion beams through on-line separation

    International Nuclear Information System (INIS)

    Joinet, A.

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO 2 , Nb, Ti, V,TiO 2 , CeO x , ThO 2 , C, ZrC 4 and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target

  20. Flow of chemically reactive magneto Cross nanoliquid with temperature-dependent conductivity

    Science.gov (United States)

    Hayat, Tasawar; Ullah, Ikram; Waqas, Muhammad; Alsaedi, Ahmed

    2018-05-01

    Influence of temperature-dependent thermal conductivity on MHD flow of Cross nanoliquid bounded by a stretched sheet is explored. The combined feature of Brownian motion and thermophoresis in nanoliquid modeling is retained. In addition, the attributes of zero mass flux at sheet are imposed. First-order chemical reaction is retained. The resulting problems are numerically computed. Plots and tabulated values are presented and examined. It is figured out that larger thermophoretic diffusion and thermal conductivity significantly rise the thermal field, whereas opposite situation is seen for heat transfer rate.

  1. Tautomeric transformation of temozolomide, their proton affinities and chemical reactivities: A theoretical approach.

    Science.gov (United States)

    Sang-Aroon, Wichien; Ruangpornvisuti, Vithaya; Amornkitbamrung, Vittaya

    2016-05-01

    The gas-phase geometry optimizations of bare, mono- and dihydrated complexes of temozolomide isomers were carried out using density functional calculation at the M06-2X/6-31+G(d,p) level of the theory. The structures and protonation energies of protonated species of temozolomide are reported. Chemical indices of all isomers and protonated species are also reported. Energies, thermodynamic quantities, rate constants and equilibrium constants of tautomeric and rotameric transformations of all isomers I1↔TZM↔HIa↔HIb↔I2↔I3 in bare and hydrated systems were obtained. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Role of tip chemical reactivity on atom manipulation process in dynamic force microscopy

    Czech Academy of Sciences Publication Activity Database

    Sugimoto, Y.; Yurtsever, A.; Abe, M.; Morita, S.; Ondráček, Martin; Pou, P.; Perez, R.; Jelínek, Pavel

    2013-01-01

    Roč. 7, č. 8 (2013), s. 7370-7376 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GPP204/11/P578 Grant - others:GA AV ČR(CZ) M100101207 Institutional support: RVO:68378271 Keywords : noncontact atomic force microscopy * atomic manipulation * force spectroscopy * chemical interaction force * DFT simulations * nudged elastic band Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 12.033, year: 2013 http://pubs.acs.org/doi/abs/10.1021/nn403097p

  3. Molecular beam studies of hot atom chemical reactions: Reactive scattering of energetic deuterium atoms

    International Nuclear Information System (INIS)

    Continetti, R.E.; Balko, B.A.; Lee, Y.T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H 2 /minus/> DH + H and the substitution reaction D + C 2 H 2 /minus/> C 2 HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible. 18 refs., 9 figs

  4. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  5. Intra-/inter-laboratory validation study on reactive oxygen species assay for chemical photosafety evaluation using two different solar simulators.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Nakamura, Kazuichi; Ohno, Yasuo; Kojima, Hajime

    2014-06-01

    A previous multi-center validation study demonstrated high transferability and reliability of reactive oxygen species (ROS) assay for photosafety evaluation. The present validation study was undertaken to verify further the applicability of different solar simulators and assay performance. In 7 participating laboratories, 2 standards and 42 coded chemicals, including 23 phototoxins and 19 non-phototoxic drugs/chemicals, were assessed by the ROS assay using two different solar simulators (Atlas Suntest CPS series, 3 labs; and Seric SXL-2500V2, 4 labs). Irradiation conditions could be optimized using quinine and sulisobenzone as positive and negative standards to offer consistent assay outcomes. In both solar simulators, the intra- and inter-day precisions (coefficient of variation; CV) for quinine were found to be below 10%. The inter-laboratory CV for quinine averaged 15.4% (Atlas Suntest CPS) and 13.2% (Seric SXL-2500V2) for singlet oxygen and 17.0% (Atlas Suntest CPS) and 7.1% (Seric SXL-2500V2) for superoxide, suggesting high inter-laboratory reproducibility even though different solar simulators were employed for the ROS assay. In the ROS assay on 42 coded chemicals, some chemicals (ca. 19-29%) were unevaluable because of limited solubility and spectral interference. Although several false positives appeared with positive predictivity of ca. 76-92% (Atlas Suntest CPS) and ca. 75-84% (Seric SXL-2500V2), there were no false negative predictions in both solar simulators. A multi-center validation study on the ROS assay demonstrated satisfactory transferability, accuracy, precision, and predictivity, as well as the availability of other solar simulators. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

    Science.gov (United States)

    Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

    2017-12-01

    Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

  7. Modeling of reactive chemical transport of leachates from a utility fly-ash disposal site

    International Nuclear Information System (INIS)

    Apps, J.A.; Zhu, M.; Kitanidis, P.K.; Freyberg, D.L.; Ronan, A.D.; Itakagi, S.

    1991-04-01

    Fly ash from fossil-fuel power plants is commonly slurried and pumped to disposal sites. The utility industry is interested in finding out whether any hazardous constituents might leach from the accumulated fly ash and contaminate ground and surface waters. To evaluate the significance of this problem, a representative site was selected for modeling. FASTCHEM, a computer code developed for the Electric Power Research Institute, was utilized for the simulation of the transport and fate of the fly-ash leachate. The chemical evolution of the leachate was modeled as it migrated along streamtubes defined by the flow model. The modeling predicts that most of the leachate seeps through the dam confining the ash pond. With the exception of ferrous, manganous, sulfate and small amounts of nickel ions, all other dissolved constituents are predicted to discharge at environmentally acceptable concentrations

  8. Coupling Chemical Kinetics and Flashes in Reactive, Thermal and Compositional Reservoir Simulation

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove

    2007-01-01

    of convergence and error test failures by more than 50% compared to direct integration without the new algorithm. To facilitate the algorithmic development we construct a virtual kinetic cell model. We use implicit one-step ESDIRK (Explicit Singly Diagonal Implicit Runge-Kutta) methods for integration...... of the kinetics. The kinetic cell model serves both as a tool for the development and testing of tailored solvers as well as a testbed for studying the interactions between chemical kinetics and phase behavior. A comparison between a Kvalue correlation based approach and a more rigorous equation of state based......Phase changes are known to cause convergence problems for integration of stiff kinetics in thermal and compositional reservoir simulations. We propose an algorithm for detection and location of phase changes based on discrete event system theory. The algorithm provides a robust way for handling...

  9. Response of the ionosphere to the injection of chemically reactive vapors

    International Nuclear Information System (INIS)

    Bernhardt, P.A.

    1976-05-01

    As a gas released in the ionosphere expands, it is rapidly cooled. When the vapor becomes sufficiently tenuous, it is reheated by collisions with the ambient atmosphere, and its flow is then governed by diffusive expansion. As the injected gas becomes well mixed with the plasma, a hole is created by chemical processes. In the case of diatomic hydrogen release, depression of the electron concentrations is governed by the charge exchange reaction between oxygen ions and hydrogen, producing positive hydroxyl ions. Hydroxyl ions rapidly react with the electron gas to produce excited oxygen and hydrogen atoms. Enhanced airglow emissions result from the transition of the excited atoms to lower energy states. The electron temperature in the depleted region rises sharply and this rise causes a thermal expansion of the plasma and a further reduction in the local plasma concentration

  10. Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

    Energy Technology Data Exchange (ETDEWEB)

    Bergren, Adam Johan [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    Electroanalytical chemistry is often utilized in chemical analysis and Fundamental studies. Important advances have been made in these areas since the advent of chemically modified electrodes: the coating of an electrode with a chemical film in order to impart desirable, and ideally, predictable properties. These procedures enable the exploitation of unique reactivity patterns. This dissertation presents studies that investigate novel reaction mechanisms at self-assembled monolayers on gold. In particular, a unique electrochemical current amplification scheme is detailed that relies on a selective electrode to enable a reactivity pattern that results in regeneration of the analyte (redox recycling). This regenerating reaction can occur up to 250 times for each analyte molecule, leading to a notable enhancement in the observed current. The requirements of electrode selectivity and the resulting amplification and detection limit improvements are described with respect to the heterogeneous and homogeneous electron transfer rates that characterize the system. These studies revealed that the heterogeneous electrolysis of the analyte should ideally be electrochemically reversible, while that for the regenerating agent should be held to a low level. Moreover, the homogeneous reaction that recycles the analyte should occur at a rapid rate. The physical selectivity mechanism is also detailed with respect to the properties of the electrode and redox probes utilized. It is shown that partitioning of the analyte into/onto the adlayer leads to the extraordinary selectivity of the alkanethiolate monolayer modified electrode. Collectively, these studies enable a thorough understanding of the complex electrode mechanism required for successful redox recycling amplification systems, Finally, in a separate (but related) study, the effect of the akyl chain length on the heterogeneous electron transfer behavior of solution-based redox probes is reported, where an odd-even oscillation

  11. Chemical reactivity of {alpha}-isosaccharinic acid in heterogeneous alkaline systems

    Energy Technology Data Exchange (ETDEWEB)

    Glaus, M. A.; Loon, L. R. Van

    2009-05-15

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, {alpha}- isosaccharinic acid ({alpha}-ISA) is the strongest complexant. The prediction of the equilibrium concentration of {alpha}-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of {alpha}-ISA in heterogeneous alkaline model systems containing either Ca(OH){sub 2} or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of {alpha}-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 {sup o}C or 90 {sup o}C, and under anaerobic atmospheres obtained by various methods. It was found that {alpha}-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than {alpha}-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was {approx} 50 % of the amount of {alpha}-ISA reacted. Sorption of {alpha}-ISA to Ca(OH){sub 2} contributed only to a minor extent to the loss of {alpha}-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of {alpha}-ISA. Under aerobic conditions {alpha}-ISA was

  12. Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

    International Nuclear Information System (INIS)

    Glaus, M. A.; Loon, L. R. Van

    2008-11-01

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α-isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, either at 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

  13. Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

    International Nuclear Information System (INIS)

    Glaus, M. A.; Loon, L. R. Van

    2009-05-01

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α- isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼ 50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

  14. Physico-chemical changes of the ground waters related to the 2011 El Hierro magmatic reactivation

    Science.gov (United States)

    Dionis, S.; Melián, G.; Padrón, E.; Padilla, G.; Nolasco, D.; Rodríguez, F.; Hernández, I.; Peraza, D.; Barrancos, J.; Hernández, P.; Calvo, D.; Pérez, N.

    2012-04-01

    The island of El Hierro (278 Km2), is the smallest, the southwesternmost and the youngest island (˜1.12 My) of the Canarian archipelago. The main geological characteristics of El Hierro consist on the presence of three convergent ridges of volcanic cones on a truncated trihedron shape and giant landslides between the three rift zones, being the most recent El Golfo on the northwest flank of the island. On July 2011 an anomalous seismic activity at Hierro Island started and suggested the initial stage of a volcanic unrest in the volcanic system. On October 10, after the occurrence of more than 10,000 earthquakes, a submarine eruption started. Evidences of this submarine volcanic eruption were visible on the sea surface to the south of La Restinga village, at the south of the island, in the form of large light-green coloured area, turbulent gas emission and the appearance of steamy volcanic fragments three days later. As part of its volcanic surveillance activities, the Instituto Volcanologico de Canarias (INVOLCAN) started a hydrogeochemical monitoring program on August 2011 in order to evaluate the temporal evolution of several physico-chemical parameters of the ground water system of El Hierro. Four observation sites were selected: three wells on the north of the island, where the seismic activity was located at the beginning of the volcano-seismic unrest (SIMO, FRON and PADO) and one horizontal well (gallery) in the south (TACO). Ground water sampling is being regularly collected, three times per week, at each observation site, and in-situ measurements of pH, conductivity and temperature measurements are performed. After 6 month of monitoring, no significant changes have been observed on pH and temperature measurements from all the observation sites. However, clear sharp decrease of conductivity was observed at SIMO on October 10 when the seismic tremor started. In addition, the strongest conductivity decrease pattern was observed later on at SIMO and PADO on

  15. Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

    International Nuclear Information System (INIS)

    Schatz, G.C.; Kuppermann, A.

    1980-01-01

    We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v-1 processes dominating

  16. Numerical solution of chemically reactive non-Newtonian fluid flow: Dual stratification

    Science.gov (United States)

    Rehman, Khalil Ur; Malik, M. Y.; Khan, Abid Ali; Zehra, Iffat; Zahri, Mostafa; Tahir, M.

    2017-12-01

    We have found that only a few attempts are available in the literature relatively to the tangent hyperbolic fluid flow induced by stretching cylindrical surfaces. In particular, temperature and concentration stratification effects have not been investigated until now with respect to the tangent hyperbolic fluid model. Therefore, we have considered the tangent hyperbolic fluid flow induced by an acutely inclined cylindrical surface in the presence of both temperature and concentration stratification effects. To be more specific, the fluid flow is attained with the no slip condition, which implies that the bulk motion of the fluid particles is the same as the stretching velocity of a cylindrical surface. Additionally, the flow field situation is manifested with heat generation, mixed convection and chemical reaction effects. The flow partial differential equations give a complete description of the present problem. Therefore, to trace out the solution, a set of suitable transformations is introduced to convert these equations into ordinary differential equations. In addition, a self-coded computational algorithm is executed to inspect the numerical solution of these reduced equations. The effect logs of the involved parameters are provided graphically. Furthermore, the variations of the physical quantities are examined and given with the aid of tables. It is observed that the fluid temperature is a decreasing function of the thermal stratification parameter and a similar trend is noticed for the concentration via the solutal stratification parameter.

  17. Chemical reactivity of precursor materials during synthesis of glasses used for conditioning high-level radioactive waste: Experiments and models

    International Nuclear Information System (INIS)

    Monteiro, A.

    2012-01-01

    The glass used to store high-level radioactive waste is produced by reaction of a solid waste residue and a glassy precursor (glass frit). The waste residue is first dried and calcined (to lose water and nitrogen respectively), then mixed with the glass frit to enable vitrification at high temperature. In order to obtain a good quality glass of constant composition upon cooling, the chemical reactions between the solid precursors must be complete while in the liquid state, to enable incorporation of the radioactive elements into the glassy matrix. The physical and chemical conditions during glass synthesis (e.g. temperature, relative proportions of frit and calcine, amount of radioactive charge) are typically empirically adjusted to obtain a satisfactory final product. The aim of this work is to provide new insights into the chemical and physical interactions that take place during vitrification and to provide data for a mathematical model that has been developed to simulate the chemical reactions. The consequences of the different chemical reactions that involve solid, liquid and gaseous phases are described (thermal effects, changes in crystal morphology and composition, variations in melt properties and structure). In a first series of experiments, a simplified analogue of the calcine (NaNO 3 -Al 2 O 3 ± MoO 3 /Nd 2 O 3 ) has been studied. In a second series of experiments, the simplified calcines have been reacted with a simplified glass frit (SiO 2 -Na 2 O-B 2 O 3 -Al 2 O 3 ) at high temperature. The results show that crystallization of the calcine may take place before interaction with the glass frit, but that the reactivity with the glass at high temperature is a function of the nature and stoichiometry of the crystalline phases which form at low temperature. The results also highlight how the mixing of the starting materials, the physical properties of the frit (viscosity, glass transition temperature) and the Na 2 O/Al 2 O 3 of the calcine but also its

  18. Influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with carcinogenic and anticoagulant effect of 17β-aminoestrogens

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: socc@puma2.zaragoza.unam.mx [Química Computacional, FES-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, Mexico City (Mexico); Raya, Angélica [Unidad Profesional Interdisciplinaria de Ingeniería Campus Guanajuato, Instituto Politécnico Nacional (IPN), Silao de la Victoria, Guanajuato (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz - Boca del Río, Universidad Veracruzana, Veracruz (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), Mexico City (Mexico)

    2014-06-25

    Highlights: • The aromatic A-ring of 17β-aminoestrogens contribute to its anticoagulant effect. • The electron-donor substituent groups favored the basicity of 17β-aminoestrogens. • The physicochemical properties are important in the carcinogenic effect of anticoagulant molecules. - Abstract: Activity of steroid hormones is dependent upon a number of factors, as solubility, transport and metabolism. The functional differences caused by structural modifications could exert an influence on the chemical reactivity and biological effect. The goal of this work is to study the influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with the carcinogenic risk that can associate with the anticoagulant effect of 17β-aminoestrogens using quantum-chemical descriptors at the DFT-B3LYP, BH and HLYP and M06-2X levels. The relative acidity of (H1) of the hydroxyl group increases with electron-withdrawing groups. Electron-donor groups favor the basicity. The steric hindrance of the substituents decreases the aromatic character and consequently diminution the carcinogenic effect. Density descriptors: hardness, electrophilic index, atomic charges, molecular orbitals, electrostatic potential and their geometric parameters permit analyses of the chemical reactivity and physicochemical features and to identify some reactive sites of 17β-aminoestrogens.

  19. Synthesis, characterisation and chemical reactivity of some new binuclear dioxouranium(VI) complexes derived from organic diazo compounds (Preprint No. CT-33)

    International Nuclear Information System (INIS)

    Pujar, M.A.; Pirgonde, B.R.

    1988-02-01

    A new series of binuclear dioxouranium(VI) complexes of polydentatate diazo compounds have been synthesised and characterised adequately by analysis, physio-chemical techniques and reactivity of these complexes. The location of bonding site of ligands, stability of complexes and status of U-O bond and probable structures of these complexes have been discussed. (author). 10 refs

  20. Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

    Science.gov (United States)

    Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

  1. Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

    International Nuclear Information System (INIS)

    Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

    2013-01-01

    In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called “interphase” between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC–TiC) n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC–TiC) n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

  2. Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

    Science.gov (United States)

    Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

    2013-06-01

    In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called "interphase" between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC-TiC)n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC-TiC)n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

  3. Eulerian-Lagrangian simulation of non-isothermal gas-solid flows: particle-turbulence interactions in pipe flows; Simulation eulerienne-lagrangienne d'ecoulements gaz-solide non isothermes: interactions particules-turbulence, application aux ecoulements en conduite

    Energy Technology Data Exchange (ETDEWEB)

    Chagras, V.

    2004-03-15

    The aim of this work is to contribute to the numerical modeling of turbulent gas-solid flows in vertical or horizontal non isothermal pipes, which can be found in many industrial processes (pneumatic transport, drying, etc). The model is based on an Eulerian-Lagrangian approach allowing a fine description of the interactions between the two phases (action of the fluid upon the particles (dispersion), action of the particles upon the fluid (two way coupling) and between particles (collisions)), more or less influential according to the characteristics of the flow. The influence of the gas phase turbulence on the particle motion is taken into account using a non-isotropic dispersion model, which allows the generation of velocity and temperature fluctuations of the fluid seen by the particles. The numerical developments brought to the model for vertical and horizontal pipe flow have been validated by comparison with available experimental results from the literature. The sensitivity tests highlight the influence of the dispersion model, collisions and turbulence modulation (direct and non direct modifications ) on the dynamic and thermal behavior of the suspension. The model is able to predict the heat exchanges in the presence of particles for a wide range of flows in vertical and horizontal pipes. However numerical problems still exist in two-way coupling for very small particles and loading ratios above one. This is related to the problems encountered when modeling the coupling terms between the two phases (parameters C{sub {epsilon}}{sub 2} and C{sub {epsilon}}{sub 3} ) involved in the turbulence dissipation balance. (author)

  4. Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

    International Nuclear Information System (INIS)

    Zhang, Xiaojuan; Wang, Bo; Zhan, Zhaolin; Huang, Feng

    2013-01-01

    V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC

  5. Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaojuan [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Wang, Bo [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); Zhan, Zhaolin [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Huang, Feng, E-mail: huangfeng@nimte.ac.cn [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China)

    2013-07-01

    V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC.

  6. Chemical reactivities of the superconducting oxides, YBa2Cu3Oy and BiSrCaCu2Oy

    International Nuclear Information System (INIS)

    Toyama, Hisashi; Mizuno, Noritaka; Misono, Makoto

    1989-01-01

    The chemical reactivities of YBa 2 Cu 3 O y and BiSrCaCu 2 O y with various gases have been studied. It was found that large quantities of NO, CO, and NO 2 were rapidly absorbed (or intercalated) in the bulk of YBa 2 Cu 3 O y (T c : 90 K) at 573 K. The amount absorbed was in the order NO ∼ CO ∼ NO 2 > O 2 ∼ CO 2 > N 2 O ∼ 0. The amount for NO was more than two times the amount of YBa 2 Cu 3 O y in molar ratio and elongation by about 0.2 angstrom along c-axis was observed. NO absorbed was almost completely recovered as NO by the evacuation at 773 K. This absorption-desorption cycle proceeded reversively. The electronic resistivity at 573 K of YBa 2 Cu 3 O y increased upon the NO absorption and was restored by the evacuation at 773 K. CO was also absorbed rapidly accompanied by evolution of CO 2 . BiSrCaCu 2 O y did not absorb either NO or CO

  7. Influence of crystal defects on the chemical reactivity of recoil atoms in oxygen-containing chromium compounds

    International Nuclear Information System (INIS)

    Costea, T.

    1969-01-01

    The influence of crystal defects on the chemical reactivity of recoil atoms produced by the reaction 50 Cr (n,γ) 51 Cr in oxygen-containing chromium compounds has been studied. Three methods have been used to introduce the defects: doping (K 2 CrO 4 doped with BaCrO 4 ), irradiation by ionizing radiation (K 2 CrO 4 irradiated in the presence of Li 2 CO 3 ) and non-stoichiometry (the semi-conducting oxides of the CrO 3 -Cr 2 O 3 series). The thermal annealing kinetics of the irradiated samples have been determined, and the activation energy has been calculated. In all cases it has been observed that there is a decrease in the activation energy for thermal annealing in the presence of the defects. In order to explain the annealing process, an electronic mechanism has been proposed based on the interaction between the recoil species and the charge-carriers (holes or electrons). (author) [fr

  8. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O) n=1-5 clusters.

    Science.gov (United States)

    Linton, Kirsty A; Wright, Timothy G; Besley, Nicholas A

    2018-03-13

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + (H 2 O) n =1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO + (H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + (H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + (H 2 O) 5 [Formula: see text] H + (H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + (H 2 O) 5 Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + (H 2 O) 5 complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  9. Chemical Reactivity of Isoproturon, Diuron, Linuron, and Chlorotoluron Herbicides in Aqueous Phase: A Theoretical Quantum Study Employing Global and Local Reactivity Descriptors

    Directory of Open Access Journals (Sweden)

    Luis Humberto Mendoza-Huizar

    2015-01-01

    Full Text Available We have calculated global and local DFT reactivity descriptors for isoproturon, diuron, linuron, and chlorotoluron herbicides at the MP2/6-311++G(2d,2p level of theory. The results suggest that, in aqueous conditions, chlorotoluron, linuron, and diuron herbicides may be degraded by elimination of urea moiety through electrophilic attacks. On the other hand, electrophilic, nucleophilic, and free radical attacks on isoproturon may cause the elimination of isopropyl fragment.

  10. Cross talk between increased intracellular zinc (Zn2+) and accumulation of reactive oxygen species in chemical ischemia.

