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Sample records for chemical kinetic oxidation

  1. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M

    2006-11-10

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

  2. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO2 production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  3. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-20

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  4. Chemical kinetics

    International Nuclear Information System (INIS)

    This book gives descriptions of chemical kinetics. It starts summary of chemical kinetics and reaction mechanism, and explains basic velocity law, experiment method for determination of reaction velocity, temperature dependence of reaction velocity, theory of reaction velocity, theory on reaction of unimolecular, process of atom and free radical, reaction in solution, catalysis, photochemical reaction, such as experiment and photochemical law and rapid reaction like flame, beam of molecule and shock tube.

  5. Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

    The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

  6. Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate.

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2009-07-21

    Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.

  7. Chemical kinetic study of the oxidation of toluene and related cyclic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mehl, M; Frassoldati, A; Fietzek, R; Faravelli, T; Pitz, W; Ranzi, E

    2009-10-01

    Chemical kinetic models of hydrocarbons found in transportation fuels are needed to simulate combustion in engines and to improve engine performance. The study of the combustion of practical fuels, however, has to deal with their complex compositions, which generally involve hundreds of compounds. To provide a simplified approach for practical fuels, surrogate fuels including few relevant components are used instead of including all components. Among those components, toluene, the simplest of the alkyl benzenes, is one of the most prevalent aromatic compounds in gasoline in the U.S. (up to 30%) and is a promising candidate for formulating gasoline surrogates. Unfortunately, even though the combustion of aromatics been studied for a long time, the oxidation processes relevant to this class of compounds are still matter of discussion. In this work, the combustion of toluene is systematically approached through the analysis of the kinetics of some important intermediates contained in its kinetic submechanism. After discussing the combustion chemistry of cyclopentadiene, benzene, phenol and, finally, of toluene, the model is validated against literature experimental data over a wide range of operating conditions.

  8. Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

    Institute of Scientific and Technical Information of China (English)

    Bambang VERIANSYAH; Jae-Duck KIM; Youn-Woo LEE

    2006-01-01

    Supercritical water oxidation (SCWO) has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate(DMMP), which is similar to the nerve agent VX and GB(Sarin) in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633 ℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon (TOC) on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

  9. Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

    Science.gov (United States)

    Kwon, Soon Gu; Hyeon, Taeghwan

    2008-12-01

    Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized

  10. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  11. Chemical kinetic study of the oxidation of a biodiesel-bioethanol surrogate fuel: methyl octanoate-ethanol mixtures.

    Science.gov (United States)

    Togbé, C; May-Carle, J-B; Dayma, G; Dagaut, P

    2010-03-25

    There is a growing interest for using bioethanol-biodiesel fuel blends in diesel engines but no kinetic data and model for their combustion were available. Therefore, the kinetics of oxidation of a biodiesel-bioethanol surrogate fuel (methyl octanoate-ethanol) was studied experimentally in a jet-stirred reactor at 10 atm and constant residence time, over the temperature range 560-1160 K, and for several equivalence ratios (0.5-2). Concentration profiles of reactants, stable intermediates, and final products were obtained by probe sampling followed by online FTIR, and off-line gas chromatography analyses. The oxidation of this fuel in these conditions was modeled using a detailed chemical kinetic reaction mechanism consisting of 4592 reversible reactions and 1087 species. The proposed kinetic reaction mechanism yielded a good representation of the kinetics of oxidation of this biodiesel-bioethanol surrogate under the JSR conditions. The modeling was used to delineate the reactions triggering the low-temperature oxidation of ethanol important for diesel engine applications. PMID:20235606

  12. Iron oxidation kinetics for H-2 and CO production via chemical looping

    Energy Technology Data Exchange (ETDEWEB)

    Stehle, RC; Bobek, MM; Hahn, DW

    2015-01-30

    Solar driven production of fuels by means of an intermediate reactive metal for species splitting has provided a practical and potentially efficient pathway for disassociating molecules at significantly lower thermal energies. The fuels of interest are of or derive from the separation of oxygen from H2O and CO2 to form hydrogen and carbon monoxide, respectively. The following study focuses on iron oxidation through water and CO2 splitting to explore the fundamental reaction kinetics and kinetic rates that are relevant to these processes. In order to properly characterize the reactive metal potential and to optimize a scaled-up solar reactor system, a monolith-based laboratory reactor was implemented to investigate reaction temperatures over a range from 990 to 1400 K. The presence of a single, solid monolith as a reacting surface allowed for a limitation in mass transport effects in order to monitor kinetically driven reaction steps. The formation of oxide layers on the iron monoliths followed Cabrera-Mott models for oxidation of metals with kinetic rates being measured using real-time mass spectrometry to calculate kinetic constants and estimate oxide layer thicknesses. Activation energies of 47.3 kJ/mol and 32.8 kJ/mol were found for water-splitting and CO2 splitting, respectively, and the conclusions of the independent oxidation reactions where applied to experimental results for syngas (H-2-CO) production to explore ideal process characteristics. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  13. Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

    OpenAIRE

    Junfeng Yang; Valeri I. Golovitchev; Pau Redón Lurbe; J. Javier López Sánchez

    2012-01-01

    The use of biodiesel in conventional diesel engines results in increased NOx emissions; this presents a barrier to the widespread use of biodiesel. The origins of this phenomenon were investigated using the chemical kinetics simulation tool: CHEMKIN-2 and the CFD KIVA3V code, which was modified to account for the physical properties of biodiesel and to incorporate semidetailed mechanisms for its combustion and the formation of emissions. Parametric ϕ-T maps and 3D engine simulations were used...

  14. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    A. Heck

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could h

  15. Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

    Directory of Open Access Journals (Sweden)

    Junfeng Yang

    2012-01-01

    Full Text Available The use of biodiesel in conventional diesel engines results in increased NOx emissions; this presents a barrier to the widespread use of biodiesel. The origins of this phenomenon were investigated using the chemical kinetics simulation tool: CHEMKIN-2 and the CFD KIVA3V code, which was modified to account for the physical properties of biodiesel and to incorporate semidetailed mechanisms for its combustion and the formation of emissions. Parametric ϕ-T maps and 3D engine simulations were used to assess the impact of using oxygen-containing fuels on the rate of NO formation. It was found that using oxygen-containing fuels allows more O2 molecules to present in the engine cylinder during the combustion of biodiesel, and this may be the cause of the observed increase in NO emissions.

  16. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler

    Directory of Open Access Journals (Sweden)

    Jun-Xia Zhang

    2016-03-01

    Full Text Available Because the air-staged combustion technology is one of the key technologies with low investment running costs and high emission reduction efficiency for the pulverized boiler, it is important to reveal the chemical reaction kinetics mechanism for developing various technologies of nitrogen oxide reduction emissions. At the present work, a three-dimensional mesh model of the large-scale four corner tangentially fired boiler furnace is established with the GAMBIT pre-processing of the FLUENT software. The partial turbulent premixed and diffusion flame was simulated for the air-staged combustion processing. Parameters distributions for the air-staged and no the air-staged were obtained, including in-furnace flow field, temperature field and nitrogen oxide concentration field. The results show that the air-staged has more regular velocity field, higher velocity of flue gas, higher turbulence intensity and more uniform temperature of flue gas. In addition, a lower negative pressure zone and lower O2 concentration zone is formed in the main combustion zone, which is conducive to the NO of fuel type reduced to N2, enhanced the effect of NOx reduction. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th November 2015; Revised: 14th January 2016; Accepted: 16th January 2016  How to Cite: Zhang, J.X., Zhang, J.F. (2016. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 100-108. (doi:10.9767/bcrec.11.1.431.100-108 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.431.100-108

  17. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  18. LLNL Chemical Kinetics Modeling Group

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  19. A comprehensive experimental and detailed chemical kinetic modelling study of 2,5-dimethylfuran pyrolysis and oxidation.

    Science.gov (United States)

    Somers, Kieran P; Simmie, John M; Gillespie, Fiona; Conroy, Christine; Black, Gráinne; Metcalfe, Wayne K; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Dagaut, Philippe; Togbé, Casimir; Yasunaga, Kenji; Fernandes, Ravi X; Lee, Changyoul; Tripathi, Rupali; Curran, Henry J

    2013-11-01

    The pyrolytic and oxidative behaviour of the biofuel 2,5-dimethylfuran (25DMF) has been studied in a range of experimental facilities in order to investigate the relatively unexplored combustion chemistry of the title species and to provide combustor relevant experimental data. The pyrolysis of 25DMF has been re-investigated in a shock tube using the single-pulse method for mixtures of 3% 25DMF in argon, at temperatures from 1200-1350 K, pressures from 2-2.5 atm and residence times of approximately 2 ms. Ignition delay times for mixtures of 0.75% 25DMF in argon have been measured at atmospheric pressure, temperatures of 1350-1800 K at equivalence ratios (ϕ) of 0.5, 1.0 and 2.0 along with auto-ignition measurements for stoichiometric fuel in air mixtures of 25DMF at 20 and 80 bar, from 820-1210 K. This is supplemented with an oxidative speciation study of 25DMF in a jet-stirred reactor (JSR) from 770-1220 K, at 10.0 atm, residence times of 0.7 s and at ϕ = 0.5, 1.0 and 2.0. Laminar burning velocities for 25DMF-air mixtures have been measured using the heat-flux method at unburnt gas temperatures of 298 and 358 K, at atmospheric pressure from ϕ = 0.6-1.6. These laminar burning velocity measurements highlight inconsistencies in the current literature data and provide a validation target for kinetic mechanisms. A detailed chemical kinetic mechanism containing 2768 reactions and 545 species has been simultaneously developed to describe the combustion of 25DMF under the experimental conditions described above. Numerical modelling results based on the mechanism can accurately reproduce the majority of experimental data. At high temperatures, a hydrogen atom transfer reaction is found to be the dominant unimolecular decomposition pathway of 25DMF. The reactions of hydrogen atom with the fuel are also found to be important in predicting pyrolysis and ignition delay time experiments. Numerous proposals are made on the mechanism and kinetics of the previously unexplored

  20. Chemical oxidation of sulfadiazine by the Fenton process: kinetics, pathways, toxicity evaluation.

    Science.gov (United States)

    Yang, Ji-Feng; Zhou, Shi-Biao; Xiao, An-Guo; Li, Wen-Jun; Ying, Guang-Guo

    2014-01-01

    This paper investigated sulfadiazine oxidation by the Fenton process under various reaction conditions. The reaction conditions tested in the experiments included the initial pH value of reaction solutions, and the dosages of ferrous ions and hydrogen peroxide. Under the reaction conditions with pH 3, 0.25 mM of ferrous ion and 2 mM of hydrogen peroxide, a removal efficiency of nearly 100% was achieved for sulfadiazine. A series of intermediate products including 4-OH-sulfadiazine/or 5-OH-sulfadiazine, 2-aminopyrimidine, sulfanilamide, formic acid, and oxalic acid were identified. Based on these products, the possible oxidation pathway of sulfadiazine by Fenton's reagent was proposed. The toxicity evaluation of reaction solutions showed increased antimicrobial effects following the Fenton oxidation process. The results from this study suggest that the Fenton oxidation process could remove sulfadiazine, but also increase solution toxicity due to the presence of more toxic products. PMID:25310806

  1. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel. PMID:18541367

  2. Oxidative desulfurization: Kinetic modelling

    International Nuclear Information System (INIS)

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H2O2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel

  3. Chemical Speciation and Oxidation Kinetics of Iron and Sulfur in Subseafloor Basement Fluids on the Juan de Fuca Ridge Flanks

    Science.gov (United States)

    Glazer, B. T.; Matzinger, M.; Cowen, J. P.

    2011-12-01

    Redox reactive chemical species circulate throughout the upper oceanic crust, and are involved in a variety of abiotic and microbially-mediated reactions. Through exchange with bottom seawater, fluids circulating in the upper basement have the potential to influence scales ranging from global-scale biogeochemical cycling to micro-scale microbe-mineral interactions. Understanding fundamental chemical speciation, distribution, bioavailability, and rates of transformations for key chemical redox species is crucial to understanding processes in the subsurface. In-situ electrochemical analyses were conducted in real-time at CORK (Circulation Obviation Retrofit Kit) observatories affixed to Integrated Ocean Drilling Program (IODP) boreholes in Cascadia Basin on the Juan de Fuca Ridge Flanks. Voltammetric electrodes were mounted into a flow cell to allow for simultaneous detection of redox species (O2, H_{2}O2, HS^{-}, S(0), Sx^{2-}, S2O_{3}2-, S_{4}O6^{2-}, Fe(II), Fe(III), FeS$_{(aq)}) concurrent to sample filtering or fluid collection. During real-time voltammetric scanning, qualitative assessment of the integrity of fluids delivered through the Fluid Delivery Lines could be made, allowing for comparisons between CORK sites and various sampling strategies. Newly installed CORKs at IODP sites 1362A and 1362B are producing the highest-integrity basement fluids collected to date, deplete in oxygen (1uM). Here, we report results of in situ electrochemical measurements at multiple borehole observatories, including the newly installed 1362A & 1362B sites, and present results of speciation analyses and kinetics of oxidation for iron and sulfur in discrete samples.

  4. Chemical Kinetics on Extrasolar Planets

    CERN Document Server

    Moses, Julianne I

    2013-01-01

    Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures < ~2000 K, and in the uppermost atmosphere at any temperature, chemical kinetics matters. The two key mechanisms by which kinetic processes drive an exoplanet atmosphere out of equilibrium are photochemistry and transport-induced quenching. We review these disequilibrium processes in detail, discuss observational consequences, and examine some of the current evidence for kinetic processes on extrasolar planets.

  5. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  6. Computer Simulation in Chemical Kinetics

    Science.gov (United States)

    Anderson, Jay Martin

    1976-01-01

    Discusses the use of the System Dynamics technique in simulating a chemical reaction for kinetic analysis. Also discusses the use of simulation modelling in biology, ecology, and the social sciences, where experimentation may be impractical or impossible. (MLH)

  7. Selected readings in chemical kinetics

    CERN Document Server

    Back, Margaret H

    2013-01-01

    Selected Readings in Chemical Kinetics covers excerpts from 12 papers in the field of general and gas-phase kinetics. The book discusses papers on the laws of connexion between the conditions of a chemical change and its amount; on the reaction velocity of the inversion of the cane sugar by acids; and the calculation in absolute measure of velocity constants and equilibrium constants in gaseous systems. The text then tackles papers on simple gas reactions; on the absolute rate of reactions in condensed phases; on the radiation theory of chemical action; and on the theory of unimolecular reacti

  8. Quantum chemical and kinetic study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals. II. The H abstraction pathway

    OpenAIRE

    Shiroudi, Abolfazl; DELEUZE, Michael

    2014-01-01

    Reaction mechanisms for the initial stages of naphthalene oxidation at high temperatures (T> 600 K) have been studied theoretically using density functional theory along with various exchange-correlation functionals, as well as the benchmark CBS-QB3 quantum chemical approach. These stages correspond to the removal of hydrogen atoms by hydroxyl radical and the formation thereby of 1- and 2-naphthyl radicals. The oxidation mechanisms of naphthalene by OH radicals under inert (He) conditions and...

  9. Biochemical ripening of dredged sediments. Part 1. Kinetics of biological organic matter mineralization and chemical sulfur oxidation

    NARCIS (Netherlands)

    Vermeulen, J.; Gool, M.P.M. van; Dorleijn, A.S.; Joziasse, J.; Bruning, H.; Rulkens, W.H.; Grotenhuis, J.T.C.

    2007-01-01

    After dredged sediments have settled in a temporary upland disposal site, ripening starts, which turns waterlogged sediment into aerated soil. Aerobic biological mineralization of organic matter (OM) and chemical oxidation of reduced sulfur compounds are the major biochemical ripening processes. Qua

  10. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  11. Chemical kinetics and combustion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  12. Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP: linking condensation, evaporation and chemical reactions of organics, oxidants and water

    Directory of Open Access Journals (Sweden)

    M. Shiraiwa

    2011-12-01

    Full Text Available We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007, and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.

    In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the

  13. Microreactor for fast chemical kinetics

    CERN Document Server

    Baroud, C N; Menetrier, L; Tabeling, P; Baroud, Charles N.; Okkels, Fridolin; Menetrier, Laure; Tabeling, Patrick

    2003-01-01

    The chemical reaction process in a T-shaped microchannel is studied experimentally through the reaction of Ca++ with a fluorescent tracer, Calcium-green. For thin channels (10 um), diffusion of species is found to behave in a way independent of the thickness direction. In such a situation, simulations of a two-dimensional reaction-diffusion model agree remarkably well with the experimental measurements. The comparison of experiments and simulations is used to measure the chemical kinetic constant, which we find to be k=3.2 x 10^5 dm^3/(mol s). Applications of the analysis to faster reactions and to micro-titration are also discussed.

  14. Oxidation kinetics of aluminum diboride

    International Nuclear Information System (INIS)

    The oxidation characteristics of aluminum diboride (AlB2) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB2 in the onset of oxidation and final conversion fraction, with AlB2 beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB2 and Al+2B in both air and oxygen. AlB2 exhibited O2-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O2 than in air. Differences in the composition and morphology between oxidized Al+2B and AlB2 suggested that Al2O3–B2O3 interactions slowed Al+2B oxidation by converting Al2O3 on aluminum particles into a Al4B2O9 shell, while the same Al4B2O9 developed a needle-like morphology in AlB2 that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB2, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB2 in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time–temperature plots, (b) conversion as a function of time, (c) Arrhenius plots used to calculate activation energies, and (d) activation energy

  15. Quantum logics and chemical kinetics

    Science.gov (United States)

    Ivanov, C. I.

    1981-06-01

    A statistical theory of chemical kinetics is presented based on the quantum logical concept of chemical observables. The apparatus of Boolean algebra B is applied for the construction of appropriate composition polynomials referring to any stipulated arrangement of the atomic constituents. A physically motivated probability measure μ( F) is introduced on the field B of chemical observables, which considers the occurrence of the yes response of a given F ɛ B. The equations for the time evolution of the species density operators and the master equations for the corresponding number densities are derived. The general treatment is applied to a superposition of elementary substitution reactions (AB) α + C ⇄ (AC) β + B. The expressions for the reaction rate coefficients are established.

  16. Oxidation kinetics of aluminum diboride

    Science.gov (United States)

    Whittaker, Michael L.; Sohn, H. Y.; Cutler, Raymond A.

    2013-11-01

    The oxidation characteristics of aluminum diboride (AlB2) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB2 in the onset of oxidation and final conversion fraction, with AlB2 beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB2 and Al+2B in both air and oxygen. AlB2 exhibited O2-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O2 than in air. Differences in the composition and morphology between oxidized Al+2B and AlB2 suggested that Al2O3-B2O3 interactions slowed Al+2B oxidation by converting Al2O3 on aluminum particles into a Al4B2O9 shell, while the same Al4B2O9 developed a needle-like morphology in AlB2 that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB2, but both appear to be resistant to oxidation in cool, dry environments.

  17. Chemical kinetic study of a novel lignocellulosic biofuel: Di-n-butyl ether oxidation in a laminar flow reactor and flames

    KAUST Repository

    Cai, Liming

    2014-03-01

    The combustion characteristics of promising alternative fuels have been studied extensively in the recent years. Nevertheless, the pyrolysis and oxidation kinetics for many oxygenated fuels are not well characterized compared to those of hydrocarbons. In the present investigation, the first chemical kinetic study of a long-chain linear symmetric ether, di-n-butyl ether (DBE), is presented and a detailed reaction model is developed. DBE has been identified recently as a candidate biofuel produced from lignocellulosic biomass. The model includes both high temperature and low temperature reaction pathways with reaction rates generated using appropriate rate rules. In addition, experimental studies on fundamental combustion characteristics, such as ignition delay times and laminar flame speeds have been performed. A laminar flow reactor was used to determine the ignition delay times of lean and stoichiometric DBE/air mixtures. The laminar flame speeds of DBE/air mixtures were measured in the stagnation flame configuration for a wide rage of equivalence ratios at atmospheric pressure and an unburned reactant temperature of 373. K. All experimental data were modeled using the present kinetic model. The agreement between measured and computed results is satisfactory, and the model was used to elucidate the oxidation pathways of DBE. The dissociation of keto-hydroperoxides, leading to radical chain branching was found to dominate the ignition of DBE in the low temperature regime. The results of the present numerical and experimental study of the oxidation of di-n-butyl ether provide a good basis for further investigation of long chain linear and branched ethers. © 2013 The Combustion Institute.

  18. Comprehensive chemical kinetic modeling of the oxidation of C8 and larger n-alkanes and 2-methylalkanes

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M; Togbe, C; Dagaut, P; Wang, H; Oehlschlaeger, M; NIemann, U; Seshadri, K; Veloo, P S; Ji, C; Egolfopoulos, F; Lu, T

    2011-03-16

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C{sub 8} to C{sub 20}. The mechanism also includes an updated version of our previously published C{sub 8} to C{sub 16} n-alkanes model. The complete detailed mechanism contains approximately 7,200 species 31,400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and nonpremixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.

  19. Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP: linking condensation, evaporation and chemical reactions of organics, oxidants and water

    Directory of Open Access Journals (Sweden)

    M. Shiraiwa

    2012-03-01

    Full Text Available We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007, and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.

    In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity (Winkler et al., 2006. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative

  20. Kinetics of iron oxidation in silicate melts

    International Nuclear Information System (INIS)

    High-temperature XANES experiments at the Fe K-edge have been used to study the kinetics of iron oxidation in a supercooled melt of Fe-bearing pyroxene composition. These experiments, made just above the glass transition between 600 and 700 deg C, show that variations in relative abundances of ferric and ferrous iron can be determined in situ at such temperatures. The kinetics of iron oxidation do not vary much with temperature down to the glass transition. This suggests that rate-limiting factor in this process is not oxygen diffusion, which is coupled to relaxation of the silicate network, but diffusion of network modifying cations along with a counter flux of electrons. To give a firmer basis to redox determinations made from XANES spectroscopy, the redox state of a series of a samples was first determined from wet chemical, Moessbauer spectroscopy and electron microprobe analyses. (authors)

  1. Copolymerization Kinetics of Ethylene Oxide and Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    尹红; 陈志荣

    2002-01-01

    The copolymerization kinetics of ethylene oxide and propylene oxide in an atomizing-circulation reactorunder semi-continuous operation is studied which is of great importance for molecular designation. The kineticparameters are obtained by numerical optimization of the kinetic model.

  2. Enhancing Thai Students' Learning of Chemical Kinetics

    Science.gov (United States)

    Chairam, Sanoe; Somsook, Ekasith; Coll, Richard K.

    2009-01-01

    Chemical kinetics is an extremely important concept for introductory chemistry courses. The literature suggests that instruction in chemical kinetics is often teacher-dominated at both the secondary school and tertiary levels, and this is the case in Thailand--the educational context for this inquiry. The work reported here seeks to shift students…

  3. Modeling of oxide fuel dissolution kinetics

    International Nuclear Information System (INIS)

    Since the 1970's, CEA [1] has carried on research on the head-end steps of PWR and FBR-Na spent fuel reprocessing and more specifically the fuel dissolution step. It consists to convert the irradiated solid oxide into a nitrate solution by a hot nitric acid attack. As complementary approach of the usual experiments performed in specific hot cells facilities, the issue of modeling the kinetics of the oxide fuel dissolution has been developed. In a first phase, numerous experimental results have allowed a simple kinetic law to be established (in which the oxide dissolution rate is normalized to the surface unit), based on the theoretical concepts of heterogeneous kinetics and on some chemical considerations in an extended temperature range (70 deg. C to boiling point), acidity (2-9 M), and uranyl concentration (0-250 g/L), defining the effects of these three main parameters as in the following equation: ν(mg.cm-2.h-1) = kapp ([HNO3] + 2[UO2(NO3)2])aexp(-Eapp/RT). The same corresponding significant factors kapp, a, Eapp of this law were determined for various tests involving either single or mixed oxide or irradiated or non-irradiated fuel. It appears that the kinetic control of the heterogeneous reactions recovers an important complexity: physical phenomena of transfer at the interface and autocatalytic chemical phenomena by nitrogen compounds. Therefore, the macrostructure of the fuel has to be taken into account like the cracks networks [2] caused by the irradiation of the fuel in its cladding either the dislodged fuel powder fraction resulting from the cladding shearing. Some mathematical development is expected to consider hydrodynamics effects in the model. Furthermore, different burn-up spent fuel kinetic behaviors have indicated that the microstructure is another influent factor and demonstrate how important is to understand irradiation effects on the oxide from the crystal to the grain scale. In the same topics, plutonium-uranium oxide fuels have been

  4. Research in chemical kinetics, v.2

    CERN Document Server

    1994-01-01

    This is the second volume in a new series, which aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the c

  5. Research in Chemical Kinetics, v.3

    CERN Document Server

    2012-01-01

    This series of volumes aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the contributions and their top

  6. Chemical Kinetic Modeling of Advanced Transportation Fuels

    Energy Technology Data Exchange (ETDEWEB)

    PItz, W J; Westbrook, C K; Herbinet, O

    2009-01-20

    Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.

  7. Chemical kinetic modeling of H{sub 2} applications

    Energy Technology Data Exchange (ETDEWEB)

    Marinov, N.M.; Westbrook, C.K.; Cloutman, L.D. [Lawrence Livermore National Lab., CA (United States)] [and others

    1995-09-01

    Work being carried out at LLNL has concentrated on studies of the role of chemical kinetics in a variety of problems related to hydrogen combustion in practical combustion systems, with an emphasis on vehicle propulsion. Use of hydrogen offers significant advantages over fossil fuels, and computer modeling provides advantages when used in concert with experimental studies. Many numerical {open_quotes}experiments{close_quotes} can be carried out quickly and efficiently, reducing the cost and time of system development, and many new and speculative concepts can be screened to identify those with sufficient promise to pursue experimentally. This project uses chemical kinetic and fluid dynamic computational modeling to examine the combustion characteristics of systems burning hydrogen, either as the only fuel or mixed with natural gas. Oxidation kinetics are combined with pollutant formation kinetics, including formation of oxides of nitrogen but also including air toxics in natural gas combustion. We have refined many of the elementary kinetic reaction steps in the detailed reaction mechanism for hydrogen oxidation. To extend the model to pressures characteristic of internal combustion engines, it was necessary to apply theoretical pressure falloff formalisms for several key steps in the reaction mechanism. We have continued development of simplified reaction mechanisms for hydrogen oxidation, we have implemented those mechanisms into multidimensional computational fluid dynamics models, and we have used models of chemistry and fluid dynamics to address selected application problems. At the present time, we are using computed high pressure flame, and auto-ignition data to further refine the simplified kinetics models that are then to be used in multidimensional fluid mechanics models. Detailed kinetics studies have investigated hydrogen flames and ignition of hydrogen behind shock waves, intended to refine the detailed reactions mechanisms.