    Science.gov (United States)

    Slepchenko, Kira G; Lu, Qiping; Li, Yang V

    2017-10-01

    Both zinc (Zn 2+ ) and reactive oxygen species (ROS) have been shown to accumulate during hypoxic-ischemic stress and play important roles in pathological processes. To understand the cross talk between the two of them, here we studied Zn 2+ and ROS accumulation by employing fluorescent probes in HeLa cells to further the understanding of the cause and effect relationship of these two important cellular signaling systems during chemical-ischemia, stimulated by oxygen and glucose deprivation (OGD). We observed two Zn 2+ rises that were divided into four phases in the course of 30 min of OGD. The first Zn 2+ rise was a transient, which was followed by a latent phase during which Zn 2+ levels recovered; however, levels remained above a basal level in most cells. The final phase was the second Zn 2+ rise, which reached a sustained plateau called Zn 2+ overload. Zn 2+ rises were not observed when Zn 2+ was removed by TPEN (a Zn 2+ chelator) or thapsigargin (depleting Zn 2+ from intracellular stores) treatment, indicating that Zn 2+ was from intracellular storage. Damaging mitochondria with FCCP significantly reduced the second Zn 2+ rise, indicating that the mitochondrial Zn 2+ accumulation contributes to Zn 2+ overload. We also detected two OGD-induced ROS rises. Two Zn 2+ rises preceded two ROS rises. Removal of Zn 2+ reduced or delayed OGD- and FCCP-induced ROS generation, indicating that Zn 2+ contributes to mitochondrial ROS generation. There was a Zn 2+ -induced increase in the functional component of NADPH oxidase, p47 phox , thus suggesting that NADPH oxidase may mediate Zn 2+ -induced ROS accumulation. We suggest a new mechanism of cross talk between Zn 2+ and mitochondrial ROS through positive feedback processes that eventually causes excessive free Zn 2+ and ROS accumulations during the course of ischemic stress. Copyright © 2017 the American Physiological Society.

  11. A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

    Directory of Open Access Journals (Sweden)

    M. De Lucia

    2015-02-01

    Full Text Available Fully coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i that the presence of CO2 is the only driving force for chemical reactions and (ii that its migration in the reservoir is only marginally affected by immobilisation due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany, both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is shown to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g. by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids of the order of millions of elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

  12. Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

    Energy Technology Data Exchange (ETDEWEB)

    Aden, Bethany [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Kite, Camille M. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Hopkins, Benjamin W. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Zetterberg, Anna [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Lokitz, Bradley S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Ankner, John Francis [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Kilbey, S. Michael [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering

    2017-01-24

    Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on the size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.

  13. Non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} on dehydrogenation high-energy ball milled MgH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Hou, Xiaojiang; Hu, Rui; Kou, Hongchao; Li, Jinshan

    2016-11-01

    MgH{sub 2}-M (M = TiF{sub 3} or Nb{sub 2}O{sub 5} or both of them) composites prepared by high-energy ball milling are used in this work to illustrate the dehydrogenation behavior of MgH{sub 2} with the addition of catalysts. The phase compositions, microstructures, particle morphologies and distributions of MgH{sub 2} with catalysts have been evaluated. The non-isothermal synergetic catalytic-dehydrogenation effect of TiF{sub 3} and Nb{sub 2}O{sub 5} evaluated by differential scanning calorimetry gives the evidences that the addition of catalysts is an effective strategy to destabilize MgH{sub 2} and reduce hydrogen desorption temperatures and activation energies. Depending on additives, the desorption peak temperatures of catalyzed MgH{sub 2} reduce from 417 °C to 341 °C for TiF{sub 3} and from 417 °C to 336 °C for Nb{sub 2}O{sub 5}, respectively. The desorption peak temperature reaches as low as 310 °C for MgH{sub 2} catalyzed by TiF{sub 3} coupling with Nb{sub 2}O{sub 5}. The non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} is mainly attributed to electronic exchange reactions with hydrogen molecules, which improve the recombination of hydrogen atoms during dehydrogenation process of MgH{sub 2}. - Highlights: • Catalytic surface for MgH{sub 2} is achieved by high-energy ball milling. • Non-isothermal dehydrogenation behavior of MgH{sub 2} with TiF{sub 3} and/or Nb{sub 2}O{sub 5} is illustrated. • Dehydrogenation activation energies of synergetic catalyzed MgH{sub 2} are obtained. • Synergetic catalytic-dehydrogenation mechanism of TiF{sub 3} and Nb{sub 2}O{sub 5} is proposed.

  14. Enhanced reactivation of UV-irradiated adenovirus 2 in HeLa cells treated with non-mutagenic chemical agents

    Energy Technology Data Exchange (ETDEWEB)

    Piperakis, S.M.; McLennan, A.G. (Liverpool Univ. (UK). Dept. of Biochemistry)

    1985-03-01

    Treatment of HeLa cells with ethanol and sodium arsenite, compounds which are known to elicit the heat-shock response, before infection with UV-irradiated adenovirus 2 has been found to result in the enhanced reactivation of the damaged virus in a manner similar to that obtained by pre-irradiation or heating of the cells. Enhanced reactivation may be the result of the inhibition of DNA synthesis caused by these agents since hydroxyurea also produced a significant enhancement.

  15. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies.

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH 2 -CH=CH-CH 2 -) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than ~1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  16. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH2-CH=CH-CH2-) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than 1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  17. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene.

    Science.gov (United States)

    Irving, Roy M; Pinkerton, Marie E; Elfarra, Adnan A

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague-Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S(2)-S(3) segments) while DCVCS primarily affected the outer cortical proximal tubules (S(1)-S(2) segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37°C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. Copyright © 2012 Elsevier Inc. All rights reserved.

  18. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene

    International Nuclear Information System (INIS)

    Irving, Roy M.; Pinkerton, Marie E.; Elfarra, Adnan A.

    2013-01-01

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S 2 –S 3 segments) while DCVCS primarily affected the outer cortical proximal tubules (S 1 –S 2 segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity

  19. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene

    Energy Technology Data Exchange (ETDEWEB)

    Irving, Roy M. [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Pinkerton, Marie E. [Department of Pathobiological Sciences, University of Wisconsin-Madison, Madison, WI 53706 (United States); Elfarra, Adnan A., E-mail: elfarra@svm.vetmed.wisc.edu [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Department of Comparative Biosciences, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S{sub 2}–S{sub 3} segments) while DCVCS primarily affected the outer cortical proximal tubules (S{sub 1}–S{sub 2} segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity.

  20. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  1. Induction of molecular endpoints by reactive oxygen species in human lung cells predicted by physical chemical properties of engineered nanoparticles

    Science.gov (United States)

    A series of six titanium dioxide and two cerium oxide engineered nanomaterials were assessed for their ability to induce cytotoxicity, reactive oxygen species (ROS), and various types of DNA and protein damage in human respiratory BEAS-2B cells exposed in vitro for 72 hours at se...

  2. How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

    Directory of Open Access Journals (Sweden)

    M. J. Prather

    2018-05-01

    Full Text Available We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25–30 % of the total reactivities, but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this

  3. Chemical Modeling of the Reactivity of Short-Lived Greenhouse Gases: A Model Inter-Comparison Prescribing a Well-Measured, Remote Troposphere

    Science.gov (United States)

    Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

    2018-01-01

    We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating over the data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14,880 parcels along 180W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10% of parcels control 25-30% of the total reactivities), but do not fully agree on which parcels comprise the top 10%. Distinct differences in specific features occur, including the regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the 6 models tested here, 3 are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify 4, effectively distinct, chemical models. Based on this work, we suggest that water vapor differences in

  4. How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

    Science.gov (United States)

    Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

    2018-05-01

    We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25-30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this work, we suggest that water vapor

  5. Study of a new hybrid process combining slurry infiltration and Reactive Chemical Vapour Infiltration for the realisation of Ceramic Matrix Composites

    International Nuclear Information System (INIS)

    Ledain, Olivier

    2014-01-01

    Ceramic matrix composites were originally developed for aerospace,military aeronautics or energy applications thanks to their good properties at high temperature. They are generally made by Chemical Vapor Infiltration (CVI). A new short hybrid process combining fiber preform slurry impregnation of ceramic powders with an innovative Reactive CVI (RCVI) route is proposed to reduce the production time. This route is based on the combination of Reactive Chemical Vapour Deposition (RCVD), which is often used to deposit coatings on fibres, with the Chemical Vapor Infiltration (CVI).In RCVD, the absence of one element of the deposited carbide in the initial gas phase involves the consumption/conversion of the solid substrate. In this work, the RCVD growth and the associated consumption were studied with different parameters in the Ti-H-Cl-C chemical system. The study has been completed with the chemical products analysis, combining XRD, XPS and FTIR. Then, the partial conversion of sub-micrometer carbon powders into titanium carbide and the consolidation of green bodies by RCVI from H 2 /TiCl 4 gaseous infiltration were studied. The residual porosity and the final TiC content were measured in the bulk of the infiltrated powders by image analysis from scanning electron microscopy. Depending on temperature, few hundred micrometers-depth infiltrations are obtained.Finally, the results have been transposed to the RCVI into CMC-type pre-forms. Despite a minimal TiC content of 25% in the overall preform, the results shown a bad homogeneity of the infiltration and a poor cohesion of fibres with RCVI consolidated powder of their environment. (author) [fr

  6. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    Science.gov (United States)

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  7. Chemical analysis of reactive species and antimicrobial activity of/nwater treated by nanosecond pulsed DBD air plasma

    Czech Academy of Sciences Publication Activity Database

    Laurita, R.; Barbieri, D.; Gherardi, M.; Colombo, V.; Lukeš, Petr

    2015-01-01

    Roč. 3, č. 2 (2015), s. 53-61 ISSN 2212-8166 R&D Projects: GA MŠk(CZ) LD14080 Grant - others:European Cooperation in Science and Technology(XE) COST TD1208 Institutional support: RVO:61389021 Keywords : Dielectric barrier discharge * Plasma activated water * Reactive species * Peroxynitrite * Phenol degradation * Candida albicans * Staphylococcus aureus * Antimicrobial activity * Nosocomial infections Subject RIV: BL - Plasma and Gas Discharge Physics http://www.sciencedirect.com/science/article/pii/S2212816615300081

  8. Generation and Role of Reactive Oxygen and Nitrogen Species Induced by Plasma, Lasers, Chemical Agents, and Other Systems in Dentistry

    Science.gov (United States)

    Jha, Nayansi; Ryu, Jae Jun

    2017-01-01

    The generation of reactive oxygen and nitrogen species (RONS) has been found to occur during inflammatory procedures, during cell ischemia, and in various crucial developmental processes such as cell differentiation and along cell signaling pathways. The most common sources of intracellular RONS are the mitochondrial electron transport system, NADH oxidase, and cytochrome P450. In this review, we analyzed the extracellular and intracellular sources of reactive species, their cell signaling pathways, the mechanisms of action, and their positive and negative effects in the dental field. In dentistry, ROS can be found—in lasers, photosensitizers, bleaching agents, cold plasma, and even resin cements, all of which contribute to the generation and prevalence of ROS. Nonthermal plasma has been used as a source of ROS for biomedical applications and has the potential for use with dental stem cells as well. There are different types of dental stem cells, but their therapeutic use remains largely untapped, with the focus currently on only periodontal ligament stem cells. More research is necessary in this area, including studies about ROS mechanisms with dental cells, along with the utilization of reactive species in redox medicine. Such studies will help to provide successful treatment modalities for various diseases. PMID:29204250

  9. Host-cell reactivation of UV-irradiated and chemically-treated herpes simplex virus-1 by xeroderma pigmentosum, xp heterozygotes and normal skin fibroblasts

    International Nuclear Information System (INIS)

    Selsky, C.A.

    1978-01-01

    The host-cell reactivation of UV-irradiated and N-acetoxy-2-acetylamino-fluorene-treated herpes simplex virus type 1 strain MP was studied in normal and xeroderma pigmentosum human skin fibroblasts. Virus treated with either agent demonstrated lower survival in XP cells from complementation groups A, B, C and D than in normal fibroblasts. The relative reactivation ability of XP cells from the different genetic complementation groups was found to be the same for both irradiated and chemically treated virus. In addition, the inactivation kinetics for virus treated with either agent in the XP variant were comparable to that seen in normal skin fibroblasts. The addition of 2 or 4 mmoles caffeine to the post-infection assay medium had no effect on the inactivation kinetics of virus treated by either agent in the XP variant or in XP cells from the different genetic complementation groups. Treatment of the virus with nitrogen mustard resulted in equivalent survival in normal and XP genetic complementation group D cells. No apparent defect was observed in the ability of XP heterozygous skin fibroblasts to repair virus damaged with up to 100 μg N-acetoxy-2-acetylaminofluorene per ml. These findings indicate that the repair of UV-irradiated and N-acetoxy-2-acetylaminofluorene-treated virus is accomplished by the same pathway or different pathways sharing a common intermediate step and that the excision defect of XP cells plays little if any role in the reactivation of nitrogen mustard treated virus. (Auth.)

  10. Oral Administration of the Japanese Traditional Medicine Keishibukuryogan-ka-yokuinin Decreases Reactive Oxygen Metabolites in Rat Plasma: Identification of Chemical Constituents Contributing to Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Yosuke Matsubara

    2017-02-01

    Full Text Available Insufficient detoxification and/or overproduction of reactive oxygen species (ROS induce cellular and tissue damage, and generated reactive oxygen metabolites become exacerbating factors of dermatitis. Keishibukuryogan-ka-yokuinin (KBGY is a traditional Japanese medicine prescribed to treat dermatitis such as acne vulgaris. Our aim was to verify the antioxidant properties of KBGY, and identify its active constituents by blood pharmacokinetic techniques. Chemical constituents were quantified in extracts of KBGY, crude components, and the plasma of rats treated with a single oral administration of KBGY. Twenty-three KBGY compounds were detected in plasma, including gallic acid, prunasin, paeoniflorin, and azelaic acid, which have been reported to be effective for inflammation. KBGY decreased level of the diacron-reactive oxygen metabolites (d-ROMs in plasma. ROS-scavenging and lipid hydroperoxide (LPO generation assays revealed that gallic acid, 3-O-methylgallic acid, (+-catechin, and lariciresinol possess strong antioxidant activities. Gallic acid was active at a similar concentration to the maximum plasma concentration, therefore, our findings indicate that gallic acid is an important active constituent contributing to the antioxidant effects of KBGY. KBGY and its active constituents may improve redox imbalances induced by oxidative stress as an optional treatment for skin diseases.

  11. Non-isothermal decomposition kinetics, heat capacity and thermal safety of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture

    International Nuclear Information System (INIS)

    Zhang, Jiao-Qiang; Gao, Hong-Xu; Ji, Tie-Zheng; Xu, Kang-Zhen; Hu, Rong-Zu

    2011-01-01

    Highlights: → Non-isothermal decomposition kinetics, heat capacity and thermal safety on 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture. → Apparent activation energy and pre-exponential constant obtained. → Thermal explosion temperature, adiabatic time-to-explosion, 50% drop height of impact sensitivity, and critical temperature of hot-spot initiation calculated. - Abstract: The specific heat capacity (C p ) of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was determined with the continuous C p mode of microcalorimeter. The equation of C p with temperature was obtained. The standard molar heat capacity of GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was 1.225 J mol -1 K -1 at 298.15 K. With the help of the peak temperature (T p ) from the non-isothermal DTG curves of the mixture at different heating rates (β), the apparent activation energy (E k and E o ) and pre-exponential constant (A K ) of thermal decomposition reaction obtained by Kissinger's method and Ozawa's method. Using density (ρ) and thermal conductivity (λ), the decomposition heat (Q d , taking half-explosion heat), Zhang-Hu-Xie-Li's formula, the values (T e0 and T p0 ) of T e and T p corresponding to β → 0, thermal explosion temperature (T be and T bp ), adiabatic time-to-explosion (t TIad ), 50% drop height (H 50 ) of impact sensitivity, and critical temperature of hot-spot initiation (T cr,hotspot ) of thermal explosion of the mixture were calculated. The following results of evaluating the thermal safety of the mixture were obtained: T be = 441.64 K, T bp = 461.66 K, t Tlad = 78.0 s (n = 2), t Tlad = 74.87s (n = 1), t Tlad = 71.85 s (n = 0), H 50 = 21.33 cm.

  12. Formulation of chemically reactive foams for the dissolution of oxides polluting the secondary circuits of steam generators

    International Nuclear Information System (INIS)

    Provens, Helene

    1999-01-01

    The fouling of the Steam Generators (SG) secondary circuits, due to oxides deposits like magnetite (Fe 3 O 4 ), induces the degradation of the internal SG equipment, the reduction of the plant power, implying to clean these circuits. This operation made in liquid phase generates an important volume of effluents with an expensive cost of treatment. The use of a reactive foam allows the reduction of this volume by ten. Among the reactive tested, oxalic acid is the most efficient to dissolve a magnetite quantity of 10 g.l -1 , at ambient temperature for 24 hours, as imposed by the industrial wishes. The dissolution is not complete in our experimental conditions and is a complex reaction of autocatalytic type, composed of an acid attack, a reductive step, both followed by a slow diffusion. The surfactants generating the foam, which transport the reactive, are adsorbed on the magnetite but this affects weakly the dissolution. Its effectiveness is evaluated varying the experimental conditions. The wetting properties and the stability of the foam induce erosion and undissolved particles transport capacities, during its circulation into the SG. These particles trapped in the inter-bubble liquid films or carried by the piston effect of the foam bed, can be recovered on filters placed out of the SG. To quantify the transport, the influence of different parameters is studied: the more stable the foam is, the more important the transport is. Innocuousness tests showed that oxalic acid was not harmful for constitutive SG materials, either they were isolated or coupled. The cleaning by oxalic acid causes ferrous oxalates precipitation, representing 10 to 15 pc of the total iron quantity depending on the sample. A rinsing out with a foam containing 1 pc oxalic acid and 5 pc hydrogen peroxide allows the dissolution of these precipitates without corrosion problems. (author) [fr

  13. Using laboratory flow experiments and reactive chemical transport modeling for designing waterflooding of the Agua Fria Reservoir, Poza Rica-Altamira Field, Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Birkle, P.; Pruess, K.; Xu, T.; Figueroa, R.A. Hernandez; Lopez, M. Diaz; Lopez, E. Contreras

    2008-10-01

    Waterflooding for enhanced oil recovery requires that injected waters must be chemically compatible with connate reservoir waters, in order to avoid mineral dissolution-and-precipitation cycles that could seriously degrade formation permeability and injectivity. Formation plugging is a concern especially in reservoirs with a large content of carbonates, such as calcite and dolomite, as such minerals typically react rapidly with an aqueous phase, and have strongly temperature-dependent solubility. Clay swelling can also pose problems. During a preliminary waterflooding pilot project, the Poza Rica-Altamira oil field, bordering the Gulf coast in the eastern part of Mexico, experienced injectivity loss after five months of reinjection of formation waters into well AF-847 in 1999. Acidizing with HCl restored injectivity. We report on laboratory experiments and reactive chemistry modeling studies that were undertaken in preparation for long-term waterflooding at Agua Frma. Using analogous core plugs obtained from the same reservoir interval, laboratory coreflood experiments were conducted to examine sensitivity of mineral dissolution and precipitation effects to water composition. Native reservoir water, chemically altered waters, and distilled water were used, and temporal changes in core permeability, mineral abundances and aqueous concentrations of solutes were monitored. The experiments were simulated with the multi-phase, nonisothermal reactive transport code TOUGHREACT, and reasonable to good agreement was obtained for changes in solute concentrations. Clay swelling caused an additional impact on permeability behavior during coreflood experiments, whereas the modeled permeability depends exclusively on chemical processes. TOUGHREACT was then used for reservoir-scale simulation of injecting ambient-temperature water (30 C, 86 F) into a reservoir with initial temperature of 80 C (176 F). Untreated native reservoir water was found to cause serious porosity and

  14. Non-isothermal crystallization kinetics of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass containing nucleation agent P{sub 2}O{sub 5}/TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin, E-mail: stra-ceo@163.com; Wang, Yongya; Luo, Wenqin; Li, Jingfen [Huzhou University, Department of Material Chemistry (China); Li, Jianyou [Huzhou Central Hospital, Orthopedic Department (China)

    2017-03-15

    Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass ceramics containing nucleation agent P{sub 2}O{sub 5}/TiO{sub 2} were prepared by sol-gel method. The samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The activation energy and kinetic parameters for crystallization of the samples were calculated by the Johnson-Mehi-Avrami (JMA) model and Augis-Bennett method according to the results of DSC. The results showed that the crystallization mechanism of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass, whose non-isothermal kinetic parameter n = 2.3, was consistent with surface crystallization of the JMA model. The kinetics model function of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass, f(α) = 2.3(1–α)[–ln(1–α)]{sup 0.57}, was also obtained. The addition of nucleation agent P{sub 2}O{sub 5}/TiO{sub 2} could reduce the activation energy, which made the crystal growth modes change from onedimensional to three-dimensional.

  15. Engineering of the chemical reactivity of the Ti/HfO₂ interface for RRAM: experiment and theory.

    Science.gov (United States)

    Calka, Pauline; Sowinska, Malgorzata; Bertaud, Thomas; Walczyk, Damian; Dabrowski, Jarek; Zaumseil, Peter; Walczyk, Christian; Gloskovskii, Andrei; Cartoixà, Xavier; Suñé, Jordi; Schroeder, Thomas

    2014-04-09

    The Ti/HfO2 interface plays a major role for resistance switching performances. However, clear interface engineering strategies to achieve reliable and reproducible switching have been poorly investigated. For this purpose, we present a comprehensive study of the Ti/HfO2 interface by a combined experimental-theoretical approach. Based on the use of oxygen-isotope marked Hf*O2, the oxygen scavenging capability of the Ti layer is clearly proven. More importantly, in line with ab initio theory, the combined HAXPES-Tof-SIMS study of the thin films deposited by MBE clearly establishes a strong impact of the HfO2 thin film morphology on the Ti/HfO2 interface reactivity. Low-temperature deposition is thus seen as a RRAM processing compatible way to establish the critical amount of oxygen vacancies to achieve reproducible and reliable resistance switching performances.

  16. Probing the reactivity of nucleophile residues in human 2,3-diphosphoglycerate/deoxy-hemoglobin complex by aspecific chemical modifications.

    Science.gov (United States)

    Scaloni, A; Ferranti, P; De Simone, G; Mamone, G; Sannolo, N; Malorni, A

    1999-06-11

    The use of aspecific methylation reaction in combination with MS procedures has been employed for the characterization of the nucleophilic residues present on the molecular surface of the human 2,3-diphosphoglycerate/deoxy-hemoglobin complex. In particular, direct molecular weight determinations by ESMS allowed to control the reaction conditions, limiting the number of methyl groups introduced in the modified globin chains. A combined LCESMS-Edman degradation approach for the analysis of the tryptic peptide mixtures yielded to the exact identification of methylation sites together with the quantitative estimation of their degree of modification. The reactivities observed were directly correlated with the pKa and the relative surface accessibility of the nucleophilic residues, calculated from the X-ray crystallographic structure of the protein. The results here described indicate that this methodology can be efficiently used in aspecific modification experiments directed to the molecular characterization of the surface topology in proteins and protein complexes.

  17. Investigating the Chemical Reactivity for Hydrogen in Siliciclastic Sediments: two Work Packages of the H2STORE Project

    Science.gov (United States)

    De Lucia, M.; Pilz, P.

    2014-12-01

    The H2STORE ("Hydrogen to Store") collaborative project, funded by the German government, investigates the feasibility of industrial-scale hydrogen storage from excess wind energy in siliciclastic depleted gas and oil reservoirs or suitable saline aquifers. In particular, two work packages (geochemical experiments and modelling) hosted at the German Research Centre for Geosciences (GFZ) focus on the possible impact of hydrogen on formation fluids and on the mineralogical, geochemical and petrophysical properties of reservoirs and caprocks. Laboratory experiments expose core samples from several potential reservoirs to pure hydrogen or hydrogen mixtures under site-specific conditions (temperatures up to 200 °C and pressure up to 300 bar). The resulting qualitative and, whereas possible, quantitative data are expected to ameliorate the precision of predictive geochemical and reactive transport modelling, which is also performed within the project. The combination of experiments and models will improve the knowledge about: (1) solubility model and mixing rule for of hydrogen and its gas mixtures in high saline formation fluids; (2) hydrogen reactivity in a broad spectrum of P-T conditions; (3) thermodynamics and kinetics of mineral dissolution or precipitation reactions and redox processes. It is known that under specific P-T conditions reactions between hydrogen and anorganic rock components such as carbonates can occur. However these conditions have never been precisely defined to date. A precise estimation of the hydrogen impact on reservoir behavior of different siliciclastic rock types is crucial for site selection and optimization of storage depth. Enhancing the overall understanding of such systems will benefit the operational reliability, the ecological tolerance, and the economic efficiency of future energy storing plants, crucial aspects for public acceptance and for industrial investors.

  18. Modeling subsurface reactive flows using leadership-class computing

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Richard Tran [Computational Earth Sciences Group, Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6015 (United States); Hammond, Glenn E [Hydrology Group, Environmental Technology Division, Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Lichtner, Peter C [Hydrology, Geochemistry, and Geology Group, Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Sripathi, Vamsi [Department of Computer Science, North Carolina State University, Raleigh, NC 27695-8206 (United States); Mahinthakumar, G [Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, NC 27695-7908 (United States); Smith, Barry F, E-mail: rmills@ornl.go, E-mail: glenn.hammond@pnl.go, E-mail: lichtner@lanl.go, E-mail: vamsi_s@ncsu.ed, E-mail: gmkumar@ncsu.ed, E-mail: bsmith@mcs.anl.go [Mathematics and Computer Science Division, Argonne National Laboratory, Argonne, IL 60439-4844 (United States)

    2009-07-01

    We describe our experiences running PFLOTRAN-a code for simulation of coupled hydro-thermal-chemical processes in variably saturated, non-isothermal, porous media- on leadership-class supercomputers, including initial experiences running on the petaflop incarnation of Jaguar, the Cray XT5 at the National Center for Computational Sciences at Oak Ridge National Laboratory. PFLOTRAN utilizes fully implicit time-stepping and is built on top of the Portable, Extensible Toolkit for Scientific Computation (PETSc). We discuss some of the hurdles to 'at scale' performance with PFLOTRAN and the progress we have made in overcoming them on leadership-class computer architectures.

  19. Modeling subsurface reactive flows using leadership-class computing

    International Nuclear Information System (INIS)

    Mills, Richard Tran; Hammond, Glenn E; Lichtner, Peter C; Sripathi, Vamsi; Mahinthakumar, G; Smith, Barry F

    2009-01-01

    We describe our experiences running PFLOTRAN-a code for simulation of coupled hydro-thermal-chemical processes in variably saturated, non-isothermal, porous media- on leadership-class supercomputers, including initial experiences running on the petaflop incarnation of Jaguar, the Cray XT5 at the National Center for Computational Sciences at Oak Ridge National Laboratory. PFLOTRAN utilizes fully implicit time-stepping and is built on top of the Portable, Extensible Toolkit for Scientific Computation (PETSc). We discuss some of the hurdles to 'at scale' performance with PFLOTRAN and the progress we have made in overcoming them on leadership-class computer architectures.

  20. Experiments on non-isothermal spreading

    International Nuclear Information System (INIS)

    Ehrhard, P.

    1992-09-01

    Experiments are performed on axisymmetric spreading of viscous drops on glass plates. Two liquids are investigated: silicone oil (M-100) spreads to 'infinity' and paraffin oil spreads to a finite-radius steady state. The experiments with silicone oil partly recover the behaviour of previous workers data; those experiments with paraffin oil provide new data. It is found that gravitational forces dominate at long enough times while at shorter times capillary forces dominate. When the plate is heated or cooled with respect to the ambient gas, thermocapillary forces generate flows that alter the spreading dynamics. Heating (cooling) the plate is found to retard (augment) the streading. Moreover, in case of partial wetting, the finally-approached drop radius is smaller (larger) for a heated (cooled) plate. These data are all new. All these observations are in excellent quantitative agreement with the related model predictions of Ehrhard and Davis (1991). A breakdown of the axisymmetric character of the flow is observed only for very long times and/or very thin liquid layers. (orig.) [de

  1. Structure, Reactivity and Dynamics

    Indian Academy of Sciences (India)

    Understanding structure, reactivity and dynamics is the core issue in chemical ... functional theory (DFT) calculations, molecular dynamics (MD) simulations, light- ... between water and protein oxygen atoms, the superionic conductors which ...

  2. Supra-molecular structure and chemical reactivity of cellulose I studied using CP/MAS (sup)13 C-NMR

    CSIR Research Space (South Africa)

    Chunilall, Viren

    2013-08-01

    Full Text Available There are a few traditional methods of analysing the chemical properties of cellulose I. Some of these methods include the Permanganate number determination, which is used to obtain the lignin content of the pulp [12]. The acid insoluble lignin content... – Fundamental Aspects 88 [10] Fengel D, Wegener G. Wood Chemistry, Ultrastructure, Reactions, Walter de Gruyter; 1984. [11] Uhlmann T. Ullmann's encyclopedia of industrial chemistry. Paper and Pulp. 1991; 18 (A). [12] Permanganate number of pulp, Tappi T...

  3. Single and double carbon vacancies in pyrene as first models for graphene defects: A survey of the chemical reactivity toward hydrogen

    Science.gov (United States)

    Nieman, Reed; Das, Anita; Aquino, Adélia J. A.; Amorim, Rodrigo G.; Machado, Francisco B. C.; Lischka, Hans

    2017-01-01

    Graphene is regarded as one of the most promising materials for nanoelectronics applications. Defects play an important role in modulating its electronic properties and also enhance its chemical reactivity. In this work the reactivity of single vacancies (SV) and double vacancies (DV) in reaction with a hydrogen atom Hr is studied. Because of the complicated open shell electronic structures of these defects due to dangling bonds, multireference configuration interaction (MRCI) methods are being used in combination with a previously developed defect model based on pyrene. Comparison of the stability of products derived from Csbnd Hr bond formation with different carbon atoms of the different polyaromatic hydrocarbons is made. In the single vacancy case the most stable structure is the one where the incoming hydrogen is bound to the carbon atom carrying the dangling bond. However, stable Csbnd Hr bonded structures are also observed in the five-membered ring of the single vacancy. In the double vacancy, most stable bonding of the reactant Hr atom is found in the five-membered rings. In total, Csbnd Hr bonds, corresponding to local energy minimum structures, are formed with all carbon atoms in the different defect systems and the pyrene itself. Reaction profiles for the four lowest electronic states show in the case of a single vacancy a complex picture of curve crossings and avoided crossings which will give rise to a complex nonadiabatic reaction dynamics involving several electronic states.

  4. Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

    Science.gov (United States)

    Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

    2014-09-01

    A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

  5. Reactive transport modeling of chemical and isotope data to identify degradation processes of chlorinated ethenes in a diffusion-dominated media

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Damgaard, Ida; Jeannottat, Simon

    . Degradation and transport processes of chlorinated ethenes are not well understood in such geological settings, therefore risk assessment and remediation at these sites are particularly challenging. In this work, a combined approach of chemical and isotope analysis on core samples, and reactive transport...... the source zone (between 6 and 12 mbs). Concentrations and stable isotope ratios of the mother compounds and their daughter products, as well as redox parameters, fatty acids and microbial data, were analyzed with discrete sub-sampling along the cores. More samples (each 5 mm) were collected around...... of dechlorination and degradation pathways (biotic reductive dechlorination or abiotic β-elimination with iron minerals) in three core profiles. The model includes diffusion in the matrix, sequential reductive dechlorination, abiotic degradation, isotope fractionation due to degradation and due to diffusion...

  6. A quantum chemical study of the reactivity of acetaminophen (paracetamol) toxic metabolite N-acetyl-p-benzoquinone imine with deoxyguanosine and glutathione.

    Science.gov (United States)

    Klopčič, Ivana; Poberžnik, Matic; Mavri, Janez; Dolenc, Marija Sollner

    2015-12-05

    Acetaminophen (APAP) forms some reactive metabolites that can react with DNA. APAP is a potentially genotoxic drug and is classified as a Group 3 drug according to International Agency for Research on Cancer (IARC). One of the possible mechanisms of APAP genotoxicity after long term of use is that its reactive quinone imine (QI) metabolite of acetaminophen (NAPQI), can chemically react with DNA after glutathione (GSH) depletion. A quantum chemical study of the reactions between the NAPQI and deoxyguanosine (dG) or GSH was performed. Activation energies (ΔG(ǂ)) for the reactions associated with the 1, 4-Michael addition were calculated on the M062X/6-311++G (d,p) level of theory. We modeled the reaction with dG as a multi-step process. The first step is rate-limiting (ΔG(ǂ) = 26.7 kcal/mol) and consists of formation of a C-N bond between the C3 atom of the QI moiety and the N7 atom of dG. The second step involves proton transfer from the C3 moiety to the nitrogen atom of the QI with ΔG(ǂ) of 13.8 kcal/mol. The depurination reaction that follows has a ΔG(ǂ) of 25.7 kcal/mol. The calculated ΔG(ǂ) for the nucleophilic attack of the deprotonated S atom of GSH on the C3 atom of the NAPQI is 12.9 kcal/mol. Therefore, the QI will react with GSH much faster than with DNA. Our study gives mechanistic insight into the genotoxicity of the APAP metabolite and will be useful for estimating the genotoxic potential of existing drugs with a QI moiety. Our results show that clinical application of APAP is safe, while in the case of severely depleted GSH levels APAP should be administered with caution. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  7. Critical Reflections on the Hydrophobic Effect, its Origins and Manifestation: Water Structure, Chemical Reactivity, Micelles and Gels.

    Directory of Open Access Journals (Sweden)

    Sosale Chandrasekhar

    2017-09-01

    Full Text Available The origins of the Hydrophobic Effect (HE, its biological significance and its experimental basis are critically addressed in this brief review. It is argued that the mechanistic work reported on the HE in recent decades needs to be reassessed, as its conclusions are apparently debatable. Essentially, it is highly inaccurate to view the HE as a repulsive interaction, which is rather an attractive one. It appears inevitable that the HE is indeed a manifestation of the perturbation of the structure of water upon the introduction of hydrocarbon molecules into its interior. There appears to be no other satisfactory explanation for the formation of micellar aggregates and the existence of the critical micelle concentration. Also, the practical significance of the HE on the reactivity of organic compounds (e.g. cycloadditions is severely limited by their minuscule solubility levels, itself a manifestation of the HE! Other related phenomena apparently include the formation of gels and the occurrence of certain esterification reactions in water, which are briefly reviewed from a conceptual viewpoint.

  8. Entropy and chemical change. 1: Characterization of product (and reactant) energy distributions in reactive molecular collisions: Information and enthropy deficiency

    Science.gov (United States)

    Bernstein, R. B.; Levine, R. D.

    1972-01-01

    Optimal means of characterizing the distribution of product energy states resulting from reactive collisions of molecules with restricted distributions of initial states are considered, along with those for characterizing the particular reactant state distribution which yields a given set of product states at a specified total energy. It is suggested to represent the energy-dependence of global-type results in the form of square-faced bar plots, and of data for specific-type experiments as triangular-faced prismatic plots. The essential parameters defining the internal state distribution are isolated, and the information content of such a distribution is put on a quantitative basis. The relationship between the information content, the surprisal, and the entropy of the continuous distribution is established. The concept of an entropy deficiency, which characterizes the specificity of product state formation, is suggested as a useful measure of the deviance from statistical behavior. The degradation of information by experimental averaging is considered, leading to bounds on the entropy deficiency.

  9. Modeling Chemically Reactive Flow of Sutterby Nanofluid by a Rotating Disk in Presence of Heat Generation/Absorption

    Science.gov (United States)

    Hayat, T.; Ahmad, Salman; Ijaz Khan, M.; Alsaedi, A.

    2018-05-01

    In this article we investigate the flow of Sutterby liquid due to rotating stretchable disk. Mass and heat transport are analyzed through Brownian diffusion and thermophoresis. Further the effects of magnetic field, chemical reaction and heat source are also accounted. We employ transformation procedure to obtain a system of nonlinear ODE’s. This system is numerically solved by Built-in-Shooting method. Impacts of different involved parameter on velocity, temperature and concentration are described. Velocity, concentration and temperature gradients are numerically computed. Obtained results show that velocity is reduced through material parameter. Temperature and concentration are enhanced with thermophoresis parameter.

  10. Comparison of coal reactivity during conversion into different oxidizing medium

    International Nuclear Information System (INIS)

    Korotkikh, A G; Slyusarskiy, K V; Larionov, K B; Osipov, V I

    2016-01-01

    Acoal conversion process of different coal samples into three different types of oxidizing medium (argon, air and steam) were studied by means of thermogravimetry. Two coal types with different metamorphism degree (lignite and bituminous coal) were used. The experimental procedure was carried out in non-isothermal conditions in temperature range from 373 K to 1273 K with 20 K/min heating rate. Purge gas consisted of argon and oxidizer with volumetric ratio 1:24 and had 250 ml/min flow rate.The ignition and burnout indexes were calculated to evaluate sample reactivity at different oxidizing mediums. The highest reactivity coefficient values in same atmosphere were obtained for lignite. It was caused by higher particle special surface area and volatile matter content. (paper)

  11. Improving the chemical compatibility of sealing glass for solid oxide fuel cells: Blocking the reactive species by controlled crystallization

    Science.gov (United States)

    Zhang, Teng; Zou, Qi; Zeng, Fanrong; Wang, Shaorong; Tang, Dian; Yang, Hiswen

    2012-10-01

    The chemical compatibility of sealing glass is of great importance for Solid oxide fuel cell (SOFC). In this work, the interfacial reaction between sealing glass and Cr-containing interconnect alloy is characterized by reacting Cr2O3 powders with a representative SrO-containing glass crystallized by different heat-treatment schedules. The crystalline structure and crystalline content of sealing glass are determined by X-ray diffraction. The results show that the fraction of Cr6+ decreases from 39.8 ± 1.9% for quenched glass to 8.2 ± 0.4% for glass crystallized at 900 °C for 2 h. In addition, the interfacial reaction can be further reduced with increasing crystallization temperature and time as well as the addition of nucleation agent (TiO2). The formation of some Sr-containing crystalline phases, Sr2SiO4 and Sr(TiO3), contributes to the improvement of chemical compatibility of sealing glass, in agreement with the results of thermodynamic calculations.

  12. Study of non-isothermal crystallization of Eu{sup 3+} doped Zn{sub 2}SiO{sub 4} powders through the application of various macrokinetic models

    Energy Technology Data Exchange (ETDEWEB)

    Janković, Bojan, E-mail: bojanjan@ffh.bg.ac.rs [Faculty of Physical Chemistry, Department of the Dynamics and Structure of Matter, University of Belgrade, Studentski trg 12-16, P.O. Box 137, 11001 Belgrade (Serbia); Marinović-Cincović, Milena; Dramićanin, Miroslav D. [Vinča Institute of Nuclear Sciences, University of Belgrade, Mike Petrovića Alasa 12-14, P.O. Box 552, 11001 Belgrade (Serbia)

    2014-02-25

    Highlights: • Europium (Eu{sup 3+}) doped zinc silicate powders. • Sol–gel method. • Stochastic geometric and semi-empirical models. • The interface controlled growth with an increasing nucleation rate. • The improved Nakamura’s model. -- Abstract: Various macrokinetic models (Avrami, Evans, Tobin, Malkin, Dietz, Nakamura, and modified first-order models) were applied to describe non-isothermal crystallization kinetics of Eu{sup 3+} doped zinc silicate powders prepared via the sol–gel method. Analysis of the experimental data was carried out using a direct-fitting method such that the experimental data were fitted directly to each macrokinetic model using a non-linear multivariable regression computation procedure. Comparison of kinetic parameters obtained from the non-linear computation approach to those obtained from the traditional analytical procedure suggested that applicability and reliability of the direct-fitting method were satisfactory. Judging from the quality of the fit, only Nakamura’s model properly describe the temperature dependence of the relative crystallinity, which resulted in the total rejection of the Tobin model in describing the crystallization. With detailed kinetic examination it was concluded that crystallization mechanism of α-willemite doped samples combusted in a microwave oven (MW) follows interface controlled growth with an increasing nucleation rate, attached with geometric process-rate function obeying the improved (corrected) Nakamura’s model. It was found that the presence of non integer Avrami exponent values may indicate that crystallization occurs by more than one reaction mechanism, including the occurrence of autocatalytic behavior of a given system.

  13. Theoretical study of coupling mechanisms between oxygen diffusion, chemical reaction, mechanical stresses in a solid-gas reactive system

    International Nuclear Information System (INIS)

    Creton, N.; Optasanu, V.; Montesin, T.; Garruchet, S.

    2008-01-01

    This paper offers a study of oxygen dissolution into a solid, and its consequences on the mechanical behaviour of the material. In fact, mechanical strains strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO 2 compound near the internal interface is consistent with some oxidation mechanisms of oxidation experimentally observed. More generally, this work will be extended to the simulation to an oxide layer growth on a metallic substrate. (authors)

  14. Chemical pneumonitis and subsequent reactive airways dysfunction syndrome after a single exposure to a household product: a case report

    Directory of Open Access Journals (Sweden)

    Khalid Imran

    2009-11-01

    Full Text Available Abstract Introduction Household products are usually safe to use. Adverse events arising from their use are mostly reported in patients with pre-existing atopy or pulmonary problems and usually only after a prolonged exposure to such products. We report the case of a patient with no prior problems who developed significant side effects from a single exposure to a domestic product. Case presentation A 43-year-old Caucasian American man, previously in good health, used a domestic aerosol product called 'Stand N' Seal "Spray-On" Grout Sealer' in an enclosed room in his house. The product contained n-butyl acetate ( Conclusion A household product may still prove unsafe to use even after it has gone through vigorous testing and approval processes. Even healthy individuals are susceptible to adverse outcomes after a brief exposure. Extra precautions should be taken when using any chemical product at home.

  15. Enhancement of chemically induced reactive oxygen species production and DNA damage in human SH-SY5Y neuroblastoma cells by 872 MHz radiofrequency radiation

    Energy Technology Data Exchange (ETDEWEB)

    Luukkonen, Jukka [Department of Environmental Science, University of Kuopio, Bioteknia 2, P.O. Box 1627, FI-70211 Kuopio (Finland)], E-mail: Jukka.Luukkonen@uku.fi; Hakulinen, Pasi; Maeki-Paakkanen, Jorma [Department of Environmental Health, National Public Health Institute, P.O. Box 95, FI-70701 Kuopio (Finland); Juutilainen, Jukka; Naarala, Jonne [Department of Environmental Science, University of Kuopio, Bioteknia 2, P.O. Box 1627, FI-70211 Kuopio (Finland)

    2009-03-09

    The objective of the study was to investigate effects of 872 MHz radiofrequency (RF) radiation on intracellular reactive oxygen species (ROS) production and DNA damage at a relatively high SAR value (5 W/kg). The experiments also involved combined exposure to RF radiation and menadione, a chemical inducing intracellular ROS production and DNA damage. The production of ROS was measured using the fluorescent probe dichlorofluorescein and DNA damage was evaluated by the Comet assay. Human SH-SY5Y neuroblastoma cells were exposed to RF radiation for 1 h with or without menadione. Control cultures were sham exposed. Both continuous waves (CW) and a pulsed signal similar to that used in global system for mobile communications (GSM) mobile phones were used. Exposure to the CW RF radiation increased DNA breakage (p < 0.01) in comparison to the cells exposed only to menadione. Comparison of the same groups also showed that ROS level was higher in cells exposed to CW RF radiation at 30 and 60 min after the end of exposure (p < 0.05 and p < 0.01, respectively). No effects of the GSM signal were seen on either ROS production or DNA damage. The results of the present study suggest that 872 MHz CW RF radiation at 5 W/kg might enhance chemically induced ROS production and thus cause secondary DNA damage. However, there is no known mechanism that would explain such effects from CW RF radiation but not from GSM modulated RF radiation at identical SAR.

  16. Enhancement of chemically induced reactive oxygen species production and DNA damage in human SH-SY5Y neuroblastoma cells by 872 MHz radiofrequency radiation

    International Nuclear Information System (INIS)

    Luukkonen, Jukka; Hakulinen, Pasi; Maeki-Paakkanen, Jorma; Juutilainen, Jukka; Naarala, Jonne

    2009-01-01

    The objective of the study was to investigate effects of 872 MHz radiofrequency (RF) radiation on intracellular reactive oxygen species (ROS) production and DNA damage at a relatively high SAR value (5 W/kg). The experiments also involved combined exposure to RF radiation and menadione, a chemical inducing intracellular ROS production and DNA damage. The production of ROS was measured using the fluorescent probe dichlorofluorescein and DNA damage was evaluated by the Comet assay. Human SH-SY5Y neuroblastoma cells were exposed to RF radiation for 1 h with or without menadione. Control cultures were sham exposed. Both continuous waves (CW) and a pulsed signal similar to that used in global system for mobile communications (GSM) mobile phones were used. Exposure to the CW RF radiation increased DNA breakage (p < 0.01) in comparison to the cells exposed only to menadione. Comparison of the same groups also showed that ROS level was higher in cells exposed to CW RF radiation at 30 and 60 min after the end of exposure (p < 0.05 and p < 0.01, respectively). No effects of the GSM signal were seen on either ROS production or DNA damage. The results of the present study suggest that 872 MHz CW RF radiation at 5 W/kg might enhance chemically induced ROS production and thus cause secondary DNA damage. However, there is no known mechanism that would explain such effects from CW RF radiation but not from GSM modulated RF radiation at identical SAR

  17. Chemically reactive and naturally convective high speed MHD fluid flow through an oscillatory vertical porous plate with heat and radiation absorption effect

    Directory of Open Access Journals (Sweden)

    S.M. Arifuzzaman

    2018-04-01

    Full Text Available This paper concerns with the modelling of an unsteady natural convective and higher order chemically reactive magnetohydrodynamics (MHD fluid flow with the effect of heat and radiation absorption. The flow is generated through a vertical oscillating porous plate. Boundary layer approximations is carried out to establish a flow model which represents the time dependent momentum, energy and diffusion balance equations. Before being solved numerically, the governing partial differential equations (PDEs were transformed into a set of nonlinear ordinary differential equation (ODEs by using non-similar technique. A very efficient numerical approach solves the obtained nonlinear coupled ODEs so called Explicit Finite Difference Method (EFDM. An algorithm is implemented in Compaq Visual Fortran 6.6a as a solving tool. In addition, the stability and convergence analysis (SCA is examined and shown explicitly. The advantages of SCA is its optimizes the accuracy of system parameters such as Prandtl number (Pr and Schmidt number (Sc.The velocity, temperature and concentration fields in the boundary layer region are studied in detail and the outcomes are shown in graphically with the influence of various pertinent parameters such as Grashof number (Gr, modified Grashof number (Gr, magnetic parameter (M, Darcy number (Da,Prandtl number (Pr, Schmidt number (Sc, radiation (R, heat sink (Q,radiation absorption (Q1, Eckert number (Ec, Dufour number (Du,Soret number (Sr, Schmidt number (Sc, reaction index (P and chemical reaction (Kr. Furthermore, the effect of skin friction coefficient (Cf, Nusselt number (Nu and Sherwood number (Sh are also examined graphically. Keywords: MHD, Oscillating porous plate, Radiation absorption, High order chemical reaction, EFDM

  18. Fixation of some chemically modified reactive dye during gamma irradiation of cotton fabrics in presence of vinyl and acrylic monomers

    International Nuclear Information System (INIS)

    Zohdy, M.H.; El-Naggar, A.M.; Abdallah, W.A.