  8. Chemical Kinetic Modeling of 2-Methylhexane Combustion

    KAUST Repository

    Mohamed, Samah Y.

    2015-03-30

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important for investigating the combustion behavior of diesel, gasoline, and aviation fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values and rate rules. These update provides a better agreement with rapid compression machine measurements of ignition delay time, while also strengthening the fundamental basis of the model.

  9. Air corona discharge chemical kinetics

    International Nuclear Information System (INIS)

    We have theoretically studied the initial chemical processing steps which occur in pulseless, negative, dc corona discharges in flowing air. A rate equation model is used because these discharges consist of a very small ionization zone near the pin with most of the pin-plane gap filled by a drift zone where both the electric field and the electron density are relatively uniform. The primary activated species are N2(A),O and O2(a1Δ). The predicted activated species density due to one discharge is 100 ppm per ms . mA cm2 assuming E/n=60 Td. In pure, dry air the final product due to these activated species is primarily O3. The NO /sub x/ production is about 0.5 ppm per mA. In moist air there is an additional production of about 1.5 ppm per mA of HO /sub x/ species. The predicted ozone formation reactions will be ''intercepted'' when impurities are present in the air. Impurities present at densities below about 0.1% will react primarily with the activated species rather than with electrons. Hence the predicted activated species density provides an estimate of the potential chemical processing performance of the discharge

  10. Inflation Rates, Car Devaluation, and Chemical Kinetics

    Science.gov (United States)

    Pogliani, Lionello; Berberan-Santos, Màrio N.

    1996-10-01

    The inflation rate problem of a modern economy shows quite interesting similarities with chemical kinetics and especially with first-order chemical reactions. In fact, capital devaluation during periods of rather low inflation rates or inflation measured over short periods shows a dynamics formally similar to that followed by first-order chemical reactions and they can thus be treated by the aid of the same mathematical formalism. Deviations from this similarity occurs for higher inflation rates. The dynamics of price devaluation for two different types of car, a compact car and a luxury car, has been followed for seven years long and it has been established that car devaluation is a process that is formally similar to a zeroth-order chemical kinetic process disregarding the type of car, if car devaluation is much faster than money devaluation. In fact, expensive cars devaluate with a faster rate than inexpensive cars.

  11. Fundamental aspects of plasma chemical physics kinetics

    CERN Document Server

    Capitelli, Mario; Colonna, Gianpiero; Esposito, Fabrizio; Gorse, Claudine; Hassouni, Khaled; Laricchiuta, Annarita; Longo, Savino

    2016-01-01

    Describing non-equilibrium "cold" plasmas through a chemical physics approach, this book uses the state-to-state plasma kinetics, which considers each internal state as a new species with its own cross sections. Extended atomic and molecular master equations are coupled with Boltzmann and Monte Carlo methods to solve the electron energy distribution function. Selected examples in different applied fields, such as microelectronics, fusion, and aerospace, are presented and discussed including the self-consistent kinetics in RF parallel plate reactors, the optimization of negative ion sources and the expansion of high enthalpy flows through nozzles of different geometries. The book will cover the main aspects of the state-to-state kinetic approach for the description of nonequilibrium cold plasmas, illustrating the more recent achievements in the development of kinetic models including the self-consistent coupling of master equations and Boltzmann equation for electron dynamics. To give a complete portrayal, the...

  12. CHEMSIMUL: A simulator for chemical kinetics

    DEFF Research Database (Denmark)

    Kirkegaard, P.; Bjergbakke, E.

    1999-01-01

    CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving theresulting coupled nonlinear ordinary...

  13. Chemical Dosing and First-Order Kinetics

    Science.gov (United States)

    Hladky, Paul W.

    2011-01-01

    College students encounter a variety of first-order phenomena in their mathematics and science courses. Introductory chemistry textbooks that discuss first-order processes, usually in conjunction with chemical kinetics or radioactive decay, stop at single, discrete dose events. Although single-dose situations are important, multiple-dose events,…

  14. Probing the chemical steps of nitroalkane oxidation catalyzed by 2-nitropropane dioxygenase with solvent viscosity, pH, and substrate kinetic isotope effects.

    Science.gov (United States)

    Francis, Kevin; Gadda, Giovanni

    2006-11-21

    Among the enzymes that catalyze the oxidative denitrification of nitroalkanes to carbonyl compounds, 2-nitropropane dioxygenase is the only one known to effectively utilize both the neutral and anionic (nitronate) forms of the substrate. A recent study has established that the catalytic pathway is common to both types of substrates, except for the initial removal of a proton from the carbon of the neutral substrates [Francis, K., Russell, B., and Gadda, G. (2005) J. Biol. Chem. 280, 5195-5204]. In the present study, the mechanistic properties of the enzyme have been investigated with solvent viscosity, pH, and kinetic isotope effects. With nitroethane or ethylnitronate, the kcat/Km and kcat values were independent of solvent viscosity, consistent with the substrate and product binding to the enzyme in rapid equilibrium. The abstraction of the proton from the alpha carbon of neutral substrates was investigated by measuring the pH dependence of the D(kcat/KNE) value with 1,1-[2H2]-nitroethane. The formation of the enzyme-bound flavosemiquinone formed during catalysis was examined by determining the pH dependence of the kcat/Km values with ethylnitronate and nitroethane and the inhibition by m-nitrobenzoate. Finally, alpha-secondary kinetic isotope effects with 1-[2H]-ethylnitronate were used to propose a non-oxidative tautomerization pathway, in which the enzyme catalyzes the interconversion of nitroalkanes between their anionic and neutral forms. The data presented suggest that enzymatic turnover of 2-nitropropane dioxygenase with neutral substrates is limited by the cleavage of the substrate CH bond at low pH, whereas that with anionic substrates is limited by the non-oxidative tautomerization of ethylnitroante to nitroethane at high pH. PMID:17105207

  15. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  16. The kinetics of the hydrogen chloride oxidation

    Directory of Open Access Journals (Sweden)

    Gonzalez Martinez Isai

    2013-01-01

    Full Text Available Hydrogen chloride (HCl oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

  17. Effect of inhibitors on macroscopical oxidation kinetics of calcium sulfite

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yi; WANG Li-dong; WANG Xiao-ming; LI Qiang-wei; XU Pei-yao

    2005-01-01

    In the presence of inhibitors, the macroscopical oxidation kinetics of calcium sulfite, the main byproduct in wet limestone scrubbing, was studied for the first time by adding different inhibitors and varying pH, concentration of calcium sulfite, oxygen partial pressure, concentration of inhibitors and temperature. The mathematical model about the general oxidation reaction was established,which was controlled by three steps involving dissolution of calcium sulfite, mass transfer of oxygen and chemical reaction in the solution.It was concluded that the general reaction was controlled by mass transfer of oxygen under uncatalyzed conditions, while it was controlled by dissolution of calcium sulfite after adding three kinds of inhibitors. Thus, the theory was provided for investigating the mechanism and oxidation kinetics of sulfite. The beneficial references were also supplied for design of oxidation technics in the wet limestone scrubbing.

  18. Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.

    2000-07-07

    Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignition in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical combustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant. However, there are many combustion factors that can influence these two major reactions, and these are the features that vary from one practical system to another.

  19. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH...

  20. Acid-catalyzed kinetics of indium tin oxide etching

    International Nuclear Information System (INIS)

    We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species

  1. ENGINEERING BULLETIN: CHEMICAL OXIDATION TREATMENT

    Science.gov (United States)

    Oxidation destroys hazardous contaminants by chemically converting them to nonhazardous or less toxic compounds that are ideally more stable, less mobile, and/or inert. However, under some conditions, other hazardous compounds may be formed. The oxidizing agents most commonly use...

  2. Kinetics and oxidation mechanisms of polycrystaline niobium

    International Nuclear Information System (INIS)

    The oxidation kinetics of annealed niobium was determined by thermogravimetric analysis between 450 and 8000C and for oxygen pressures varying from 20 to 700 mmHg. The oxidation kinetics of cold worked and/or irradiated niobium for temperatures between 500 and 7000C, with oxygen pressures varying from 100 to 300 mmHg. Was also determined. Using X-ray diffraction it was found that the oxide formed in the range of temperature and oxygen pressure considered in this research is γ-Nb2O5. Optical and scanning eletronic microscopy showed that for annealed niobium oxidized under 6000C there was formation of non-uniform oxide layers, containing cracks and pores, presenting very irregular metal/pentoxide interface. The presence of sub-oxide NbOsub(z) platelets was observed in this interface. This sub-oxide platelets where not observed in annealed oxidized niobium samples over 6000C; the oxide layers formed were compact. At 8000C and the beginning at 7000C the interfaces were quite regular. Through microhardness measurements for the metal near the metal/pentoxide interface, the formation of oxygen solid solution was found and the oxygen diffusion coefficient was calculated. The results showed that at 6000C the oxygen diffusion coefficient in cold worked niobium is three times larger than the value obtained for annealed niobium. The results suggest that the reaction between annealed niobium and oxygen undaer 6000C is controlled by reaction in interface where the oxide layers are not compacted, parcially due to Nb sub(z) platelets formation.(Author)

  3. Oxidation and hydrolysis kinetic studies on UN

    Science.gov (United States)

    Rao, G. A. Rama; Mukerjee, S. K.; Vaidya, V. N.; Venugopal, V.; Sood, D. D.

    1991-11-01

    The reaction of oxygen and water vapour with UN microspheres containing 0.78 and 10.9 mol% UO 2 as impurity was studied under non-isothermal heating conditions in a thermobalance under different partial pressures of oxygen, a fixed pressure of water vapour in argon, and in air. Uranium mononitride was ultimately converted to U 3O 8, with the formation of UO 2 and U 2N 3 as intermediates. The end product of pyrohydrolysis was UO 2. The kinetic parameters were evaluated and the mechanism of the reaction was suggested. Different kinetic models were used to explain the oxidation behaviour of UN.

  4. The Kinetics of Oxidation of Molybdenite Concentrate by Water Vapor

    Science.gov (United States)

    Blanco, Edgar; Sohn, Hong Yong; Han, Gilsoo; Hakobyan, Kliment Y.

    2007-08-01

    A thermodynamic and kinetics investigation on the oxidation of MoS2 in molybdenite concentrate to MoO2 by water vapor was carried out as part of new process development. The kinetics of the reaction were determined by measuring the weight change of a sample with time in water vapor at temperatures between 700 °C and 1000 °C. The reaction rate followed the shrinking-unreacted-core model under chemical reaction control, which showed activation energy of 102 kJ/mol. In addition, the behavior of rhenium and selenium in molybdenum concentrate during the process was investigated. While most rhenium remained with the molybdenum dioxide during the water vapor oxidation, almost all selenium was volatilized in agreement with thermodynamic analysis.

  5. Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot

    Directory of Open Access Journals (Sweden)

    R. Prasad

    2011-01-01

    Full Text Available To comply with the stringent emission regulations on soot, diesel vehicles manufacturers more and more commonly use diesel particulate filters (DPF. These systems need to be regenerated periodically by burning soot that has been accumulated during the loading of the DPF. Design of the DPF requires rate of soot oxidation. This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions. Kinetics data were collected in a specially designed mini-semi-batch reactor. Under the high air flow rate assuming pseudo first order reaction the activation energy of soot oxidation was found to be, Ea = 160 kJ/ mol. ©2010 BCREC UNDIP. All rights reserved(Received: 14th June 2010, Revised: 18th July 2010, Accepted: 9th August 2010[How to Cite: R. Prasad, V.R. Bella. (2010. Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot. Bulletin of Chemical Reaction Engineering and Catalysis, 5(2: 95-101. doi:10.9767/bcrec.5.2.796.95-101][DOI:http://dx.doi.org/10.9767/bcrec.5.2.796.95-101 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/796]Cited by in: ACS 1 |

  6. The kinetic of photoreactions in zinc oxide microrods

    Science.gov (United States)

    Fiedot, M.; Rac, O.; Suchorska-Woźniak, P.; Nawrot, W.; Teterycz, H.

    2016-01-01

    Zinc oxide is the oldest sensing material used in the chemical resistive gas sensors which allow to detect many gases, such as carbon oxide, nitrogen oxides and other. This material is also widely used in medicine and daily life as antibacterial agent. For this reason this semiconductor is often synthesized on the polymer substrates such as foils and textiles. In presented results zinc oxide was deposited on the surface of poly(ethylene terephthalate) foil to obtain antibacterial material. As synthesis method chemical bath deposition was chosen. The growth of zinc oxide structures was carried out in water solution of zinc nitrate (V) and hexamethylenetetramine in 90°C during 9 h. Because antibacterial properties of ZnO are strongly depended on photocatalytic and electric properties of this semiconductor impedance spectroscopy measurements were carried out. During the measurements material was tested with and without UV light to determinate the kinetic of photoreactions in zinc oxide. Moreover the composite was analyzed by XRD diffraction and scanning electron microscope. The X-ray analysis indicated that obtained material has the structure of wurtzite which is typical of zinc oxide. SEM images showed that on the PET foil microrods of ZnO were formed. The impedance spectroscopy measurements of ZnO layer showed that in UV light significant changes in the conductivity of the material are observed.

  7. Chemical Kinetic Modeling of Biofuel Combustion

    Science.gov (United States)

    Sarathy, Subram Maniam

    Bioalcohols, such as bioethanol and biobutanol, are suitable replacements for gasoline, while biodiesel can replace petroleum diesel. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This study's contribution is experimentally validated chemical kinetic combustion mechanisms for biobutanol and biodiesel. Fundamental combustion data and chemical kinetic mechanisms are presented and discussed to improve our understanding of biofuel combustion. The net environmental impact of biobutanol (i.e., n-butanol) has not been studied extensively, so this study first assesses the sustainability of n-butanol derived from corn. The results indicate that technical advances in fuel production are required before commercializing biobutanol. The primary contribution of this research is new experimental data and a novel chemical kinetic mechanism for n-butanol combustion. The results indicate that under the given experimental conditions, n-butanol is consumed primarily via abstraction of hydrogen atoms to produce fuel radical molecules, which subsequently decompose to smaller hydrocarbon and oxygenated species. The hydroxyl moiety in n-butanol results in the direct production of the oxygenated species such as butanal, acetaldehyde, and formaldehyde. The formation of these compounds sequesters carbon from forming soot precursors, but they may introduce other adverse environmental and health effects. Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents high quality experimental data for one large fatty acid methyl ester, methyl decanoate, and models its combustion using an improved skeletal mechanism. The results indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which ultimately lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular

  8. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong

    2015-07-01

    Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

  9. Kinetics of molybdenite oxidizing leaching in alkali medium by ozone

    International Nuclear Information System (INIS)

    On the basis of investigation of the process kinetics proposed is a model of oxidizing leaching of molybdenite in alkali medium while ozonization of the solution by ozoneair mixture. A kinetic equation is derived, that describes experimental data satisfactorily

  10. Theory of the Kinetics of Chemical Potentials in Heterogeneous Catalysis

    OpenAIRE

    Cheng, Jun; Hu, P

    2011-01-01

    Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and =standard chemical potential).

  11. Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation

    Science.gov (United States)

    Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert

    2008-08-01

    The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.

  12. pyJac: analytical Jacobian generator for chemical kinetics

    CERN Document Server

    Niemeyer, Kyle E; Sung, Chih-Jen

    2016-01-01

    Accurate simulations of combustion phenomena require the use of detailed chemical kinetics in order to capture limit phenomena such as ignition and extinction as well as predict pollutant formation. However, the chemical kinetic models for hydrocarbon fuels of practical interest typically have large numbers of species and reactions and exhibit high levels of mathematical stiffness in the governing differential equations, particularly for larger fuel molecules. In order to integrate the stiff equations governing chemical kinetics, generally reactive-flow simulations rely on implicit algorithms that require frequent Jacobian matrix evaluations. Some in situ and a posteriori computational diagnostics methods also require accurate Jacobian matrices, including computational singular perturbation and chemical explosive mode analysis. Typically, finite differences numerically approximate these, but for larger chemical kinetic models this poses significant computational demands since the number of chemical source ter...

  13. A complex chemical kinetic mechanism for the oxidation of gasoline surrogate fuels: n heptane, iso octane and toluene - Mechanism development and validation

    CERN Document Server

    Da Cruz, A Pires; Anderlohr, Jörg; Bounaceur, Roda; Battin-Leclerc, Frédérique

    2009-01-01

    The development and validation against experimental results of a new gasoline surrogate complex kinetic mechanism is presented in this paper. The surrogate fuel is a ternary mixture of n heptane, iso octane and toluene. The full three components mechanism is based on existing n heptane/iso octane (gasoline PRF) and toluene mechanisms which were modified and coupled for the purpose of this work. Mechanism results are compared against available experimental data from the literature. Simulations with the PRF plus toluene mechanism show that its behavior is in agreement with experimental results for most of the tested settings. These include a wide variety of thermodynamic conditions and fuel proportions in experimental configurations such as HCCI engine experiments, rapid compression machines, a shock tube and a jet stirred reactor.

  14. Numerical investigation of soot formation and oxidation processes under large two-stroke marine diesel engine-like conditions using integrated CFD-chemical kinetics

    DEFF Research Database (Denmark)

    Pang, Kar Mun; Karvounis, Nikolas; Walther, Jens Honore;

    2016-01-01

    skeletal model are close to those produced by the larger and more comprehensive chemical mechanisms, apart from those at the low pressure condition. The current study also demonstrates that the variation of averaged soot volume fraction with respect to the change of combustion chamber pressure captured...

  15. Empiricism or self-consistent theory in chemical kinetics?

    International Nuclear Information System (INIS)

    To give theoretical background for mechanochemical kinetics, we need first of all to find a possibility to predict the kinetic parameters for real chemical processes by determining rate constants and reaction orders without developing strictly specialized and, to a great extent, artificial models, i.e. to derive the kinetic law of mass action from 'first principles'. However, the kinetic law of mass action has had only an empirical basis from the first experiments of Gulberg and Waage until now, in contrast to the classical law of mass action for chemical equilibrium rigorously derived in chemical thermodynamics from equilibrium condition. Nevertheless, in this paper, an attempt to derive the kinetic law of mass action from 'first principles' is made in macroscopic formulation. It has turned out to be possible owing to the methods of thermodynamics of irreversible processes that were unknown in Gulberg and Waage's time

  16. Simulation of chemical kinetics in sodium-concrete interactions

    International Nuclear Information System (INIS)

    Sodium-concrete interaction is a key safety-related issue in safety analysis of liquid metal cooled fast breeder reactors (LMFBRs). The chemical kinetics model is a key component of the sodium-concrete interaction model. Conservation equations integrated in sodium-concrete interaction model cannot be solved without a set of relationships that couple the equations together, and this may be done by the chemical kinetics model. Simultaneously, simulation of chemical kinetics is difficult due to complexity of the mechanism of chemical reactions between sodium and concrete. This paper describes the chemical kinetics simulation under some hypotheses. The chemical kinetics model was integrated with the conservation equations to form a computer code. Penetration depth, penetration rate, hydrogen flux, reaction heat, etc. can be provided by this code. Theoretical models and computational procedure were recounted in detail. Good agreements of an overall transient behavior were obtained in a series of sodium-concrete interaction experiment analysis. Comparison between analytical and experimental results showed that the chemical kinetics model presented in this paper was creditable and reasonable for simulating the sodium-concrete interactions. (authors)

  17. Simulation of chemical kinetics in sodium-concrete interactions

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Sodium-concrete interaction is a key safety-related issue in safety analysis of liquid metal cooled fast breeder reactors (LMFBRs). The chemical kinetics model is a key component of the sodium-concrete interaction model. Conservation equations integrated in sodium-concrete interaction model cannot be solved without a set of relationships that couple the equations together, and this may be done by the chemical kinetics model. Simultaneously,simulation of chemical kinetics is difficult due to complexity of the mechanism of chemical reactions between sodium and concrete. This paper describes the chemical kinetics simulation under some hypotheses. The chemical kinetics model was integrated with the conservation equations to form a computer code. Penetration depth, penetration rate,hydrogen flux, reaction heat, etc. can be provided by this code. Theoretical models and computational procedure were recounted in detail. Good agreements of an overall transient behavior were obtained in a series of sodium-concrete interaction experiment analysis. Comparison between analytical and experimental results showed that the chemical kinetics model presented in this paper was creditable and reasonable for simulating the sodium-concrete interactions.

  18. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    Science.gov (United States)

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  19. Kinetic study of neodymium oxide chlorination with gaseous chlorine

    Energy Technology Data Exchange (ETDEWEB)

    Bosco, Marta V., E-mail: marta.bosco@cab.cnea.gov.ar [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Fouga, Gaston G. [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Complejo Tecnologico Pilcaniyeu, Comision Nacional de Energia Atomica, Avenida Bustillo 9500, CP 8400 San Carlos de Bariloche (Argentina); Bohe, Ana E. [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Complejo Tecnologico Pilcaniyeu, Comision Nacional de Energia Atomica, Avenida Bustillo 9500, CP 8400 San Carlos de Bariloche (Argentina); Centro Regional Universitario Bariloche, Universidad Nacional del Comahue, CP 8400 San Carlos de Bariloche (Argentina)

    2012-07-20

    Highlights: Black-Right-Pointing-Pointer We analyze the kinetics of the neodymium oxide chlorination reactions. Black-Right-Pointing-Pointer For temperatures below 425 Degree-Sign C the system is under chemical control. Black-Right-Pointing-Pointer The formation of oxychloride progresses through a nucleation and growth mechanism. Black-Right-Pointing-Pointer A reaction order of 0.40 with respect to chlorine partial pressure was determined. Black-Right-Pointing-Pointer An activation energy of 161 {+-} 4 kJ mol{sup -1} was determined. - Abstract: The kinetics of the chlorination of neodymium oxide has been investigated by thermogravimetry between 312 Degree-Sign C and 475 Degree-Sign C, and for partial pressures of chlorine ranging from 10 kPa to 50 kPa. The starting temperature for the reaction of neodymium oxide with chlorine was determined to be about 250 Degree-Sign C, leading to neodymium oxychloride as product. The results showed that, for temperatures below 425 Degree-Sign C, the system is under chemical control and the formation of the oxychloride progresses through a nucleation and growth mechanism. The influence of chlorine mass transport through the bulk gas phase and through the boundary layer on the overall reaction rate was analyzed. In the absence of these two mass-transfer steps, a reaction order of 0.39 with respect to chlorine partial pressure, and an activation energy of 161 {+-} 4 kJ mol{sup -1} were determined. A complete rate equation has been successfully developed.

  20. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Homogeneous gas-phase kinetics of tritium oxidation (2T2 + O2 →2T2O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10-4 -1.0 mol% T2 in O2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T2O production, each with a different overall rate expression and a different order with respect to the T2 concentration. The effects of self-radiolysis of pure T2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T2-O2 reaction. Ozone, an important intermediate in T2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T2 an 1 atm O2. The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T2 concentration ([T2]0.6o), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O3]ss) was predicted to be dependent on [T2]0.3o, but the measured value was [T2]0.6o, resulting in four times higher [O3]ss than predicted for a 1.0% T2-O2 mixture. Adding H2 to the T2-O2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O3]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  1. Kinetics and Modelling of Glucose Wet Air Oxidation over Pd/C Catalyst.

    Czech Academy of Sciences Publication Activity Database

    Gogová, Zuzana; Zedníková, Mária; Hanika, Jiří

    Bratislava: Slovak Society of Chemical Engineering, 2007 - (Markoš, J.; Štefuca, V.), s. 309 ISBN 978-80-227-2640-5. [International Conference of Slovak Society of Chemical Engineering /34./. Tatranské Matliare (SK), 21.05.2007-25.05.2007] R&D Projects: GA ČR(CZ) GD203/03/H140 Institutional research plan: CEZ:AV0Z40720504 Keywords : glucose * wet air oxidation * kinetics Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  2. Kinetic study of the alkaline metals oxidation by dry oxygen

    International Nuclear Information System (INIS)

    The oxidation of lithium, sodium, potassium, rubidium, cesium and sodium-potassium alloys by dry oxygen is studied at several temperatures and in the oxygen pressure range 40 to 400 mmHg. One distinguishes three different oxidation behaviours (inflammation, ignition and slow combustion) whose zones are precised in function of the temperature. The slow oxidation kinetic laws, the composition of oxides and the motive of oxides colorations are determined. At least, the experimental data are construed theoretically. (author)

  3. The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Osborne, David L.; Zou, Peng; Johnsen, Howard; Hayden, Carl C.; Taatjes, Craig A.; Knyazev, Vadim D.; North, Simon W.; Peterka, Darcy S.; Ahmed, Musahid; Leone, Stephen R.

    2008-08-28

    We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

  4. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author)

  5. Optimization of KINETICS Chemical Computation Code

    Science.gov (United States)

    Donastorg, Cristina

    2012-01-01

    NASA JPL has been creating a code in FORTRAN called KINETICS to model the chemistry of planetary atmospheres. Recently there has been an effort to introduce Message Passing Interface (MPI) into the code so as to cut down the run time of the program. There has been some implementation of MPI into KINETICS; however, the code could still be more efficient than it currently is. One way to increase efficiency is to send only certain variables to all the processes when an MPI subroutine is called and to gather only certain variables when the subroutine is finished. Therefore, all the variables that are used in three of the main subroutines needed to be investigated. Because of the sheer amount of code that there is to comb through this task was given as a ten-week project. I have been able to create flowcharts outlining the subroutines, common blocks, and functions used within the three main subroutines. From these flowcharts I created tables outlining the variables used in each block and important information about each. All this information will be used to determine how to run MPI in KINETICS in the most efficient way possible.