    1999-01-01

    The radiation grafting of vinyl sulfone dye having an activated double bond in presence of styrene monomer or its mixtures with ethyl acrylate onto cotton fabric has been investigated. The chemical reaction of the vinyl sulfone form with peroxy radicals on cotton fabric through covalent bonding is tested by extracting the dyed samples in 50% aqueous DMF solution. It was found that the presence of styene monomer in the dyeing solution is essential for the reaction or grafting of the vinyl sulfone dye. However, when a constant styrene concentration of 5% was used in the dye bath, the color strength expressed as K/S was found to increase by increasing the dye concentration. The results showed that the color strength obtained in case of using 10% ethyl acrylate is much lower than in the case of using the same concentration of styrene monomer. A solvent composition of equal ratios of methanol and water has been proven to be suitable to produce the highest improvement in the color strength. The irradiation dose was found to play an important role in initiating the reaction of the vinyl sulfone dye

  19. Hybrid graphene oxide/DAB-Am-16 dendrimer: Preparation, characterization chemical reactivity and their electrocatalytic detection of L-Dopamine

    Science.gov (United States)

    Do Carmo, Devaney Ribeiro; Fernandes, Daniela Silvestrini

    2017-09-01

    Graphene oxide (GO) was chemically modified with a poly(propylene)imine Generation 3.0 dendrimer (DAB-Am-16). The characterization, structure and properties of hybrid graphene oxide/DAB-Am-16 dendrimer was studied by Raman spectroscopy, Fourier-Transforming Infrared Spectroscopy (FT-IR), X-Ray Photoelectron Spectroscopic (XPS), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis. After functionalized the hybrid material (GOD) can interact with copper and subsequently with hexacyanoferrate (III) ions (GODHCu). The GODHCu incorporated into a graphite paste electrode (20% w/w) was applied to an electrocatalytic detection of neurotransmitter L-dopamine using differential pulse voltammetry. The analytical curve showed a linear response in the concentration range from 1.0 × 10-7 to 1.0 × 10-5 mol L-1 with a corresponding equation Y(A) = 1.706 × 10-5 + 0.862 [L-dopamine] and a correlation coefficient r2 = 0.998. The detection limit was 6.36 × 10-7 mol L-1 with a relative standard deviation of ±4% (n = 3) and an amperometric sensitivity of 0.862 A/mol L-1.

  20. A numerical analysis for non-linear radiation in MHD flow around a cylindrical surface with chemically reactive species

    Directory of Open Access Journals (Sweden)

    Junaid Ahmad Khan

    2018-03-01

    Full Text Available Boundary layer flow around a stretchable rough cylinder is modeled by taking into account boundary slip and transverse magnetic field effects. The main concern is to resolve heat/mass transfer problem considering non-linear radiative heat transfer and temperature/concentration jump aspects. Using conventional similarity approach, the equations of motion and heat transfer are converted into a boundary value problem whose solution is computed by shooting method for broad range of slip coefficients. The proposed numerical scheme appears to improve as the strengths of magnetic field and slip coefficients are enhanced. Axial velocity and temperature are considerably influenced by a parameter M which is inversely proportional to the radius of cylinder. A significant change in temperature profile is depicted for growing wall to ambient temperature ratio. Relevant physical quantities such as wall shear stress, local Nusselt number and local Sherwood number are elucidated in detail. Keywords: Stretchable boundary, Thermal radiation, Chemical reaction, Mathematical modeling, Non-linear differential system, Mass transfer

  1. Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins.

    Science.gov (United States)

    Junginger, Andrej; Duvenbeck, Lennart; Feldmaier, Matthias; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

    2017-08-14

    In chemical or physical reaction dynamics, it is essential to distinguish precisely between reactants and products for all times. This task is especially demanding in time-dependent or driven systems because therein the dividing surface (DS) between these states often exhibits a nontrivial time-dependence. The so-called transition state (TS) trajectory has been seen to define a DS which is free of recrossings in a large number of one-dimensional reactions across time-dependent barriers and thus, allows one to determine exact reaction rates. A fundamental challenge to applying this method is the construction of the TS trajectory itself. The minimization of Lagrangian descriptors (LDs) provides a general and powerful scheme to obtain that trajectory even when perturbation theory fails. Both approaches encounter possible breakdowns when the overall potential is bounded, admitting the possibility of returns to the barrier long after the trajectories have reached the product or reactant wells. Such global dynamics cannot be captured by perturbation theory. Meanwhile, in the LD-DS approach, it leads to the emergence of additional local minima which make it difficult to extract the optimal branch associated with the desired TS trajectory. In this work, we illustrate this behavior for a time-dependent double-well potential revealing a self-similar structure of the LD, and we demonstrate how the reflections and side-minima can be addressed by an appropriate modification of the LD associated with the direct rate across the barrier.

  2. Integration of On-Column Chemical Reactions in Protein Characterization by Liquid Chromatography/Mass Spectrometry: Cross-Path Reactive Chromatography.

    Science.gov (United States)

    Pawlowski, Jake W; Carrick, Ian; Kaltashov, Igor A

    2018-01-16

    Profiling of complex proteins by means of mass spectrometry (MS) frequently requires that certain chemical modifications of their covalent structure (e.g., reduction of disulfide bonds), be carried out prior to the MS or MS/MS analysis. Traditionally, these chemical reactions take place in the off-line mode to allow the excess reagents (the majority of which interfere with the MS measurements and degrade the analytical signal) to be removed from the protein solution prior to MS measurements. In addition to a significant increase in the analysis time, chemical reactions may result in a partial or full loss of the protein if the modifications adversely affect its stability, e.g,, making it prone to aggregation. In this work we present a new approach to solving this problem by carrying out the chemical reactions online using the reactive chromatography scheme on a size exclusion chromatography (SEC) platform with MS detection. This is achieved by using a cross-path reaction scheme, i.e., by delaying the protein injection onto the SEC column (with respect to the injection of the reagent plug containing a disulfide-reducing agent), which allows the chemical reactions to be carried out inside the column for a limited (and precisely controlled) period of time, while the two plugs overlap inside the column. The reduced protein elutes separately from the unconsumed reagents, allowing the signal suppression in ESI to be avoided and enabling sensitive MS detection. The new method is used to measure fucosylation levels of a plasma protein haptoglobin at the whole protein level following online reduction of disulfide-linked tetrameric species to monomeric units. The feasibility of top-down fragmentation of disulfide-containing proteins is also demonstrated using β 2 -microglobulin and a monoclonal antibody (mAb). The new online technique is both robust and versatile, as the cross-path scheme can be readily expanded to include multiple reactions in a single experiment (as

  3. Intercomparison of reactive transport models applied to degradation of a concrete / clay interface

    International Nuclear Information System (INIS)

    Burnol, A.; Blanc, P.; Tournassat, C.; Lassin, A.; Gaucher, E.C.

    2005-01-01

    's guide to PHREEQC (version 2) U.S. Geological Survey, Water-Resources Investigations. Report 99-4259, 312 p.; [3] Parkhurst D.L, Kipp K.L., Engesgaard P. (2002) - PHAST a program for simulating groundwater flow and multicomponent reactions. User's guide. http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phast; [4] Xu, T., Pruess, K. (1998). Coupled modeling of non-isothermal multiphase flow, solute transport and reactive chemistry in porous and fractured media: 1. Model development and validation. LBNL-42050, Berkeley, California. [5] Gaucher E., Blanc Ph., Matray J.M., Michau N., (2004).Applied Geochemistry, 19, 1505-1515. (authors)

  4. Host-guest complex of N-(2-chloroethyl), N-nitroso, N‧, N‧ -dicyclohexylsulfamid with β-cyclodextrin: Fluorescence, QTAIM analysis and structure-chemical reactivity

    Science.gov (United States)

    Bensouilah, Nadjia; Fisli, Hassina; Bensouilah, Hamza; Zaater, Sihem; Abdaoui, Mohamed; Boutemeur-Kheddis, Baya

    2017-10-01

    In this work, the inclusion complex of DCY/CENS: N-(2-chloroethyl), N-nitroso, N‧, N‧-dicyclohexylsulfamid and β-cyclodextrin (β-CD) is investigated using the fluorescence spectroscopy, PM3, ONIOM2 and DFT methods. The experimental part reveals that DCY/CENS forms a 1:1 stoichiometric ratio inclusion complex with β-CD. The constant of stability is evaluated using the Benesi-Hildebrand equation. The results of the theoretical optimization showed that the lipophilic fraction of molecule (cyclohexyl group) is inside of β-CD. Accordingly, the Nitroso-Chloroethyl moiety is situated outside the cavity of the macromolecule host. The favorable structure of the optimized complex indicates the existence of weak intermolecular hydrogen bonds and the most important van der Waals (vdW) interactions which are studied on the basis of Natural Bonding Orbital (NBO) analysis. The NBO is employed to compute the electronic donor-acceptor exchanges between drug and β-CD. Furthermore, a detailed topological charge density analysis based on the quantum theory of atoms in molecules (QTAIM), has been accomplished on the most favorable complex using B3LYP/6-31G(d) method. The presence of stabilizing intermolecular hydrogen bonds and van der Waals interactions in the most favorable complex is predicted. Also, the energies of these interactions are estimated with Espinosa's formula. The findings of this investigation reveal that the correlation between the structural parameters and the electronic density is good. Finally, and based on DFT calculations, the reactivity of the interesting molecule in free state was studied and compared with that in the complexed state using chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors.

  5. Chemical Dynamics and Critical Phenomena: Electrical Conductivity and Reactivity of Benzyl Bromide in Triethylamine+Water Near its Consolute Point

    Science.gov (United States)

    Specker, Christopher D.; Ellis, Joel M.; Baird, James K.

    2007-06-01

    The binary liquid mixture of triethylamine+water has a lower consolute point at a critical composition of 32.27mass% triethylamine. Starting at a temperature within the one-phase region, the electrical conductivity of a sample of this mixture was measured and found to increase smoothly with increasing temperature before falling sharply at 291.24K (18.09°C). Since opalescence was visible at this temperature, it was identified with the critical solution temperature of the binary mixture. A solution of 90 μL of benzyl bromide dissolved in 90mL of 32.27mass% triethylamine+water was prepared, and the resulting Menschutkin reaction between benzyl bromide and triethylamine was allowed to come to equilibrium. The electrical conductivity of this equilibrium mixture was measured in the one-phase region and was found to increase smoothly with increasing temperature before rising sharply at 291.55K (18.40°C). This temperature was identified as the critical temperature of the ternary. The rate of approach of the ternary mixture to chemical equilibrium was also measured and shown to be governed by a first-order rate law. The temperature dependence of the rate coefficient followed the Arrhenius equation up to a temperature of about 290.74K (17.59°C). Above this temperature, the rate coefficient fell by as much as 22% below the value predicted by extrapolation of the Arrhenius equation. This suppression in the rate reaction in the vicinity of the critical temperature can be interpreted as evidence for the existence of critical slowing down.

  6. CHEMICALS

    CERN Multimedia

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  7. chemical studies on the reactivity of some organic extractants for extraction and separation of certain elements from aqueous solutions

    International Nuclear Information System (INIS)

    Aly, M.M.I.

    2010-01-01

    Lanthanide elements such as lanthanum and neodymium are important elements in photo-electronic and metallurgical industries as well as in nuclear technology. The main constituents of the spent nuclear fuel are actinides like uranium, thorium and various fission products including lanthanides. The co-ordination compounds of the trivalent lanthanum and neodymium continues to be an active research area, which includes the specific spectroscopic and magnetic properties of rare earth ions and their applications as super molecular device, contrast-enhancing agents in magnetic resonance imaging, optical signal amplifiers and electroluminescent (EL) devices. Hence, the separation and purification of these elements is of great concern. Solvent extraction technique is employed to separate and purify rare earth elements in an industrial scale, but the separation of lanthanum and neodymium is a difficult task, as lanthanide ions exhibit similar chemical and physical properties. They have generally common and stable +3 oxidation state that requires synthesis of certain extractants which are able to extract them from different aqueous solutions. During the last twenty years, different publications have pointed out the remarkable properties of alkyl amide in the field of separation chemistry. These extractants are able to form stable co-ordination compounds with different metallic ions. In this concern, this thesis deals with the synthesis of different amide extractants namely N, N diethylacetoamide (DEAA), N, N Teteraphenyl malonamide (TPMA), N, N diphenylbenzamide (DPBA), N, N' diphenylacetoamide (DPAA), and N, N' Teteraethyl malonamide (TEMA), which were synthesized, characterized and compared with Aliquat-336 in kerosene for extraction and separation of La (III) and Nd (III). The effect of the different parameters affecting the extraction of these metals from aqueous nitric acid medium in the different systems has been studied in terms of shaking time, nitric acid, hydrogen

  8. Steepest-entropy-ascent quantum thermodynamic modeling of the relaxation process of isolated chemically reactive systems using density of states and the concept of hypoequilibrium state

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R.

    2016-01-01

    This paper presents a study of the nonequilibrium relaxation process of chemically reactive systems using steepest-entropy-ascent quantum thermodynamics (SEAQT). The trajectory of the chemical reaction, i.e., the accessible intermediate states, is predicted and discussed. The prediction is made using a thermodynamic-ensemble approach, which does not require detailed information about the particle mechanics involved (e.g., the collision of particles). Instead, modeling the kinetics and dynamics of the relaxation process is based on the principle of steepest-entropy ascent (SEA) or maximum-entropy production, which suggests a constrained gradient dynamics in state space. The SEAQT framework is based on general definitions for energy and entropy and at least theoretically enables the prediction of the nonequilibrium relaxation of system state at all temporal and spatial scales. However, to make this not just theoretically but computationally possible, the concept of density of states is introduced to simplify the application of the relaxation model, which in effect extends the application of the SEAQT framework even to infinite energy eigenlevel systems. The energy eigenstructure of the reactive system considered here consists of an extremely large number of such levels (on the order of 10130) and yields to the quasicontinuous assumption. The principle of SEA results in a unique trajectory of system thermodynamic state evolution in Hilbert space in the nonequilibrium realm, even far from equilibrium. To describe this trajectory, the concepts of subsystem hypoequilibrium state and temperature are introduced and used to characterize each system-level, nonequilibrium state. This definition of temperature is fundamental rather than phenomenological and is a generalization of the temperature defined at stable equilibrium. In addition, to deal with the large number of energy eigenlevels, the equation of motion is formulated on the basis of the density of states and a set of

  9. Patch testing with a new fragrance mix - reactivity to the individual constituents and chemical detection in relevant cosmetic products.

    Science.gov (United States)

    Frosch, Peter J; Rastogi, Suresh C; Pirker, Claudia; Brinkmeier, Thomas; Andersen, Klaus E; Bruze, Magnus; Svedman, Cecilia; Goossens, An; White, Ian R; Uter, Wolfgang; Arnau, Elena Giménez; Lepoittevin, Jean-Pierre; Johansen, Jeanne Duus; Menne, Torkil

    2005-04-01

    A new fragrance mix (FM II), with 6 frequently used chemicals not present in the currently used fragrance mix (FM I), was evaluated in 6 dermatological centres in Europe, as previously reported. In this publication, test results with the individual constituents and after repeated open application test (ROAT) of FM II are described. Furthermore, cosmetic products which had caused a contact dermatitis in patients were analysed for the presence of the individual constituents. In 1701 patients, the individual constituents of the medium (14%) and the highest (28%) concentration of FM II were simultaneously applied with the new mix at 3 concentrations (break-down testing for the lowest concentration of FM II (2.8%) was performed only if the mix was positive). ROAT was performed with the concentration of the FM II which had produced a positive or doubtful (+ or ?+) patch test reaction. Patients' products were analysed for the 6 target compounds by gas chromatography-mass spectrometry (GC-MS). 50 patients (2.9%) showed a positive reaction to 14% FM II and 70 patients (4.1%) to 28% FM II. 24/50 (48%) produced a positive reaction to 1 or more of the individual constituents of 14% FM II and 38/70 (54.3%) to 28% FM II, respectively. If doubtful reactions to individual constituents are included, the break-down testing was positive in 74% and 70%, respectively. Patients with a positive reaction to 14% FM II showed a higher rate of reactions to the individual constituent of the 28% FM II: 36/50 (72%). Positive reactions to individual constituents in patients negative to FM II were exceedingly rare. If doubtful reactions are regarded as negative, the sensitivity, specificity, positive predictive value and negative predictive value for the medium concentration of FM II towards at least 1 individual constituent was 92.3% (exact 95% confidence interval 74.9-99.1%), 98.4% (97.7-99.0%), 48% (33.7-62.6%) and 99.9% (99.6-"100.0%), respectively. For the high concentration, the figures

  10. TOGA: A TOUGH code for modeling three-phase, multi-component, and non-isothermal processes involved in CO2-based Enhanced Oil Recovery

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Lehua [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Oldenburg, Curtis M. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    2016-10-10

    TOGA is a numerical reservoir simulator for modeling non-isothermal flow and transport of water, CO2, multicomponent oil, and related gas components for applications including CO2-enhanced oil recovery (CO2-EOR) and geologic carbon sequestration in depleted oil and gas reservoirs. TOGA uses an approach based on the Peng-Robinson equation of state (PR-EOS) to calculate the thermophysical properties of the gas and oil phases including the gas/oil components dissolved in the aqueous phase, and uses a mixing model to estimate the thermophysical properties of the aqueous phase. The phase behavior (e.g., occurrence and disappearance of the three phases, gas + oil + aqueous) and the partitioning of non-aqueous components (e.g., CO2, CH4, and n-oil components) between coexisting phases are modeled using K-values derived from assumptions of equal-fugacity that have been demonstrated to be very accurate as shown by comparison to measured data. Models for saturated (water) vapor pressure and water solubility (in the oil phase) are used to calculate the partitioning of the water (H2O) component between the gas and oil phases. All components (e.g., CO2, H2O, and n hydrocarbon components) are allowed to be present in all phases (aqueous, gaseous, and oil). TOGA uses a multiphase version of Darcy’s Law to model flow and transport through porous media of mixtures with up to three phases over a range of pressures and temperatures appropriate to hydrocarbon recovery and geologic carbon sequestration systems. Transport of the gaseous and dissolved components is by advection and Fickian molecular diffusion. New methods for phase partitioning and thermophysical property modeling in TOGA have been validated against experimental data published in the literature for describing phase partitioning and phase behavior. Flow and transport has been verified by testing against related TOUGH2 EOS modules and

  11. Calcium oxide/carbon dioxide reactivity in a packed bed reactor of a chemical heat pump for high-temperature gas reactors

    International Nuclear Information System (INIS)

    Kato, Yukitaka; Yamada, Mitsuteru; Kanie, Toshihiro; Yoshizawa, Yoshio

    2001-01-01

    The thermal performance of a chemical heat pump that uses a calcium oxide/carbon dioxide reaction system was discussed as a heat storage system for utilizing heat output from high temperature gas reactors (HTGR). Calcium oxide/carbon dioxide reactivity for the heat pump was measured using a packed bed reactor containing 1.0 kg of reactant. The reactor was capable of storing heat at 900 deg. C by decarbonation of calcium carbonate and generating up to 997 deg. C by carbonation of calcium oxide. The amount of stored heat in the reactor was 800-900 kJ kg -1 . The output temperature of the reactor could be controlled by regulating the carbonation pressure. The thermal storage performance of the reactor was superior to that of conventional sensible heat storage systems. A heat pump using this CaO/CO 2 reactor is expected to contribute to thermal load leveling and to realize highly efficient utilization of HTGR output due to the high heat storage density and high-quality temperature output of the heat pump

  12. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters

    Science.gov (United States)

    Linton, Kirsty A.; Wright, Timothy G.; Besley, Nicholas A.

    2018-03-01

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO+.(H2O) that is too high and incorrectly predict the lowest energy structure of NO+.(H2O)2, and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO+. Ab initio molecular dynamics (AIMD) simulations were performed to study the NO+.(H2O)5 H+.(H2O)4 + HONO reaction to investigate the formation of HONO from NO+.(H2O)5. Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO+.(H2O)5 complex following its formation. This article is part of the theme issue `Modern theoretical chemistry'.

  13. Potential energy profile, structural, vibrational and reactivity descriptors of trans-2-methoxycinnamic acid by FTIR, FT-Raman and quantum chemical studies

    Science.gov (United States)

    Arjunan, V.; Anitha, R.; Thenmozhi, S.; Marchewka, M. K.; Mohan, S.

    2016-06-01

    The stable conformers of trans-2-methoxycinnamic acid (trans-2MCA) are determined by potential energy profile analysis. The energies of the s-cis and s-trans conformers of trans-2MCA determined by B3LYP/cc-pVTZ method are -612.9788331 Hartrees and -612.9780953 Hartrees, respectively. The vibrational and electronic investigations of the stable s-cis and s-trans conformers of trans-2-methoxycinnamic acid have been carried out extensively with FTIR and FT-Raman spectral techniques. The s-cis conformer (I) with a (C16-C17-C18-O19) dihedral angle equal to 0° is found to be more favoured relative to the one s-trans (II) with (C16-C17-C18-O19) = 180°, possibly due to delocalization, hydrogen bonding and steric repulsion effects between the methoxy and acrylic acid groups. The DFT studies are performed with B3LYP method by utilizing 6-311++G** and cc-pVTZ basis sets to determine the structure, thermodynamic properties, vibrational characteristics and chemical shifts of the compound. The total dipole moments of the conformers determined by B3LYP/cc-pVTZ method are 3.35 D and 4.87 D for s-cis and s-trans, respectively. It reveals the higher polarity of s-trans conformer of trans-2MCA molecule. The electronic and steric influence of the methoxy group on the skeletal frequencies has been analysed. The energies of the frontier molecular orbitals and the LUMO-HOMO energy gap have been determined. The MEP of s-cis conformer lie in the range +1.374e × 10-2 to -1.374e × 10-2 while for s-trans it is +1.591e × 10-2 to -1.591e × 10-2. The total electron density of s-cis conformer lie in the range +5.273e × 10-2 to -5.273e × 10-2 while for s-trans it is +5.403e × 10-2 to -5.403e × 10-2. The MEP and total electron density shows that the s-cis conformer is less polar, less reactive and more stable than the s-trans conformer. All the reactivity descriptors of the molecule have been discussed. Intramolecular electronic interactions and their stabilisation energies have analysed

  14. Biodecolorization and biodegradation of Reactive Blue by ...

    African Journals Online (AJOL)

    SERVER

    2007-06-18

    Jun 18, 2007 ... Aspergillus sp. effectively decolorized Reactive Blue and other structurally different synthetic dyes. Agitation was found to be an important ... Few chemically different dyes such as Reactive Black (75%), Reactive Yellow (70%),. Reactive Red (33%) and ..... Degradation of azo dyes by the lignin degrading ...

  15. Synthesis, spectroscopic analyses (FT-IR and NMR), vibrational study, chemical reactivity and molecular docking study and anti-tubercular activity of condensed oxadiazole and pyrazine derivatives

    Science.gov (United States)

    El-Azab, Adel S.; Mary, Y. Sheena; Abdel-Aziz, Alaa A. M.; Miniyar, Pankaj B.; Armaković, Stevan; Armaković, Sanja J.

    2018-03-01

    The Fourier transform infrared spectra of the compounds 2-(5-phenyl-1,3,4-oxadiazol-2-yl)pyrazine (PHOXPY), 2-(5-styryl-1,3,4-oxadiazol-2-yl)pyrazine (STOXPY) and 2-(5-(furan-2-yl)-1,3,4-oxadiazol-2-yl)pyrazine (FUOXPY) have been recorded and the wavenumbers are computed at the density functional theory level. The assignments of all the fundamental bands of each molecule are made using potential energy distribution. The computed values of dipole moment, polarizability and hyperpolarizability values indicate that the title molecules exhibit NLO properties. The HOMO and LUMO energies demonstrate the chemical stability of the molecules and NBO analysis is made to study the stability of molecules arising from hyper conjugative interactions and charge delocalization. Detailed computational analysis and spectroscopic characterization has been performed for three newly synthesized oxadiazole derivatives. Obtained computational and experimental results have been mutually compared in order to understand the influence of structural parts specific for each derivative. From the MIC determination, MTb H37Rv was found to be sensitive to compounds, PHOXPY, STOXPY and FUOXPY. The results obtained from anti-TB activity are more promising as the compounds were found to be more potent than reference standards, streptomycin and pyrazinamide. Efforts were made in order to predict both global and local reactive properties of the title oxadiazole derivatives, including their sensitivity towards autoxidation mechanism and influence of water. The results obtained from anti-TB activity are more promising for the title compounds. Interaction with representative protein Pterindeaminase inhibitor asricin A was also investigated using the molecular docking procedure. The docked ligands form stable complexes with the receptor ricin A and the docking results suggest that these compounds can be developed as new anti-cancer drugs.

  16. Novel Semi-Direct OH Reactivity (kOH) Measurements by Chemical Ionization Mass Spectrometry during a Chamber Instrument Comparison Campaign and Continuous Ambient Air Sampling at a Central European GAW Station

    Science.gov (United States)

    Muller, J.; Kubistin, D.; Elste, T.; Plass-Duelmer, C.; Claude, A.; Englert, J.; Holla, R.; Fuchs, H.; Hofzumahaus, A.; Holland, F.; Novelli, A.; Tillmann, R.; Wegener, R.; Rohrer, F.; Yu, Z.; Bohn, B.; Williams, J.; Pfannerstill, E.; Edtbauer, A.; Kluepfel, T.

    2016-12-01

    Total OH reactivity (kOH) has been recognized as a useful measure to gauge the potential atmospheric oxidation capacity and a few different in-situ measurement techniques have been developed over the last 15 years. Here results are presented from a novel semi-direct method developed by the German Weather Service (DWD) utilizing a chemical ionization mass spectrometer (CIMS). Recently in April 2016, the CIMS system participated in a half-blind kOH instrument comparison campaign at the Forschungszentrum Jülich (FZJ) SAPHIR chamber. Experiments provided controlled conditions with a range of different VOC mixtures and varying NOx levels, representing environments dominated by biogenic or urban emissions. Alongside CIMS, kOH was also measured by systems using the comparative reactivity method (CRM) and the pump-probe technique with OH detection. The intercomparison revealed a good performance of CIMS at lower OH reactivities (0-15 s-1), a range for which the instrumental set up was optimized. Limitations of the CIMS system consist of an upper limit for kOH detection and the need for applying a chemical correction function as a result of instrument-internal HOx recycling. Findings and instrument parameters obtained from the FZJ SAPHIR campaign and flow tube experiments are then applied to ambient air kOH measurements at the Meteorological Observatory Hohenpeissenberg (MOHp), Germany. The CIMS instrument is used there for long-term measurements of OH, H2SO4, ROx and kOH. Here, we show ambient air kOH measurements, interpreted in conjunction with volatile organic compounds (VOC) and inorganic trace gases also measured at the GAW station Hohenpeissenberg. These observations provide a unique dataset to investigate turnover rates and seasonal cycles of reactive trace gases, i.e. sources that make up total OH reactivity in this central European, rural setting.

  17. pH-Specific structural speciation of the ternary V(V)-peroxido-betaine system: a chemical reactivity-structure correlation.

    Science.gov (United States)

    Gabriel, C; Kioseoglou, E; Venetis, J; Psycharis, V; Raptopoulou, C P; Terzis, A; Voyiatzis, G; Bertmer, M; Mateescu, C; Salifoglou, A

    2012-06-04

    (V)-diperoxido units, thereby stabilizing a dinuclear V(V)-tetraperoxido dianion. Structural comparisons of the anions in 1-3 with other known dinuclear V(V)-tetraperoxido binary anionic species provide insight into the chemical reactivity of V(V)-diperoxido systems and their potential link to cellular events such as insulin mimesis and anitumorigenicity modulated by the presence of betaine.

  18. Molecular structure, chemical reactivity, nonlinear optical activity and vibrational spectroscopic studies on 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one: A combined density functional theory and experimental approach

    Science.gov (United States)

    Pegu, David; Deb, Jyotirmoy; Saha, Sandip Kumar; Paul, Manoj Kumar; Sarkar, Utpal

    2018-05-01

    In this work, we have synthesized new coumarin Schiff base molecule, viz., 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one and characterized its structural, electronic and spectroscopic properties experimentally and theoretically. The theoretical analysis of UV-visible absorption spectra reflects a red shift in the absorption maximum in comparison to the experimental results. Most of the vibrational assignments of infrared and Raman spectra predicted using density functional theory approach match well with the experimental findings. Further, the chemical reactivity analysis confirms that solvent highly affects the reactivity of the studied compound. The large hyperpolarizability value of the compound concludes that the system exhibits significant nonlinear optical features and thus, points out their possibility in designing material with high nonlinear activity.

  19. Reactive Arthritis

    Directory of Open Access Journals (Sweden)

    Eren Erken

    2013-06-01

    Full Text Available Reactive arthritis is an acute, sterile, non-suppurative and inflammatory arthropaty which has occured as a result of an infectious processes, mostly after gastrointestinal and genitourinary tract infections. Reiter syndrome is a frequent type of reactive arthritis. Both reactive arthritis and Reiter syndrome belong to the group of seronegative spondyloarthropathies, associated with HLA-B27 positivity and characterized by ongoing inflammation after an infectious episode. The classical triad of Reiter syndrome is defined as arthritis, conjuctivitis and urethritis and is seen only in one third of patients with Reiter syndrome. Recently, seronegative asymmetric arthritis and typical extraarticular involvement are thought to be adequate for the diagnosis. However, there is no established criteria for the diagnosis of reactive arthritis and the number of randomized and controlled studies about the therapy is not enough. [Archives Medical Review Journal 2013; 22(3.000: 283-299

  20. Host-cell reactivation of uv-irradiated and chemically treated Herpes simplex virus type 1 strain MP in normal and xeroderma pigmentosum skin fibroblasts

    International Nuclear Information System (INIS)

    Selsky, C.A.

    1976-01-01

    The host-cell reactivation of UV-irradiated and N-acetoxy-2-acetylaminofluorene-treated herpes simplex virus type 1 strain mp was studied in normal human skin fibroblasts and xeroderma pigmentosum skin fibroblasts from XP genetic complementation groups A-D and in an XP variant. The increasing relative order for the host-cell reactivation of both types of damaged virus in the different complementation groups is A = D < B < C; XP variant = normal controls. XP complementation group D cells, which manifest the most severe inhibition of her ability for both UV-irradiated and N-acetoxy-2-acetylaminofluorene-treated virus, can reactivate nitrogen mustard treated HSV-1 mp to the same extent as normal cells. Together, these results indicate that (1) Excision repair of UV and N-acetoxy-2-acetylaminofluorene DNA damaged viruses share a common rate limiting enzymatic step and (2) The repair defect in xeroderma pigmentosum cells plays little or no role in the recovery of nitrogen mustard treated virus. The results of studies on the effect of caffeine on the survival of both UV- and N-acetoxy-2-acetylaminofluorene-treated virus in normal and XP cells imply that the reactivation of HSV-1 mp is mediated by an excision repair process with little if any recovery contributed by post-replication repair mechanisms. The host-cell reactivation of N-acetoxy-2-acetylaminofluorene-treated HSV-1 mp was also correlated with the defective UV-induced unscheduled DNA synthesis in two skin fibroblast strains established from a skin biopsy obtained from each of two juvenile females who had been clinically diagnosed as xeroderma pigmentosum. These findings are discussed in relation to the further characterization of the xeroderma pigmentosum phenotype and their possible utilization for the selection and isolation of new mammalian cell DNA repair mutants

  1. Chemical and mineralogical characterization of highly and less reactive coal from Northern Natal and Venda-Pafuri coalfields in South Africa

    Science.gov (United States)

    Kataka, M. O.; Matiane, A. R.; Odhiambo, B. D. O.

    2018-01-01

    Spontaneous combustion of coal is a major hazard associated with the coal mining industry over centuries. It also a major cause of underground fires in South African collieries and in opencast operations, spoil heaps and stockpiles. Spontaneous combustion incidents are manifested in all major aspects of coal mining namely, underground mining, surface mining, including during sea-borne transportation, storage and waste disposal. Previous studies indicate that there are various factors (both intrinsic and extrinsic) that influence the spontaneous combustion of coals. This paper characterizes highly reactive coal from the Vryheid coalfields and less reactive coal from at Venda-Pafuri coalfield, to identify and delineate some intrinsic coal parameters that are considered to be most critical in terms of heat 'generation' and relationships between the two coals types by tracing their similarities and differences in their spontaneous combustion parameters. Various tests were carried out to characterize these coals in terms of their intrinsic properties, namely: ultimate, proximate, petrographic analysis and Glasser spontaneous tests. The ultimate and proximate analysis showed that spontaneous coal has high contents of carbon, oxygen, and volatile matter as compared to non-spontaneous coal, making it more susceptible to spontaneous combustion. Non-spontaneous coal has higher ash content than the spontaneous coal. Furthermore, the petrographic analysis showed that spontaneous coal has high total reactivity compared to the non-spontaneous coal. Results from Glasser spontaneous test indicate that spontaneous coal absorbs more oxygen than non-spontaneous coal, which explains why spontaneous coal is more susceptible to spontaneous combustion. High reactive coal has low values of critical self-heating temperature (CSHT), indicating that this coal has potential of spontaneous ignition.

  2. Assessment of surface reactivity of thorium oxide in conditions close to chemical equilibrium by isotope exchange {sup 229}Th/{sup 232}Th method

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki-Muresan, Tomo; Perrigaud, Katy; Vandenborre, Johan; Ribet, Solange; Grambow, Bernd [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Takamasa, Inai [TOKAI Univ., Kanagawa (Japan)

    2017-08-01

    This work aims to assess the solubility and the surface reactivity of crystallized thorium at pH 3.0 in presence of three types of solids: synthesized powder at 1300 C, crushed kernel, and intact kernel. In this study, the kernel is composed by the core solid from high temperature reactors (HTR) sphere particles. The originality of this work consisted in following in a sequential order the kinetic of dissolution, the surface reactivity in presence of isotope tracer {sup 229}Th, and its desorption process. Long time experiments (634 days) allowed to get deeper understanding on the behavior of the surface reactivity in contact with the solution. Solubility values are ranging from 0.3 x 10{sup -7} mol.L{sup -1} to 3 x 10{sup -7} mol.L{sup -1} with a dissolution rate of 10{sup -6}-10{sup -4} g.m{sup -2} day{sup -1}. PHREEQC modeling showed that crystallized ThO{sub 2}(cr, 20 nm) phase controls the equilibrium in solution. Isotope exchange between {sup 229}Th and {sup 232}Th indicated that well-crystallized phase exist as an inert surface regarding to the absence of exchange between surface solid and solution.

  3. Analysis Of Convective Plane Stagnation Point Chemically Reactive Mhd Flow Past A Vertical Porous Plate With A Convective Boundary Condition In The Presence Of A Uniform Magnetic Field.

    OpenAIRE

    Adeniyan, A.,

    2013-01-01

    The numerical investigation of a stagnation point boundary layer flow , mass and heat transfer of a steady two dimensional , incompressible , viscous electrically conducting, chemically reacting laminar fluid over a vertical convectively heated , electrically neutral flat plate exposed to a transverse uniform magnetic field has been carried out to examine the influence of the simultaneous presence of the effects of a convective boundary condition, chemical reaction, heat transfer and suctio...

  4. Glass-crystal transformation under non-isothermal conditions: Kinetic analysis of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy by using a new theoretical method based on nucleation and growth processes, which depend on time as a power law

    Energy Technology Data Exchange (ETDEWEB)

    Vazquez, J., E-mail: jose.vazquez@uca.e [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain); Cardenas-Leal, J.L.; Garcia-G Barreda, D.; Gonzalez-Palma, R.; Lopez-Alemany, P.L.; Villares, P. [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain)

    2010-11-01

    A theoretical method, which we have published in two previous works, has been applied to the study of the glass-crystal transformation of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} semiconductor glass under non-isothermal conditions. This method allows one to obtain an evolution equation with temperature for the actual volume fraction, to calculate the kinetic parameters of the quoted transformation, to establish the thermal process type, to determine the dimensionality of the crystal growth and to evaluate the exponents of the power laws of the time-dependence both for the nucleation frequency and for the crystal growth rate in non-isothermal transformations. The quoted method assumes the concept of extended volume of the transformed material, the condition of randomly located nuclei and the supposition of mutual interference of regions growing from separated nuclei, considering moreover the case presented in the practice of a kinetic exponent with a value larger than 4. To study the quoted case it is proposed that both the nucleation frequency and the crystal growth rate depend on time as a power law. The above-mentioned Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy presents two exothermic peaks. The second peak gives for the kinetic exponent a value large enough than 4 and it is necessary to resort to the hypotheses of the considered method to justify the unexpectedly high value of the kinetic exponent. Following the quoted method it has been found that the thermal process type is continuous nucleation with three-dimensional growth for the two peaks of crystallization of the studied alloy. Moreover, the experimental curve of the transformed fraction shows a satisfactory agreement with the theoretical curve corresponding to the considered method, confirming the reliability of the quoted method in order to analyze the transformation kinetics of the above-mentioned alloy.

  5. A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

    Directory of Open Access Journals (Sweden)

    Marc Philippe

    2018-01-01

    Full Text Available Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the “true” chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

  6. A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

    Science.gov (United States)

    Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

    2018-03-01

    Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

  7. Quantum mechanical calculations of vibrational population inversion in chemical reactions - Numerically exact L-squared-amplitude-density study of the H2Br reactive system

    Science.gov (United States)

    Zhang, Y. C.; Zhang, J. Z. H.; Kouri, D. J.; Haug, K.; Schwenke, D. W.

    1988-01-01

    Numerically exact, fully three-dimensional quantum mechanicl reactive scattering calculations are reported for the H2Br system. Both the exchange (H + H-prime Br to H-prime + HBr) and abstraction (H + HBR to H2 + Br) reaction channels are included in the calculations. The present results are the first completely converged three-dimensional quantum calculations for a system involving a highly exoergic reaction channel (the abstraction process). It is found that the production of vibrationally hot H2 in the abstraction reaction, and hence the extent of population inversion in the products, is a sensitive function of initial HBr rotational state and collision energy.

  8. Subsurface Transport Over Reactive Multiphases (STORM): A general, coupled, nonisothermal multiphase flow, reactive transport, and porous medium alteration simulator, Version 2 user's guide

    International Nuclear Information System (INIS)

    Bacon, D.H.; White, M.D.; McGrail, B.P.

    2000-01-01

    The Hanford Site, in southeastern Washington State, has been used extensively to produce nuclear materials for the US strategic defense arsenal by the Department of Energy (DOE) and its predecessors, the US Atomic Energy Commission and the US Energy Research and Development Administration. A large inventory of radioactive and mixed waste has accumulated in 177 buried single- and double shell tanks. Liquid waste recovered from the tanks will be pretreated to separate the low-activity fraction from the high-level and transuranic wastes. Vitrification is the leading option for immobilization of these wastes, expected to produce approximately 550,000 metric tons of Low Activity Waste (LAW) glass. This total tonnage, based on nominal Na 2 O oxide loading of 20% by weight, is destined for disposal in a near-surface facility. Before disposal of the immobilized waste can proceed, the DOE must approve a performance assessment, a document that described the impacts, if any, of the disposal facility on public health and environmental resources. Studies have shown that release rates of radionuclides from the glass waste form by reaction with water determine the impacts of the disposal action more than any other independent parameter. This report describes the latest accomplishments in the development of a computational tool, Subsurface Transport Over Reactive Multiphases (STORM), Version 2, a general, coupled non-isothermal multiphase flow and reactive transport simulator. The underlying mathematics in STORM describe the rate of change of the solute concentrations of pore water in a variably saturated, non-isothermal porous medium, and the alteration of waste forms, packaging materials, backfill, and host rocks

  9. Can hydroxylamine be a more potent nucleophile for the reactivation of tabun-inhibited AChE than prototype oxime drugs? An answer derived from quantum chemical and steered molecular dynamics studies.

    Science.gov (United States)

    Lo, Rabindranath; Ganguly, Bishwajit

    2014-07-29

    Organophosphorus nerve agents are highly toxic compounds which strongly inhibit acetylcholinesterase (AChE) in the blood and in the central nervous system (CNS). Tabun is one of the highly toxic organophosphorus (OP) compounds and is resistant to many oxime drugs formulated for the reactivation of AChE. The reactivation mechanism of tabun-conjugated AChE with various drugs has been examined with density functional theory and ab initio quantum chemical calculations. The presence of a lone-pair located on the amidic group resists the nucleophilic attack at the phosphorus center of the tabun-conjugated AChE. We have shown that the newly designed drug candidate N-(pyridin-2-yl)hydroxylamine, at the MP2/6-31+G*//M05-2X/6-31G* level in the aqueous phase with the polarizable continuum solvation model (PCM), is more effective in reactivating the tabun-conjugated AChE than typical oxime drugs. The rate determining activation barrier with N-(pyridin-2-yl)hydroxylamine was found to be ∼1.7 kcal mol(-1), which is 7.2 kcal mol(-1) lower than the charged oxime trimedoxime (one of the most efficient reactivators in tabun poisonings). The greater nucleophilicity index (ω(-)) and higher CHelpG charge of pyridinylhydroxylamine compared to TMB4 support this observation. Furthermore, we have also examined the reactivation process of tabun-inhibited AChE with some other bis-quaternary oxime drug candidates such as methoxime (MMB4) and obidoxime. The docking analysis suggests that charged bis-quaternary pyridinium oximes have greater binding affinity inside the active-site gorge of AChE compared to the neutral pyridinylhydroxylamine. The peripheral ligand attached to the neutral pyridinylhydroxylamine enhanced the binding with the aromatic residues in the active-site gorge of AChE through effective π-π interactions. Steered molecular dynamics (SMD) simulations have also been performed with the charged oxime (TMB4) and the neutral hydroxylamine. From protein-drug interaction

  10. Reactive Systems

    DEFF Research Database (Denmark)

    Aceto, Luca; Ingolfsdottir, Anna; Larsen, Kim Guldstrand

    A reactive system comprises networks of computing components, achieving their goals through interaction among themselves and their environment. Thus even relatively small systems may exhibit unexpectedly complex behaviours. As moreover reactive systems are often used in safety critical systems......, the need for mathematically based formal methodology is increasingly important. There are many books that look at particular methodologies for such systems. This book offers a more balanced introduction for graduate students and describes the various approaches, their strengths and weaknesses, and when...... they are best used. Milner's CCS and its operational semantics are introduced, together with the notions of behavioural equivalences based on bisimulation techniques and with recursive extensions of Hennessy-Milner logic. In the second part of the book, the presented theories are extended to take timing issues...

  11. The iodine reactivity

    International Nuclear Information System (INIS)

    2003-01-01

    The iodine is an important element because it has long life isotopes (such as iodine 129) and a great mobility in natural media. Iodine presents a complex chemistry because of its volatility and its strong redox reactivity. The S.E.C.R. works to better understand the reactivity of this element in different natural, industrial or biological environments. It plays a part in thermochemical sites as a possible way of hydrogen formation. This seminar gives some aspects relative to the chemical reactivity of iodine, since its thermochemistry in the I/S cycles to produce hydrogen to its reactivity in the natural medium and its potential radiological impact. This document includes 4 presentations transparencies) dealing with: the 129 I cycle rejected in the low radioactive gaseous and liquid effluents of the La Hague reprocessing plant (C. Frechou); a bibliographic review of iodine retention in soils (F. Bazer-Bachi); the hydrogen production and the iodine/sulfur thermochemical cycle (role of iodine in the process); and the direct characterization by electro-spray ionization mass spectroscopy of iodine fixation by fulvic acids (P. Reiller, B. Amekraz, C. Moulin, V. Moulin)

  12. An expeditious and green synthesis of new enaminones and study their chemical reactivity toward some different amines and binucleophiles under environmentally friendly conditions

    Directory of Open Access Journals (Sweden)

    Khadijah M. Al-Zaydi

    2017-05-01

    Full Text Available The condensation reaction of 3-heteroaromatic-3-oxopropanenitriles 3, 4 and 7 with dimethylformamide–dimethylacetal (DMF–DMA gave the corresponding enaminones 8, 9 and 10, respectively. Nucleophilic substitution of 8 and 9 with different amines resulted in a new derivatives of enaminones 11–18. The reactivity of enaminones 8 and 9 toward some nitrogen nucleophiles was investigated with a view to synthesize new heterocyclic systems. Thus, treatment of compounds 8 and 9 with phenylhydrazine afforded the pyrazole derivatives 19 and 20, respectively. On the other hand, reacting 8 and 9 with guanidine gave the pyrimidines 21 and 22, respectively. Treatment of compound 9 with hydroxylamine hydrochloride afforded the aminoisoxazoles 23. The foregoing reactions were carried out with conventional heating and under green conditions [ultrasound (US irradiations or ionic liquids (ILs] and a comparative study was employed. All the new structures are fully characterized.

  13. Chemical properties and reactive oxygen and nitrogen species quenching activities of dry sugar-amino acid maillard reaction mixtures exposed to baking temperatures.