  6. Hungarian University Students' Misunderstandings in Thermodynamics and Chemical Kinetics

    Science.gov (United States)

    Turanyi, Tamas; Toth, Zoltan

    2013-01-01

    The misunderstandings related to thermodynamics (including chemical equilibrium) and chemical kinetics of first and second year Hungarian students of chemistry, environmental science, biology and pharmacy were investigated. We demonstrated that Hungarian university students have similar misunderstandings in physical chemistry to those reported in…

  7. Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

    DEFF Research Database (Denmark)

    Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild;

    2013-01-01

    Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS) and......-spot downstream of a force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order of...... reactivity: total inorganic sulfide >EtSH≥MeSH>>DMS. Except for total inorganic sulfide oxidation in wastewater, kinetic parameters for each VSC were of similar magnitude for the two locations. In the wastewater from the odor hot-spot, sulfide inorganic oxidation rates were approximately 12 times faster than...

  8. Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

    DEFF Research Database (Denmark)

    Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild;

    2013-01-01

    Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS) and...... force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order of reactivity......: total inorganic sulfide > EtSH > MeSH >> DMS. Except for total inorganic sulfide oxidation in wastewater, kinetic parameters for each VSC were of similar magnitude for the two locations. In the wastewater from the odor hot-spot, sulfide oxidation rates were approximately 12 times faster than in the...

  9. The oxidation kinetics of zircaloy - 4 under isothermal conditions

    International Nuclear Information System (INIS)

    The oxidation kinetics of zircaloy-4 tubes was studied by means of isothermal tests in the temperature interval 5000C to 9000C. Dry oxygen and water steam, were used as oxidant agents. The results show that the oxidation kinetics law exhibits a behaviour from cubic to parabolic in the range of the time and temperatures of the experiment. Dry oxygen shows a stronger oxidation effect than water steam. A special mechanical test to study the embrittlement effect in the small samples of zircaloy tubes was used. (Author)

  10. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

    Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

  11. Kinetics and mechanism of synthetic CoS oxidation process

    OpenAIRE

    Štrbac N.; Mihajlović I.; Živković D.; Boyanov B.; Živković Ž.; Cocić M.

    2006-01-01

    The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

  12. Neptunium_Oxide_Precipitation_Kinetics_AJohnsen

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, A M; Roberts, K E; Prussin, S G

    2012-06-08

    We evaluate the proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation system at elevated temperatures to obtain primary information on the effects of temperature, ionic strength, O{sub 2} and CO{sub 2}. Experiments conducted on unfiltered solutions at 10{sup -4} M NpO{sub 2}{sup +}(aq), neutral pH, and 200 C indicated that solution colloids strongly affect precipitation kinetics. Subsequent experiments on filtered solutions at 200, 212, and 225 C showed consistent and distinctive temperature-dependent behavior at reaction times {le} 800 hours. At longer times, the 200 C experiments showed unexpected dissolution of neptunium solids, but experiments at 212 C and 225 C demonstrated quasi steady-state neptunium concentrations of 3 x 10{sup -6} M and 6 x 10{sup -6} M, respectively. Solids from a representative experiment analyzed by X-ray diffraction were consistent with NpO{sub 2}(cr). A 200 C experiment with a NaCl concentration of 0.05 M showed a dramatic increase in the rate of neptunium loss. A 200 C experiment in an argon atmosphere resulted in nearly complete loss of aqueous neptunium. Previously proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation mechanisms in the literature specified a 1:1 ratio of neptunium loss and H{sup +} production in solution over time. However, all experiments demonstrated ratios of approximately 0.4 to 0.5. Carbonate equilibria can account for only about 40% of this discrepancy, leaving an unexpected deficit in H+ production that suggests that additional chemical processes are occurring.

  13. Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

    Science.gov (United States)

    Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

    2008-01-01

    A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

  14. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander;

    2015-01-01

    conditions ( U = 1.03 and 0.05). At very oxidizing conditions (O 2 atmosphere, U = 0.0009), the temperature for onset of reaction was reduced to 775–798 K. The data were interpreted in terms of a detailed chemical kinetic model, drawn mostly from work of Burke and coworkers. In the present study, the rate...

  15. The kinetic study of oxidation of iodine by hydrogen peroxide

    International Nuclear Information System (INIS)

    Iodine chemistry is one of the most important subjects of research in the field of reactor safety because this element can form volatile species which represent a biological hazard for environment. As the iodine and the peroxide are both present in the sump of the containment in the event of a severe accident on a light water nuclear reactor, it can be important to improve the knowledge on the reaction of oxidation of iodine by hydrogen peroxide. The kinetics of iodine by hydrogen peroxide has been studied in acid solution using two different analytical methods. The first is a UV/Vis spectrophotometer which records the transmitted intensity at 460 nm as a function of time to follow the decrease of iodine concentration, the second is an amperometric method which permits to record the increase of iodine+1 with time thanks to the current of reduction of iodine+1 to molecular iodine. The iodine was generated by Dushman reaction and the series of investigations were made at 40oC in a continuous stirring tank reactor. The influence of the initial concentrations of iodine, iodate, hydrogen peroxide, H+ ions has been determined. The kinetics curves comprise two distinct chemical phases both for molecular iodine and for iodine+1. The relative importance of the two processes is connected to the initial concentrations of [I2], [IO3-], [H2O2] and [H+]. A rate law has been determined for the two steps for molecular iodine. (author) figs., tabs., 22 refs

  16. Thermodynamically consistent model calibration in chemical kinetics

    Directory of Open Access Journals (Sweden)

    Goutsias John

    2011-05-01

    Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new

  17. Chemical Kinetic Models for HCCI and Diesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Sarathy, S M

    2010-11-15

    Predictive engine simulation models are needed to make rapid progress towards DOE's goals of increasing combustion engine efficiency and reducing pollutant emissions. These engine simulation models require chemical kinetic submodels to allow the prediction of the effect of fuel composition on engine performance and emissions. Chemical kinetic models for conventional and next-generation transportation fuels need to be developed so that engine simulation tools can predict fuel effects. The objectives are to: (1) Develop detailed chemical kinetic models for fuel components used in surrogate fuels for diesel and HCCI engines; (2) Develop surrogate fuel models to represent real fuels and model low temperature combustion strategies in HCCI and diesel engines that lead to low emissions and high efficiency; and (3) Characterize the role of fuel composition on low temperature combustion modes of advanced combustion engines.

  18. Experimental and kinetic modeling study of C2H4 oxidation at high pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Lund; Alzueta, Maria;

    2009-01-01

    A detailed chemical kinetic model for oxidation of C2H4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C2H3 + O-2 reaction was used to obtain rate coefficients over a wide range...... bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C2H4 are more complex...

  19. Physical Chemistry Chemical Kinetics and Reaction Mechanism

    CERN Document Server

    Trimm, Harold H

    2011-01-01

    Physical chemistry covers diverse topics, from biochemistry to materials properties to the development of quantum computers. Physical chemistry applies physics and math to problems that interest chemists, biologists, and engineers. Physical chemists use theoretical constructs and mathematical computations to understand chemical properties and describe the behavior of molecular and condensed matter. Their work involves manipulations of data as well as materials. Physical chemistry entails extensive work with sophisticated instrumentation and equipment as well as state-of-the-art computers. This

  20. Cure kinetics and chemorheology of EPDM/graphene oxide nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Allahbakhsh, Ahmad [Department of Polymer Engineering, Islamic Azad University, South Tehran Branch, 17776-13651 Tehran (Iran, Islamic Republic of); Mazinani, Saeedeh, E-mail: s.mazinani@aut.ac.ir [Amirkabir Nanotechnology Research Institute (ANTRI), Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Kalaee, Mohammad Reza [Department of Polymer Engineering, Islamic Azad University, South Tehran Branch, 17776-13651 Tehran (Iran, Islamic Republic of); Sharif, Farhad [Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of)

    2013-07-10

    Graphical abstract: - Highlights: • Graphene oxide content and dispersion as effective parameters on cure kinetics. • Graphene oxide as an effective controlling factor of crosslink density. • Interaction of graphene oxide with curing system (ZnO) during curing process. - Abstract: In this study, the effect of graphene oxide on cure behavior of ethylene–propylene–diene rubber (EPDM) nanocomposite is studied. In this regard, the cure kinetics of nanocomposite is studied employing different empirical methods. The required activation energy of nth-order cure process shows about 160 kJ/mol increments upon 5 phr graphene oxide loading compared to 1 phr graphene oxide loading. However, the required activation energy is significantly reduced followed by incorporation of graphene oxide in nanocomposites compared to neat EPDM sample. Furthermore, the effect of graphene oxide on structural properties of nanocomposites during the cure process is studied using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectrometry techniques. As the results show, graphene oxide interestingly affects the structure of zinc oxide during the vulcanization process. This behavior could be probably related to high tendency of zinc oxide to react with oxidized surface of graphene oxide.

  1. The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1990-01-01

    A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

  2. Optimization of radiation-chemical process of trichloroethylene oxidation

    International Nuclear Information System (INIS)

    Kinetics of trichloroethylene (TCE) oxidation under the effect of gamma-irradiation is investigated. It is shown that the reaction of TCE oxidation proceeds according to the chain mechanism. At the temperature of 60 deg C in the dose rate range from 1.1015 to 1.5x1016 eV(cm3xs) radiation-chemical yield changes from 1.5x104 to 5x103 molecules/100 eV. It is found that the reaction rate practically does not depend upon oxygen concentration and is directly proportional to the TCE concentration and the dose rate. The process optimization is studied

  3. Oxidation kinetics of UPb3 compound

    International Nuclear Information System (INIS)

    UPb3 is planned to be used as a shielding material for high energy gamma, but there are some problems associated with its oxidation in air. Therefore, the oxidation behaviour of this compound was investigated in dry air using TG-DTA. The compound was oxidized at different heating rates from room temperature to 1073 K. The isothermal weight gain data at 473 K, 623 K, 773 K and 973 K, was used to find the activation energy of oxidation of UPb3. (author)

  4. Kinetic model of continuous-wave flow chemical lasers

    Science.gov (United States)

    Gao, Z.; X., E.

    1982-02-01

    A kinetic approach to modeling the gain in a chemical wave continuous laser when the lasing frequency is coincident with the center of the line shape is presented. Governing equations are defined for the relaxing behavior of an initially nonequilibrium distribution toward the local equilibrium Boltzmann-Maxwellian distribution. A new gain is introduced which is related to the thermal motion of the molecules and cold-reaction and premixed CW models are discussed. Coincidence of the lasing frequency with the line shape is demonstrated to result in a radiative intensity within the homogeneous broadening limit. The rate model predictions are compared with those of the kinetic model. It is found that when the broadening parameter is less than 0.2 the kinetic model more accurately describes the behavior of the CW chemical laser.

  5. Investigation of Chemical Kinetics on Soot Formation Event of n-Heptane Spray Combustion

    DEFF Research Database (Denmark)

    Pang, Kar Mun; Jangi, Mehdi; Bai, Xue-Song;

    2014-01-01

    In this reported work, 2-dimsensional computational fluid dynamics studies of n-heptane combustion and soot formation processes in the Sandia constant-volume vessel are carried out. The key interest here is to elucidate how the chemical kinetics affects the combustion and soot formation events....... Numerical computation is performed using OpenFOAM and chemistry coordinate mapping (CCM) approach is used to expedite the calculation. Three n-heptane kinetic mechanisms with different chemistry sizes and comprehensiveness in oxidation pathways and soot precursor formation are adopted. The three examined...... chemical models use acetylene (C2H2), benzene ring (A1) and pyrene (A4) as soot precursor. They are henceforth addressed as nhepC2H2, nhepA1 and nhepA4, respectively for brevity. Here, a multistep soot model is coupled with the spray combustion solver to simulate the soot formation/oxidation processes...

  6. Simulation; an everyday tool for research in chemical kinetics

    International Nuclear Information System (INIS)

    In order to make apparent the facilities offered by the NEPTUNIX package in solving some complex problems in chemical kinetics, the paper deals with its application to a particular example taken from material science: assistance to the validation of mechanisms governing colloids growth in a fluorite crystal when it is irradiated by an electron beam

  7. Prospective Chemistry Teachers' Conceptions of Chemical Thermodynamics and Kinetics

    Science.gov (United States)

    Sozbilir, Mustafa; Pinarbasi, Tacettin; Canpolat, Nurtac

    2010-01-01

    This study aimed at identifying specifically prospective chemistry teachers' difficulties in determining the differences between the concepts of chemical thermodynamics and kinetics. Data were collected from 67 prospective chemistry teachers at Kazim Karabekir Education Faculty of Ataturk University in Turkey during 2005-2006 academic year. Data…

  8. Dynamic Simulation of Chemical Kinetics in Microcontroller

    Directory of Open Access Journals (Sweden)

    Renato Dutra Pereira Filho

    2014-12-01

    Full Text Available Arduino boards are interesting computational tools due to low cost and power consumption, as well as I/O ports, both analogs and digitals. Yet, small memory and clock frequency with truncation errors may disrupt numerical processing. This study aimed to design and evaluate the performance of a dynamic simulation based on ODEs in the Arduino, with three evaluated microprocessors; ATMEGA 328P and 2560, both 8 bits, and SAM3X8E Atmel ARM CORTEX – 32 bits. The study case was a batch reactor dynamic simulation. The Runge-Kutta 4th order algorithm was written in C++ and compiled for EPROM utilization. The output was a 115000bit/s serial connection. Processing time was almost identical for 8 bits architectures, while 32 bits was 25% faster. Without the serial connection the 8 bits architectures were 16 times faster and the 32 bits was 42 times faster. Error truncation was similar, since the floating points are done through software. The Arduino platform, despite its modest hardware, allows simple chemical systems simulation

  9. Experimental kinetic study and modeling of calcium oxide carbonation

    International Nuclear Information System (INIS)

    Anthropogenic carbon dioxide (CO2) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/de-carbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO2, so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO3 which causes a change in the porosity

  10. QUIC: a chemical kinetics code for use with the chemical equilibrium code QUIL

    International Nuclear Information System (INIS)

    A chemical rate kinetics code QUIC is described, along with a support code RATE. QUIC is designed to allow chemical kinetics calculations on a wide variety of chemical environments while operating in the overlay environment of the chemical equilibrium code QUIL. QUIC depends upon a rate-data library called LIBR. This library is maintained by RATE. RATE enters into the library all reactions in a standardized format. The code QUIC, operating in conjunction with QUIL, is interactive and written to be used from a remote terminal, with paging control provided. Plotted output is also available

  11. Thorium oxide dissolution kinetics for hydroxide and carbonate complexation

    International Nuclear Information System (INIS)

    The purpose of this project was to determine the kinetics and thermodynamics of thorium oxide dissolution in the environment. Solubility is important because it establishes an upper concentration limit on the concentration of a dissolved radionuclide in solution L1. While understanding the behavior of thorium fuels in the proposed repository at Yucca Mountain is most applicable, a more rigorous study of thorium solubility over a wide pH range was performed so that the data could also be used to model the behavior of thorium fuels in any environmental system. To achieve this, the kinetics and thermodynamics of thorium oxide dissolution under both pure argon and argon with PCO2 of 0. 1 were studied under the full pH range available in each atmosphere. In addition, thorium oxide powder remnants were studied after each experiment to examine structural changes that may affect kinetics

  12. Chemical kinetic performance losses for a hydrogen laser thermal thruster

    Science.gov (United States)

    Mccay, T. D.; Dexter, C. E.

    1985-01-01

    Projected requirements for efficient, economical, orbit-raising propulsion systems have generated investigations into several potentially high specific impulse, moderate thrust, advanced systems. One of these systems, laser thermal propulsion, utilizes a high temperature plasma as the enthalpy source. The plasma is sustained by a focused laser beam which maintains the plasma temperature at levels near 20,000 K. Since such temperature levels lead to total dissociation and high ionization, the plasma thruster system potentially has a high specific impulse decrement due to recombination losses. The nozzle flow is expected to be sufficiently nonequilibrium to warrant concern over the achievable specific impluse. This investigation was an attempt at evaluation of those losses. The One-Dimensional Kinetics (ODK) option of the Two-Dimensional Kinetics (TDK) Computer Program was used with a chemical kinetics rate set obtained from available literature to determine the chemical kinetic energy losses for typical plasma thruster conditions. The rates were varied about the nominal accepted values to band the possible losses. Kinetic losses were shown to be highly significant for a laser thermal thruster using hydrogen. A 30 percent reduction in specific impulse is possible simply due to the inability to completely extract the molecular recombination energy.

  13. Chemical kinetic reaction mechanism for the combustion of propane

    Science.gov (United States)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  14. Computer-Aided Construction of Chemical Kinetic Models

    Energy Technology Data Exchange (ETDEWEB)

    Green, William H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

    2014-12-31

    The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriate refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.

  15. Chemical kinetics and combustion modelling with CFX 4

    Energy Technology Data Exchange (ETDEWEB)

    Stopford, P. [AEA Technology, Computational Fluid Dynamics Services Harwell, Oxfordshire (United Kingdom)

    1997-12-31

    The presentation describes some recent developments in combustion and kinetics models used in the CFX software of AEA Technology. Three topics are highlighted: the development of coupled solvers in a traditional `SIMPLE`-based CFD code, the use of detailed chemical kinetics mechanism via `look-up` tables and the application of CFD to large-scale multi-burner combustion plant. The aim is identify those physical approximations and numerical methods that are likely to be most useful in the future and those areas where further developments are required. (author) 6 refs.

  16. Infrared absorption spectroscopy and chemical kinetics of free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  17. The kinetic study of oxidation of iodine by hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Cantrel, L. [Institut de Protection et de Surete Nucleaire, IPNS, CEN Cadarache, Saint Paul lez Durance (France); Chopin, J. [Laboratoire d`Electrochimie Inorganique, ENSSPICAM, Marseille (France)

    1996-12-01

    Iodine chemistry is one of the most important subjects of research in the field of reactor safety because this element can form volatile species which represent a biological hazard for environment. As the iodine and the peroxide are both present in the sump of the containment in the event of a severe accident on a light water nuclear reactor, it can be important to improve the knowledge on the reaction of oxidation of iodine by hydrogen peroxide. The kinetics of iodine by hydrogen peroxide has been studied in acid solution using two different analytical methods. The first is a UV/Vis spectrophotometer which records the transmitted intensity at 460 nm as a function of time to follow the decrease of iodine concentration, the second is an amperometric method which permits to record the increase of iodine+1 with time thanks to the current of reduction of iodine+1 to molecular iodine. The iodine was generated by Dushman reaction and the series of investigations were made at 40{sup o}C in a continuous stirring tank reactor. The influence of the initial concentrations of iodine, iodate, hydrogen peroxide, H{sup +} ions has been determined. The kinetics curves comprise two distinct chemical phases both for molecular iodine and for iodine+1. The relative importance of the two processes is connected to the initial concentrations of [I{sub 2}], [IO{sub 3}{sup -}], [H{sub 2}O{sub 2}] and [H{sup +}]. A rate law has been determined for the two steps for molecular iodine. (author) figs., tabs., 22 refs.

  18. Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

    Energy Technology Data Exchange (ETDEWEB)

    Leone, Stephen R.; Ahmed, Musahid; Wilson, Kevin R.

    2010-03-14

    Scientists at the Chemical Dynamics Beamline of the Advanced Light Source in Berkeley are continuously reinventing synchrotron investigations of physical chemistry and chemical physics with vacuum ultraviolet light. One of the unique aspects of a synchrotron for chemical physics research is the widely tunable vacuum ultraviolet light that permits threshold ionization of large molecules with minimal fragmentation. This provides novel opportunities to assess molecular energetics and reaction mechanisms, even beyond simple gas phase molecules. In this perspective, significant new directions utilizing the capabilities at the Chemical Dynamics Beamline are presented, along with an outlook for future synchrotron and free electron laser science in chemical dynamics. Among the established and emerging fields of investigations are cluster and biological molecule spectroscopy and structure, combustion flame chemistry mechanisms, radical kinetics and product isomer dynamics, aerosol heterogeneous chemistry, planetary and interstellar chemistry, and secondary neutral ion-beam desorption imaging of biological matter and materials chemistry.

  19. Graphene composites containing chemically bonded metal oxides

    Indian Academy of Sciences (India)

    K Pramoda; S Suresh; H S S Ramakrishna Matte; A Govindaraj

    2013-08-01

    Composites of graphene involving chemically bonded nano films of metal oxides have been prepared by reacting graphene containing surface oxygen functionalities with metal halide vapours followed by exposure to water vapour. The composites have been characterized by electron microscopy, atomic force microscopy and other techniques. Magnetite particles chemically bonded to graphene dispersible in various solvents have been prepared and they exhibit fairly high magnetization.

  20. Fast algorithm for calculating chemical kinetics in turbulent reacting flow

    International Nuclear Information System (INIS)

    The design of a very fast, automatic black-box code for homogeneous, gas-phase chemical kinetics problems requires an understanding of the physical and numerical sources of computational inefficiency. Some major sources reviewed in this paper are stiffness of the governing ordinary differential equations and its detection, choice of appropriate method (i.e., integration algorithm plus stepsize control strategy), nonphysical initial conditions, and too frequent evaluation of thermochemical and kinetic properties. Specific techniques are recommended (and some advised against) for improving or overcoming the identified problem areas. It is argued that, because reactive species increase exponentially with time during induction and early heat release, and all species exhibit asymptotic, exponential decay with time during late heat release and equilibration, exponential-fitted integration algorithms are inherently more accurate for kinetics modeling than classical, polynomial-interpolant methods for the same computational work

  1. Chemical oxidative polymerization of benzocaine

    Czech Academy of Sciences Publication Activity Database

    Marjanovic, B.; Juranic, I.; Ciric-Marjanovic, G.; Pašti, I.; Trchová, Miroslava; Holler, Petr

    2011-01-01

    Roč. 71, č. 7 (2011), s. 704-712. ISSN 1381-5148 R&D Projects: GA ČR GA203/08/0686 Institutional research plan: CEZ:AV0Z40500505 Keywords : benzocaine * electro-active oligomer * oxidative polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.479, year: 2011

  2. Oxidation kinetic analysis of a mixed uranium dicarbide and graphite compound

    Energy Technology Data Exchange (ETDEWEB)

    Marchand, M., E-mail: mickael.marchand@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Fiquet, O., E-mail: olivier.fiquet@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Brothier, M. [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France)

    2013-06-15

    Highlights: ► Experimental study of uranium carbides and graphite powder oxidations. ► Single rate limiting step identification by extensive kinetic analysis. ► Pseudo-steady-state validation during chemical conversion. ► Combination of TGA, TDA, XRD and gas phase chromatography results. -- Abstract: The oxidation of a mixed uranium dicarbide and graphite powder has been investigated by simultaneous thermal gravimetric (TGA) and differential thermal (DTA) analyses coupled with gas phase chromatography. For isothermal oxidation conditions with temperatures below 330 °C, only the UC{sub 2} chemical phase is progressively oxidised into U{sub 3}O{sub 8} oxides. Parabolic weight gain curves as a function of oxidation over time were obtained. A detailed kinetic study is proposed to establish a pseudo-steady-state during the oxidation process. Using an experimental method based on the sudden temperature increases, a single rate-limiting step has been validated and then modelled by a 3D diffusion law. An apparent activation energy calculated from the Arrhenius representation has been evaluated at −35 kJ/mol, thus describing the diffusion of oxygen through the oxide layer.

  3. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    Science.gov (United States)

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  4. Kinetic study of nitric dissolution of uranium oxide

    International Nuclear Information System (INIS)

    The kinetic study of uranium oxide dissolution efficiency was determined at the following temperatures: 20, 40, 60 and 80 C. The rate constant and activation energy could not be calculated by logarithmic and integral methods. This shows the complexity of the reaction mechanism of dissolution

  5. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.;

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  6. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten;

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5–23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  7. Chemical Kinetics of the TPS and Base Bleeding During Flight Test

    Science.gov (United States)

    Osipov, Viatcheslav; Ponizhovskaya, Ekaterina; Hafiychuck, Halyna; Luchinsky, Dmitry; Smelyanskiy, Vadim; Dagostino, Mark; Canabal, Francisco; Mobley, Brandon L.

    2012-01-01

    The present research deals with thermal degradation of polyurethane foam (PUF) during flight test. Model of thermal decomposition was developed that accounts for polyurethane kinetics parameters extracted from thermogravimetric analyses and radial heat losses to the surrounding environment. The model predicts mass loss of foam, the temperature and kinetic of release of the exhaust gases and char as function of heat and radiation loads. When PUF is heated, urethane bond break into polyol and isocyanate. In the first stage, isocyanate pyrolyses and oxidizes. As a result, the thermo-char and oil droplets (yellow smoke) are released. In the second decomposition stage, pyrolysis and oxidization of liquid polyol occur. Next, the kinetics of chemical compound release and the information about the reactions occurring in the base area are coupled to the CFD simulations of the base flow in a single first stage motor vertically stacked vehicle configuration. The CFD simulations are performed to estimate the contribution of the hot out-gassing, chemical reactions, and char oxidation to the temperature rise of the base flow. The results of simulations are compared with the flight test data.

  8. Variable elimination in chemical reaction networks with mass action kinetics

    OpenAIRE

    Feliu, Elisenda; Wiuf, Carsten

    2011-01-01

    We consider chemical reaction networks taken with mass action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are paramet...

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

    International Nuclear Information System (INIS)

    The kinetics of molybdenite oxidation was studied by non-isothermal TGA-DTA with heating rate 5degC.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 108 sec-1 for extent of reaction less than 0.5

  10. Chemical Kinetic Models for HCCI and Diesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbook, C K; Mehl, M

    2008-10-30

    Hydrocarbon fuels for advanced combustion engines consist of complex mixtures of hundreds or even thousands of different components. These components can be grouped into a number of chemically distinct classes, consisting of n-paraffins, branched paraffins, cyclic paraffins, olefins, oxygenates, and aromatics. Biodiesel contains its own unique chemical class called methyl esters. The fractional amounts of these chemical classes are quite different in gasoline, diesel fuel, oil-sand derived fuels and bio-derived fuels, which contributes to the very different combustion characteristics of each of these types of combustion systems. The objectives of this project are: (1) Develop detailed chemical kinetic models for fuel components used in surrogate fuels for diesel and HCCI engines; (2) Develop surrogate fuel models to represent real fuels and model low temperature combustion strategies in HCCI and diesel engines that lead to low emissions and high efficiency; and (3) Characterize the role of fuel composition on low temperature combustion modes of advanced combustion engines.