    Science.gov (United States)

    Chen, Xiu-Min; Liang, Ningjian; Kitts, David D

    2015-10-01

    Maillard reaction products (MRPs) derived from 10 different, dry sugar-amino acid reaction model systems were examined for changes in color index (E), sugar loss, and formation of α-dicarbonyl compounds; the changes were correlated with relative activities to quench both reactive oxygen (ROS) and reactive nitrogen (RNS) species. Reducing sugars, xylose, ribose, fructose, glucose, and non-reducing sucrose were reacted with glycine (Xyl-Gly, Rib-Gly, Fru-Gly, Glc-Gly, and Suc-Gly), or lysine (Xyl-Lys, Rib-Lys, Fru-Lys, Glc-Lys, and Suc-Lys), respectively, at temperatures of 150°C and 180°C for time periods ranging from 5 to 60min. ROS quenching capacity was negatively correlated with color index (E) (r=-0.604, P<0.001), and positively correlated with sugar loss (r=0.567, P<0.001). MRPs also exhibited activity to quench RNS as assessed by nitric oxide (NO) inhibition in differentiated Caco-2 cells that were induced with interferon-γ (IFN-γ) and phorbol ester (PMA) cocktail. We also showed a correlation between RNS and color index, sugar loss, and ROS quenching activities for MR mixtures that were heated for a short time (e.g. 10min) at 150°C. MRP quenching of ROS was largely influenced by sugar type, whereas, RNS quenching was dependent more so on the interaction between reactants and reaction conditions used to generate MRPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Chemical synthesis, characterization studies and reactivity of a catalytic material based on ZrO2-H3PW12O40

    International Nuclear Information System (INIS)

    Hernandez Enriquez, Juan Manuel; Garcia Alamilla, Ricardo; Paramo Garcia, Ulises; Rodrigo, Rebeca Silva; Garcia Serrano, Luz Arcelia

    2013-01-01

    In this work, the preparation and characterization of materials such as zirconium oxide (ZrO 2 ) and phosphotungstic acid promoted zirconium oxide (ZrO 2 -H 3 PW 12 O 40 ) is presented. Physico-chemical characterization results showed that addition of H 3 PW 12 O 40 acted as both a textural and chemical promoter of zirconium oxide. The incorporation of phosphotungstic acid into the ZrO 2 matrix delayed the sintering of the material and stabilized ZrO 2 in the tetragonal phase. ZrO 2 acidity was also enhanced, developing strong acid sites on its surface. The Pt/ZrO 2 -H 3 PW 12 O 40 catalyst was active for n-pentane isomerization at 250 deg C, exhibiting high selectivity to iso-pentane (95%). This result is probably due to its suitable acidity (author)

  15. 1D Thermal-Hydraulic-Chemical (THC) Reactive transport modeling for deep geothermal systems: A case study of Groß Schönebeck reservoir, Germany

    Science.gov (United States)

    Driba, D. L.; De Lucia, M.; Peiffer, S.

    2014-12-01

    Fluid-rock interactions in geothermal reservoirs are driven by the state of disequilibrium that persists among solid and solutes due to changing temperature and pressure. During operation of enhanced geothermal systems, injection of cooled water back into the reservoir disturbs the initial thermodynamic equilibrium between the reservoir and its geothermal fluid, which may induce modifications in permeability through changes in porosity and pore space geometry, consequently bringing about several impairments to the overall system.Modeling of fluid-rock interactions induced by injection of cold brine into Groß Schönebeck geothermal reservoir system situated in the Rotliegend sandstone at 4200m depth have been done by coupling geochemical modeling Code Phreeqc with OpenGeoSys. Through batch modeling the re-evaluation of the measured hydrochemical composition of the brine has been done using Quintessa databases, the results from the calculation indicate that a mineral phases comprising of K-feldspar, hematite, Barite, Calcite and Dolomite was found to match the hypothesis of equilibrium with the formation fluid, Reducing conditions are presumed in the model (pe = -3.5) in order to match the amount of observed dissolved Fe and thus considered as initial state for the reactive transport modeling. based on a measured composition of formation fluids and the predominant mineralogical assemblage of the host rock, a preliminary 1D Reactive transport modeling (RTM) was run with total time set to 30 years; results obtained for the initial simulation revealed that during this period, no significant change is evident for K-feldspar. Furthermore, the precipitation of calcite along the flow path in the brine results in a drop of pH from 6.2 to a value of 5.2 noticed over the simulated period. The circulation of cooled fluid in the reservoir is predicted to affect the temperature of the reservoir within the first 100 -150m from the injection well. Examination of porosity change in

  16. Production of chemically reactive radioactive ion beams through on-line separation; Production de faisceaux d'ions radioactifs chimiquement reactifs par separation en ligne

    Energy Technology Data Exchange (ETDEWEB)

    Joinet, A

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO{sub 2}, Nb, Ti, V,TiO{sub 2}, CeO{sub x}, ThO{sub 2}, C, ZrC{sub 4} and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target.

  17. Electrochemical investigations of the interaction of C-reactive protein (CRP) with a CRP antibody chemically immobilized on a gold surface

    International Nuclear Information System (INIS)

    Hennessey, Hooman; Afara, Nadia; Omanovic, Sasha; Padjen, Ante L.

    2009-01-01

    A possibility of using a range of dc and ac electrochemical techniques to probe associative interactions of C-reactive protein (CRP) with CRP antibody (aCRP) immobilized on a gold electrode surface was investigated. It was demonstrated that the investigated electrochemical techniques can be used efficiently to probe these interactions over a wide CRP concentration range, from 1.15 x 10 -5 to 1.15 mg L -1 . The measured sensitivity of the techniques is in the following decreasing order: differential pulse voltammetry, charge-transfer resistance obtained from electrochemical impedance spectroscopy (EIS), cyclic voltammetry, chronoamperometry, and double-layer capacitance deduced from EIS measurements which gave the poorest sensitivity. Measurements of kinetic parameters demonstrated that the associative interactions of CRP with the immobilized aCRP reached quasi-equilibrium after 20-30 min. The kinetics of these interactions was modeled successfully using a two-step kinetic model. In this model, the first step represents reversible CRP-aCRP associative-dissociative interactions, while the second step represents the irreversible transformation of the bound CRP into a thermodynamically stable configuration. It was demonstrated that the thermodynamically stable configuration of CRP starts prevailing after 7 min of interaction of CRP with the immobilized aCRP.

  18. Production of chemically reactive radioactive ion beams through on-line separation; Production de faisceaux d'ions radioactifs chimiquement reactifs par separation en ligne

    Energy Technology Data Exchange (ETDEWEB)

    Joinet, A

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO{sub 2}, Nb, Ti, V,TiO{sub 2}, CeO{sub x}, ThO{sub 2}, C, ZrC{sub 4} and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target.

  19. The synthesis and coupling of photoreactive collagen-based peptides to restore integrin reactivity to an inert substrate, chemically-crosslinked collagen

    Science.gov (United States)

    Malcor, Jean-Daniel; Bax, Daniel; Hamaia, Samir W.; Davidenko, Natalia; Best, Serena M.; Cameron, Ruth E.; Farndale, Richard W.; Bihan, Dominique

    2016-01-01

    Collagen is frequently advocated as a scaffold for use in regenerative medicine. Increasing the mechanical stability of a collagen scaffold is widely achieved by cross-linking using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). However, this treatment consumes the carboxylate-containing amino acid sidechains that are crucial for recognition by the cell-surface integrins, abolishing cell adhesion. Here, we restore cell reactivity to a cross-linked type I collagen film by covalently linking synthetic triple-helical peptides (THPs), mimicking the structure of collagen. These THPs are ligands containing an active cell-recognition motif, GFOGER, a high-affinity binding site for the collagen-binding integrins. We end-stapled peptide strands containing GFOGER by coupling a short diglutamate-containing peptide to their N-terminus, improving the thermal stability of the resulting THP. A photoreactive Diazirine group was grafted onto the end-stapled THP to allow covalent linkage to the collagen film upon UV activation. Such GFOGER-derivatized collagen films showed restored affinity for the ligand-binding I domain of integrin α2β1, and increased integrin-dependent cell attachment and spreading of HT1080 and Rugli cell lines, expressing integrins α2β1 and α1β1, respectively. The method we describe has wide application, beyond collagen films or scaffolds, since the photoreactive diazirine will react with many organic carbon skeletons. PMID:26854392

  20. Size distribution, chemical composition and oxidation reactivity of particulate matter from gasoline direct injection (GDI) engine fueled with ethanol-gasoline fuel

    International Nuclear Information System (INIS)

    Luo, Yueqi; Zhu, Lei; Fang, Junhua; Zhuang, Zhuyue; Guan, Chun; Xia, Chen; Xie, Xiaomin; Huang, Zhen

    2015-01-01

    Ethanol-gasoline blended fuels have been widely applied in markets recently, as ethanol reduces life-cycle greenhouse gas emissions and improves anti-knock performance. However, its effects on particulate matter (PM) emissions from gasoline direct injection (GDI) engine still need further investigation. In this study, the effects of ethanol-gasoline blended fuels on particle size distributions, number concentrations, chemical composition and soot oxidation activity of GDI engine were investigated. It was found that ethanol-gasoline blended fuels increased the particle number concentration in low-load operating conditions. In higher load conditions, the ethanol-gasoline was effective for reducing the particle number concentration, indicating that the chemical benefits of ethanol become dominant, which could reduce soot precursors such as large n-alkanes and aromatics in gasoline. The volatile organic mass fraction in ethanol-gasoline particulates matter was higher than that in gasoline particulate matter because ethanol reduced the amount of soot precursors during combustion and thereby reduced the elemental carbon proportions in PM. Ethanol addition also increased the proportion of small particles, which confirmed the effects of ethanol on organic composition. Ethanol-gasoline reduced the concentrations of most PAH species, except those with small aromatic rings, e.g., naphthalene. Soot from ethanol-gasoline has lower activation energy of oxidation than that from gasoline. The results in this study indicate that ethanol-gasoline has positive effects on PM emissions control, as the soot oxidation activity is improved and the particle number concentrations are reduced at moderate and high engine loads. - Highlights: • Ethanol-gasoline reduces elemental carbon in PM. • Ethanol-gasoline increases volatile organic fraction in PM. • Soot generated from ethanol-gasoline has higher oxidation activity.

  1. Immunological reactivity

    International Nuclear Information System (INIS)

    Shubik, V.M.

    1984-01-01

    Materials on comparative characteristics of state of some immunological parameters under the effect of toxic radioactive and non-radioactive chemical substances on organism of experimental animas as well as data on possible role of disclosed immunological changes are presented. Data on the possible role of immunological mechanisms in shortening life span and distortions of reproduction function are given

  2. Ignition delay and soot oxidative reactivity of MTBE blended diesel fuel

    KAUST Repository

    Yang, Seung Yeon; Naser, Nimal; Chung, Suk-Ho; Al-Qurashi, Khalid

    2014-01-01

    Methyl tert-butyl ether (MTBE) was added to diesel fuel to investigate the effect on ignition delay and soot oxidative reactivity. An ignition quality tester (IQT) was used to study the ignition propensity of MTBE blended diesel fuels in a reactive spray environment. The IQT data showed that ignition delay increases linearly as the MTBE fraction increases in the fuel. A four-stroke single cylinder diesel engine was used to generate soot samples for a soot oxidation study. Soot samples were pre-treated using a tube furnace in a nitrogen environment to remove any soluble organic fractions and moisture content. Non-isothermal oxidation of soot samples was conducted using a thermogravimetric analyzer (TGA). It was observed that oxidation of 'MTBE soot' started began at a lower temperature and had higher reaction rate than 'diesel soot' across a range of temperatures. Several kinetic analyses including an isoconversional method and a combined model fitting method were carried out to evaluate kinetic parameters. The results showed that Diesel and MTBE soot samples had similar activation energy but the pre-exponential factor of MTBE soot was much higher than that of the Diesel soot. This may explain why MTBE soot was more reactive than Diesel soot. It is suggested that adding MTBE to diesel fuel is better for DPF regeneration since an MTBE blend can significantly influence the ignition characteristics and, consequently, the oxidative reactivity of soot. Copyright © 2014 SAE International.

  3. Ignition delay and soot oxidative reactivity of MTBE blended diesel fuel

    KAUST Repository

    Yang, Seung Yeon

    2014-04-01

    Methyl tert-butyl ether (MTBE) was added to diesel fuel to investigate the effect on ignition delay and soot oxidative reactivity. An ignition quality tester (IQT) was used to study the ignition propensity of MTBE blended diesel fuels in a reactive spray environment. The IQT data showed that ignition delay increases linearly as the MTBE fraction increases in the fuel. A four-stroke single cylinder diesel engine was used to generate soot samples for a soot oxidation study. Soot samples were pre-treated using a tube furnace in a nitrogen environment to remove any soluble organic fractions and moisture content. Non-isothermal oxidation of soot samples was conducted using a thermogravimetric analyzer (TGA). It was observed that oxidation of \\'MTBE soot\\' started began at a lower temperature and had higher reaction rate than \\'diesel soot\\' across a range of temperatures. Several kinetic analyses including an isoconversional method and a combined model fitting method were carried out to evaluate kinetic parameters. The results showed that Diesel and MTBE soot samples had similar activation energy but the pre-exponential factor of MTBE soot was much higher than that of the Diesel soot. This may explain why MTBE soot was more reactive than Diesel soot. It is suggested that adding MTBE to diesel fuel is better for DPF regeneration since an MTBE blend can significantly influence the ignition characteristics and, consequently, the oxidative reactivity of soot. Copyright © 2014 SAE International.

  4. Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Ahmed, Farouq; Nagumo, Ryo; Miura, Ryuji; Ai, Suzuki; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Miyamoto, Akira

    2011-01-01

    The notion of 'active sites' is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.

  5. Structural, chemical and nanomechanical investigations of SiC/polymeric a-C:H films deposited by reactive RF unbalanced magnetron sputtering

    Science.gov (United States)

    Tomastik, C.; Lackner, J. M.; Pauschitz, A.; Roy, M.

    2016-03-01

    Amorphous carbon (or diamond-like carbon, DLC) films have shown a number of important properties usable for a wide range of applications for very thin coatings with low friction and good wear resistance. DLC films alloyed with (semi-)metals show some improved properties and can be deposited by various methods. Among those, the widely used magnetron sputtering of carbon targets is known to increase the number of defects in the films. Therefore, in this paper an alternative approach of depositing silicon-carbide-containing polymeric hydrogenated DLC films using unbalanced magnetron sputtering was investigated. The influence of the C2H2 precursor concentration in the deposition chamber on the chemical and structural properties of the deposited films was investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and elastic recoil detection analysis. Roughness, mechanical properties and scratch response of the films were evaluated with the help of atomic force microscopy and nanoindentation. The Raman spectra revealed a strong correlation of the film structure with the C2H2 concentration during deposition. A higher C2H2 flow rate results in an increase in SiC content and decrease in hydrogen content in the film. This in turn increases hardness and elastic modulus and decreases the ratio H/E and H3/E2. The highest scratch resistance is exhibited by the film with the highest hardness, and the film having the highest overall sp3 bond content shows the highest elastic recovery during scratching.

  6. Site-Specific Three-Color Labeling of α-Synuclein via Conjugation to Uniquely Reactive Cysteines during Assembly by Native Chemical Ligation.

    Science.gov (United States)

    Lee, Taehyung C; Moran, Crystal R; Cistrone, Philip A; Dawson, Philip E; Deniz, Ashok A

    2018-04-12

    Single-molecule fluorescence is widely used to study conformational complexity in proteins, and has proven especially valuable with intrinsically disordered proteins (IDPs). Protein studies using dual-color single-molecule Förster resonance energy transfer (smFRET) are now quite common, but many could benefit from simultaneous measurement of multiple distances through multi-color labeling. Such studies, however, have suffered from limitations in site-specific incorporation of more than two dyes per polypeptide. Here we present a fully site-specific three-color labeling scheme for α-synuclein, an IDP with important putative functions and links to Parkinson disease. The convergent synthesis combines native chemical ligation with regiospecific cysteine protection of expressed protein fragments to permit highly controlled labeling via standard cysteine-maleimide chemistry, enabling more global smFRET studies. Furthermore, this modular approach is generally compatible with recombinant proteins and expandable to accommodate even more complex experiments, such as by labeling with additional colors. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Experimental study of chemical-mechanical coupling during percolation of reactive fluid through rocks under stress, in the context of the CO2 geological sequestration

    International Nuclear Information System (INIS)

    Le Guen, Y.

    2006-10-01

    CO 2 injection into geological repositories will induce chemical and mechanical instabilities. The study of these instabilities is based on experimental deformation of natural rock samples under stress, in the presence of fluids containing, or not, dissolved CO 2 . Triaxial cells used for the experiments permitted an independent control and measurement of stress, temperature, fluid pressure and composition. Vertical strains were measured during several months, with a resolution of 1.10 -12 s -1 on the strain rate. Simultaneously, fluids were analysed in order to quantify fluid-rock interactions. For limestone samples, percolation of CO 2 -rich fluids increases strain rate by a factor 1.7 up to 5; on the other hand, sandstone deformation remained almost the same. Increase in strain rate with limestone samples was explained by injected water acidification by the CO 2 which increases rock solubility and reaction kinetics. On the opposite, small effect of CO 2 on quartz explains the absence of deformation. X-ray observations confirmed the importance of rock composition and structure on the porosity evolution. Numerical simulations of rock elastic properties showed increasing shear stress into the sample. Measured deformation showed an evolution of reservoir rocks mechanical properties. It was interpreted as the consequence of pressure solution mechanisms both at grains contacts and on grain free surfaces. (author)

  8. Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

    Science.gov (United States)

    Marin, I. S.; Molson, J. W.

    2013-05-01

    Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

  9. The Maillard reaction of a shrimp by-product protein hydrolysate: chemical changes and inhibiting effects of reactive oxygen species in human HepG2 cells.

    Science.gov (United States)

    Zha, Fengchao; Wei, Binbin; Chen, Shengjun; Dong, Shiyuan; Zeng, Mingyong; Liu, Zunying

    2015-06-01

    Recently, much attention has been given to improving the antioxidant activity of protein hydrolysates via the Maillard reaction, but little is known about the cellular antioxidant activity of Maillard reaction products (MRPs) from protein hydrolysates. We first investigated chemical characterization and the cellular antioxidant activity of MRPs in a shrimp (Litopenaeus vannamei) by-product protein hydrolysate (SBH)-glucose system at 110 °C for up to 10 h of heating. Solutions of SBH and glucose were also heated alone as controls. The Maillard reaction greatly resulted in the increase of hydroxymethylfurfural (HMF) and browning intensity, high molecular weight fraction, and reduction of the total amino acid in SBH with the heating time, which correlated well with the free radical scavenging activity of MRPs. MRPs had stronger inhibiting effects on oxidative stress of human HepG2 cells than the original SBH, and its cellular antioxidant activity strongly correlated with free radical scavenging activity, but less affected by the browning intensity and HMF level. The caramelization of glucose partially affected the HMF level and free radical scavenging activity of MRPs, but it was not related to the cellular antioxidant activity. The cellular antioxidant activity of MRPs for 5 h of heating time appeared to reach a maximum level, which was mainly due to carbonyl ammonia condensation reaction. In conclusion, the Maillard reaction is a potential method to increase the cellular antioxidant activity of a shrimp by-product protein hydrolysate, but the higher HMF levels and the lower amino acid content in MRPs should also be considered.

  10. High temperature chemical reactivity in the system (U, Zr,Fe, O). A contribution to the study of zirconia as a ''core catcher''

    International Nuclear Information System (INIS)

    Maurizi, A.; CEA Centre d'Etudes de Saclay, 91 - Gif-sur-Yvette

    1996-01-01

    Within the framework of the improvement of nuclear reactor safety, a device to recover corium is proposed to be installed under the reactor vessel to limit the consequences of a core melting. According to our bibliographic study, stabilised zirconia seems to be the best refractory material to play this role and to support the physicochemical, mechanical and thermal requirements imposed to the corium catcher. The nature of the chemical interactions between zirconia and iron of high temperature were established and experimental data on the (U, Fe, Zr, O) quaternary system which stands for the corium were determined. First of all, the Knudsen effusion mass-spectrometric method was used to establish the liquidus position for a (U, Zr, O) alloy representative of the corium (U/Zr = 1,5) at 2000 deg C. The oxygen solubility limit in a (U, Zr, O) liquid alloy is about 7 atomic %. In oxidising conditions, the reaction between zirconia and iron leads to the formation of a stabilised zirconia-iron oxide solid solution. Up to 10 atomic % of iron can be incorporated in the structure, leading to the stabilisation of cubic zirconia and a modification of lattice constants. The valence and localisation of those iron measured as a function of time and temperature from 1500 to 2400 deg C, after high frequency inductive heating, both on laboratory materials are commercial bricks. The reaction rate is governed by an activation energy of about 80 kJ/mol. Our results demonstrate that stabilised zirconia is able to efficiently absorb oxidised iron. (author)

  11. Development of a Transferable Reactive Force Field of P/H Systems: Application to the Chemical and Mechanical Properties of Phosphorene.

    Science.gov (United States)

    Xiao, Hang; Shi, Xiaoyang; Hao, Feng; Liao, Xiangbiao; Zhang, Yayun; Chen, Xi

    2017-08-17

    We developed ReaxFF parameters for phosphorus and hydrogen to give a good description of the chemical and mechanical properties of pristine and defected black phosphorene. ReaxFF for P/H is transferable to a wide range of phosphorus- and hydrogen-containing systems including bulk black phosphorus, blue phosphorene, edge-hydrogenated phosphorene, phosphorus clusters, and phosphorus hydride molecules. The potential parameters were obtained by conducting global optimization with respect to a set of reference data generated by extensive ab initio calculations. We extended ReaxFF by adding a 60° correction term, which significantly improved the description of phosphorus clusters. Emphasis was placed on the mechanical response of black phosphorene with different types of defects. Compared to the nonreactive SW potential ( Jiang , J.-W. Nanotechnology 2015 , 26 , 315706 ), ReaxFF for P/H systems provides a significant improvement in describing the mechanical properties of the pristine and defected black phosphorene, as well as the thermal stability of phosphorene nanotubes. A counterintuitive phenomenon is observed that single vacancies weaken the black phosphorene more than double vacancies with higher formation energy. Our results also showed that the mechanical response of black phosphorene is more sensitive to defects in the zigzag direction than that in the armchair direction. In addition, we developed a preliminary set of ReaxFF parameters for P/H/O/C to demonstrate that the ReaxFF parameters developed in this work could be generalized to oxidized phosphorene and P-containing 2D van der Waals heterostructures. That is, the proposed ReaxFF parameters for P/H systems establish a solid foundation for modeling of a wide range of P-containing materials.

  12. Non-isothermal spreading of liquid drops on horizontal plates

    International Nuclear Information System (INIS)

    Ehrhard, P.; Davis, S.H.

    1990-05-01

    A viscous-liquid drop spreads on a smooth horizontal surface, which is uniformly heated or cooled. Lubrication theory is used to study thin drops subject to capillary, thermocapillary and gravity forces, and a variety of contact-angle-versus-speed conditions. It is found for isothermal drops that gravity is very important at large times and determines the power law for unlimited spreading. Predictions compare well with the experimental data on isothermal spreading for both two-dimensional and axisymmetric configurations. It is found that heating (cooling) retards (augments) the spreading process. When the advancing contact angle is zero, heating will cause the drop to spread only finitely far. For positive advancing contact angles, sufficient cooling will cause unlimited spreading. Thus, the heat transfer serves as a sentitive control on the spreading. (orig.) [de

  13. Abareshi Maryam Non-isothermal crystallization kinetics of ...

    Indian Academy of Sciences (India)

    Administrator

    A new sonochemical method for preparation of different morphologies of CuInS2 .... aluminium- and gallium- doped zinc oxide transparent conducting sol–gel thin films ... heterojunction for optoresponse applications. 1509. Dalagan Juliet Q.