  11. An Experimental and Chemical Kinetics Study of the Combustion of Syngas and High Hydrogen Content Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Santoro, Robers [Pennsylvania State Univ., State College, PA (United States); Dryer, Frederick [Princeton Univ., NJ (United States); Ju, Yiguang [Princeton Univ., NJ (United States)

    2013-09-30

    An integrated and collaborative effort involving experiments and complementary chemical kinetic modeling investigated the effects of significant concentrations of water and CO2 and minor contaminant species (methane [CH4], ethane [C2H6], NOX, etc.) on the ignition and combustion of HHC fuels. The research effort specifically addressed broadening the experimental data base for ignition delay, burning rate, and oxidation kinetics at high pressures, and further refinement of chemical kinetic models so as to develop compositional specifications related to the above major and minor species. The foundation for the chemical kinetic modeling was the well validated mechanism for hydrogen and carbon monoxide developed over the last 25 years by Professor Frederick Dryer and his co-workers at Princeton University. This research furthered advance the understanding needed to develop practical guidelines for realistic composition limits and operating characteristics for HHC fuels. A suite of experiments was utilized that that involved a high-pressure laminar flow reactor, a pressure-release type high-pressure combustion chamber and a high-pressure turbulent flow reactor.

  12. Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

    2015-08-07

    In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

  13. Mesoscopic Kinetic Basis of Macroscopic Chemical Thermodynamics: A Mathematical Theory

    CERN Document Server

    Ge, Hao

    2016-01-01

    From a mathematical model that describes a complex chemical kinetic system of $N$ species and $M$ elementrary reactions in a rapidly stirred vessel of size $V$ as a Markov process, we show that a macroscopic chemical thermodynamics emerges as $V\\rightarrow\\infty$. The theory is applicable to linear and nonlinear reactions, closed systems reaching chemical equilibrium, or open, driven systems approaching to nonequilibrium steady states. A generalized mesoscopic free energy gives rise to a macroscopic chemical energy function $\\varphi^{ss}(\\vx)$ where $\\vx=(x_1,\\cdots,x_N)$ are the concentrations of the $N$ chemical species. The macroscopic chemical dynamics $\\vx(t)$ satisfies two emergent laws: (1) $(\\rd/\\rd t)\\varphi^{ss}[\\vx(t)]\\le 0$, and (2)$(\\rd/\\rd t)\\varphi^{ss}[\\vx(t)]=\\text{cmf}(\\vx)-\\sigma(\\vx)$ where entropy production rate $\\sigma\\ge 0$ represents the sink for the chemical energy, and chemical motive force $\\text{cmf}\\ge 0$ is non-zero if the system is driven under a sustained nonequilibrium chemos...

  14. Nitric oxide synthesis in the lung. Regulation by oxygen through a kinetic mechanism.

    OpenAIRE

    Dweik, R A; Laskowski, D; Abu-Soud, H M; Kaneko, F; Hutte, R; Stuehr, D J; Erzurum, S. C.

    1998-01-01

    In this study, we show that oxygen regulates nitric oxide (NO) levels through effects on NO synthase (NOS) enzyme kinetics. Initially, NO synthesis in the static lung was measured in bronchiolar gases during an expiratory breath-hold in normal individuals. NO accumulated exponentially to a plateau, indicating balance between NO production and consumption in the lung. Detection of NO2-, NO3-, and S-nitrosothiols in lung epithelial lining fluids confirmed NO consumption by chemical reactions in...

  15. Evolution of zirconium-based precipitates during oxidation and irradiation of Zr alloys (impact on the oxidation kinetics of Zr alloys)

    International Nuclear Information System (INIS)

    As the oxidation of the zircaloy sheath is one of the factors which limit the lifetime of nuclear fuel rods, this research thesis aims at a better knowledge of the involved oxidation mechanisms and to improve the oxidation resistance in order to increase rod lifetime. Oxidation test performed in autoclave to study zirconium alloy oxidation without irradiation showed that oxidation kinetics is significantly higher under irradiation. This difference is attributed to a different evolution of the sheath material under irradiation. Thus, this research focused on the role of precipitates in the oxidation process of zirconium alloys, and on the impact of their amorphization on this oxidation. After a detailed description of the context and of the various implemented experimental means, the author presents the results obtained on a reference material on the one hand, and on a material irradiated by ions or neutrons on the other hand. More particularly, the author studied in these both cases the introduction of precipitates in the oxide layer by transmission electronic microscopy, and oxidation kinetics obtained in autoclave on these two types of material. He reports the analysis of the introduction of precipitates in the oxide layer formed on the reference material. He proposes interpretations for the evolutions of structure and of chemical compositions of precipitates in the oxide layer. These observations are then correlated with oxidation kinetics in these alloys. Finally, the author discusses results of oxidation tests obtained on materials irradiated by ions and by neutrons

  16. Oxidative stress and oxidative damage in chemical carcinogenesis

    International Nuclear Information System (INIS)

    Reactive oxygen species (ROS) are induced through a variety of endogenous and exogenous sources. Overwhelming of antioxidant and DNA repair mechanisms in the cell by ROS may result in oxidative stress and oxidative damage to the cell. This resulting oxidative stress can damage critical cellular macromolecules and/or modulate gene expression pathways. Cancer induction by chemical and physical agents involves a multi-step process. This process includes multiple molecular and cellular events to transform a normal cell to a malignant neoplastic cell. Oxidative damage resulting from ROS generation can participate in all stages of the cancer process. An association of ROS generation and human cancer induction has been shown. It appears that oxidative stress may both cause as well as modify the cancer process. Recently association between polymorphisms in oxidative DNA repair genes and antioxidant genes (single nucleotide polymorphisms) and human cancer susceptibility has been shown.

  17. Kinetics of Fe3O4 formation by air oxidation

    Institute of Scientific and Technical Information of China (English)

    杨喜云; 龚竹青; 刘丰良

    2004-01-01

    The kinetics of Fe3O4 formation by air oxidation of slightly acidic suspension of Fe(OH)2 was studied. The effects of initial concentration of Fe(Ⅱ), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe3O4 formation is composed of two-step reaction, the first step is the formation of Fe(OH)+2 by oxidation of Fe(OH)+ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)+ and Fe(OH)+2. The oxidation reaction is zero-order with respect to the concentration of Fe(Ⅱ) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ·mol-1.

  18. Kinetics of ethylene oxide desorption from sterilized materials.

    Science.gov (United States)

    Mendes, Gisela C; Brandão, Teresa R S; Silva, Cristina L M

    2013-01-01

    Ethylene oxide gas is commonly used to sterilize medical devices, and concerns about using this agent on biological systems are well-established. Medical devices sterilized by ethylene oxide must be properly aerated to remove residual gas and by-products. In this work, kinetics of ethylene oxide desorption from different sterilized materials were studied in a range of aeration temperatures. The experimental data were well-described by a Fickian diffusion mass transfer behavior, and diffusivities were estimated for two textile and two polymeric materials within the temperature range of 1.5 to 59.0 degrees C. The results will allow predictions of ethylene oxide desorption, which is a key step for the design of sterilization/aeration processes, contributing to an efficient removal of residual ethylene oxide content. PMID:23513954

  19. Phototrophic sulfide oxidation: environmental insights and a method for kinetic analysis

    Directory of Open Access Journals (Sweden)

    Thomas E Hanson

    2013-12-01

    Full Text Available Previously, we presented data that indicated microbial sulfide oxidation would out-compete strictly chemical, abiotic sulfide oxidation reactions under nearly all conditions relevant to extant ecosystems (Luther et al., 2011. In particular, we showed how anaerobic microbial sulfide oxidation rates were several orders of magnitude higher than even metal catalyzed aerobic sulfide oxidation processes. The fact that biotic anaerobic sulfide oxidation is kinetically superior to abiotic reactions implies that nearly all anaerobic and sulfidic environments should host microbial populations that oxidize sulfide at appreciable rates. This was likely an important biogeochemical process during long stretches of euxinia in the oceans suggested by the geologic record. In particular, phototrophic sulfide oxidation allows the utilization of carbon dioxide as the electron acceptor suggesting that this process should be particularly widespread rather than relying on the presence of other chemical oxidants. Using the Chesapeake Bay as an example, we argue that phototrophic sulfide oxidation may be more important in many environments than is currently appreciated. Finally, we present methodological considerations to assist other groups that wish to study this process.

  20. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  1. Developments in kinetic modelling of chalcocite particle oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

    1997-12-31

    A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

  2. Oxidation Kinetics of K Basin Fuel (OCRWM)

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    2000-09-25

    Oxidation testing of K Basin-stored N Reactor fuel in dry air, moist air, and moist helium provided reaction rate data for the Spent Nuclear Fuel Project. The tests were performed on small samples from two spent nuclear fuel elements retrieved from the closed canisters of the K West Basin. The spent nuclear fuel samples were tested using a thermogravimetric analysis system modified for moist-gas operation to allow testing in moist environments. The tests were run at constant temperature and water vapor pressure. The moist helium tests used 6.5 H a water vapor, producing seventeen data between 75 C and 210 C. Eight of these data were excluded from primary consideration due to testing anomalies and balance drift issues. Regression analysis of the nine acceptable data provided good assurance that the moist-helium results are consistent with literature data within the temperature range of 25 C to 210 C. Concerns about possible oxygen poisoning from air in-leakage and mass transfer limitations on the test data were reviewed. If oxygen poisoning occurred it was not likely to have biased the data sufficiently to change the basic conclusions of comparability to the literature data. Mass transfer limitations did not appear to have had significant effect on the moist-helium data.

  3. Chemical kinetic modeling of H{sub 2} applications

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Marinov, N.; Pitz, W.J.; Curran, H. [Lawrence Livermore National Lab., CA (United States)

    1996-10-01

    This project is intended to develop detailed and simplified kinetic reaction mechanisms for the combustion of practical systems fueled by hydrogen, and then to use those mechanisms to examine the performance, efficiency, pollutant emissions, and other characteristics of those systems. During the last year, a H2/NOx mechanism has been developed that gives much improved predictions of NOx emissions compared to experimental data. Preliminary chemical kinetic and equilibrium calculations have been performed in support of Br2-H2O experiments to be conducted at NREL. Hydrogen, hydrogen/methane and hydrogen/natural gas mixtures have been investigated in a knock-rating engine to assess their automotive knock characteristics. The authors are currently developing the simplified analog reaction mechanisms that are computationally simple, yet still reproduce many of the macroscopic features of flame propagation.

  4. Kinetic investigations of oxidative roasting and afterwards leaching of copper-lead matte

    Directory of Open Access Journals (Sweden)

    Minić Duško

    2004-01-01

    Full Text Available In this paper, results of copper - lead matte investigations are presented. Investigated copper-lead matte is intermediate product of lead production in TREPCA-Zvecan. In the first part of the paper characterization of starting material is presented, consisting of: chemical composition analysis (XRQ, sceaning electron microscopy (SEM and diffractometry (XRD. Thermal properties of matte investigated were determined using differential thermal analysis (DTA at characteristic temperatures. Using results of induced analysis, mechanism of matte oxidation process was determined. In second part of the paper kinetic parameters describing oxidative roasting and afterwards leaching in sulfuric acid of copper-lead mate are presented.

  5. Accelerating moderately stiff chemical kinetics in reactive-flow simulations using GPUs

    CERN Document Server

    Niemeyer, Kyle E

    2014-01-01

    The chemical kinetics ODEs arising from operator-split reactive-flow simulations were solved on GPUs using explicit integration algorithms. Nonstiff chemical kinetics of a hydrogen oxidation mechanism (9 species and 38 irreversible reactions) were computed using the explicit fifth-order Runge-Kutta-Cash-Karp method, and the GPU-accelerated version performed faster than single- and six-core CPU versions by factors of 126 and 25, respectively, for 524,288 ODEs. Moderately stiff kinetics, represented with mechanisms for hydrogen/carbon-monoxide (13 species and 54 irreversible reactions) and methane (53 species and 634 irreversible reactions) oxidation, were computed using the stabilized explicit second-order Runge-Kutta-Chebyshev (RKC) algorithm. The GPU-based RKC implementation demonstrated an increase in performance of nearly 59 and 10 times, for problem sizes consisting of 262,144 ODEs and larger, than the single- and six-core CPU-based RKC algorithms using the hydrogen/carbon-monoxide mechanism. With the met...

  6. Progress in Chemical Kinetic Modeling for Surrogate Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Herbinet, O; Silke, E J

    2008-06-06

    Gasoline, diesel, and other alternative transportation fuels contain hundreds to thousands of compounds. It is currently not possible to represent all these compounds in detailed chemical kinetic models. Instead, these fuels are represented by surrogate fuel models which contain a limited number of representative compounds. We have been extending the list of compounds for detailed chemical models that are available for use in fuel surrogate models. Detailed models for components with larger and more complicated fuel molecular structures are now available. These advancements are allowing a more accurate representation of practical and alternative fuels. We have developed detailed chemical kinetic models for fuels with higher molecular weight fuel molecules such as n-hexadecane (C16). Also, we can consider more complicated fuel molecular structures like cyclic alkanes and aromatics that are found in practical fuels. For alternative fuels, the capability to model large biodiesel fuels that have ester structures is becoming available. These newly addressed cyclic and ester structures in fuels profoundly affect the reaction rate of the fuel predicted by the model. Finally, these surrogate fuel models contain large numbers of species and reactions and must be reduced for use in multi-dimensional models for spark-ignition, HCCI and diesel engines.

  7. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  8. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  9. EFFECTIVE SOLUTION METHOD OF CHEMICAL REACTION KINETICS WITH DIFFUSE

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples,shows that the method is effective.

  10. Kinetics of chemical interactions between zirconium alloys and stainless steels

    International Nuclear Information System (INIS)

    The chemical interaction kinetics of reactor core component zirconium alloys and stainless steels at high temperatures was examined. Interaction of as-received and preoxidized Zr1%Nb with X18H10T stainless steel used in WWER type nuclear reactors, and also that of Zircaloy-4 and AISI-316 stainless steel, for comparison, were investigated. The reaction rate measurements were supplemented with post-test metallographical examinations. Results are presented and evaluated, and compared with literature data. (author). 14 refs., 31 figs., 8 tabs

  11. Large deviations for two scale chemical kinetic processes

    CERN Document Server

    Li, Tiejun

    2015-01-01

    We formulate the large deviations for a class of two scale chemical kinetic processes motivated from biological applications. The result is successfully applied to treat a genetic switching model with positive feedbacks. The corresponding Hamiltonian is convex with respect to the momentum variable as a by-product of the large deviation theory. This property ensures its superiority in the rare event simulations compared with the result obtained by formal WKB asymptotics. The result is of general interest to understand the large deviations for multiscale problems.

  12. Kinetics and mechanism of nitric oxidation of carbon black

    International Nuclear Information System (INIS)

    After some generalities about carbon blacks (preparation by various processes, structure, industrial use), the author notices that carbon black is often dispersed in aqueous solutions and, as it is hydrophobic, must therefore be submitted to treatment to become hydrophilic. Oxidation in liquid phase suits perfectly, and oxidation by nitric acid gives good results. Thus, this research thesis reports the study of the oxidation reaction mechanism in the case of oxidation of carbon black by nitric acid in aqueous solution. After having defined the different types of carbon blacks used in this study, and given an overview of the oxidation process (methods, purification and purity control of the obtained blacks, determination of the efficiency in terms of oxidised or purified black, difficulties faced during the elemental analysis of oxidised blacks), the author discusses the mechanism of formation of carbon dioxide during the oxidation of Philblack 0 carbon black by nitric acid. He reports the study of the oxidation kinetics, and the study of a thermal treatment of oxidised carbon blacks. The last part reports the study of the evolution of various properties of carbon blacks during oxidation: specific surface (BET method), density, examination by electronic microscopy and X-rays, magnetic susceptibility

  13. Deracemization By Simultaneous Bio-oxidative Kinetic Resolution and Stereoinversion**

    OpenAIRE

    Schrittwieser, Joerg H.; Groenendaal, Bas; Resch, Verena; Ghislieri, Diego; Wallner, Silvia; Fischereder, Eva-Maria; Fuchs, Elisabeth; Grischek, Barbara; Sattler, Johann H.; Macheroux, Peter; Turner, Nicholas J.; Kroutil, Wolfgang

    2014-01-01

    Deracemization, that is, the transformation of a racemate into a single product enantiomer with theoretically 100 % conversion and 100 % ee, is an appealing but also challenging option for asymmetric synthesis. Herein a novel chemo-enzymatic deracemization concept by a cascade is described: the pathway involves two enantioselective oxidation steps and one non-stereoselective reduction step, enabling stereoinversion and a simultaneous kinetic resolution. The concept was exemplified for the tra...

  14. Kinetics of the thermal oxidation of Fe(2+) in talc

    International Nuclear Information System (INIS)

    The thermally induced oxidation of Fe2+ in talc has been investigated by Moessbauer spectroscopy. The heating temperature range of the sample was from 600degC to 750degC with variable times of treatment going from 6 hours up to 192 hours. The obtained isothermals could be well fitted by a first order kinetic model. The activation energy deduced from an Arrhenius plot is 178 kJ/mol. (orig.)

  15. Chemical kinetics of low and high temperature oxidation of reference fuels and of some additives at up to 40 bars; Cinetique chimique de l`oxydation de basse et haute temperature de combustibles de reference et de certains additifs jusqu`a 40 bars

    Energy Technology Data Exchange (ETDEWEB)

    Cathonnet, M.; Dagaut, Ph.; Reuillon, M.; Voisin, D. [Centre National de la Recherche Scientifique (CNRS), 45 - Orleans-la-Source (France). Laboratoire de Combustion et Systemes Reactifs

    1996-12-31

    A study of the oxidation of reference fuels for controlled ignition engines (n-heptane and iso-octane) and for turbojet engines (n-decane and TR0 kerosene) has been carried out in a self-agitated engine using gas jets at 1 to 40 bars and 550 to 1250 deg. K. Experimental results obtained have been used to propose a detailed kinetics mechanism for kerosene combustion. The study of the oxidation of oxygenated additives used in petrol (MTBE, ETBE, TAME, DIPE) and of the oxidation of a diesel substitute (DME) has been carried out in a self-agitated engine using gas jets at 1 to 10 bars and 800 to 1275 deg. K. These studies indicate that the oxidation of ether-type additives (MTBE, ETBE, TAME, DIPE) produces important oxygenated intermediates which are potential pollutants: formaldehyde, acetaldehyde, acrolein, and meth-acrolein. Butadiene and isoprene concentrations have been measured too. However, DME does not produce higher compounds but formaldehyde is one of its main oxidation intermediates. Chemical mechanisms leading to the formation of these pollutants are included in the proposed combustion models. (J.S.)

  16. Detailed Chemical Kinetic Mechanisms for Combustion of Oxygenated Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, E.M.; Pitz, W.J.; Curran, H.J.; Westbrook, C.K.

    2000-01-11

    Thermodynamic properties and detailed chemical kinetic models have been developed for the combustion of two oxygenates: methyl butanoate, a model compound for biodiesel fuels, and methyl formate, a related simpler molecule. Bond additivity methods and rules for estimating kinetic parameters were adopted from hydrocarbon combustion and extended. The resulting mechanisms have been tested against the limited combustion data available in the literature, which was obtained at low temperature, subatmospheric conditions in closed vessels, using pressure measurements as the main diagnostic. Some qualitative agreement was obtained, but the experimental data consistently indicated lower overall reactivities than the model, differing by factors of 10 to 50. This discrepancy, which occurs for species with well-established kinetic mechanisms as well as for methyl esters, is tentatively ascribed to the presence of wall reactions in the experiments. The model predicts a region of weak or negative dependence of overall reaction rate on temperature for each methyl ester. Examination of the reaction fluxes provides an explanation of this behavior, involving a temperature-dependent competition between chain-propagating unimolecular decomposition processes and chain-branching processes, similar to that accepted for hydrocarbons. There is an urgent need to obtain more complete experimental data under well-characterized conditions for thorough testing of the model.

  17. Incorporation of chemical kinetic models into process control

    International Nuclear Information System (INIS)

    An important consideration in chemical process control is to determine the precise rationing of reactant streams, particularly when a large time delay exists between the mixing of the reactants and the measurement of the product. In this paper, a method is described for incorporating chemical kinetic models into the control strategy in order to achieve optimum operating conditions. The system is first characterized by determining a reaction rate surface as a function of all input reactant concentrations over a feasible range. A nonlinear constrained optimization program is then used to determine the combination of reactants which produces the specified yield at minimum cost. This operating condition is then used to establish the nominal concentrations of the reactants. The actual operation is determined through a feedback control system employing a Smith predictor. The method is demonstrated on a laboratory bench scale enzyme reactor

  18. Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature

    Institute of Scientific and Technical Information of China (English)

    QIU Ting-sheng; NIE Guang-hua; WANG Jun-feng; CUI Li-feng

    2007-01-01

    Kinetic process of oxidative leaching of chalcopyrite in chloride acid hydroxide medium under oxygen pressure and low temperature was investigated. The effect on leaching rate of chalcopyrite caused by these factors such as ore granularity, vitriol concentration, sodium chloride concentration, oxygen pressure and temperature was discussed. The results show that the leaching rate of chalcopyrite increases with decreasing the ore granularity. At the early stage of oxidative reaction, the copper leaching rate increases with increasing the oxygen pressure and dosage of vitriol concentration, while oxygen pressure affects leaching less at the later stage. At low temperature, the earlier oxidative leaching process of chalcopyrite is controlled by chemical reactions while the later one by diffusion. The chalcopyrite oxidative leaching rate has close relation with ion concentration in the leaching solution. The higher ion concentration is propitious for chalcopyrite leaching.

  19. Kinetics and mechanism of methane oxidation in supercritical water

    International Nuclear Information System (INIS)

    This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

  20. CHEMKIN-III: A FORTRAN chemical kinetics package for the analysis of gas-phase chemical and plasma kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Kee, R.J.; Rupley, F.M.; Meeks, E.; Miller, J.A.

    1996-05-01

    This document is the user`s manual for the third-generation CHEMKIN package. CHEMKIN is a software package whose purpose is to facilitate the formation, solution, and interpretation of problems involving elementary gas-phase chemical kinetics. It provides a flexible and powerful tool for incorporating complex chemical kinetics into simulations of fluid dynamics. The package consists of two major software components: an Interpreter and a Gas-Phase Subroutine Library. The Interpreter is a program that reads a symbolic description of an elementary, user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Gas-Phase Subroutine Library. This library is a collection of about 100 highly modular FORTRAN subroutines that may be called to return information on equations of state, thermodynamic properties, and chemical production rates. CHEMKIN-III includes capabilities for treating multi-fluid plasma systems, that are not in thermal equilibrium. These new capabilities allow researchers to describe chemistry systems that are characterized by more than one temperature, in which reactions may depend on temperatures associated with different species; i.e. reactions may be driven by collisions with electrons, ions, or charge-neutral species. These new features have been implemented in such a way as to require little or no changes to CHEMKIN implementation for systems in thermal equilibrium, where all species share the same gas temperature. CHEMKIN-III now has the capability to handle weakly ionized plasma chemistry, especially for application related to advanced semiconductor processing.

  1. 2-chlorophenol oxidation kinetic by photo-assisted Fenton process

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Experimental data are presented to test and validate a kinetic model for the oxidation of 2-chlorophenol wastewater by photo-assistedFenton process. The data showed that this process had produced good effects under acidic conductions. Up to 90% 2-chlorophenol was removedafter 90-minute reaction time with H2 O2 of 25 % CODcr in while in UV/H2 O2 system only 16.8% 2-chlorophenol was removed after one hourtreatment. The optimal pH in this reaction occurred between pH 3.0 and pH 4.0. The reaction kinetics for photo-assisted Fenton processexperimented in this research was investigated. Kinetic models were proposed for the treatment of 2-chlorophenol wastewater. The reaction wasfound to follow the 2nd order. The equations of reaction kinetics are as follows: - dt/d[RH]= KRH [ RH] [ H2O2 ]0exp(-KH2O2t); -dt/d[CODcr]= KCODCr[CODCr][ H2O2 ]0exp( - K't). The prediction of the models was found to be in a good agreement with experimentalresults, thus confirming the proposed reaction mechanism.

  2. Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

    Science.gov (United States)

    Couet, Adrien; Motta, Arthur T.; Comstock, Robert J.

    2014-08-01

    The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport. document>

  3. Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

    International Nuclear Information System (INIS)

    The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport

  4. Kinetics of pyrite oxidation by hydrogen peroxide in phosphoric acid solutions

    Directory of Open Access Journals (Sweden)

    VALENTINA DIMITRIJEVIC

    1999-12-01

    Full Text Available The kinetics of pyrite oxidation by hydrogen peroxide in phosphoric acid solutions were investigated. The effects of stirring, temperature, and particle size, as well as of the hydrogen peroxide and phosphoric acid concentrations were studied. The effect of phosphate ion addition was also examined. The oxidation kinetics was found to follow a shrinking core model, with the surface chemical reaciton as the rate-controlling step. This is in accord with an activation energy of 57 kJ mol-1 and a linear relationship between the rate constant and the reciprocal of the particle radius. The reaction order with respect to the hydrogen peroxide concentration was found to be equal to unity. Variation of the phosphoric acid concentration had practically no effect on the rate of pyrite oxidation. Addition of the phosphate ion in the relatively low concentration range (0.005-0.1 mol dm-3 had a highly negative influence on the rate of pyrite oxidation, indicating that this ion has an inhibiting effect on the oxidation of pyrite by hydrogen peroxide.

  5. Kinetic modeling of the oxidative degradation of additive free PE in bleach disinfected water

    Science.gov (United States)

    Mikdam, Aïcha; Colin, Xavier; Billon, Noëlle; Minard, Gaëlle

    2016-05-01

    The chemical interactions between PE and bleach were studied at 60°C in immersion in bleach solutions kept at a free chlorine concentration of 100 ppm and a pH of 5 or 7.2. It was found that the polymer undergoes a severe oxidation from the earliest weeks of exposure, in a superficial layer whose thickness (of about 50-70 µm) is almost independent of the pH value, although the superficial oxidation rate is faster in acidic than in neutral medium. Oxidation leads to the formation and accumulation of a large variety of carbonyl products (mostly ketones and carboxylic acids) and, after a few weeks, to a decrease in the average molar mass due to the large predominance of chain scissions over crosslinking. A scenario was elaborated for explaining such unexpected results. According to this scenario, the non-ionic molecules (Cl2 and ClOH) formed from the disinfectant in the water phase, would migrate deeply into PE and dissociate into highly reactive radicals (Cl• and HO•) in order to initiate a radical chain oxidation. A kinetic model was derived from this scenario for predicting the general trends of the oxidation kinetics and its dependence on environmental factors such as temperature, free chlorine concentration and pH. The validity of this model was successfully checked by comparing the numerical simulations with experimental data.