  14. Non-isothermal crystallization kinetics of polyethylene–clay ...

    Indian Academy of Sciences (India)

    Administrator

    The results showed that the activation energy of nanocomposite was lower than that of MDPE. .... from the difference between the apparent ending and the .... index (g = 1 for interface-controlled growth and g = 0∙5 .... With the use of the iso-.

  15. Synthesis, characterisation and non-isothermal degradation kinetics ...

    Indian Academy of Sciences (India)

    Synthesis of a novel co-polymer made by the addition polymerisation between MEGDMA and 4-AB by aza-Michael addition (AMA) polymerisation method is a fascinating field of research. The present investigationyielded a hazardous metal catalyst-free and toxic solvent-free methodology. The AMA polymerisation was ...

  16. Non-isothermal kinetics of thermal degradation of chitosan

    Directory of Open Access Journals (Sweden)

    Georgieva Velyana

    2012-08-01

    Full Text Available Abstract Background Chitosan is the second most abundant nitrogen containing biopolymer in nature, obtained from the shells of crustaceans, particularly crabs, shrimp and lobsters, which are waste products of seafood processing industries. It has great potential application in the areas of biotechnology, biomedicine, food industries, and cosmetics. Chitosan is also capable of adsorbing a number of metal ions as its amino groups can serve as chelation sites. Grafted functional groups such as hydroxyl, carboxyl, sulfate, phosphate, and amino groups on the chitosan have been reported to be responsible for metal binding and sorption of dyes and pigments. The knowledge of their thermal stability and pyrolysis may help to better understand and plan their industrial processing. Results Thermogravimetric studies of chitosan in air atmosphere were carried out at six rates of linear increasing of the temperature. The kinetics and mechanism of the thermal decomposition reaction were evaluated from the TG data using recommended from ICTAC kinetics committee iso-conversional calculation procedure of Kissinger-Akahira-Sunose, as well as 27 mechanism functions. The comparison of the obtained results showed that they strongly depend on the selection of proper mechanism function for the process. Therefore, it is very important to determine the most probable mechanism function. In this respect the iso-conversional calculation procedure turned out to be the most appropriate. Conclusion Chitosan have excellent properties such as hydrophilicity, biocompatibility, biodegradability, antibacterial, non-toxicity, adsorption application. The thermal degradation of chitosan occurs in two stages. The most probable mechanism function for both stages is determined and it was best described by kinetic equations of n-th order (Fn mechanism. For the first stage, it was established that n is equal to 3.0 and for the second stage – to 1.0 respectively. The values of the apparent activation energy E, pre-exponential factor A in Arrhenius equation, as well as the changes of entropy ΔS≠, enthalpy ΔH≠ and free Gibbs energy ΔG≠ for the formation of the activated complex from the reagent are calculated.

  17. Calorimetric studies of non-isothermal crystallization in amorphous

    Indian Academy of Sciences (India)

    Administrator

    the peak crystallization temperature. Amorphous alloys of Cu–Ti system are of special interest (Koster et al 1995) due to the fact that Cu–Ti is a congruently melting compound, which should allow static under-cooling experiments. Several works ... tion when mixed with another metal or rare earth metals. (Suzuki et al 2003).

  18. Synthesis, characterisation and non-isothermal degradation kinetics ...

    Indian Academy of Sciences (India)

    Thus, obtained co-polymer was charac- terized by Fourier transform ... used, the Kissinger method yielded the lowest degradation kinetics. The degradation ... addition of amines with alkenes in methanol water medium, report is available in the ...

  19. Synthesis, non-isothermal crystallization and magnetic properties of ...

    Indian Academy of Sciences (India)

    perties and modifies the physical properties of the matrix considerably. However ... perties and harmlessness to health. PEVA, in their different ..... crystals causing a depression in Tm and Tp. In all the cases, the crystallization enthalpy peak ...

  20. Modeling of Non-Isothermal Cryogenic Fluid Sloshing

    Science.gov (United States)

    Agui, Juan H.; Moder, Jeffrey P.

    2015-01-01

    A computational fluid dynamic model was used to simulate the thermal destratification in an upright self-pressurized cryostat approximately half-filled with liquid nitrogen and subjected to forced sinusoidal lateral shaking. A full three-dimensional computational grid was used to model the tank dynamics, fluid flow and thermodynamics using the ANSYS Fluent code. A non-inertial grid was used which required the addition of momentum and energy source terms to account for the inertial forces, energy transfer and wall reaction forces produced by the shaken tank. The kinetics-based Schrage mass transfer model provided the interfacial mass transfer due to evaporation and condensation at the sloshing interface. The dynamic behavior of the sloshing interface, its amplitude and transition to different wave modes, provided insight into the fluid process at the interface. The tank pressure evolution and temperature profiles compared relatively well with the shaken cryostat experimental test data provided by the Centre National D'Etudes Spatiales.

  1. Non-isothermal crystallization kinetics and thermal behaviour of ...

    Indian Academy of Sciences (India)

    Administrator

    The thermal behaviour and crystallization kinetics of PA12/SEBS-g-MA blends .... was determined using Perkin Elmer Pyris 1 TGA. ..... such as difference in the thermal conductivity of the .... glasses (Columbus: American Ceramics Society) p 166.

  2. Simulation of non-isothermal transient flow in gas pipeline

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira Junior, Luis Carlos; Soares, Matheus; Lima, Enrique Luis; Pinto, Jose Carlos [Coordenacao dos Programas de Pos-graduacao de Engenharia (COPPE/UFRJ), Rio de Janeiro, RJ (Brazil). Programa de Engenharia Quimica; Muniz, Cyro; Pires, Clarissa Cortes; Rochocz, Geraldo [ChemTech, Rio de Janeiro, RJ (Brazil)

    2009-07-01

    Modeling of gas pipeline usually considers that the gas flow is isothermal (or adiabatic) and that pressure changes occur instantaneously (quasi steady state approach). However, these assumptions are not valid in many important transient applications (changes of inlet and outlet flows/pressures, starting and stopping of compressors, changes of controller set points, among others). Besides, the gas properties are likely to depend simultaneously on the pipe position and on the operation time. For this reason, a mathematical model is presented and implemented in this paper in order to describe the gas flow in pipeline when pressure and temperature transients cannot be neglected. The model is used afterwards as a tool for reconciliation of available measured data. (author)

  3. On a non-isothermal model for nematic liquid crystals

    Czech Academy of Sciences Publication Activity Database

    Feireisl, Eduard; Rocca, E.; Schimperna, G.

    2011-01-01

    Roč. 24, č. 1 (2011), s. 243-257 ISSN 0951-7715 R&D Projects: GA ČR GA201/09/0917; GA MŠk LC06052 Institutional research plan: CEZ:AV0Z10190503 Keywords : Navier-Stokes equations * system * flows Subject RIV: BA - General Mathematics Impact factor: 1.386, year: 2011 http://iopscience.iop.org/0951-7715/24/1/012/

  4. The reactivity meter and core reactivity

    International Nuclear Information System (INIS)

    Siltanen, P.

    1999-01-01

    This paper discussed in depth the point kinetic equations and the characteristics of the point kinetic reactivity meter, particularly for large negative reactivities. From a given input signal representing the neutron flux seen by a detector, the meter computes a value of reactivity in dollars (ρ/β), based on inverse point kinetics. The prompt jump point of view is emphasised. (Author)

  5. Structure, spectroscopic analyses (FT-IR and NMR), vibrational study, chemical reactivity and molecular docking study on 3,3'-((4-(trifluoromethyl)phenyl)methylene)bis(2-hydroxynaphthalene-1,4-dione), a promising anticancerous bis-lawsone derivative

    Science.gov (United States)

    Yadav, Krishna Kant; Kumar, Abhishek; Kumar, Amarendra; Misra, Neeraj; Brahmachari, Goutam

    2018-02-01

    Lawsone (2-hydroxy-1,4-naphthoquinone)has been evaluated to possess a wide range of biological and pharmacological activities. The interesting structural pattern of lawsone coupled with its so-called multifaceted pharmacological potential have made this scaffolds useful in certain chemical processes, particularly in synthesizing ligands for metal complexations, and also few of its derivatives have shown a number of biological activities. The equilibrium geometry of 3,3‧-((4-(trifluoromethyl)phenyl)methylene)bis(2-hydroxynaphthalene-1,4-dione) (1; TPMHD), a promising anticancerous lawsone derivative, has been determined and analyzed at DFT method employingB3LYP/6-311++G(d,p) level of theory. The reactivity descriptors such as Fukui functions and HOMO-LUMO gap are calculated and discussed. The infrared spectra of TPMHD(1) are calculated and compared with the experimentally observed ones. Moreover, 1H and 13C NMR spectra have been calculated by using the gauge independent atomic orbital method. The docking studies reveal that the TPMHD has strong binding affinity toward target protein 2SHP. Thus the compound has a possible use as a drug in cancer therapy. The study suggests further investigation on TPMHD for their in-depth biological and pharmaceutical importance.

  6. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    DFT global chemical reactivity descriptors (chemical hardness, total energy, electronic chemical potential, and electrophilicity) are calculated for the isomers and used to predict their relative stability and reactivity. The chemical reactivity indices are found to be related to the bond angle defined by the cis carbonyls and the ...

  7. Wiley guide to chemical incompatibilities

    National Research Council Canada - National Science Library

    Pohanish, Richard P; Greene, Stanley A

    2009-01-01

    .... A portable and easy-to-use reference on reactive substances commonly found in commerce, the Wiley Guide to Chemical Incompatibilities, Third Edition compiles hard-to-find data on over 11,000 chemical...

  8. Reactive sites influence in PMMA oligomers reactivity: a DFT study

    Science.gov (United States)

    Paz, C. V.; Vásquez, S. R.; Flores, N.; García, L.; Rico, J. L.

    2018-01-01

    In this work, we present a theoretical study of methyl methacrylate (MMA) living anionic polymerization. The study was addressed to understanding two important experimental observations made for Michael Szwarc in 1956. The unexpected effect of reactive sites concentration in the propagation rate, and the self-killer behavior of MMA (deactivating of living anionic polymerization). The theoretical calculations were performed by density functional theory (DFT) to obtain the frontier molecular orbitals values. These values were used to calculate and analyze the chemical interaction descriptors in DFT-Koopmans’ theorem. As a result, it was observed that the longest chain-length species (related with low concentration of reactive sites) exhibit the highest reactivity (behavior associated with the increase of the propagation rate). The improvement in this reactivity was attributed to the crosslinking produced in the polymethyl methacrylate chains. Meanwhile, the self-killer behavior was associated with the intermolecular forces present in the reactive sites. This behavior was associated to an obstruction in solvation, since the active sites remained active through all propagation species. The theoretical results were in good agreement with the Szwarc experiments.

  9. Allergic contact dermatitis due to highly reactive halogenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, F C; Ive, F A

    1983-11-01

    Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

  10. Original Paper Chemical reactivity and supramolecular susceptibility ...

    African Journals Online (AJOL)

    Safou-Tchiana

    The morphological structure of Testulea gabonensis (T. ... That morphology is defined by elementary fibrils, microfibrils and microfibrillar bands (Habibi et al., 2012). Microfibrillar bands are composed with crystalline and non-crystalline regions of varying dimension. ...... cellulose in the silver tree fern Cyathea dealbata.

  11. Original Paper Chemical reactivity and supramolecular susceptibility ...

    African Journals Online (AJOL)

    Safou-Tchiana

    The morphological structure of Testulea gabonensis (T. ..... and 2d), and its cellulose trend to bundle in macrofribrils ..... relative strength differences supporting the ..... of microstructure in native celluloses .... crystallinity in wood by carbon-13.

  12. Reactive polymer fused deposition manufacturing

    Science.gov (United States)

    Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

    2017-05-16

    Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

  13. Framework for reactive mass transport

    DEFF Research Database (Denmark)

    Jensen, Mads Mønster; Johannesson, Björn; Geiker, Mette Rica

    2014-01-01

    Reactive transport modeling is applicable for a range of porous materials. Here the modeling framework is focused on cement-based materials, where ion diffusion and migration are described by the Poisson-Nernst-Planck equation system. A two phase vapor/liquid flow model, with a sorption hysteresis...... description is coupled to the system. The mass transport is solved by using the finite element method where the chemical equilibrium is solved explicitly by an operator splitting method. The IPHREEQC library is used as chemical equilibrium solver. The equation system, solved by IPHREEQC, is explained...

  14. Efficacy studies of Reactive Skin Decontamination Lotion, M291 Skin Decontamination Kit, 0.5% bleach, 1% soapy water, and Skin Exposure Reduction Paste Against Chemical Warfare Agents, part 2: guinea pigs challenged with soman.

    Science.gov (United States)

    Braue, Ernest H; Smith, Kelly H; Doxzon, Bryce F; Lumpkin, Horace L; Clarkson, Edward D

    2011-03-01

    This report, the second in a series of five, directly compares the efficacy of Reactive Skin Decontamination Lotion (RSDL), the M291 Skin Decontamination Kit (SDK), 0.5% bleach (sodium or calcium hypochlorite solution), 1% soapy water, and Skin Exposure Reduction Paste Against Chemical Warfare Agents (SERPACWA) in the haired guinea pig model following exposure to soman (GD). In all experiments, guinea pigs were close-clipped and given anesthesia. In the decontamination experiments, the animals were challenged with GD and decontaminated after a 2-minute delay for the standard procedure or at longer times for the delayed-decontamination experiments. Positive control animals were challenged with GD in the same manner as the treated animals, except that they received no treatment. All animals were observed during the first 4 hours and again at 24 hours after exposure for signs of toxicity and death. The protective ratio (PR, defined as the median lethal dose [LD(50)] of the treatment group divided by the LD(50) of the untreated positive control animals) was calculated from the derived probit dose-response curves established for each treatment group and nontreated control animals. SERPACWA was applied as a thin coating (0.1 mm thick), allowed to dry for 15 minutes, and challenged with GD. After a 2-hour challenge, any remaining GD was blotted off the animal, but no additional decontamination was done. Significance in this report is defined as p decontamination experiments, the calculated PRs for RSDL, 0.5% bleach, 1% soapy water, and M291 SDK were 14, 2.7, 2.2, and 2.6, respectively. RSDL was by far the most effective decontamination product tested and significantly better than any of the other products. Bleach, soapy water, and the M291 SDK provided equivalent and modest protection. Since only RSDL provided at least good protection (PR > 5), it was the only decontamination product evaluated for delayed decontamination. In the GD delayed-decontamination experiments

  15. Efficacy studies of Reactive Skin Decontamination Lotion, M291 Skin Decontamination Kit, 0.5% bleach, 1% soapy water, and Skin Exposure Reduction Paste Against Chemical Warfare Agents, part 1: guinea pigs challenged with VX.

    Science.gov (United States)

    Braue, Ernest H; Smith, Kelly H; Doxzon, Bryce F; Lumpkin, Horace L; Clarkson, Edward D

    2011-03-01

    This report, first in a series of five, directly compares the efficacy of 4 decontamination products and Skin Exposure Reduction Paste Against Chemical Warfare Agents (SERPACWA) in the haired guinea pig model following exposure to VX. In all experiments, guinea pigs were close-clipped and given anesthesia. In the decontamination experiments, the animals were challenged with VX and decontaminated after a 2-minute delay for the standard procedure or at longer times for the delayed-decontamination experiments. Skin Exposure Reduction Paste Against Chemical Warfare Agents was applied as a thin coating (0.1 mm thick), allowed to dry for 15 minutes, and challenged with VX. After a 2-hour challenge, any remaining VX was blotted off the animal, but no additional decontamination was done. Positive control animals were challenged with VX in the same manner as the treated animals, except that they received no treatment. In addition, the positive control animals were always challenged with 5% VX in isopropyl alcohol (IPA) solution, whereas the treatment animals received either neat (undiluted) VX or 5% VX in IPA solution. All animals were observed during the first 4 hours and again at 24 hours after exposure for signs of toxicity and death. The protective ratio (PR, defined as the median lethal dose [LD(50)] of the treatment group divided by the LD(50) of the untreated positive control animals) was calculated from the probit dose-response curves established for each treatment group and nontreated control animals. Significance in this report was defined as p decontamination experiments, the calculated PRs for Reactive Skin Decontamination Lotion (RSDL), 0.5% bleach, 1% soapy water, and the M291 Skin Decontamination Kit (SDK) were 66, 17, 16, and 1.1, respectively. Reactive Skin Decontamination Lotion was by far the most effective decontamination product tested and was significantly better than any of the other products. Bleach and soapy water provided equivalent and good (PR

  16. Reactive Kripke semantics

    CERN Document Server

    Gabbay, Dov M

    2013-01-01

    This text offers an extension to the traditional Kripke semantics for non-classical logics by adding the notion of reactivity. Reactive Kripke models change their accessibility relation as we progress in the evaluation process of formulas in the model. This feature makes the reactive Kripke semantics strictly stronger and more applicable than the traditional one. Here we investigate the properties and axiomatisations of this new and most effective semantics, and we offer a wide landscape of applications of the idea of reactivity. Applied topics include reactive automata, reactive grammars, rea

  17. Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem

    KAUST Repository

    Nick, H.M.

    2013-02-01

    The reactive mixing between seawater and terrestrial water in coastal aquifers influences the water quality of submarine groundwater discharge. While these waters come into contact at the seawater groundwater interface by density driven flow, their chemical components dilute and react through dispersion. A larger interface and wider mixing zone may provide favorable conditions for the natural attenuation of contaminant plumes. It has been claimed that the extent of this mixing is controlled by both, porous media properties and flow conditions. In this study, the interplay between dispersion and reactive processes in coastal aquifers is investigated by means of numerical experiments. Particularly, the impact of dispersion coefficients, the velocity field induced by density driven flow and chemical component reactivities on reactive transport in such aquifers is studied. To do this, a hybrid finite-element finite-volume method and a reactive simulator are coupled, and model accuracy and applicability are assessed. A simple redox reaction is considered to describe the degradation of a contaminant which requires mixing of the contaminated groundwater and the seawater containing the terminal electron acceptor. The resulting degradation is observed for different scenarios considering different magnitudes of dispersion and chemical reactivity. Three reactive transport regimes are found: reaction controlled, reaction-dispersion controlled and dispersion controlled. Computational results suggest that the chemical components\\' reactivity as well as dispersion coefficients play a significant role on controlling reactive mixing zones and extent of contaminant removal in coastal aquifers. Further, our results confirm that the dilution index is a better alternative to the second central spatial moment of a plume to describe the mixing of reactive solutes in coastal aquifers. © 2012 Elsevier B.V.

  18. Modeling and simulation of reactive flows

    CERN Document Server

    Bortoli, De AL; Pereira, Felipe

    2015-01-01

    Modelling and Simulation of Reactive Flows presents information on modeling and how to numerically solve reactive flows. The book offers a distinctive approach that combines diffusion flames and geochemical flow problems, providing users with a comprehensive resource that bridges the gap for scientists, engineers, and the industry. Specifically, the book looks at the basic concepts related to reaction rates, chemical kinetics, and the development of reduced kinetic mechanisms. It considers the most common methods used in practical situations, along with equations for reactive flows, and va

  19. Reactive perforating collagenosis

    Directory of Open Access Journals (Sweden)

    Yadav Mukesh

    2009-01-01

    Full Text Available Reactive perforating collagenosis is a rare cutaneous disorder of unknown etiology. We hereby describe a case of acquired reactive perforating collagenosis in a patient of diabetes and chronic renal failure.

  20. Reactivity on the Web

    OpenAIRE

    Bailey, James; Bry, François; Eckert, Michael; Patrânjan, Paula Lavinia

    2005-01-01

    Reactivity, the ability to detect simple and composite events and respond in a timely manner, is an essential requirement in many present-day information systems. With the emergence of new, dynamic Web applications, reactivity on the Web is receiving increasing attention. Reactive Web-based systems need to detect and react not only to simple events but also to complex, real-life situations. This paper introduces XChange, a language for programming reactive behaviour on the Web,...

  1. Monadic Functional Reactive Programming

    NARCIS (Netherlands)

    A.J. van der Ploeg (Atze); C Shan

    2013-01-01

    htmlabstractFunctional Reactive Programming (FRP) is a way to program reactive systems in functional style, eliminating many of the problems that arise from imperative techniques. In this paper, we present an alternative FRP formulation that is based on the notion of a reactive computation: a

  2. Structure, reactivity, and biological properties of hidantoines

    International Nuclear Information System (INIS)

    Oliveira, Silvania Maria de; Silva, Joao Bosco Paraiso da; Hernandes, Marcelo Zaldini; Lima, Maria do Carmo Alves de; Galdino, Suely Lins; Pitta, Ivan da Rocha

    2008-01-01

    Hydantoin (imidazolidine-2,4-dione) is a 2,4-diketotetrahydroimidazole discovered by Baeyer in 1861. Thiohydantoins and derivatives were prepared, having chemical properties similar to the corresponding carbonyl compounds. Some biological activities (antimicrobial, anticonvulsant, schistosomicidal) are attributed to the chemical reactivity and consequent affinity of hydantoinic rings towards biomacromolecules. Therefore, knowledge about the chemistry of hydantoins has increased enormously. In this review, we present important aspects such as reactivity of hydantoins, acidity of hydantoins, spectroscopy and crystallographic properties, and biological activities of hydantoin and its derivatives. (author)

  3. Digital reactivity meter

    International Nuclear Information System (INIS)

    Akkus, B.; Anac, H.; Alsan, S.; Erk, S.

    1991-01-01

    Nowadays, various digital methods making use of microcomputers for neutron detector signals and determining the reactivity by numerical calculations are used in reactor control systems in place of classical reactivity meters. In this work, a calculation based on the ''The Time Dependent Transport Equation'' has been developed for determining the reactivity numerically. The reactivity values have been obtained utilizing a computer-based data acquisition and control system and compared with the analog reactivity meter values as well as the values calculated from the ''Inhour Equation''

  4. Method of controlling reactivity

    International Nuclear Information System (INIS)

    Tochihara, Hiroshi.

    1982-01-01

    Purpose: To improve the reactivity controlling characteristics by artificially controlling the leakage of neutron from a reactor and providing a controller for controlling the reactivity. Method: A reactor core is divided into several water gaps to increase the leakage of neutron, its reactivity is reduced, a gas-filled control rod or a fuel assembly is inserted into the gap as required, the entire core is coupled in a system to reduce the leakage of the neutron, and the reactivity is increased. The reactor shutdown is conducted by the conventional control rod, and to maintain critical state, boron density varying system is used together. Futher, a control rod drive is used with that similar to the conventional one, thereby enabling fast reactivity variation, and the positive reactivity can be obtained by the insertion, thereby improving the reactivity controlling characteristics. (Yoshihara, H.)

  5. Chemical and physical changes at sodium-stainless steel interfaces in fast reactors

    Energy Technology Data Exchange (ETDEWEB)

    Mathews, C K [Bhabha Atomic Research Centre, Bombay (India). Radiochemistry Div.

    1977-01-01

    In the sodium loops of a fast reactor, mass transfer occurs due to the interaction of flowing sodium on stainless steel surfaces. Under the non-isothermal conditions prevailing in the loop some elements are preferentially leached from the surface layers of the hot zone and transported by sodium to the cooled zone where deposition may take place. The available information on the mass transport in non-isothermal sodium loops has been summarised, and an attempt has been made to understand the mechanisms involved, of which the chemical reactions at the sodium-stainless steel interface are especially important. The rate of diffusion towards the solid/liquid interface may be the rate-determining step in some of these reactions. When a ferritic surface layer is formed by the selective removal of austenitic stabilizing elements, diffusion of alloying constituents through the ferritic layer limits the growth of this layer. Only when the surface film is adherent, the diffusion across this layer becomes important. NaCrO/sub 2/, for instance, has poor adherence, and a surface film of this compound may not inhibit further corrosion.

  6. Hazards in the chemical laboratory

    International Nuclear Information System (INIS)

    Bretherick, L.

    1987-01-01

    The contents of this book are: Preface; Introduction; Health and Safety at Work Act 1974; Safety Planning and Management; Fire Protection; Reactive Chemical Hazards; Chemical Hazards and Toxicology; Health Care and First Aid; Hazardous Chemicals; Precautions against Radiations; and An American View

  7. Reactive Programming in Java

    CERN Document Server

    CERN. Geneva

    2017-01-01

    Reactive Programming in gaining a lot of excitement. Many libraries, tools, and frameworks are beginning to make use of reactive libraries. Besides, applications dealing with big data or high frequency data can benefit from this programming paradigm. Come to this presentation to learn about what reactive programming is, what kind of problems it solves, how it solves them. We will take an example oriented approach to learning the programming model and the abstraction.

  8. Quantum-chemical insight into structure-reactivity relationship in 4,5,6,7-tetrahalogeno-1H-benzimidazoles: a combined X-ray, DSC, DFT/QTAIM, Hirshfeld surface-based, and molecular docking approach.

    Science.gov (United States)

    Latosińska, Jolanta Natalia; Latosińska, Magdalena; Maurin, Jan Krzysztof; Orzeszko, Andrzej; Kazimierczuk, Zygmunt

    2014-03-20

    The weak interaction patterns in 4,5,6,7-tetrahalogeno-1H-benzimidazoles, protein kinase CK2 inhibitors, in solid state are studied by the X-ray method and quantum chemistry calculations. The crystal structures of 4,5,6,7-tetrachloro- and 4,5,6,7-tetrabromo-1H-benzimidazole are determined by X-ray diffraction and refined to a final R-factor of 3.07 and 3.03%, respectively, at room temperature. The compound 4,5,6,7-tetrabromo-1H-benzimidazole, which crystallizes in the I41/a space group, is found to be isostructural with previously studied 4,5,6,7-tetraiodo-1H-benzimidazole in contrast to 4,5,6,7-tetrachloro-1H-benzimidazole, which crystallizes as triclinic P1̅ with 4 molecules in elementary unit. For 4,5,6,7-tetrachloro-1H-benzimidazole, differential scanning calorimetry (DSC) revealed a second order glassy phase transition at Tg = 95°/106° (heating/cooling), an indication of frozen disorder. The lack of 3D isostructurality found in all 4,5,6,7-tetrahalogeno-1H-benzimidazoles is elucidated on the basis of the intra- and intermolecular interactions (hydrogen bonding, van der Waals contacts, and C-H···π interactions). The topological Bader's Quantum Theory of Atoms in Molecules (QTAIM) and Spackman's Hirshfeld surface-based approaches reveal equilibration of electrostatic matching and dispersion van der Waals interactions between molecules consistent with the crystal site-symmetry. The weakening of van der Waals forces accompanied by increasing strength of the hydrogen bond (N-H···N) result in a decrease in the crystal site-symmetry and a change in molecular packing in the crystalline state. Crystal packing motifs were investigated with the aid of Hirshfeld surface fingerprint plots. The ordering 4,5,6,7-tetraiodo > 4,5,6,7-tetrabromo > 4,5,6,7-tetrachloro > 4,5,6,7-tetrafluoro reflects not only a decrease in crystal symmetry but also increase in chemical reactivity (electronic activation), which could explain some changes in biological activity of

  9. BN600 reactivity definition

    International Nuclear Information System (INIS)

    Zheltyshev, V.; Ivanov, A.

    2000-01-01

    Since 1980, the fast BN600 reactor with sodium coolant has been operated at Beloyarsk Nuclear Power Plant. The periodic monitoring of the reactivity modifications should be implemented in compliance with the standards and regulations applied in nuclear power engineering. The reactivity measurements are carried out in order to confirm the basic neutronic features of a BN600 reactor. The reactivity measurements are aimed to justify that nuclear safety is provided in course of the in-reactor installation of the experimental core components. Two reactivity meters are to be used on BN600 operation: 1. Digital on-line reactivity calculated under stationary reactor operation on power (approximation of the point-wise kinetics is applied). 2. Second reactivity meter used to define the reactor control rod operating components efficiency under reactor startup and take account of the changing efficiency of the sensor, however, this is more time-consumptive than the on-line reactivity meter. The application of two reactivity meters allows for the monitoring of the reactor reactivity under every operating mode. (authors)

  10. TMVOC, simulator for multiple volatile organic chemicals

    International Nuclear Information System (INIS)

    Pruess, Karsten; Battistelli, Alfredo

    2003-01-01

    TMVOC is a numerical simulator for three-phase non-isothermal flow of water, soil gas, and a multicomponent mixture of volatile organic chemicals (VOCs) in multidimensional heterogeneous porous media. It is an extension of the TOUGH2 general-purpose simulation program developed at the Lawrence Berkeley National Laboratory. TMVOC is designed for applications to contamination problems that involve hydrocarbon fuel or organic solvent spills in saturated and unsaturated zones. It can model contaminant behavior under ''natural'' environmental conditions, as well as for engineered systems, such as soil vapor extraction, groundwater pumping, or steam-assisted source remediation. TMVOC is upwards compatible with T2VOC (Falta et al., 1995) and can be initialized from T2VOC-style initial conditions. The main enhancements in TMVOC relative to T2VOC are as follows: a multicomponent mixture of volatile organic chemicals can be modeled; any and all combinations of the three phases water-oil-gas are treated; several non-condensible gases may be present; diffusion is treated in all phases in a manner that is fully coupled with phase partitioning. This paper gives a brief summary of the methodology used in TMVOC as well as highlighting some implementation issues. Simulation of a NAPL spill and subsequent remediation is discussed for a 2-D vertical section of a saturated-unsaturated flow problem

  11. Parameters estimation for reactive transport: A way to test the validity of a reactive model

    Science.gov (United States)

    Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

    The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

  12. Chemical reagent and process for refuse disposal

    International Nuclear Information System (INIS)

    Somerville, R.B.; Fan, L.T.

    1989-01-01

    A process for treating refuse by mixing them with a reactive chemical and a puzzolana-type material. Said chemical includes a retarding agent which modifies the viscosity and an accelerating agent. (author)

  13. Reactivity descriptors and electron density analysis for ligand ...

    Indian Academy of Sciences (India)

    WINTEC

    1Physical Chemistry Division, National Chemical Laboratory, Pune 411 008. 2Scientific and ... 1. Introduction. The prediction of changes in reactivity and selectivity at particular ...... The diimine part of the bipyridine delocalizes the. Figure 3.

  14. Electrospinning of reactive mesogens

    NARCIS (Netherlands)

    Yao, J.; Picot, O.T.; Hughes-Brittain, N.F.; Bastiaansen, C.W.M.; Peijs, T.

    2016-01-01

    The reinforcement potential of reactive liquid crystals or reactive mesogens (RMs) in electrospun fibers was investigated through the blending of two types of RMs (RM257 and RM82) with two types of thermoplastics; polyamide 6 (PA6) and poly(methyl methacrylate) (PMMA). Polymer/RM blends were

  15. Plasma diagnostics with electrostatic probes in the reactive low voltage ion plating process

    International Nuclear Information System (INIS)

    Lechleitner, T.; Huber, D.; Pulker, H.K.

    2002-01-01

    The analysis of cold plasmas, which are used in thin film coating techniques, is mainly important for the understanding of the correlation between the film properties and the plasma (or the process) parameters. With the knowledge of these correlations, one is able to optimise and eventually improve the coating processes for the production of films with certain desirable properties. The plasma for the reactive-low-voltage-ion-plating processes is a cold non-isothermal plasma produced by a low-pressure dc non-self sustained arc discharge, controlled by two main parameters, the arc current and the total gas pressure in the chamber. It was shown that the arc current is in a direct linear relation to the degree of ionization and the increase of the total gas pressure has a contrary effect. Besides, it was also demonstrated, that the usage of electrostatic probes for the plasma analysis od deposition processes is a powerful tool to complete the common plasma monitor measurements (energy analysing quadrupol mass spectrometer) and to improve the understanding of industrially used plasma. (nevyjel)

  16. Reactive transport models and simulation with ALLIANCES

    International Nuclear Information System (INIS)

    Leterrier, N.; Deville, E.; Bary, B.; Trotignon, L.; Hedde, T.; Cochepin, B.; Stora, E.

    2009-01-01

    Many chemical processes influence the evolution of nuclear waste storage. As a result, simulations based only upon transport and hydraulic processes fail to describe adequately some industrial scenarios. We need to take into account complex chemical models (mass action laws, kinetics...) which are highly non-linear. In order to simulate the coupling of these chemical reactions with transport, we use a classical Sequential Iterative Approach (SIA), with a fixed point algorithm, within the mainframe of the ALLIANCES platform. This approach allows us to use the various transport and chemical modules available in ALLIANCES, via an operator-splitting method based upon the structure of the chemical system. We present five different applications of reactive transport simulations in the context of nuclear waste storage: 1. A 2D simulation of the lixiviation by rain water of an underground polluted zone high in uranium oxide; 2. The degradation of the steel envelope of a package in contact with clay. Corrosion of the steel creates corrosion products and the altered package becomes a porous medium. We follow the degradation front through kinetic reactions and the coupling with transport; 3. The degradation of a cement-based material by the injection of an aqueous solution of zinc and sulphate ions. In addition to the reactive transport coupling, we take into account in this case the hydraulic retroaction of the porosity variation on the Darcy velocity; 4. The decalcification of a concrete beam in an underground storage structure. In this case, in addition to the reactive transport simulation, we take into account the interaction between chemical degradation and the mechanical forces (cracks...), and the retroactive influence on the structure changes on transport; 5. The degradation of the steel envelope of a package in contact with a clay material under a temperature gradient. In this case the reactive transport simulation is entirely directed by the temperature changes and

  17. Design and synthesis of reactive separation systems

    Energy Technology Data Exchange (ETDEWEB)

    Doherty, M.F.

    1992-01-01

    During the last decade there has been a rapid upturn in interest in reactive distillation. The chemical process industry recognizes the favorable economics of carrying out reaction simultaneously with distillation for certain classes of reacting systems, and many new processes have been built based on this technology. Interest is also increasing by academics and software vendors. Systematic design methods for reactive distillation systems have only recently begun to emerge. In this report we survey the available design techniques and point out the contributions made by our group at the University of Massachusetts.

  18. Chemical effects of radiation

    International Nuclear Information System (INIS)

    Philips, G.O.

    1986-01-01

    Ionizing radiations initiate chemical changes in materials because of the high energy of their quanta. In water, highly reactive free radicals are produced which can initiate secondary changes of solutes, and in chemical of biological molecules in contact with the water. Free radicals can also be directly produced in irradiated medical products. Their fate can be identified and the molecular basis of radiation inactivation clarified. Methods have now been developed to protect and minimise such radiation damage. (author)

  19. From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

    Science.gov (United States)

    Quilez, Juan

    2009-01-01

    With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: "incomplete…

  20. Reactive modification of polyesters and their blends

    Science.gov (United States)

    Wan, Chen

    2004-12-01

    As part of a broader research effort to investigate the chemical modification of polyesters by reactive processing a low molecular weight (MW) unsaturated polyester (UP) and a higher MW saturated polyester, polyethylene terephthalate (PET), alone or blended with polypropylene (PP) were melt processed in a batch mixer and continuous twin screw extruders. Modification was monitored by on-line rheology and the products were characterized primarily by off-line rheology, morphology and thermal analysis. Efforts were made to establish processing/property relationships and provide an insight of the accompanying structural changes. The overall response of the reactively modified systems was found to be strongly dependent on the component characteristics, blend composition, type and concentrations of reactive additives and processing conditions. The work concluded that UP can be effectively modified through reactive melt processing. Its melt viscosity and MW can be increased through chemical reactions between organic peroxides (POX) and chain unsaturation or between MgO and carboxyl/hydroxyl end groups. Reactive blending of PP/UP blends through peroxide modification gave finer and more uniform morphology than unreacted blends and at a given PP/UP weight ratio more thermoplastic elastomers-like rheological behavior. This is due to the continuously decreasing viscosity ratio of PP/UP towards unity by the competing reactions between POX and the blend components and formation of PP-UP copolymers which serve as in-situ compatibilizers to promote better interfacial adhesion. Kinetics of the competing reactions were analyzed through a developed model. In addition to POX concentration and mixing efficiency, rheology and morphology of UP/PP bends were significantly affected by the addition of inorganic and organic coagents. Addition of coagents such as a difunctional maleimide, MgO and/or an anhydride functionalized PP during reactive blending offers effective means for tailoring

  1. Digital reactivity meter

    International Nuclear Information System (INIS)

    Jiang Zongbing

    1996-02-01

    The importance and the usual methods of reactivity measurement in a nuclear reactor are presented. Emphasis is put upon the calculation principle, software and hardware components, main specifications, application, as well as the features of the digital reactivity meter. The test results of operation in various reactors shown that the meter possess the following features: high accuracy, short response time, low output noise, high resolution, wide measuring range, simple and flexible to operate, high stability and reliability. In addition, the reactivity meter can save the measuring data automatically and have a perfect capability of self-verifying. It not only meet the requirement of the reactivity measurement in nuclear power plant, but also can be applied to various types of reactors. (1 tab.)

  2. Stress Reactivity in Insomnia.

    Science.gov (United States)

    Gehrman, Philip R; Hall, Martica; Barilla, Holly; Buysse, Daniel; Perlis, Michael; Gooneratne, Nalaka; Ross, Richard J

    2016-01-01

    This study examined whether individuals with primary insomnia (PI) are more reactive to stress than good sleepers (GS). PI and GS (n = 20 per group), matched on gender and age, completed three nights of polysomnography. On the stress night, participants received a mild electric shock and were told they could receive additional shocks during the night. Saliva samples were obtained for analysis of cortisol and alpha amylase along with self-report and visual analog scales (VAS). There was very little evidence of increased stress on the stress night, compared to the baseline night. There was also no evidence of greater stress reactivity in the PI group for any sleep or for salivary measures. In the GS group, stress reactivity measured by VAS scales was positively associated with an increase in sleep latency in the experimental night on exploratory analyses. Individuals with PI did not show greater stress reactivity compared to GS.

  3. Taskable Reactive Agent Communities

    National Research Council Canada - National Science Library

    Myers, Karen

    2002-01-01

    The focus of Taskable Reactive Agent Communities (TRAC) project was to develop mixed-initiative technology to enable humans to supervise and manage teams of agents as they perform tasks in dynamic environments...

  4. Reactive sputter deposition

    CERN Document Server

    Mahieu, Stijn

    2008-01-01

    In this valuable work, all aspects of the reactive magnetron sputtering process, from the discharge up to the resulting thin film growth, are described in detail, allowing the reader to understand the complete process. Hence, this book gives necessary information for those who want to start with reactive magnetron sputtering, understand and investigate the technique, control their sputtering process and tune their existing process, obtaining the desired thin films.

  5. Burning characteristics of chemically isolated biomass ingredients

    International Nuclear Information System (INIS)

    Haykiri-Acma, H.; Yaman, S.; Kucukbayrak, S.

    2011-01-01

    This study was performed to investigate the burning characteristics of isolated fractions of a biomass species. So, woody shells of hazelnut were chemically treated to obtain the fractions of extractives-free bulk, lignin, and holocellulose. Physical characterization of these fractions were determined by SEM technique, and the burning runs were carried out from ambient to 900 o C applying thermal analysis techniques of TGA, DTG, DTA, and DSC. The non-isothermal model of Borchardt-Daniels was used to DSC data to find the kinetic parameters. Burning properties of each fraction were compared to those of the raw material to describe their effects on burning, and to interpret the synergistic interactions between the fractions in the raw material. It was found that each of the fractions has its own characteristic physical and thermal features. Some of the characteristic points on the thermograms of the fractions could be followed definitely on those of the raw material, while some of them seriously shifted to other temperatures or disappeared as a result of the co-existence of the ingredients. Also, it is concluded that the presence of hemicellulosics and celluloses makes the burning of lignin easier in the raw material compared to the isolated lignin. The activation energies can be arranged in the order of holocellulose < extractives-free biomass < raw material < lignin.

  6. Reactivity of polychlorinated biphenyls in nucleophilic and electrophilic substitutions

    Energy Technology Data Exchange (ETDEWEB)

    Gorbunova, Tatyana I., E-mail: gorbunova@ios.uran.ru [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation); Subbotina, Julia O. [Ural Federal University named after the first President of Russia B.N. Yeltsin, Mira St., 19, Ekaterinburg 620002 (Russian Federation); Saloutin, Viktor I.; Chupakhin, Oleg N. [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation)

    2014-08-15

    Graphical abstract: - Highlights: • Quantum chemical calculations were carried out for PCBs congeners. • Calculated descriptors were used to explain the PCBs reactivity in S{sub N} and S{sub E} substitutions. • Obtained data were used to estimate the PCBs reactivity in the S{sub N} reactions. • Calculated descriptors were insufficient to explain the PCBs reactivity in the S{sub E} reactions. • New neutralization methods of the large-capacity PCBs were discussed. - Abstract: To explain the chemical reactivity of polychlorinated biphenyls in nucleophilic (S{sub N}) and electrophilic (S{sub E}) substitutions, quantum chemical calculations were carried out at the B3LYP/6-31G(d) level of the Density Functional Theory in gas phase. Carbon atomic charges in biphenyl structure were calculated by the Atoms-in-Molecules method. Chemical hardness and global electrophilicity index parameters were determined for congeners. A comparison of calculated descriptors and experimental data for congener reactivity in the S{sub N} and S{sub E} reactions was made. It is shown that interactions in the S{sub N} mechanism are reactions of the hard acid–hard base type, these are the most effective in case of highly chlorinated substrates. To explain the congener reactivity in the S{sub E} reactions, correct descriptors were not established. The obtained results can be used to carry out chemical transformations of the polychlorinated biphenyls in order to prepare them for microbiological destruction or preservation.

  7. Two modelling approaches to water-quality simulation in a flooded iron-ore mine (Saizerais, Lorraine, France): a semi-distributed chemical reactor model and a physically based distributed reactive transport pipe network model.

    Science.gov (United States)

    Hamm, V; Collon-Drouaillet, P; Fabriol, R

    2008-02-19

    The flooding of abandoned mines in the Lorraine Iron Basin (LIB) over the past 25 years has degraded the quality of the groundwater tapped for drinking water. High concentrations of dissolved sulphate have made the water unsuitable for human consumption. This problematic issue has led to the development of numerical tools to support water-resource management in mining contexts. Here we examine two modelling approaches using different numerical tools that we tested on the Saizerais flooded iron-ore mine (Lorraine, France). A first approach considers the Saizerais Mine as a network of two chemical reactors (NCR). The second approach is based on a physically distributed pipe network model (PNM) built with EPANET 2 software. This approach considers the mine as a network of pipes defined by their geometric and chemical parameters. Each reactor in the NCR model includes a detailed chemical model built to simulate quality evolution in the flooded mine water. However, in order to obtain a robust PNM, we simplified the detailed chemical model into a specific sulphate dissolution-precipitation model that is included as sulphate source/sink in both a NCR model and a pipe network model. Both the NCR model and the PNM, based on different numerical techniques, give good post-calibration agreement between the simulated and measured sulphate concentrations in the drinking-water well and overflow drift. The NCR model incorporating the detailed chemical model is useful when a detailed chemical behaviour at the overflow is needed. The PNM incorporating the simplified sulphate dissolution-precipitation model provides better information of the physics controlling the effect of flow and low flow zones, and the time of solid sulphate removal whereas the NCR model will underestimate clean-up time due to the complete mixing assumption. In conclusion, the detailed NCR model will give a first assessment of chemical processes at overflow, and in a second time, the PNM model will provide more

  8. Enhancing Reactivity in Structural Energetic Materials

    Science.gov (United States)

    Glumac, Nick

    2017-06-01

    In many structural energetic materials, only a small fraction of the metal oxidizes, and yet this provides a significant boost in the overall energy release of the system. Different methodologies to enhance this reactivity include alloying and geometric modifications of microstructure of the reactive material (RM). In this presentation, we present the results of several years of systematic study of both chemical (alloy) and mechanical (geometry) effects on reactivity for systems with typical charge to case mass ratios. Alloys of aluminum with magnesium and lithium are considered, as these are common alloys in aerospace applications. In terms of geometric modifications, we consider surface texturing, inclusion of dense additives, and inclusion of voids. In all modifications, a measurable influence on output is observed, and this influence is related to the fragment size distribution measured from the observed residue. Support from DTRA is gratefully acknowledged.

  9. Reactive power compensator

    Science.gov (United States)

    El-Sharkawi, Mohamed A.; Venkata, Subrahmanyam S.; Chen, Mingliang; Andexler, George; Huang, Tony

    1992-01-01

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation.

  10. Reactive power compensator

    Energy Technology Data Exchange (ETDEWEB)

    El-Sharkawi, Mohamed A. (Renton, WA); Venkata, Subrahmanyam S. (Woodinville, WA); Chen, Mingliang (Kirkland, WA); Andexler, George (Everett, WA); Huang, Tony (Seattle, WA)

    1992-01-01

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation.

  11. Long-term effects of alum-treated litter, untreated litter and NH4NO3 application on phosphorus speciation, distribution and reactivity in soils using K-edge XANES and chemical fractionation

    Science.gov (United States)

    Whereas soil test information on the fertility and chemistry of soils has been important to elaborate safe and sound agricultural practices, microscopic information can give a whole extra dimension to understand the chemical processes occurring in soils. The objective of this study was to evaluate t...

  12. Digital reactivity meter

    International Nuclear Information System (INIS)

    Copie, M.; Valantic, B.

    1978-01-01

    Digital reactivity meters (DRM) are mostly used as measuring instruments, e.g. for calibration of control rods, and there are only a few cases of their incorporation into the control systems of the reactors. To move in this direction there is more development work needed. First of all, fast algorithms are needed for inverse kinetics equations to relieve the computer for more important tasks of reactor model solving in real time. The next problem, currently under investigation, is the incorporation of the reactor thermal-hydraulic model into the DRM so that it can be used in the power range. Such an extension of DHM allows presentation not only of the instantaneous reactivity of the system, but also the inserted reactivity can be estimated from the temperature reactivity feed-backs. One of the applications of this concept is the anomalous digital reactivity monitor (ADRN) as part of the reactor protection system. As a solution of the first problem, a fast algorithm for solving the inverse kinetics equations has been implemented in the off-line program RODCAL on CDC 1700 computer and tested for its accuracy by performing different control rod calibrations on the reactor TRIGA

  13. Chemical composition and heterogeneous reactivity of soot generated in the combustion of diesel and GTL (Gas-to-Liquid) fuels and amorphous carbon Pr