  6. Exact non-additive kinetic potentials in realistic chemical systems.

    Science.gov (United States)

    de Silva, Piotr; Wesolowski, Tomasz A

    2012-09-01

    In methods based on frozen-density embedding theory or subsystem formulation of density functional theory, the non-additive kinetic potential (v(t)(nad)(r)) needs to be approximated. Since v(t)(nad)(r) is defined as a bifunctional, the common strategies rely on approximating v(t)(nad)[ρ(A),ρ(B)](r). In this work, the exact potentials (not bifunctionals) are constructed for chemically relevant pairs of electron densities (ρ(A) and ρ(B)) representing: dissociating molecules, two parts of a molecule linked by a covalent bond, or valence and core electrons. The method used is applicable only for particular case, where ρ(A) is a one-electron or spin-compensated two-electron density, for which the analytic relation between the density and potential exists. The sum ρ(A) + ρ(B) is, however, not limited to such restrictions. Kohn-Sham molecular densities are used for this purpose. The constructed potentials are analyzed to identify the properties which must be taken into account when constructing approximations to the corresponding bifunctional. It is comprehensively shown that the full von Weizsäcker component is indispensable in order to approximate adequately the non-additive kinetic potential for such pairs of densities. PMID:22957558

  7. Isobutane ignition delay time measurements at high pressure and detailed chemical kinetic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Healy, D.; Curran, H.J. [Combustion Chemistry Centre, School of Chemistry, NUI Galway (Ireland); Donato, N.S.; Aul, C.J.; Petersen, E.L. [Department of Mechanical Engineering, Texas A and M University, College Station, TX (United States); Zinner, C.M. [Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL (United States); Bourque, G. [Rolls-Royce Canada Limited, 9500 Cote de Liesse, Lachine, Quebec (Canada)

    2010-08-15

    Rapid compression machine and shock-tube ignition experiments were performed for real fuel/air isobutane mixtures at equivalence ratios of 0.3, 0.5, 1, and 2. The wide range of experimental conditions included temperatures from 590 to 1567 K at pressures of approximately 1, 10, 20, and 30 atm. These data represent the most comprehensive set of experiments currently available for isobutane oxidation and further accentuate the complementary attributes of the two techniques toward high-pressure oxidation experiments over a wide range of temperatures. The experimental results were used to validate a detailed chemical kinetic model composed of 1328 reactions involving 230 species. This mechanism has been successfully used to simulate previously published ignition delay times as well. A thorough sensitivity analysis was performed to gain further insight to the chemical processes occurring at various conditions. Additionally, useful ignition delay time correlations were developed for temperatures greater than 1025 K. Comparisons are also made with available isobutane data from the literature, as well as with 100% n-butane and 50-50% n-butane-isobutane mixtures in air that were presented by the authors in recent studies. In general, the kinetic model shows excellent agreement with the data over the wide range of conditions of the present study. (author)

  8. Radio-Oxidation in Polyolefins: Non-Stationary Kinetic Conditions

    International Nuclear Information System (INIS)

    In the last fifty years, many authors have been interested in the radio-oxidation processes occurring in polymers. The polymer degradation under ionising radiations in presence of dioxygen is well described by a radical chemistry. The radio-oxidation process occurs in three steps: the first one is the production of radicals P degree by interaction between the polymer and the ionising radiations; then radicals P degree react spontaneously with O2 solved in the polymer giving a peroxy radical POO degree which attacks the polymer forming a hydroperoxide POOH and a new radical P degree (propagation). The third step corresponds to the termination step, that is bimolecular reactions between radicals. It is generally assumed that the stationary state is rapidly reached and consequently that the oxidation induced during the built-up period of the radical concentration can be neglected. However, to our best knowledge, the temporal evolution of radical concentrations before reaching the steady state regime has never been studied in details. We recently performed a complete study of oxygen consumption under electron irradiation for an EPDM elastomer. An analysis, as function of dose rate and oxygen pressure, and assuming steady state conditions, allowed extracting all the kinetic constants. Starting for these experimental data, we calculated the build-up of the radical concentration by solving numerically the differential equations with help of the Minichem code. We conclude that, in fact, the oxidation induced during the built-up period is negligible. In this paper we show that [P degree] could present a quasi-stationary plateau before reaching its stationary level. Consequently, the full radical time evolution is essentially determined by two characteristic times for reaching the quasi and stationary levels and three concentrations: [P degree] and [POO degree] at the stationary level and [P degree] at the quasi-stationary plateau. We show that realistic approximations can

  9. Variable elimination in chemical reaction networks with mass action kinetics

    CERN Document Server

    Feliu, Elisenda

    2011-01-01

    We consider chemical reaction networks taken with mass action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are parameterized algebraically by the core variables, and a graphical condition is given for when a steady state with positive core variables necessarily have all variables positive. Further, we characterize graphically the sets of eliminated variables that are constrained by a conservation law and show that this conservation law takes a specific form.

  10. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  11. Kinetics of the Oxidation of Bismuthinite in Oxygen-Nitrogen Atmospheres

    Science.gov (United States)

    Padilla, Rafael; Villa, Ricardo; Ruiz, Maria C.; Reddy, Ramana G.

    2011-10-01

    Bismuth is present in copper concentrates mainly as the mineral bismuthinite (Bi2S3). In some cases of smelting of concentrates, a substantial amount of bismuth can lead to contaminated copper cathodes. Thus, understanding the behavior of Bi2S3 at high temperatures is crucial to assessing the potential of bismuth removal in the pyrometallurgical process. Therefore, the oxidation of bismuthinite in mixtures of oxygen-nitrogen atmospheres was investigated using a thermogravimetric analysis technique. The results indicate that the oxidation process occurs through the following consecutive reactions: {{First stage: }}{{Bi}}_{ 2} {{S}}_{ 3} ( {{s,l}} ) + 3{{O}}2 ( {{g}} ) = 2{{Bi}}( {{l}} ) + 3{{SO}}_{ 2} ( {{g}} ) {{Second stage: }}2{{Bi}}( {{l}} ) + 3/2{{O}}2 ( {{g}} ) = {{Bi}}2 {{O}}3 ( {{s,l}} ) The kinetics of the oxidation of bismuthinite (first stage) was studied, and the model ln(1 - X) = -kapp t describes the kinetics of this reaction well. The bismuthinite oxidation dependence on oxygen partial pressure was of 0.9 order, and the intrinsic kinetic constants were obtained in the temperature range of 873 K to 1273 K (600 °C to 1000 °C), which were used to determine the activation energy of 91 kJ/mol. The results indicate that the oxidation of bismuthinite is a process controlled by chemical reactions. From this study, it can be concluded that the removal of bismuth from the Bi2S3-containing concentrates through a mechanism involving gaseous bismuth compounds is not feasible during an oxidizing roasting and/or smelting of concentrates containing Bi2S3.

  12. Kinetics of transuranium element oxidation-reduction reactions in solution

    International Nuclear Information System (INIS)

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author)

  13. Kinetics of the Oxidation of N-Aminopiperidine with Chloramine

    OpenAIRE

    Darwich, Chaza; Elkhatib, Mazen; Steinhauser, Georg; Delalu, Henri

    2009-01-01

    The kinetics of the oxidation of N-aminopiperidine with chloramine was studied at different temperatures, with variable concentrations of the two reactants and at a pH ranging between 12 and 13.5. The reaction showed to be involving two steps: the first corresponded to the formation of a diazene intermediate, the second to the evolution of this intermediate into numerous compounds within a complex reactional chain. The rate law of the first step was determined by the Ostwald method and found ...

  14. An open-source chemical kinetics network: VULCAN

    Science.gov (United States)

    Tsai, Shang-Min; Lyons, James; Heng, Kevin

    2015-12-01

    I will present VULCAN, an open-source 1D chemical kinetics code suited for the temperature and pressure range relevant to observable exoplanet atmospheres. The chemical network is based on a set of reduced rate coefficients for C-H-O systems. Most of the rate coefficients are based on the NIST online database, and validated by comparing withthermodynamic equilibrium codes (TEA, STANJAN). The difference between the experimental rates and those from the thermodynamical data is carefully examined and discussed. For the numerical method, a simple, quick, semi-implicit Euler integrator is adopted to solve the stiff chemical reactions, within an operator-splitting scheme for computational efficiency.Several test runs of VULCAN are shown in a hierarchical way: pure H, H+O, H+O+C, including controlled experiments performed with a simple analytical temperature-pressure profiles, so that different parameters, such as the stellar irradiation, atmospheric opacities and albedo can be individually explored to understand how these properties affect the temperaturestructure and hence the chemical abundances. I will also revisit the "transport-induced-quenching” effects, and discuss the limitation of this approximation and its impact on observations. Finally, I will discuss the effects of C/O ratio and compare with published work in the literature.VULCAN is written in Python and is part of the publicly-available set of community tools we call the Exoclimes Simulation Platform (ESP; www.exoclime.org). I am a Ph.D student of Kevin Heng at the University of Bern, Switzerland.

  15. Change of chemical states of niobium in the oxide layer of zirconium–niobium alloys with oxide growth

    International Nuclear Information System (INIS)

    The change of chemical states of niobium with oxide growth was examined in the oxide layers of Zr–2.5Nb around the first kinetic transition by the conversion electron yield – X-ray absorption near-edge structure measurements. The detailed depth profiles of niobium chemical states were obtained in both the pre- and the post-transition oxide layers of Zr–2.5Nb formed in water at 663 K for 40–280 d. The depth profiling revealed that the inner oxide layer remained protective to oxidizing species even though in the post-transition region and this excellent stability of barrierness would be attributed the suppression of hydrogen pickup. (author)

  16. The Main Plasma Chemical Process of Nitric Oxide Production by Arc Discharge

    Science.gov (United States)

    Yang, Qi; Hu, Hui; Chen, Weipeng; Xu, Jie; Zhang, Jinli; Wu, Shuang

    2011-12-01

    By adopting the optical multi-channel analyzer combined with fourier transform infrared (FTIR) spectrometer, the dominant free radicals and products generated by arc discharge were measured and studied, and the main plasma chemical reaction process in the nitric oxide production by arc discharge was identified. Plasma chemical kinetic curves of O, O2, N2, N and NO were simulated by using CHEMKIN and MATLAB. The results show that the main plasma chemical reaction process of nitric oxide production by arc discharge is a replacement reaction between O and N2, where NO can be generated instantaneously when discharging reaches stable.

  17. The Main Plasma Chemical Process of Nitric Oxide Production by Arc Discharge

    International Nuclear Information System (INIS)

    By adopting the optical multi-channel analyzer combined with fourier transform infrared (FTIR) spectrometer, the dominant free radicals and products generated by arc discharge were measured and studied, and the main plasma chemical reaction process in the nitric oxide production by arc discharge was identified. Plasma chemical kinetic curves of O, O2, N2, N and NO were simulated by using CHEMKIN and MATLAB. The results show that the main plasma chemical reaction process of nitric oxide production by arc discharge is a replacement reaction between O and N2, where NO can be generated instantaneously when discharging reaches stable. (15th asian conference on electrical discharge)

  18. Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: Uptake kinetics and condensed-phase products

    Directory of Open Access Journals (Sweden)

    I. J. George

    2007-05-01

    Full Text Available The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl sebacate (BES particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS and scanning mobility particle sizer (SMPS was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0 = 1.26 (±0.04, confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.

  19. Kinetics of gaseous atoms in uranium plutonium mixed oxide

    International Nuclear Information System (INIS)

    The kinetics of fission gas atoms in nuclear fuel are much different from those discussed in academic fields such as statistical mechanics and/or statistical thermodynamics established by Ludwig Boltzmann. The field of movement should have unique microstructure such as pore, grain boundary, and especially plutonium enriched zone (Pu spot) in case of Uranium Plutonium Mixed Oxide (MOX). The mechanism of fission gas release has been studied by many researchers for these nearly fifty years since Booth first set down the simple approximations to fission gas release from irradiated UO2. However, there is still no general agreement what mechanisms are responsible for observed coalescence of intergranular bubbles during their growth. It might be due to the complexity of the kinetics of gaseous atoms in nuclear fuel pellet having unique microstructure, temperature gradient and irradiation damage. The objectives of this paper are to introduce brief review of fundamental process of kinetics of gaseous atom in nuclear fuel and to develop effective fission gas release model. The fission gas release mechanism for MOX fuel which has heterogeneous microstructure including Pu spot is introduced based on the result of post-irradiation examination with MOX having high plutonium content. (authors)

  20. Kinetics of lactate turnover and oxidation in man

    International Nuclear Information System (INIS)

    The turnover and oxidation of lactic acid have been studied in man by means of 14C-lactic acid, 14C-glucose, and 14C-alanine. The use of these labels in separate studies has enabled us to describe a complete scheme for the kinetics of lactic acid in man. We have determined that lactate arises from a minimum of two sources in overnight fasted man. 66% of lactate at this time arises from the metabolism of glucose while approximately 15% is derived from alanine. These sources and others unidentified supply lactate to the body pool at a rate of approximately 95 mg per kg per h. The disposal of this quantity of lactate is achieved through a minimum of three routes. Approximately 57% of the lactate turnover is oxidized to carbon dioxide, 15% is reduced to glucose, and approximately 25% is converted to alanine. The quantitative changes in the kinetics of this system that are brought on by fasting add an interesting dimension to the system. In agreement with the concepts of fuel economy in fasting the contribution of glucose carbon to lactic acid falls and, in turn, the contribution of lactate carbon to body glucose rises. The study of additional permutations of this system suggest that lactate, with pyruvate, is in the main stream of the intermediary metabolism of the body. The authors suggest that the study of this system offers promise of a fuller understanding of the derangements of metabolic disease. (author)

  1. Chemical Sensors Based on Metal Oxide Nanostructures

    Science.gov (United States)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  2. Tin Oxide Microheater for Chemical Sensors

    Science.gov (United States)

    Gharesi, Mohsen; Ansari, Mohammad

    2016-03-01

    Tin oxide is the main material utilized for the fabrication of chemical sensing pellets which operate at elevated temperatures. The heating is commonly carried out with ruthenium dioxide resistors. Here, a tin oxide-based microheater is developed for microsensor applications. These microheaters are fabricated on 0.5 mm thick alumina substrates using spray pyrolysis technique. The optimum SnO2 heaters have a sheet resistivity in the 40-70 Ω/a range. Ohmic Ag/SnO2 contacts are formed by silver paste printing followed by an appropriate thermal annealing, which provide connections to the external circuitry. Durability tests are carried out on several samples; the long-term performance of the fabricated devices is satisfactory. The method allows the elimination of the expensive ruthenium dioxide from the structure of generic gas sensors.

  3. 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.

  4. Decontamination of discharged aluminum brass condenser tubes of a BWR. Evolving the chemical formulation for copper oxide dissolution

    International Nuclear Information System (INIS)

    Chemical formulations for copper oxide dissolution have been evaluated primarily for the minimum ionic load resulting in the spent formulation along with other desirable qualities. Peroxydisulfuric acid prepared freshly through ion exchange route has shown almost stoichiometric dissolution of the copper oxide as per the acidic oxidative action with efficient kinetics. Stability of the prepared formulation for its application and its effective oxidizing behaviour and aqueous cupric ion stabilizing by its redox product has been established experimentally. (author)

  5. Upper D region chemical kinetic modeling of LORE relaxation times

    Science.gov (United States)

    Gordillo-Vázquez, F. J.; Luque, A.; Haldoupis, C.

    2016-04-01

    The recovery times of upper D region electron density elevations, caused by lightning-induced electromagnetic pulses (EMP), are modeled. The work was motivated from the need to understand a recently identified narrowband VLF perturbation named LOREs, an acronym for LOng Recovery Early VLF events. LOREs associate with long-living electron density perturbations in the upper D region ionosphere; they are generated by strong EMP radiated from large peak current intensities of ±CG (cloud to ground) lightning discharges, known also to be capable of producing elves. Relaxation model scenarios are considered first for a weak enhancement in electron density and then for a much stronger one caused by an intense lightning EMP acting as an impulsive ionization source. The full nonequilibrium kinetic modeling of the perturbed mesosphere in the 76 to 92 km range during LORE-occurring conditions predicts that the electron density relaxation time is controlled by electron attachment at lower altitudes, whereas above 79 km attachment is balanced totally by associative electron detachment so that electron loss at these higher altitudes is controlled mainly by electron recombination with hydrated positive clusters H+(H2O)n and secondarily by dissociative recombination with NO+ ions, a process which gradually dominates at altitudes >88 km. The calculated recovery times agree fairly well with LORE observations. In addition, a simplified (quasi-analytic) model build for the key charged species and chemical reactions is applied, which arrives at similar results with those of the full kinetic model. Finally, the modeled recovery estimates for lower altitudes, that is <79 km, are in good agreement with the observed short recovery times of typical early VLF events, which are known to be associated with sprites.

  6. Reduced Models in Chemical Kinetics via Nonlinear Data-Mining

    Directory of Open Access Journals (Sweden)

    Eliodoro Chiavazzo

    2014-01-01

    Full Text Available The adoption of detailed mechanisms for chemical kinetics often poses two types of severe challenges: First, the number of degrees of freedom is large; and second, the dynamics is characterized by widely disparate time scales. As a result, reactive flow solvers with detailed chemistry often become intractable even for large clusters of CPUs, especially when dealing with direct numerical simulation (DNS of turbulent combustion problems. This has motivated the development of several techniques for reducing the complexity of such kinetics models, where, eventually, only a few variables are considered in the development of the simplified model. Unfortunately, no generally applicable a priori recipe for selecting suitable parameterizations of the reduced model is available, and the choice of slow variables often relies upon intuition and experience. We present an automated approach to this task, consisting of three main steps. First, the low dimensional manifold of slow motions is (approximately sampled by brief simulations of the detailed model, starting from a rich enough ensemble of admissible initial conditions. Second, a global parametrization of the manifold is obtained through the Diffusion Map (DMAP approach, which has recently emerged as a powerful tool in data analysis/machine learning. Finally, a simplified model is constructed and solved on the fly in terms of the above reduced (slow variables. Clearly, closing this latter model requires nontrivial interpolation calculations, enabling restriction (mapping from the full ambient space to the reduced one and lifting (mapping from the reduced space to the ambient one. This is a key step in our approach, and a variety of interpolation schemes are reported and compared. The scope of the proposed procedure is presented and discussed by means of an illustrative combustion example.

  7. HCT, Time Dependent 1-D Gas Hydrodynamics, Chemical Kinetics, Chemical Transport

    International Nuclear Information System (INIS)

    1 - Description of program or function: HCT is a general program for calculating time-dependent problems involving one-dimensional gas hydrodynamics, transport, and detailed chemical kinetics. It is capable of modeling in detail one-dimensional time-dependent combustion phenomena of gases. The physical processes modeled are chemical reactions, thermal conduction, species diffusion, and hydrodynamics. Problem initialization is by input deck; output available includes a complete set of general line printer edits. The basic difference equations allow one to efficiently calculate stiff kinetics systems and systems evolving slowly compared to sound transit times. Hydrodynamics calculation may be done in either a Lagrange or Eulerian framework. An option gives a variable spatial mesh with high resolution in areas of high-temperature gradients. 2 - Method of solution: For maximum robustness, the implicitly differenced hydrodynamics, transport, and kinetics equations are solved simultaneously using a generalized Newton iteration scheme. This method requires the inversion of a block tridiagonal matrix with block size proportional to the number of species. Optimized assembly language matrix-manipulation routines which take advantage of the CDC7600 pipeline architecture are included

  8. Chemical Vapor Synthesis of Nanocrystalline Oxides

    Science.gov (United States)

    Djenadic, Ruzica; Winterer, Markus

    The generation of nanoparticles in the gas phase by Chemical Vapor Synthesis (CVS) may be described from the point of view of chemical engineering as a sequence of unit operations among which reactant delivery, reaction energy input, and product separation are key processes which determine the product characteristics and quality required by the applications of nanoparticles and powders. In case of CVS, the volatility of the reactants (precursors) may severely limit the possible type of products as well as the production rate. It is shown that these limits can be lifted by use of a laser flash evaporator which also enables the use of precursor mixtures for the production of complex oxides as shown for Co-doped ZnO and the pulsed operation to influence powder characteristics. The mode in which energy is supplied to the particle synthesis reactor has also substantial influence on particle and powder characteristics as is shown for TiO2 using different time-temperatureprofiles.

  9. The Kinetics Of Ti-1Al-1Mn Alloy Thermal Oxidation And Charcteristic Of Oxide Layer

    Directory of Open Access Journals (Sweden)

    Klimecka-Tatar D.

    2015-06-01

    Full Text Available The main goal of the study was to carry out the treatment of cyclic oxidation of Ti alloy (Ti-1Al-1Mn in air atmosphere. Based on measurements of mass gain of titanium alloy samples (Ti-1Al-1Mn the kinetic oxidation curves during cyclic annealing were determined. The oxidized surface of the titanium alloy was carefully observed with optical microscopy equipment and the geometrical development, shape and surface morphology were defined. The phase composition of the obtained oxide layers on the Ti-alloy with qualitative analysis of the X-ray were defined. Since titanium alloys are among the most widely used metallic materials in dental prosthetics the corrosion measurements in a solution simulating the environment of the oral cavity were carried out. The results confirmed that the used titanium alloy easily covered with oxides layers, which to some extent inhibit the processes of electrochemical corrosion in artificial saliva solution.

  10. A Review of Research on the Teaching and Learning of Chemical Kinetics

    Science.gov (United States)

    Bain, Kinsey; Towns, Marcy H.

    2016-01-01

    We review literature on the teaching and learning of chemical kinetics at both the secondary and tertiary levels. Our aim in doing so is to summarize research literature, synthesize recommendations for future research, and suggest implications for practitioners. Two main bodies of literature emerged from the chemical kinetics education research:…

  11. Influence of the Radio-Oxidation Kinetic Model on the Critical Oxided Thickness

    International Nuclear Information System (INIS)

    The diffusion-controlled oxidation (also named physical effect of the dose rate) is an unavoidable phenomenon that occurs in polymers under ionising radiation in presence of oxygen. Indeed, oxygen is consumed inside the polymer consecutively to radio-oxidative processes. When oxygen molecules are consumed faster than they can diffuse inside the sample, oxidation is not homogeneous within the sample thickness. This leads to a heterogeneous oxidation profile with a minimum of oxidation at the centre of the sample. In this context, the concept of critical thickness Lc has been introduced. It corresponds to the thickness for which the cumulative oxygen consumption is equal to 90 % of the oxygen consumption which would occur if the oxidation was not limited by the oxygen diffusion. Gillen and Clough have determined a practical way to estimate the value of Lc from several parameters linked to the experimental conditions in the frame of the homogeneous steady?state kinetic model simplified by a relation giving the reaction constant for the recombination between the macroradicals, P degree and the peroxyl radicals, POO degree. This common assumption has the unique purpose of providing an analytical solution of the oxidation rate but is in fact unfounded. Consequently, we reconsidered the calculus, still in the frame of the homogeneous steady-state kinetic model, but without this unrealistic hypothesis on the reaction rate between P degree and POO degree. We compared the results obtained in both cases. And it appears that, exception made of the very low oxygen pressure region, Lc is not significantly affected by choosing the simplified kinetic model

  12. A fundamental research on combustion chemical kinetic model’s precision property

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Uncertainty analysis was used to investigate the precision property of detailed chemical kinetic models.A general-purpose algorithm for assessing and evaluating the impact of uncertainties in chemical kinetic models is presented.The method was also validated through analysis of different kinetic mechanisms applied in the process of modeling NOx emission in methane flame. The algorithm,which provided a basis for further studies,was more efficient and general compared with other methods.

  13. The Mechanism of Surface Chemical Kinetics of Dissolution of Minerals

    Institute of Scientific and Technical Information of China (English)

    谭凯旋; 张哲儒; 等

    1996-01-01

    This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δHn0+,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.

  14. Cometary impact and amino acid survival - Chemical kinetics and thermochemistry

    Science.gov (United States)

    Ross, D.S.

    2006-01-01

    The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9?? above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometa??ry delivery of amino acids to early Earth is highly unlikely. ?? 2006 American Chemical Society.

  15. Integration Strategies for Efficient Multizone Chemical Kinetics Models

    Energy Technology Data Exchange (ETDEWEB)

    McNenly, M J; Havstad, M A; Aceves, S M; Pitz, W J

    2009-10-15

    Three integration strategies are developed and tested for the stiff, ordinary differential equation (ODE) integrators used to solve the fully coupled multizone chemical kinetics model. Two of the strategies tested are found to provide more than an order of magnitude of improvement over the original, basic level of usage for the stiff ODE solver. One of the faster strategies uses a decoupled, or segregated, multizone model to generate an approximate Jacobian. This approach yields a 35-fold reduction in the computational cost for a 20 zone model. Using the same approximate Jacobian as a preconditioner for an iterative Krylov-type linear system solver, the second improved strategy achieves a 75-fold reduction in the computational cost for a 20 zone model. The faster strategies achieve their cost savings with no significant loss of accuracy. The pressure, temperature and major species mass fractions agree with the solution from the original integration approach to within six significant digits; and the radical mass fractions agree with the original solution to within four significant digits. The faster strategies effectively change the cost scaling of the multizone model from cubic to quadratic, with respect to the number of zones. As a consequence of the improved scaling, the 40 zone model offers more than a 250-fold cost savings over the basic calculation.

  16. Approximate method for stochastic chemical kinetics with two-time scales by chemical Langevin equations.

    Science.gov (United States)

    Wu, Fuke; Tian, Tianhai; Rawlings, James B; Yin, George

    2016-05-01

    The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in the work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766-1793 (1996); ibid. 56, 1794-1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence. PMID:27155630

  17. Nanodispersed Oxides-Plasma-Chemical Synthesis and Properties

    Institute of Scientific and Technical Information of China (English)

    Gheorghi VISSOKOV; Katerina ZAHARIEVA

    2007-01-01

    We discuss the plasma-chemical synthesis and the properties of transition metals oxides, Al2O3, SiO2, rare-earth oxides, oxides for ceramics and metal-ceramics, and oxides used as catalysts. Bearing in mind the indisputable advantages of using plasma-chemically synthesized nanodispersed oxides for the needs of various industrial fields, we set out to review the articles published in the past few years devoted to the problems of plasma-chemical synthesis and characterization of nanodispersed oxides.

  18. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  19. Kinetic modeling of antimony(III) oxidation and sorption in soils.

    Science.gov (United States)

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-01

    Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. PMID:27214003

  20. Kinetic Deuterium Isotope Effects in Cytochrome P450 Oxidation Reactions

    Science.gov (United States)

    Guengerich, F. Peter

    2016-01-01

    Cytochrome P450 (P450) enzymes account for ~ 75% of the metabolism of drugs. Most of the reactions catalyzed by P450s are mixed-function oxidations, and a C-H bond is (usually) broken. The rate-limiting nature of this step can be analyzed using the kinetic isotope effect (KIE) approach. The most relevant type of KIE is one termed intermolecular non-competitive, indicative of rate-limiting C-H bond breaking. A KIE vs. kcat for several P450s showed a correlation coefficient (r2) of 0.62. Deuterium substitution has been considered as a potential means of slowing drug metabolism or redirecting sites of metabolism in some cases, and several general points can be made regarding the potential for application of deuterium in drug design/development based on what is known about P450 KIEs. PMID:24285515

  1. The role of layer structure in tin oxidation kinetics

    Science.gov (United States)

    Duhalde, S.; Arcondo, B.; Sirkin, H.

    1991-11-01

    Tin exhibits different oxidation kinetics which are composition dependent, when it forms intermetallic compounds with the chalcogenides S and Se. This phenomenon is related to the layer compounds SnS2 and SnSe2 crystalline structure. These minerals have anisotropic bonding characteristics, due to Van der Waals bonds presence between chalcogenides adjoining planes. The mentioned weak bonds allow the oxygen diffusion to the bulk, favouring the reaction with the inner tin atoms. In this work we study samples of Sn-S alloy with different thermal treatment by XRD and Mössbauer spectroscopy. Results are discussed and compared with those obtained for Sn-Se alloy in an early work [1].

  2. Kinetics of Uranium Extraction from Uranium Tailings by Oxidative Leaching

    Science.gov (United States)

    Zhang, Biao; Li, Mi; Zhang, Xiaowen; Huang, Jing

    2016-07-01

    Extraction of uranium from uranium tailings by oxidative leaching with hydrogen peroxide (H2O2) was studied. The effects of various extraction factors were investigated to optimize the dissolution conditions, as well as to determine the leaching kinetic parameters. The behavior of H2O2 in the leaching process was determined through scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray diffraction analysis of leaching residues. Results suggest that H2O2 can significantly improve uranium extraction by decomposing the complex gangue structures in uranium tailings and by enhancing the reaction rate between uranium phases and the leaching agent. The extraction kinetics expression was changed from 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)-0.14903(S/L)-1.80435( R o)0.20023 e -1670.93/T t ( t ≥ 5) to 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)0.01382(S/L)-1.83275( R o)0.25763 e -1654.59/T t ( t ≥ 5) by the addition of H2O2 in the leaching process. The use of H2O2 in uranium leaching may help in extracting uranium more efficiently and rapidly from low-uranium-containing ores or tailings.

  3. Kinetics of Uranium Extraction from Uranium Tailings by Oxidative Leaching

    Science.gov (United States)

    Zhang, Biao; Li, Mi; Zhang, Xiaowen; Huang, Jing

    2016-05-01

    Extraction of uranium from uranium tailings by oxidative leaching with hydrogen peroxide (H2O2) was studied. The effects of various extraction factors were investigated to optimize the dissolution conditions, as well as to determine the leaching kinetic parameters. The behavior of H2O2 in the leaching process was determined through scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray diffraction analysis of leaching residues. Results suggest that H2O2 can significantly improve uranium extraction by decomposing the complex gangue structures in uranium tailings and by enhancing the reaction rate between uranium phases and the leaching agent. The extraction kinetics expression was changed from 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)-0.14903(S/L)-1.80435(R o)0.20023 e -1670.93/T t (t ≥ 5) to 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)0.01382(S/L)-1.83275(R o)0.25763 e -1654.59/T t (t ≥ 5) by the addition of H2O2 in the leaching process. The use of H2O2 in uranium leaching may help in extracting uranium more efficiently and rapidly from low-uranium-containing ores or tailings.

  4. Kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium

    Institute of Scientific and Technical Information of China (English)

    WANG Yun-shan; LI Zuo-hu; LI Hao-ran

    2005-01-01

    The kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium was investigated in terms of the gas-flow rate, stirring rate, reaction time, reaction temperature and partial pressure of oxygen on the ratio of manganese conversion in ocean polymetallic nodules. The category of the rate controlling step was determined. The process of the liquid-phase oxidation reaction can be described by surface chemical reaction-controlled non-reaction shrinking core model(SCM), the apparent activation energy was achieved and the rate equation was put forward. From the equation, it can be concluded that the reaction rate mainly depends on the reaction temperature and the partial pressure of oxygen.

  5. Gas-Phase Oxidation Kinetics and Organic Aerosol Products of Ethanolamine

    Science.gov (United States)

    Borduas, N.; Abbatt, J.; Murphy, J. G.

    2012-12-01

    Ethanolamine is currently the solvent of choice in carbon capture and storage technology (CCS) which aims to reduce CO2 emissions to the atmosphere in coal powered pilot plants. CCS technology represents an unprecedented large scale application of ethanolamine and little is known of its fate if it was unintentionally released into the atmosphere. Relative kinetic experiments were conducted in a 1m3 smog chamber using online proton-transfer-reaction mass spectrometry. The kinetics of oxidation with hydroxyl radicals from light and dark sources converge to a value of (7.6 ± 1.1) x 10-11 cm3 molec-1 s-1. The reaction of ethanolamine with ozone was determined to be (1.05 ± 0.08) x 10-18 cm3 molec-1 s-1. We find that ethanolamine has a short lifetime in the atmosphere and readily deposits onto wall and particle surfaces, as observed by considerable formation of organonitrogen aerosol products. An investigation into the oxidation product formation using a combination of reagent ions with online chemical ionization mass spectrometry approaches lead to the detection of higher order products. The formation of these high molecular weight products is simultaneous with the oxidation of ethanolamine and implies substantial organic aerosol chemistry.

  6. Deactivation kinetics of V/Ti-oxide in toluene partial oxidation

    OpenAIRE

    Bulushev, D. A.; Reshetnikov, S. I.; Kiwi-Minsker, L; Renken, A.

    2001-01-01

    The deactivation kinetics of a V/Ti oxide catalyst were studied in partial oxidn. of toluene to PhCHO and PhCO2H at 523-573 K. The catalyst consists of a monolayer of VOx species, and after oxidative pretreatment, contains isolated monomeric and polymeric metavanadate-like vanadia species under dehydrated conditions as was shown by FT Raman spectroscopy. Under the reaction conditions via in situ DRIFTS, fast formation of adsorbed carboxylate and benzoate species was obsd. accompanied by disap...

  7. Stochastic chemical kinetics theory and (mostly) systems biological applications

    CERN Document Server

    Érdi, Péter

    2014-01-01

    This volume reviews the theory and simulation methods of stochastic kinetics by integrating historical and recent perspectives, presents applications, mostly in the context of systems biology and also in combustion theory. In recent years, due to the development in experimental techniques, such as optical imaging, single cell analysis, and fluorescence spectroscopy, biochemical kinetic data inside single living cells have increasingly been available. The emergence of systems biology brought renaissance in the application of stochastic kinetic methods.

  8. Pyrolysis and thermal oxidation kinetics of sugar mill press mud

    International Nuclear Information System (INIS)

    Press mud, a solid waste obtained from the sugar mills, has the potential of energy generation through pyrolysis and gasification. The paper reports its proximate and ultimate analyses, deformation and fusion ash temperatures, lower and higher heating values, physico-chemical and thermal degradation in nitrogen and air atmospheres. The thermal degradation was conducted in a thermogravimetric analyzer from room temperature to 900 deg C at heating rates of 20 and 40 K min-1. The thermogravimetric, derivative thermogravimetric and differential thermal analyses were carried out to determine the rate of volatiles evolution, the effect of heating rates on the thermal degradation characteristics and to determine the global mass loss kinetics of thermal degradation. The thermal degradation was found to occur in several distinct phases: each phase giving volatile evolution in an independent parallel lump. Each decomposition phase was modeled by a single irreversible reaction with respect to the solid mass. Global mass loss kinetics was also determined for the entire decomposition process, as if occurring in one single step. The integral and differential techniques were used for the determination of kinetic parameters. Using the method of Agrawal and Sivasubramanian [R.K. Agrawal, M.S. Sivasubramanian, AIChE J. 33 (1987) 7] for the total degradation zone, the orders of reaction were found in the range of 1.00-2.50 in both the atmospheres (i.e. nitrogen and air) and the activation energy in the range of 27.84-33.44 and 57.41-88.92 kJ mol-1 in nitrogen and air, respectively. The pre-exponential factor was found in the range of 32.1-95.1 and 5.10 x 104 to 5.46 x 109 min-1 in nitrogen and air atmospheres, respectively

  9. Significance of Xenobiotic Metabolism for Bioaccumulation Kinetics of Organic Chemicals in Gammarus pulex

    OpenAIRE

    Ashauer, Roman; Hintermeister, Anita; O’Connor, Isabel; Elumelu, Maline; Hollender, Juliane; Escher, Beate I

    2012-01-01

    Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen 14C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacry...

  10. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)

    2014-12-15

    Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

  11. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    International Nuclear Information System (INIS)

    Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells

  12. Adsorption kinetics for the removal of soluble manganese by oxide- coated filter media

    OpenAIRE

    Hungate, Robert W.

    1988-01-01

    This study was conducted to examine the kinetics of manganese sorption on oxide-coated filter media. Initial experimentation confirmed the findings of other investigators, the Mn2+ sorption capacity of oxide-coated media increases as solution pH increases. Further study revealed that uptake rate kinetics could be described by first order kinetics and also increased with increasing solution pH. The addition of free chlorine (HOCl) to solution greatly enhanced Mn2+ uptak...

  13. Development of chemical kinetic models for lean NOx traps.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Richard S.

    2010-04-01

    Overall project goal: Obtain the fundamental surface chemistry knowledge needed for the design and optimal utilization of NOx trap catalysts, thereby helping to speed the widespread adoption of this technology. Relevance to VT Program goals: Effective, durable advanced aftertreatment systems for lean-burn engines must be available if the fuel economy advantages of these engines are to be realized. Specific current year objective: Identify and correct any deficiencies in the previously developed reaction mechanism describing normal storage/regeneration cycles, and complete development of a supplementary mechanism accounting for the effects of sulfation. A fundamental understanding of LNT chemistry is needed to realize the full potential of this aftertreatment technology, which could lead to greater use of fuel-efficient lean-burn engines. We have used a multi-tiered approach to developing an elementary chemical mechanism benchmarked against experimental data: (1) Simulate a set of steady flow experiments, with storage effects minimized, to infer a tentative mechanism for chemistry on precious metal sites (completed). (2) Simulate a set of long cycle experiments to infer a mechanism for NOx and oxygen storage sites while simultaneously finalizing precious metal chemistry (completed). (3) Simulate a simplified sulfation/desulfation protocol to obtain a supplementary set of reactions involving sulfur on all three kinds of sites (nearly completed). (4) Investigate the potential role of reductants other than CO and H{sub 2}. While simulation of isothermal experiments is the preferred way to extract kinetic parameters, simulation of realistic storage/regeneration cycles requires that exotherms be considered. Our ultimate goal is to facilitate improved designs for LNT-based aftertreatment systems and to assist in the development of improved catalysts.

  14. Growth kinetics of thin oxide layers; oxidation of Fe and Fe-N phases at room temperature

    OpenAIRE

    Kooi, Bart J.; Somers, Marcel A. J.; Mittemeijer, Eric J.

    1996-01-01

    The evolution of iron-oxide layers at room temperature on pure polycrystalline α-Fe and on the Fe-N phases γ-Fe[N], γ'-Fe4N1-x and ε-Fe2N1-z was followed in situ with Auger-Electron Spectroscopy. The observed oxidation kinetics of the Fe and Fe-N phases were interpreted using a model considering coupled fluxes of cations and (tunnelling) electrons and an electrostatic potential difference over the oxide layer changing during oxidation. It was concluded that the oxidation kinetics are largely ...

  15. Chemical oxidation methods in the closure of paper mill water circulations; Hapetustekniikoiden kaeyttoe metsaeteollisuuden vesikiertojen sulkemisessa - EKT 04

    Energy Technology Data Exchange (ETDEWEB)

    Laari, A.; Kallas, J. [Lappeenranta Univ. of Technology (Finland); Korhonen, S. [Kuopio Univ. (Finland); Tuhkanen, T. [Mikkelin Ammattikorkeakoulu, Mikkeli (Finland)

    1998-12-31

    When water circulations are closed some harmful compounds tend to accumulate in the circulation waters. These compounds include lipophilic extractives, like resin and fatty acids, triglycerides and sterols, but also other compounds, like lignins, lignans and sugars. Microbial growth will increase due to elevated organic concentrations. The purpose of this project is to find out the possibilities of the use of ozonation and wet oxidation in the treatment of paper mill water circulations. In chemical oxidation organic matter is destroyed in oxidation reactions. Especially lipophilic extractives are selectively oxidated by ozone. Chemical oxidation reactions are carried out in gas-liquid reactors, where ozone or oxygen are transferred from gas to liquid phase where the oxidation reactions happen. One target of the project is to estimate kinetic parameters for different groups of compounds on the basis of experimental data. Kinetic parameters are then used in modelling of reactors and in estimation of process costs. (orig.)

  16. ADVANCED OXIDATION PROCESSES (AOP'S FOR THE TREATMENT OF CCL CHEMICALS

    Science.gov (United States)

    Research on treatment of Contaminant Candidate List (CCL) chemicals is being conducted. Specific groups of contaminants on the CCL will be evaluated using numerous advanced oxidation processes (AOPs). Initially, these CCL contaminants will be evaluated in groups based on chemical...

  17. Isothermal Kinetics of Diesel Soot Oxidation over La0.7K0.3ZnOy Catalysts

    Directory of Open Access Journals (Sweden)

    Ram Prasad

    2014-10-01

    Full Text Available This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions (320-350 oC. Isothermal kinetics data were collected in a mini-semi-batch reactor. Experiments were performed over the best selected catalyst composition La0.7K0.3ZnOy prepared by sol-gel method. Characterization of the catalyst by XRD and FTIR confirmed that La1-xKxZnOy did not exhibit perovskite phase but formed mixed metal oxides. 110 mg of the catalyst-soot mixture in tight contact (10:1 ratio was taken in order to determine the kinetic model, activation energy and Arrhenius constant of the oxidation reaction under the high air flow rate assuming pseudo first order reaction. The activation energy and Arrhenius constant were found to be 138 kJ/mol and 6.46x1010 min-1, respectively. © 2014 BCREC UNDIP. All rights reservedReceived: 26th April 2014; Revised: 27th May 2014; Accepted: 28th June 2014How to Cite: Prasad, R., Kumar, A., Mishra, A. (2014. Isothermal Kinetics of Diesel Soot Oxidation over La0.7K0.3ZnOy Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 9(3: 192-200. (doi: 10.9767/bcrec.9.3.6773.192-200Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.6773.192-200

  18. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    Energy Technology Data Exchange (ETDEWEB)

    O' Day, Peggy A. [Univ. of California, Merced, CA (United States); Asta, Maria P. [Univ. of California, Merced, CA (United States); Kanematsu, Masakazu [Univ. of California, Merced, CA (United States); Beller, Harry [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhou, Peng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Steefel, Carl [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  19. n-Butane: Ignition delay measurements at high pressure and detailed chemical kinetic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Healy, D.; Curran, H.J. [Combustion Chemistry Centre, School of Chemistry, NUI Galway (Ireland); Donato, N.S.; Aul, C.J.; Petersen, E.L. [Department of Mechanical Engineering, Texas A and M University, College Station, TX (United States); Zinner, C.M. [Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL (United States); Bourque, G. [Rolls-Royce Canada Limited, 9500 Cote de Liesse, Lachine, Quebec, H8T 1A2 (Canada)

    2010-08-15

    Ignition delay time measurements were recorded at equivalence ratios of 0.3, 0.5, 1, and 2 for n-butane at pressures of approximately 1, 10, 20, 30 and 45 atm at temperatures from 690 to 1430 K in both a rapid compression machine and in a shock tube. A detailed chemical kinetic model consisting of 1328 reactions involving 230 species was constructed and used to validate the delay times. Moreover, this mechanism has been used to simulate previously published ignition delay times at atmospheric and higher pressure. Arrhenius-type ignition delay correlations were developed for temperatures greater than 1025 K which relate ignition delay time to temperature and concentration of the mixture. Furthermore, a detailed sensitivity analysis and a reaction pathway analysis were performed to give further insight to the chemistry at various conditions. When compared to existing data from the literature, the model performs quite well, and in several instances the conditions of earlier experiments were duplicated in the laboratory with overall good agreement. To the authors' knowledge, the present paper presents the most comprehensive set of ignition delay time experiments and kinetic model validation for n-butane oxidation in air. (author)

  20. Kinetic Studies on the Selective Oxidation of Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis

    Directory of Open Access Journals (Sweden)

    K. Bijudas

    2014-07-01

    Full Text Available Kinetic studies on the oxidation of benzyl alcohol and substituted benzyl alcohols in benzene as the reaction medium have been studied by using potassium dichromate under phase transfer catalysis (PTC. The phase transfer catalysts (PT catalysts used were tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB.  Benzyl alcohols were selectively oxidised to corresponding benzaldehydes in good yield (above 90%.  The order of reactivity among the studied benzyl alcohols is p - OCH3 > p - CH3 > - H > p - Cl.  Plots of log k2 versus Hammett's substituent constant (s has been found to be curve shaped and this suggests that there should be a continuous change in transition state with changes in substituent present in the substrate from electron donating to electron withdrawing. A suitable mechanism has been suggested in which the rate determining step involves both C - H bond cleavage and C - O bond formations in concerted manner. © 2014 BCREC UNDIP. All rights reserved.Received: 16th March 2014; Revised: 18th May 2014; Accepted: 18th May 2014[How to Cite: Bijudas, K., Bashpa, P., Nair, T.D.R. (2014. Kinetic Studies on the Selective Oxidation of Benzyl Alcohol and Substituted Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-147. (doi:10.9767/bcrec.9.2.6476.142-147][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6476.142-147] 

  1. Crystallization kinetics of a solid oxide fuel cell seal glass by differential thermal analysis

    Science.gov (United States)

    Bansal, Narottam P.; Gamble, Eleanor A.

    Crystallization kinetics of a barium-calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells (SOFC), have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol using a kinetic model. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder X-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO 3 and hexacelsian (BaAl 2Si 2O 8) were the primary crystalline phases whereas monoclinic celsian (BaAl 2Si 2O 8) and (Ba xCa y)SiO 4 were also detected as minor phases. Needle-shaped BaSiO 3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long-term heat treatments at 750-900 °C. Devitrification of the glass seal over a long period of time during operation of the SOFC would generate thermal stresses in the seal and may have adverse effects on its mechanical performance. This may lead to cracking of the seal, resulting in mixing of the fuel and the oxidant gases.

  2. Influence of diffusion on extraction kinetics in porous bodies. The case of uranium oxides

    International Nuclear Information System (INIS)

    The study of the leaching of heaped uranium ore can be considered theoretically as the problem of the diffusion of liquids in porous bodies and in particular as that of its influence on the chemical reaction rates of conventional uranium oxides. Below a certain value of the pore diameter, it is diffusion which is responsible for mass transfer. The porous structure can be characterized by various physical constants which modify the free diffusion equation and, as long as the pores have a diameter greater than a few microns, it can be shown that the pore walls have a negligible effect on the diffusion. The diffusion coefficients for the nitrate, the sulfate, the chloride, the acetate and the perchlorate of uranium have been determined. In the case of the reaction of uranium trioxide with acids in a porous body, the reaction kinetics are governed by the arrival of the reagent by diffusion. The attack of uranium dioxide by an acid ferric iron solution has been studied under the same conditions and it has been found that the diffusion modifies the influence of the ferrous and ferric iron concentrations on the reaction kinetics. The same is true for the oxide U3O8. All the results concerning these reactions studied in the absence of the influence of diffusion should be modified to take this factor into account when it intervenes in an extraction process. (authors)

  3. Kinetic Study of Zn2+ and Cd2+ Ions Sorption by Ceric Oxide Powder

    International Nuclear Information System (INIS)

    Ceric Oxide powder was chemically synthesized and characterized using infrared spectra and x-ray diffraction. The sorptive removal of Zinc and Cadmium ions from aqueous waste solution using synthetic ceric oxide powder was investigated using batch technique. Experiments were carried out as a function of ph, particle size, solute concentration and temperature. The uptake of zinc was found to be greater than that of cadmium. A comparison of kinetic models applied to the sorption process of each ion was evaluated for the pseudo first order, the pseudo second order, and homogeneous particle diffusion kinetic models, respectively. The results showed that both the pseudo second order and the homogeneous particle diffusion model (HPDM) were found to best correlate the experimental rate data. The numerical values of the rate constants and particle diffusion coefficients were determined from the graphical representation of the proposed models. Activation energy (Εa) and entropy (δ S*) of activation for each sorption process were also calculated from the linearized form of Arrhenius equation

  4. Critical evaluation of Jet-A spray combustion using propane chemical kinetics in gas turbine combustion simulated by KIVA-2

    Science.gov (United States)

    Nguyen, H. L.; Ying, S.-J.

    1990-07-01

    Jet-A spray combustion has been evaluated in gas turbine combustion with the use of propane chemical kinetics as the first approximation for the chemical reactions. Here, the numerical solutions are obtained by using the KIVA-2 computer code. The KIVA-2 code is the most developed of the available multidimensional combustion computer programs for application of the in-cylinder combustion dynamics of internal combustion engines. The released version of KIVA-2 assumes that 12 chemical species are present; the code uses an Arrhenius kinetic-controlled combustion model governed by a four-step global chemical reaction and six equilibrium reactions. Researchers efforts involve the addition of Jet-A thermophysical properties and the implementation of detailed reaction mechanisms for propane oxidation. Three different detailed reaction mechanism models are considered. The first model consists of 131 reactions and 45 species. This is considered as the full mechanism which is developed through the study of chemical kinetics of propane combustion in an enclosed chamber. The full mechanism is evaluated by comparing calculated ignition delay times with available shock tube data. However, these detailed reactions occupy too much computer memory and CPU time for the computation. Therefore, it only serves as a benchmark case by which to evaluate other simplified models. Two possible simplified models were tested in the existing computer code KIVA-2 for the same conditions as used with the full mechanism. One model is obtained through a sensitivity analysis using LSENS, the general kinetics and sensitivity analysis program code of D. A. Bittker and K. Radhakrishnan. This model consists of 45 chemical reactions and 27 species. The other model is based on the work published by C. K. Westbrook and F. L. Dryer.

  5. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    KAUST Repository

    Nagaraju, Doddahalli H.

    2014-12-01

    Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.

  6. Low-temperature oxidation of alkali overlayers: Ionic species and reaction kinetics

    International Nuclear Information System (INIS)

    Clean and oxidized alkali metal films have been studied using X-ray photoelectron spectroscopy (XPS). Thin films, typically 10 nm thick, of lithium, sodium, potassium, rubidium and cesium have been deposited on silicon substrates and oxidized at 120 K. Plasmon losses were found to dress the primary photo emission structures of the metals’ core lines which confirms the metallic, bulk like nature of the films. The emission from the O 1s core levels was used to determine the chemical composition and the reaction kinetics during the exposure to molecular oxygen at low pressures. Molecular oxide ions O2− and O22− as well as atomic oxygen ions O2− were detected in varying amounts depending on the alkali metal used. Diffusive transport of material in the film is shown to greatly determine the composition of the oxides. Especially, the growth of potassium superoxide is explained by the diffusion of potassium atoms to the surface and growth at the surface in a Deal–Grove like model.

  7. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  8. Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WAN Jia-feng; FENG Yu-jie; CAI Wei-min; YANG Shao-xia; SUN Xiao-jun

    2004-01-01

    Four metal oxide catalysts composed of copper (Cu), stannum (Sn), copper-stannum (Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al2O3) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu-10%Ce/γ-Al2O3 showed the best catalytic activity. This is consistent with the result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 min. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.

  9. New Chemical Kinetics Approach for DSMC Applications to Nonequilibrium Flows Project

    Data.gov (United States)

    National Aeronautics and Space Administration — A new chemical kinetics model and database will be developed for aerothermodynamic analyses on entry vehicles. Unique features of this model include (1) the ability...

  10. Kinetic Model of Hypophosphite Oxidation on a Nickel Electrode in D2O Solution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Kinetic model of hypophosphite oxidation on a nickel electrode was studied in D2Osolution in order to reach a better understanding of the oxidation mechanism. In the model the electrooxidation of hypophosphite undergo a H abstraction of hypophosphite from the P-H bond to form the phosphorus-centered radical PHO2-, which subsequently is electrochemically reacted with water to form the final product, phosphite. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The process of hypophosphite electrooxidation could be well simulated by this model

  11. Carbon-13 kinetic isotope effects in CO oxidation by Ag

    International Nuclear Information System (INIS)

    In the catalytic oxidation of carbon monoxide over silver wool the 13C kinetic isotope effects in the 343--453 K temperature range were experimentally determined and the following temperature dependence was found: 100 ln(k12/k13) = (3.398--630/T) ± 0.083. A reaction CO/O2gas mixture of 1:2 ratio was used in a static system with initial pressures ranging from 20 to 40 kPa. Under these conditions the reaction is of order 1 with respect to CO and order 0 with respect to O2 and CO2 pressure. The apparent activation energy is 59.3 ± 1.7 kJ/mol. In the authors theoretical interpretation of the experimental data various geometries of (CO2)* and (CO3)* transition states were applied, and only a (CO2)* with an interbond angle of 110degree and CO stretching force constants of 1,700 and 1,000--1,400 N/m, respectively, with an asymmetric reaction coordinate was found to be acceptable

  12. Kinetic Equation for Internal Oxidation of Cu-Al Alloy Spheres

    Institute of Scientific and Technical Information of China (English)

    SONG Kexing; GAO Jianxin; XU Xiaofeng; LI Peiquan; TIAN Baohong; GUO Xiuhua

    2007-01-01

    The kinetics of internal oxidation of Cu-Al alloy spheres, containing up to 2.214% mole fraction Al was investigated in the temperature range 1 023 K to 1 273 K, and the depth of internal oxidation was measured in the microscopy. A kinetic equation was derived to describe the internal oxidation of Cu-Al alloy spheres, which was checked experimentally by means of oxidation depth measurements. The results show that the derived equation is exact enough to describe the kinetics of internal oxidation of Cu-Al alloy spheres.Based on this equation and the oxidation depth measurements, the permeability of oxygen in solid copper has been obtained. Investigation also shows that in the process of internal oxidation, there is no evidence for preferential diffusion along grain boundaries.

  13. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker;

    2003-01-01

    It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...... mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models...

  14. The kinetics of iodide oxidation by the manganese oxide mineral birnessite

    Science.gov (United States)

    Fox, P.M.; Davis, J.A.; Luther, G. W., III

    2009-01-01

    The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

  15. Kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

    Science.gov (United States)

    Toyoda, Kazuhiro; Tebo, Bradley M.

    2016-09-01

    The kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1 was measured under controlled conditions of the initial Mn(II) concentration, spore concentration, chemical speciation, pH, O2, and temperature. Mn(II) oxidation experiments were performed with spore concentrations ranging from 0.7 to 11 × 109 spores/L, a pH range from 5.8 to 8.1, temperatures between 4 and 58 °C, a range of dissolved oxygen from 2 to 270 μM, and initial Mn(II) concentrations from 1 to 200 μM. The Mn(II) oxidation rates were directly proportional to the spore concentrations over these ranges of concentration. The Mn(II) oxidation rate increased with increasing initial Mn(II) concentration to a critical concentration, as described by the Michaelis-Menten model (Km = ca. 3 μM). Whereas with starting Mn(II) concentrations above the critical concentration, the rate was almost constant in low ionic solution (I = 0.05, 0.08). At high ionic solution (I = 0.53, 0.68), the rate was inversely correlated with Mn(II) concentration. Increase in the Mn(II) oxidation rate with the dissolved oxygen concentration followed the Michaelis-Menten model (Km = 12-19 μM DO) in both a HEPES-buffered commercial drinking (soft) water and in artificial and natural seawater. Overall, our results suggest that the mass transport limitations of Mn(II) ions due to secondary Mn oxide products accumulating on the spores cause a significant decrease of the oxidation rate at higher initial Mn(II) concentration on a spore basis, as well as in more concentrated ionic solutions. The optimum pH for Mn(II) oxidation was approximately 7.0 in low ionic solutions (I = 0.08). The high rates at the alkaline side (pH > 7.5) may suggest a contribution by heterogeneous reactions on manganese bio-oxides. The effect of temperature on the Mn(II) oxidation rate was studied in three solutions (500 mM NaCl, ASW, NSW solutions). Thermal denaturation occurred at 58 °C and spore germination was evident at 40 °C in all three

  16. Testing for supply-limited and kinetic-limited chemical erosion in field measurements of regolith production and chemical depletion

    Science.gov (United States)

    Ferrier, Ken L.; Riebe, Clifford S.; Jesse Hahm, W.

    2016-06-01

    Chemical erosion contributes solutes to oceans, influencing atmospheric CO2 and thus global climate via the greenhouse effect. Quantifying how chemical erosion rates vary with climate and tectonics is therefore vital to understanding feedbacks that have maintained Earth's environment within a habitable range over geologic time. If chemical erosion rates are strongly influenced by the availability of fresh minerals for dissolution, then there should be strong connections between climate, which is modulated by chemical erosion, and tectonic uplift, which supplies fresh minerals to Earth's surface. This condition, referred to as supply-limited chemical erosion, implies strong tectonic control of chemical erosion rates. It differs from kinetic-limited chemical erosion, in which dissolution kinetics and thus climatic factors are the dominant regulators of chemical erosion rates. Here we present a statistical method for determining whether chemical erosion of silicate-rich bedrock is supply limited or kinetic limited, as an approach for revealing the relative importance of tectonics and climate in Earth's silicate weathering thermostat. We applied this method to published data sets of mineral supply rates and regolith chemical depletion and were unable to reject the null hypothesis that chemical erosion is supply limited in 8 of 16 cases. In seven of the remaining eight cases, we found behavior that is closer to supply limited than kinetic limited, suggesting that tectonics may often dominate over climate in regulating chemical erosion rates. However, statistical power analysis shows that new measurements across a wider range of supply rates are needed to help quantify feedbacks between climate and tectonics in Earth's long-term climatic evolution.

  17. Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

    Institute of Scientific and Technical Information of China (English)

    罗伟平; 刘大为; 孙俊; 邓伟; 盛文兵; 刘强; 郭灿城

    2014-01-01

    Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

  18. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  19. Analysis of exergy loss of gasoline surrogate combustion process based on detailed chemical kinetics

    International Nuclear Information System (INIS)

    Highlights: • We explored the exergy loss sources of gasoline engine like combustion process. • The model combined non-equilibrium thermodynamics with detailed chemical kinetics. • We explored effects of initial conditions on exergy loss of combustion process. • Exergy loss decreases 15% of fuel chemical exergy by design of initial conditions. • Correspondingly, the second law efficiency increases from 38.9% to 68.9%. - Abstract: Chemical reaction is the most important source of combustion irreversibility in premixed conditions, but details of the exergy loss mechanisms have not been explored yet. In this study numerical analysis based on non-equilibrium thermodynamics combined with detailed chemical kinetics is conducted to explore the exergy loss mechanism of gasoline engine like combustion process which is simplified as constant volume combustion. The fuel is represented by the common accepted gasoline surrogates which consist of four components: iso-octane (57%), n-heptane (16%), toluene (23%), and 2-pentene (4%). We find that overall exergy loss is mainly composed of three peaks along combustion generated from chemical reactions in three stages, the conversion from large fuel molecules into small molecules (as Stage 1), the H2O2 loop-related reactions (as Stage 2), and the violent oxidation reactions of CO, H, and O (as Stage 3). The effects of individual combustion boundaries, including temperature, pressure, equivalence ratio, oxygen concentration, on combustion exergy loss have been widely investigated. The combined effects of combustion boundaries on the total loss of gasoline surrogates are also investigated. We find that in a gasoline engine with a compression ratio of 10, the total loss can be reduced from 31.3% to 24.3% using lean combustion. The total loss can be further reduced to 22.4% by introducing exhaust gas recirculation and boosting the inlet charge. If the compression ratio is increased to 17, the total loss can be decreased to 20

  20. Capture of gas-phase arsenic oxide by lime: kinetic and mechanistic studies.

    Science.gov (United States)

    Jadhav, R A; Fan, L S

    2001-02-15

    Trace metal emission from coal combustion is a major concern for coal-burning utilities. Toxic compounds such as arsenic species are difficult to control because of their high volatility. Mineral sorbents such as lime and hydrated lime have been shown to be effective in capturing arsenic from the gas phase over a wide temperature range. In this study, the mechanism of interaction between arsenic oxide (As2O3) and lime (CaO) is studied over the range of 300-1000 degrees C. The interaction between these two components is found to depend on the temperature; tricalcium orthoarsenate (Ca3As2O8) is found to be the product of the reaction below 600 degrees C, whereas dicalcium pyroarsenate (Ca2As2O7) is found to be the reaction product in the range of 700-900 degrees C. Maximum capture of arsenic oxide is found to occur in the range of 500-600 degrees C. At 500 degrees C, a high reactivity calcium carbonate is found to capture arsenic oxide by a combination of physical and chemical adsorption. Intrinsic kinetics of the reaction between calcium oxide and arsenic oxide in the medium-temperature range of 300-500 degrees C is studied in a differential bed flow-through reactor. Using the shrinking core model, the order of reaction with respect to arsenic oxide concentration is found to be about 1, and the activation energy is calculated to be 5.1 kcal/mol. The effect of initial surface area of CaO sorbent is studied over a range of 2.7-45 m2/g using the grain model. The effect of other major acidic flue gas species (SO2 and HCl) on arsenic capture is found to be minimal under the conditions of the experiment. PMID:11349294

  1. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

    Indian Academy of Sciences (India)

    Garima Goswami; Seema Kothari; Kalyan K Banerji

    2001-02-01

    The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (/) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

  2. Optimization of a Reduced Chemical Kinetic Model for HCCI Engine Simulations by Micro-Genetic Algorithm

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A reduced chemical kinetic model (44 species and 72 reactions) for the homogeneous charge compression ignition (HCCI) combustion of n-heptane was optimized to improve its autoignition predictions under different engine operating conditions. The seven kinetic parameters of the optimized model were determined by using the combination of a micro-genetic algorithm optimization methodology and the SENKIN program of CHEMKIN chemical kinetics software package. The optimization was performed within the range of equivalence ratios 0.2-1.2, initial temperature 310-375 K and initial pressure 0.1-0.3 MPa. The engine simulations show that the optimized model agrees better with the detailed chemical kinetic model (544 species and 2 446 reactions) than the original model does.

  3. Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

    OpenAIRE

    Leone, Stephen R.

    2010-01-01

    Scientists at the Chemical Dynamics Beamline of the Advanced Light Source in Berkeley are continuously reinventing synchrotron investigations of physical chemistry and chemical physics with vacuum ultraviolet light. One of the unique aspects of a synchrotron for chemical physics research is the widely tunable vacuum ultraviolet light that permits threshold ionization of large molecules with minimal fragmentation. This provides novel opportunities to assess molecular energetics and reaction me...

  4. Solving stochastic chemical kinetics by Metropolis Hastings sampling

    OpenAIRE

    Moosavi, Azam S. Zavar; Tranquilli, Paul; Sandu, Adrian

    2014-01-01

    This study considers using Metropolis-Hastings algorithm for stochastic simulation of chemical reactions. The proposed method uses SSA (Stochastic Simulation Algorithm) distribution which is a standard method for solving well-stirred chemically reacting systems as a desired distribution. A new numerical solvers based on exponential form of exact and approximate solutions of CME (Chemical Master Equation) is employed for obtaining target and proposal distributions in Metropolis-Hastings algori...

  5. Kinetic determination of iodide by the oxidation reaction of benzidine with chloramine B

    International Nuclear Information System (INIS)

    Iodide catalyzed oxidation of benzidine with Chloramine B is studied for its possible application to kinetic determination of iodides. Based on the results of kinetic studies performed, optimal conditions for the catalytic reaction are revealed and a kinetic method for iodide determination is developed. The determination limit of iodide is 2x10-4 μg/ml. It was demonstrated that the proposed method can be used for the determination of iodides in water, soil, and kelp

  6. Compatibility of polymers and chemical oxidants for enhanced groundwater remediation.

    Science.gov (United States)

    Smith, Megan M; Silva, Jeff A K; Munakata-Marr, Junko; McCray, John E

    2008-12-15

    Polymer floods provide a promising method to more effectively deliver conventional groundwater treatment agents to organic contaminants distributed within heterogeneous aquifer systems. Combinations of nontoxic polymers (xanthan and hydrolyzed polyacrylamide) and common chemical oxidants (potassium permanganate and sodium persulfate) were investigated to determine the suitability of these mixtures for polymer-enhanced in situ chemical oxidation applications. Oxidant demand and solution viscosity were utilized as initial measures of chemical compatibility. After 72 h of reaction with both test oxidants, solution viscosities in mixtures containing hydrolyzed polyacrylamide were decreased by more than 90% (final viscosities approximately 2 cP), similar to the 95% viscosity loss (final viscosities approximately 1 cP, near that of water) observed in xanthan/persulfate experiments. In contrast, xanthan solutions exposed to potassium permanganate preserved 60-95% of initial viscosity after 72 h. Permanganate depletion in xanthan-containing experiments ranged from 2% to 24% over the same test period. Although oxidant consumption in xanthan/permanganate solutions appeared to be correlated with increasing xanthan concentrations, solutions of up to 2000 mg/L xanthan did not inhibit permanganate from oxidizing a dissolved-phase test contaminant (tetrachloroethene, PCE) in xanthan solution. These advantageous characteristics (high viscosity retention, moderate oxidant demand, and lack of competitive effects on PCE oxidation rate) render xanthan/permanganate the most compatible polymer/oxidant combination of those tested for remediation by polymer-enhanced chemical oxidation. PMID:19174907

  7. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina

    2007-01-01

    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  8. Composition effects on the early-stage oxidation kinetics of (001) Cu-Au alloys

    Science.gov (United States)

    Zhou, G.-W.; Eastman, J. A.; Birtcher, R. C.; Baldo, P. M.; Pearson, J. E.; Thompson, L. J.; Wang, L.; Yang, J. C.

    2007-02-01

    An in situ environmental transmission electron microscopy study of the nucleation and growth of oxide islands during the early-stage oxidation of (001) Cu1-xAux alloys (x⩽38at.%) was undertaken in order to investigate the effects of alloying on oxide island nucleation behavior and growth kinetics. The kinetic data reveal that Au enhances the nucleation density of oxide islands and suppresses their growth rate. Our results provide insight into reasons for the decreased passivation properties of Cu when alloyed with Au.

  9. Reduced chemically modified graphene oxide for supercapacitor electrode

    OpenAIRE

    Rajagopalan, Balasubramaniyan; Chung, Jin Suk

    2014-01-01

    An efficient active material for supercapacitor electrodes is prepared by reacting potassium hydroxide (KOH) with graphene oxide followed by chemical reduction with hydrazine. The electrochemical performance of KOH treated graphene oxide reduced for 24 h (reduced chemically modified graphene oxide, RCMGO-24) exhibits a specific capacitance of 253 F g-1 at 0.2 A g-1 in 2 M H2SO4 compared to a value of 141 F g-1 for graphene oxide reduced for 24 h (RGO-24), and good cyclic stability up to 3,000...

  10. Comparison and Parametric Study of Flameless Oxidation in a Gas Turbine Using Two Kinetics Mechanisms

    Directory of Open Access Journals (Sweden)

    Mohamed Hamdi

    2008-01-01

    Full Text Available The so-called “Flameless Oxidation” is a novel combustion mode, in which combustion products are re-circulated and mixed into the fresh incoming fuel and air streams. This reduces the concentration of the reactants and thereby reducing the reaction rate through avoiding the formation of sharp high temperature zones in the combustion chamber. Flameless combustion has been acknowledged as one of the most interesting combustion technologies to meet both the targets of high energy efficiency and low pollutant emissions. This technology has already been successfully applied and exploited in industrial burners. The present investigation is concerned with the application of the flameless combustion mode to an adiabatic combustor, typically used in gas turbine engines. Detailed chemical kinetics calculations, by means of a specific zero-dimensional loop reactor model, have been performed to analyze its chemical aspects. The model simulates the combustor by a number of reactors that represent different zones in the combustion chamber. The main objective of this study is to increase the understanding of NOx formation from flameless mode, where currently very few experimental data are available. The investigation is focused on a comparison of the influence of pressure, residence time and temperature on the NOx and CO emissions, using two reaction mechanisms of the C/H/O/N system: the Miller-Bowman mechanism and the GRI_MECH3.0 mechanism. Simulation results clearly illustrate that even at high operating temperatures and pressures, NOx emissions could be reduced by flameless combustion to very low levels. A comparison between the predictions obtained by using the two chemical kinetics mechanisms is presented and discussed. It is shown that the predictions of the Miller-Bowman mechanism deviate from the predictions of the GRI3.0 mechanism in many aspects, especially as related to NOx emission results.

  11. Influence of organic substrates on the kinetics of bacterial As(III) oxidation

    Science.gov (United States)

    Lescure, T.; Joulian, C.; Bauda, P.; Hénault, C.; Battaglia-Brunet, F.

    2012-04-01

    Soil microflora plays a major role on the behavior of metals and metalloids. Arsenic speciation, in particular, is related to the activity of bacteria able to oxidize, reduce or methylate this element, and determines mobility, bioavailability and toxicity of As. Arsenite (AsIII) is more toxic and more mobile than arsenate (AsV). Bacterial As(III)-oxidation tends to reduce the toxicity of arsenic in soils and the risk of transfer toward underlying aquifers, that would affect the quality of water resources. Previous results suggest that organic matter may affect kinetics or efficiency of bacterial As(III)-oxidation in presence of oxygen, thus in conventional physico-chemical conditions of a surface soil. Different hypothesis can be proposed to explain the influence of organic matter on As(III) oxidation. Arsenic is a potential energy source for bacteria. The presence of easily biodegradable organic matter may inhibit the As(III) oxidation process because bacteria would first metabolize these more energetic substrates. A second hypothesis would be that, in presence of organic matter, the Ars system involved in bacterial resistance to arsenic would be more active and would compete with the Aio system of arsenite oxidation, decreasing the global As(III) oxidation rate. In addition, organic matter influences the solubility of iron oxides which often act as the main pitfalls of arsenic in soils. The concentration and nature of organic matter could therefore have a significant influence on the bioavailability of arsenic and hence on its environmental impact. The influence of organic matter on biological As(III) oxidation has not yet been determined in natural soils. In this context, soil amendment with organic matter during operations of phytostabilization or, considering diffuse pollutions, through agricultural practices, may affect the mobility and bio-availability of the toxic metalloid. The objective of the present project is to quantify the influence of organic matter

  12. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. PMID:17363148

  13. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    International Nuclear Information System (INIS)

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (PO2) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and PO2 were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of PO2, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (CODRB) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture

  14. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P{sub O{sub 2}} were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P{sub O{sub 2}}, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD{sub RB}) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  15. The preparation and chemical reaction kinetics of tungsten bronze thin films and nitrobenzene with and without a catalyst

    Science.gov (United States)

    Materer, Nicholas F.; Apblett, Allen; Kadossov, Evgueni B.; Khan, Kashif Rashid; Casper, Walter; Hays, Kevin; Shams, Eman F.

    2016-06-01

    Microcrystalline tungsten bronze thin films were prepared using wet chemical techniques to reduce a tungsten oxide thin film that was prepared by thermal oxidation of a sputter deposited tungsten metal film on a quartz substrate. The crystallinity of these films was determined by X-ray diffraction and the surface was characterized by X-ray and Ultra-Violet Photoelectron spectroscopy. The total amount of hydrogen incorporated in the film was monitored using absorbance spectroscopy at 900 nm. The oxidation kinetics of the film and the hydrogenation of nitrobenzene in hexane were measured as a function of film thickness. A satisfactory fit of the resulting kinetics was obtained using a model that involves two simultaneous processes. The first one is the proton diffusion from the bulk of the film to the surface, and the second is a reaction of the surface protons with the oxidants. Finally, the dependence of the reaction rates on the presence of catalytic amounts of first row transition metals on the surface of the film was explored.

  16. Reaction diffusion and solid state chemical kinetics handbook

    CERN Document Server

    Dybkov, V I

    2010-01-01

    This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

  17. The chemical state of complex uranium oxides

    OpenAIRE

    Kvashnina, K. O.; Butorin, S. M.; Martin, P.; P. Glatzel

    2013-01-01

    We report here the first direct observation of U(V) in uranium binary oxides and analyze the gradual conversion of the U oxidation state in the mixed uranium systems. Our finding clarifies previous contradicting results and provides important input for the geological disposal of spent fuel, recycling applications and chemistry of uranium species.

  18. A Rapid Compression Expansion Machine (RCEM) for studying chemical kinetics: Experimental principle and first applications

    CERN Document Server

    Werler, Marc; Maas, Ulrich

    2016-01-01

    A novel extension of a rapid compression machine (RCM), namely a Rapid Compression Expansion Machine (RCEM), is described and its use for studying chemical kinetics is demonstrated. Like conventional RCMs, the RCEM quickly compresses a fuel/air mixture by pushing a piston into a cylinder; the resulting high temperatures and pressures initiate chemical reactions. In addition, the machine can rapidly expand the compressed gas in a controlled way by pulling the piston outwards again. This freezes chemical activity after a pre-defined reaction duration, and therefore allows a convenient probe sampling and ex-situ gas analysis of stable species. The RCEM therefore is a promising instrument for studying chemical kinetics, including also partially reacted fuel/air mixtures. The setup of the RCEM, its experimental characteristics and its use for studying chemical reactions are outlined in detail. To allow comparisons of RCEM results with predictions of chemical reaction mechanisms, a simple numerical model of the RCE...

  19. Validity conditions for moment closure approximations in stochastic chemical kinetics

    OpenAIRE

    Schnoerr, David; Sanguinetti, Guido; Grima, Ramon

    2014-01-01

    Approximations based on moment-closure (MA) are commonly used to obtain estimates of the mean molecule numbers and of the variance of fluctuations in the number of molecules of chemical systems. The advantage of this approach is that it can be far less computationally expensive than exact stochastic simulations of the chemical master equation. Here, we numerically study the conditions under which the MA equations yield results reflecting the true stochastic dynamics of the system. We show tha...

  20. Uncovering Oscillations, Complexity, and Chaos in Chemical Kinetics Using Mathematica

    Science.gov (United States)

    Ferreira, M. M. C.; Ferreira, W. C., Jr.; Lino, A. C. S.; Porto, M. E. G.

    1999-06-01

    Unlike reactions with no peculiar temporal behavior, in oscillatory reactions concentrations can rise and fall spontaneously in a cyclic or disorganized fashion. In this article, the software Mathematica is used for a theoretical study of kinetic mechanisms of oscillating and chaotic reactions. A first simple example is introduced through a three-step reaction, called the Lotka model, which exhibits a temporal behavior characterized by damped oscillations. The phase plane method of dynamic systems theory is introduced for a geometric interpretation of the reaction kinetics without solving the differential rate equations. The equations are later numerically solved using the built-in routine NDSolve and the results are plotted. The next example, still with a very simple mechanism, is the Lotka-Volterra model reaction, which oscillates indefinitely. The kinetic process and rate equations are also represented by a three-step reaction mechanism. The most important difference between this and the former reaction is that the undamped oscillation has two autocatalytic steps instead of one. The periods of oscillations are obtained by using the discrete Fourier transform (DFT)-a well-known tool in spectroscopy, although not so common in this context. In the last section, it is shown how a simple model of biochemical interactions can be useful to understand the complex behavior of important biological systems. The model consists of two allosteric enzymes coupled in series and activated by its own products. This reaction scheme is important for explaining many metabolic mechanisms, such as the glycolytic oscillations in muscles, yeast glycolysis, and the periodic synthesis of cyclic AMP. A few of many possible dynamic behaviors are exemplified through a prototype glycolytic enzymatic reaction proposed by Decroly and Goldbeter. By simply modifying the initial concentrations, limit cycles, chaos, and birhythmicity are computationally obtained and visualized.

  1. Validity conditions for moment closure approximations in stochastic chemical kinetics

    International Nuclear Information System (INIS)

    Approximations based on moment-closure (MA) are commonly used to obtain estimates of the mean molecule numbers and of the variance of fluctuations in the number of molecules of chemical systems. The advantage of this approach is that it can be far less computationally expensive than exact stochastic simulations of the chemical master equation. Here, we numerically study the conditions under which the MA equations yield results reflecting the true stochastic dynamics of the system. We show that for bistable and oscillatory chemical systems with deterministic initial conditions, the solution of the MA equations can be interpreted as a valid approximation to the true moments of the chemical master equation, only when the steady-state mean molecule numbers obtained from the chemical master equation fall within a certain finite range. The same validity criterion for monostable systems implies that the steady-state mean molecule numbers obtained from the chemical master equation must be above a certain threshold. For mean molecule numbers outside of this range of validity, the MA equations lead to either qualitatively wrong oscillatory dynamics or to unphysical predictions such as negative variances in the molecule numbers or multiple steady-state moments of the stationary distribution as the initial conditions are varied. Our results clarify the range of validity of the MA approach and show that pitfalls in the interpretation of the results can only be overcome through the systematic comparison of the solutions of the MA equations of a certain order with those of higher orders

  2. Chemically Locked Bicelles with High Thermal and Kinetic Stability.

    Science.gov (United States)

    Matsui, Ryoichi; Ohtani, Masataka; Yamada, Kuniyo; Hikima, Takaaki; Takata, Masaki; Nakamura, Takashi; Koshino, Hiroyuki; Ishida, Yasuhiro; Aida, Takuzo

    2015-11-01

    In situ polymerization of a bicellar mixture composed of a phospholipid and polymerizable surfactants afforded unprecedented stable bicelles. The polymerized composite showed an aligned phase over a wide thermal range (25 to >90 °C) with excellent (2)H quadrupole splitting of the solvent signal, thus implying versatility as an alignment medium for NMR studies. Crosslinking of the surfactants also brought favorable effects on the kinetic stability and alignment morphology of the bicelles. This system could thus offer a new class of scaffolds for biomembrane models. PMID:26373898

  3. Chemical Kinetics in Support of Syngas Turbine Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, Frederick

    2007-07-31

    This document is the final report on an overall program formulated to extend our prior work in developing and validating kinetic models for the CO/hydrogen/oxygen reaction by carefully analyzing the individual and interactive behavior of specific elementary and subsets of elementary reactions at conditions of interest to syngas combustion in gas turbines. A summary of the tasks performed under this work are: 1. Determine experimentally the third body efficiencies in H+O{sub 2}+M = HO{sub 2}+M (R1) for CO{sub 2} and H{sub 2}O. 2. Using published literature data and the results in this program, further develop the present H{sub 2}/O{sub 2}/diluent and CO/H{sub 2}/O{sub 2}/diluent mechanisms for dilution with CO{sub 2}, H{sub 2}O and N{sub 2} through comparisons with new experimental validation targets for H{sub 2}-CO-O{sub 2}-N{sub 2} reaction kinetics in the presence of significant diluent fractions of CO{sub 2} and/or H{sub 2}O, at high pressures. (task amplified to especially address ignition delay issues, see below). 3. Analyze and demonstrate issues related to NOx interactions with syngas combustion chemistry (task amplified to include interactions of iron pentacarbonyl with syngas combustion chemistry, see below). 4. Publish results, including updated syngas kinetic model. Results are summarized in this document and its appendices. Three archival papers which contain a majority of the research results have appeared. Those results not published elsewhere are highlighted here, and will appear as part of future publications. Portions of the work appearing in the above publications were also supported in part by the Department of Energy under Grant No. DE-FG02-86ER-13503. As a result of and during the research under the present contract, we became aware of other reported results that revealed substantial differences between experimental characterizations of ignition delays for syngas mixtures and ignition delay predictions based upon homogenous kinetic modeling. We

  4. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

    Science.gov (United States)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss. PMID:27295099

  5. VULCAN: an Open-Source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

    OpenAIRE

    Tsai, Shang-Min; Lyons, James R.; Grosheintz, Luc; Rimmer, Paul B.; Kitzmann, Daniel; Heng, Kevin

    2016-01-01

    We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K using a reduced C- H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing ...

  6. KINETICS OF CHEMICAL TRANSFORMATIONS OF HYDROCARBONS WORKING LIQUID FH-51 AT OPERATING AIRCRAFT

    OpenAIRE

    Кузнєцова, О.; Національний авіаційний університет; Нетреба, Ж.; Національний авіаційний університет

    2013-01-01

    Today the French hydraulic liquid «Hydronicoil» FH-51 is used in aircraft hydrosystems of Ukraine airlines.During aircraft exploitation under the action of external factors there are chemical transformations in molecules of liquid hydrocarbons. Research on kinetics of chemical transformations of hydrocarbons of working liquidFH-51 is carried out. The model of the noted chemical transformations, which provide achievement of necessary quality level of the liquid and aircraft reliability, is fou...

  7. CERENA: ChEmical REaction Network Analyzer—A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics

    Science.gov (United States)

    Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J.; Hasenauer, Jan

    2016-01-01

    Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/. PMID:26807911

  8. A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

    Science.gov (United States)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

    This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

  9. A Visual Demonstration of Solvent Effect in Chemical Kinetics through Blue Bottle Experiment

    Directory of Open Access Journals (Sweden)

    *R. Azmat

    2013-03-01

    Full Text Available In the study of chemical kinetics, usually solvent effect was explained to show the consequences on rate of reaction theoretically which is difficult to understand for under graduate students. The blue bottle experiment as a “one day activity” can be used to explain well visually the solvent effect through demonstration of color change. Kinetics of reduction of methylene green by sucrose and mannose in pure and aqueous methanol medium in presence of NaOH has been investigated for demonstration of solvent effect. The two sugars sucrose and mannose were selected for the experiment those acts as a reducing agents in a basic solution and reduces the methylene green into colorless form. The progress of this reduction reaction was followed by the color changes that the methylene green goes through in variable percentage of alcohol. When the bottle is shaken the oxygen in the air mixes with the solution and oxidizes the methylene green back to its intermediate state (purple. The color of the solution will gradually change and become purple (intermediate and then colorless in 5-10% methanol but in pure methanol color transition were Blue-> purple-> pink indicate the color due to the alcoholic medium. It was observed that increase in percentage in the solvent composition decrease the rate of reduction. The pink color continues due to alcoholic medium which may be attributed with the solvent effect. The observed variation in reading with solvent compositions has been interpreted in terms of interactions of media with the reacting species and the transitions state involved in this reaction.

  10. Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

    OpenAIRE

    Madi Abilev; Bulat Kenessov; Svetlana Batyrbekova; Tim Grotenhuis

    2015-01-01

    Oxidation of unsymmetrical dimethylhydrazine (UDMH) during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of chemical oxidants in respect to main metabolites of UDMH – 1-formyl-2,2-dimethylhydrazine, dimethylaminoacetontrile, N-nitrosodimethylamine and 1-methyl-1H-1,2,4-triazole. Experiments on chemical o...

  11. Chemical aspects of mixed oxide fuel production

    International Nuclear Information System (INIS)

    The paper describes and compares the available head end techniques for production of pelletized mixed oxide fuel. It discusses the solubility of PuO2 in nitric acid as well as its radioactivity, both of which influence the choice of the head end process. The paper also describes several ways to convert the mixed plutonium-uranium nitrates from fuel reprocessing into mixed oxides, and proposes a SOL-GEL-type process as a preferred way. (orig.)

  12. Complex Metal Oxide Chemical Gas Sensors

    OpenAIRE

    Šutka, A

    2015-01-01

    The demand for alternative gas sensor materials is increasing following the progress in the electronic industry. Complex ternary oxide materials have been emerging rapidly over 10 last years. Among ternary metal oxide compounds, the spinel ferrites are the most attractive materials due to structural and compositional versatility. This report will highlight the recent developments and will show the potential of the spinel ferrites on gas sensor technology. Sensing mechanisms for a range of gas...

  13. Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: obs = + [H+]. The oxidation of -deuterioformic acid exhibits a substantial primary kinetic isotope effect (H/D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed

  14. Chemical Composition of Seed Oil from Roselle (Hibiscus sabdariffa L. and the Kinetics of Degradation of the Oil During Heating

    Directory of Open Access Journals (Sweden)

    G. Bouanga-Kalou

    2011-02-01

    Full Text Available The aim of the study was to investigate the chemical composition and the kinetics of degradation of roselle seed oil during heating. The seed is a good source of oil (23.27%. The physical properties of the oil extracts showed the state to be liquid at room temperature and indicated that the oil had refractive index, 1.4652; the peroxide value, 3.15 (meq O2/kg oil; free fatty acid, 0.82%; iodine value, 97.78%; saponification value, 198.45 and viscosity, 15.15 (mPa.s at 25ºC. Gas liquid chromatography technique has been developed for identification and quantitative determination of total unsaturated and saturated fatty acids shows that the crude oil had 73.4 and 26.57%, respectively. DSC indicates the presence of two components in oil extracted. The first peak at low melting point appears at -20.53°C (Hf = +3.00 J/g and the second peak appears to -2.17°C (Hf = +0.49 J/g. The degradation kinetic of the oil was also investigated. The thermal oxidation of the double bonds of the oil showed a first-order thermal oxidation kinetic and the Arrhenius plot yielded a straight line with a slope equivalent to activation energy of 9.041 KJ/mol. There is the possibility of considering the seed as feed supplement and its oil for industrial application.

  15. Oxidation behaviour of Zr-Ce alloys. Kinetic and microstructure aspects

    International Nuclear Information System (INIS)

    As Zircaloy alloys are used for fuel rods in pressurized water nuclear reactors, this research thesis aims at studying and improving corrosion resistance of zirconium alloys while maintaining their mechanical properties. It more precisely deals with the kinetic and microstructure aspects of the external corrosion of the cladding by the coolant. In the case of Zircaloys, this corrosion is characterized by a kinetic transition from an initially parabolic to a linear regime. This research aims at intervening on this transition by elaborating zirconium alloys containing an element which stabilizes zirconia, in this case cerium. After having reported a bibliographical study on sheath oxidation, on parameters which influence sheath oxidation kinetics, on zirconia stabilization by doping elements, on the interest of lanthanide oxides, the author reports a feasibility study on the use of cerium (choice and preparation, sintered ceramic characterization, annealing of stabilized zirconia), reports a metallurgical study of Zr-Ce alloys, reports the study of the oxidation behaviour of these alloys (in autoclave, in presence of oxygen, under oxygen and then water) and the characterization of the microstructures of the oxide layers. He finally discusses the relationship between microstructure and oxidation kinetics, the role of cerium in the oxidation process, and the role of water in the oxidation process

  16. Kinetics of combined reduction of Fe-Cr and Fe-Cr-Ni oxide systems

    International Nuclear Information System (INIS)

    Kinetic regularities of combined reduction of Fe-Cr and Fe-Cr-Ni oxide systems with hydrogen and solid carbon are investigated. Possibility of attaining high degree of reduction and decarbonization of iron-chromium-nickel alloys with chromium content up to 23% (by mass) using combined reduction of oxides at the temperature of 1573 K is shown

  17. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du

    2002-01-01

    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  18. Crystallization kinetics of a solid oxide fuel cell seal glass by differential thermal analysis

    Energy Technology Data Exchange (ETDEWEB)

    Bansal, Narottam P.; Gamble, Eleanor A. [National Aeronautics and Space Administration, Glenn Research Center, Cleveland, OH 44135 (United States)

    2005-09-09

    Crystallization kinetics of a barium-calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells (SOFC), have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259kJ/mol using a kinetic model. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder X-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO{sub 3} and hexacelsian (BaAl{sub 2}Si{sub 2}O{sub 8}) were the primary crystalline phases whereas monoclinic celsian (BaAl{sub 2}Si{sub 2}O{sub 8}) and (Ba{sub x}Ca{sub y})SiO{sub 4} were also detected as minor phases. Needle-shaped BaSiO{sub 3} crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long-term heat treatments at 750-900{sup o}C. Devitrification of the glass seal over a long period of time during operation of the SOFC would generate thermal stresses in the seal and may have adverse effects on its mechanical performance. This may lead to cracking of the seal, resulting in mixing of the fuel and the oxidant gases. (author)

  19. Parameter Estimates in Differential Equation Models for Chemical Kinetics

    Science.gov (United States)

    Winkel, Brian

    2011-01-01

    We discuss the need for devoting time in differential equations courses to modelling and the completion of the modelling process with efforts to estimate the parameters in the models using data. We estimate the parameters present in several differential equation models of chemical reactions of order n, where n = 0, 1, 2, and apply more general…

  20. CFD analysis of municipal solid waste combustion using detailed chemical kinetic modelling.

    Science.gov (United States)

    Frank, Alex; Castaldi, Marco J

    2014-08-01

    Nitrogen oxides (NO x ) emissions from the combustion of municipal solid waste (MSW) in waste-to-energy (WtE) facilities are receiving renewed attention to reduce their output further. While NO x emissions are currently 60% below allowed limits, further reductions will decrease the air pollution control (APC) system burden and reduce consumption of NH3. This work combines the incorporation of the GRI 3.0 mechanism as a detailed chemical kinetic model (DCKM) into a custom three-dimensional (3D) computational fluid dynamics (CFD) model fully to understand the NO x chemistry in the above-bed burnout zones. Specifically, thermal, prompt and fuel NO formation mechanisms were evaluated for the system and a parametric study was utilized to determine the effect of varying fuel nitrogen conversion intermediates between HCN, NH3 and NO directly. Simulation results indicate that the fuel nitrogen mechanism accounts for 92% of the total NO produced in the system with thermal and prompt mechanisms accounting for the remaining 8%. Results also show a 5% variation in final NO concentration between HCN and NH3 inlet conditions, demonstrating that the fuel nitrogen intermediate assumed is not significant. Furthermore, the conversion ratio of fuel nitrogen to NO was 0.33, revealing that the majority of fuel nitrogen forms N2. PMID:25005043

  1. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    International Nuclear Information System (INIS)

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L-1). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  2. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Wei-Lung, E-mail: wlchou@sunrise.hk.edu.tw [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China); Wang, Chih-Ta [Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan Hsien 717, Taiwan (China); Chang, Wen-Chun; Chang, Shih-Yu [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China)

    2010-08-15

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L{sup -1}). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  3. High-temperature steam oxidation kinetics of the E110G cladding alloy

    Science.gov (United States)

    Király, Márton; Kulacsy, Katalin; Hózer, Zoltán; Perez-Feró, Erzsébet; Novotny, Tamás

    2016-07-01

    In the course of recent years, several experiments were performed at MTA EK (Centre for Energy Research, Hungarian Academy of Sciences) on the isothermal high-temperature oxidation of the improved Russian cladding alloy E110G in steam/argon atmosphere. Using these data and designing additional supporting experiments, the oxidation kinetics of the E110G alloy was investigated in a wide temperature range, between 600 °C and 1200 °C. For short durations (below 500 s) or high temperatures (above 1065 °C) the oxidation kinetics was found to follow a square-root-of-time dependence, while for longer durations and in the intermediate temperature range (800-1000 °C) it was found to approach a cube-root-of-time dependence rather than a square-root one. Based on the results a new best-estimate and a conservative oxidation kinetics model were created.

  4. Kinetics of Wet Air Oxidation of Wastewater from Natural Fiber Web Desizing

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    This work described the application of wet air oxidation (WAO) to the treatment of desizing wastewater from natural fiber processing. A two-liter autoclave batch reactor was used for the experiments. The range of operating temperature examined was between 150 and 290℃, and partial pressure of oxygen ranged from 0.375 to 2.25 MPa standardized at 25℃. Variations in Chemical Oxygen Demand(COD) and Total Organic Carbon(TOC) were monitored during each experiment and used to assess the performance of the process. Experimental results showed that WAO can be an efficient method for the treatment of desizing wnstewater. Furthermore, Catalytic Wet Air Oxidation (CWAO) was applied to reduce the reaction temperature and pressure in WAO process. A higher COD removal ratio was achieved under more mild reaction condition with the aid of CWAO. A mathematical model was also proposed to simulate the WAO process of desizing wastewater, in which three distinct kinetics steps were considered to describe the degradation of starch. The model simulations were in well agreement with the experimental data.

  5. Thermodynamic and kinetic modeling of oxide precipitation in nanostructured ferritic alloys

    International Nuclear Information System (INIS)

    The mechanical properties and radiation tolerance of nanostructured ferritic alloys rely on a dense population of nanometer-scale Y–Ti oxides. The stability of these nano-oxides during extended service is critical in high temperature applications. Here, a model framework is developed for the thermodynamics and kinetics of Y–Ti oxide nucleation, growth and coarsening. The model, which is based upon available thermodynamic and kinetic data as well as key density functional theory calculations, shows that nano-oxide nucleation and growth are highly driven and that pipe diffusion is the dominant mode of their coarsening, in agreement with previous analyses of experimental high temperature data. The model predicts that the nano-oxides are thermally stable for 80 or more years below 1175 K. This analysis also provides insights into the effect of O and Ti on nano-oxide sizes, and on optimization of alloy microstructure

  6. Kinetics study on photochemical oxidation of polyacrylamide by ozone combined with hydrogen peroxide and ultraviolet radiation

    Institute of Scientific and Technical Information of China (English)

    REN Guang-meng; SUN De-zhi; CHUNG Jong Shik

    2006-01-01

    An investigation on the process of ozone combined with hydrogen peroxide and ultraviolet radiation has been carried out in order to establish the kinetics for photochemical oxidation of polyacrylamide (PAM) in aqueous solution. Effects of operating parameters, including initial PAM concentration, dosages of ozone and hydrogen peroxide, UV radiation and pH value on the photochemical oxidation of PAM, have been studied. There was an increase in photochemical oxidation rate of PAM with increasing of dosages of O3, H2O2 and ultraviolet radiation. Upon increasing of the initial PAM concentration, the photochemical oxidation rate of PAM decreased. Slight effect of pH value on the photochemical oxidation rate of PAM was observed in the experiments. The kinetics equation for the photochemical oxidation of PAM by the system has been established.

  7. On kinetics and mechanism of' furfural oxidation by ions of heterovalent metals

    International Nuclear Information System (INIS)

    Real constants of rate of furfural oxidation by Cu2+, Fe3+, Ce4+, Ag+, Hg2+2 ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested

  8. Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate

    Indian Academy of Sciences (India)

    Poonam Gupta; Seema Kothari

    2001-04-01

    The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic isotope effect. Addition of benzyltrimethylammonium chloride enhances the rate. It is proposed that the reactive oxidizing species is [(PhCH2Me3N)+ (IZn2Cl6)−]. Suitablemechanisms have been proposed.

  9. Kinetic modeling of low temperature oxidation of copper nanoparticles by O2

    OpenAIRE

    Mansour, Mounir; Favergeon, LoÏc; Pijolat, Michèle

    2013-01-01

    The mechanism and kinetics of copper nanoparticles oxidation at low temperature were investigated using thermogravimetry (TGA), differential scanning calorimetry (DSC), X-Ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal and isobaric studies of the oxidation reaction were carried out at various temperatures. It was found that working under an oxygen partial pressure of 1kPa in the temperature range 125 -145°C leads to reaction where nucleation of the oxide phase is ...

  10. Oxygen Reduction Kinetics Enhancement on a 2 Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Crumlin, Ethan [Massachusetts Institute of Technology (MIT); Mutoro, Eva [ORNL; Ahn, Sung Jin [Massachusetts Institute of Technology (MIT); Jose la O' , Gerardo [Massachusetts Institute of Technology (MIT); Leonard, Donovan N [ORNL; Borisevich, Albina Y [ORNL; Biegalski, Michael D [ORNL; Christen, Hans M [ORNL; Shao-Horn, Yang [Massachusetts Institute of Technology (MIT)

    2010-01-01

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of {approx}85 nm thick La{sub 0.8}Sr{sub 0.2}CoO{sub 3-{delta}} (LSC{sub 113}) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced ({approx} 3-4 orders of magnitude above bulk LSC{sub 113}) by surface decorations of (La{sub 0.5}Sr{sub 0.5}){sub 2}CoO{sub 4{+-}{delta}} (LSC{sub 214}) with coverage in the range from {approx}0.1 to {approx}15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC{sub 113}/LSC{sub 214} regions, which were shown to be atomically sharp.

  11. Synergic effect of chelating agent and oxidant on chemical mechanical planarization

    International Nuclear Information System (INIS)

    Chemically dominant alkaline slurry, which is free of BTA (benzotriazole) and other inhibitors, was investigated. The synergic effect of the chelating agent and oxidant on the chemical mechanical planarization (CMP) was taken into consideration. Copper CMP slurry is mainly composed of an oxidizer, nonionic surfactant, chelating agent and abrasive particles. The effect of different synergic ratios of oxidant with chelating agent on the polishing removal rate, static etch rate and planarization were detected. The planarization results reveal that with the increase of oxidant concentration, the dishing value firstly diminished and then increased again. When the synergic ratios is 3, the dishing increases the least. A theoretical model combined with chemical-mechanical kinetics process was proposed in the investigation, which can explain this phenomenon. Based on the theoretical model, the effect of synergic ratios of oxidant with chelating agent on velocity D-value (convex removal rate minus recessed removal rate) was analyzed. The results illustrate that when the synergic ratio is between 2.5–3.5, the velocity D-value is relatively higher, thereby good planarization can be achieved in this interval. This investigation provides a new guide to analyze and study copper line corrosion in the recessed region during copper clearing polishing. (semiconductor technology)

  12. Less Stress : Oxidative stress and glutathione kinetics in preterm infants

    OpenAIRE

    Rook, Denise

    2013-01-01

    textabstractDue to immature antioxidant defenses, preterm infants are at susceptible to oxidative stress, which is associated with bronchopulmonary dysplasia, retinopathy of prematurity and periventricular leukomalacia. The general aim of this thesis was to study oxidative stress in preterm infants and to explore possible options to reduce the impact of oxidative stress in neonatal care. The studies presented in this thesis concern the optimal oxygen concentration for the resuscitation at bir...

  13. Size control, quantum confinement, and oxidation kinetics of silicon nanocrystals synthesized at a high rate by expanding thermal plasma

    Energy Technology Data Exchange (ETDEWEB)

    Han, Lihao, E-mail: hanlihao@gmail.com, E-mail: A.H.M.Smets@tudelft.nl; Zeman, Miro; Smets, Arno H. M., E-mail: hanlihao@gmail.com, E-mail: A.H.M.Smets@tudelft.nl [Photovoltaic Materials and Devices (PVMD) Laboratory, Delft University of Technology, P.O. Box 5031, 2600 GA Delft (Netherlands)

    2015-05-25

    The growth mechanism of silicon nanocrystals (Si NCs) synthesized at a high rate by means of expanding thermal plasma chemical vapor deposition technique are studied in this letter. A bimodal Gaussian size distribution is revealed from the high-resolution transmission electron microscopy images, and routes to reduce the unwanted large Si NCs are discussed. Photoluminescence and Raman spectroscopies are employed to study the size-dependent quantum confinement effect, from which the average diameters of the small Si NCs are determined. The surface oxidation kinetics of Si NCs are studied using Fourier transform infrared spectroscopy and the importance of post-deposition passivation treatments of hydrogenated crystalline silicon surfaces are demonstrated.

  14. Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

    International Nuclear Information System (INIS)

    The dissolution of UO2 in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol-1. This relatively high activation energy value indicates a chemically controlled behavior of UO2 dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity. (author). 18 refs., 6 figs

  15. Chemical kinetics of flue gas cleaning by electron beam

    International Nuclear Information System (INIS)

    By electron beam treatment of flue gases, NOx and SO2 are converted to nitric and sulfuric acids simultaneously. Upon ammonia addition, the corresponding salts are collected in solid state and can be sold as fertilizer. Both homogeneous gas phase reactions and physico-chemical aerosol dynamics are involved in product formation. These processes have been analyzed by model calculations. In part 1, the present report summarizes the model results and gives an account of the theoretical understanding of the EBDS process and its performance characteristics. Part 2 of this report gives a complete listing of the reactions used in the AGATE code. (orig.)

  16. Chemical interaction of Ce-Fe mixed oxides for methane selective oxidation

    Institute of Scientific and Technical Information of China (English)

    祝星; 杜云鹏; 王华; 魏永刚; 李孔斋; 孙令玥

    2014-01-01

    Chemical interaction of Ce-Fe mixed oxides was investigated in methane selective oxidation via methane temperature pro-grammed reduction and methane isothermal reaction tests over Ce-Fe oxygen carriers. In methane temperature programmed reduction test, Ce-Fe oxide behaved complete oxidation at the lower temperature and selective oxidation at higher temperatures. Ce-Fe mixed oxides with the Fe content in the range of 0.1-0.5 was able to produce syngas with high selectivity in high-temperature range (800-900 °C), and a higher Fe amount over 0.5 seemed to depress the CO formation. In isothermal reaction, complete oxidation oc-curred at beginning following with selective oxidation later. Ce1-xFexO2-δ oxygen carriers (x≤0.5) were proved to be suitable for the selective oxidation of methane. Ce-Fe mixed oxides had the well-pleasing reducibility with high oxygen releasing rate and CO selec-tivity due to the interaction between Ce and Fe species. Strong chemical interaction of Ce-Fe mixed oxides originated from both Fe* activated CeO2 and Ce3+ activated iron oxides (FeOm), and those chemical interaction greatly enhanced the oxygen mobility and se-lectivity.

  17. Applications of direct chemical oxidation to demilitarization

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, J.F., LLNL

    1998-06-01

    Research is reported concerning an aqueous process for oxidative destruction of solid- and liquid organic wastes, including ongoing work relevant to demilitarization This process uses acidified ammonium- or sodium peroxydisulfate and operates at ambient pressure and at temperatures of 80- 100 C The oxidant may be regenerated by electrolysis of the sulfate by- product at Pt anodes at roughly 80% coulombic efficiency, even in the presence of inorganic contaminants (e g , nitrate, phosphate or chloride) found in the original waste and entrained in the recycle stream Integral rate constants have been determined for the oxidation of diverse organic compounds at low concentrations (50 ppm, C), with rate constants (based on equivalents) of 0 004-O 02 miri Higher concentrations generally react at a 2-4X higher rate. The process has been carried through full- scale laboratory tests and initial pilot plant tests on chlorinated solvents, using a hydrolysis pretreatment Integral rate data indicate throughput rates of about 200 kg- C/m3-day The process may benefit the demilitarization efforts in various specialized applications destruction of solvents; destruction of trace propellants and explosives in shell casings remaining after bulk removal, destruction of red and pink waters, in situ remediation of soils at open pit burning/detonation sites; and as a regenerative filter for offgas carrying toxic or explosive substances.

  18. Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm

    Institute of Scientific and Technical Information of China (English)

    刘平乐; 邹丽珊; 罗和安; 王良芥; 郑金华

    2004-01-01

    A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed. This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data. Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

  19. Kinetics of chemical vapor deposition of boron on molybdenum

    International Nuclear Information System (INIS)

    Experimental rate data of chemical vapor deposition of boron by reduction of boron trichloride with hydrogen are analyzed to determine the reaction mechanism. The experiments were conducted at atmospheric pressure. The weight change of the sample was noted by means of a thermobalance. Molybdenum was used as the substrate. It has been found that the outer layer of the deposited film is Mo/sub 2/B/sub 5/ and the inner layer is MoB, and in the stational state of the reaction, the diffusion in the solid state is considered not to be rate controlling. When mass transport limitation was absent, the reaction orders with respect to boron trichloride and hydrogen were one third and one half, respectively. By comparing these orders with those obtained from Langmuir-Hinshelwood type equations, the rate controlling mechanism is identified to be the desorption of hydrogen chloride from the substrate

  20. Perturbation of parabolic kinetics resulting from the accumulation of stress in protective oxide layers

    International Nuclear Information System (INIS)

    A frequent observation in metal oxidation is the development of subparabolic kinetics, variously described as cubic or quartic. Although a number of detailed mechanisms have been proposed to account for this effect, none seem generally applicable. A model is presented of the oxidation process which is divorced from such restrictions. It is argued that deviations from parabolic behavior occur as a result of the concurrent development of stresses within the oxide. It is shown that the presence of stress fields can influence significantly the rate of transport of vacancy defects within the oxide such that tensile stresses produce positive deviations and compressive stresses, negative deviations from parabolic behavior. The model is applied in detail to Zircaloy-2 oxidation at 7730K. It is predicted that the kinetics should be insensitive to the oxygen potential of the environment and this has been confirmed by previous experimental work. 31 refs

  1. Effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Chlorine content and position of chlorinated phenols have many significant effects on the reactivity of oxido-reduction. The effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate were evaluated through different kinetics studies. Since chlorine was an electron withdrawing atom, the substitution of chlorine on the aromatic ring decreased the oxidation rate constant by σ-electron withdrawing conductive effect; at the same time, the substitution of chlorine at ortho or para position on the aromatic ring increased the oxidation rate constant by π-electron donating conjugative effect, and the conjugative effect could counteract the negative impact of the conductive effect to some extent. On the other hand, the substitution of chlorine at ortho position on the aromatic ring decreased the oxidation rate constant by steric hindrance effect. The oxidation rate constants of phenol and chlorinated phenols studied decreased as follow order: 4-chlorophenol>2,4-dichlorophenol>phenol>2,6-dichlorophenol.

  2. Kinetics and thermodynamics of chemical reactions in Li/SOCl2 cells

    Science.gov (United States)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

    Work is described that was designed to determine the kinetic constants necessary to extrapolate kinetic data on Li/SOCl2 cells over the temperature range from 25 to 75 C. A second objective was to characterize as far as possible the chemical reactions that occur in the cells since these reactions may be important in understanding the potential hazards of these cells. The kinetics of the corrosion processes in undischarged Li/SOCl2 cells were determined and separated according to their occurrence at the anode and cathode; the effects that switching the current on and off has on the corrosion reactions was determined; and the effects of discharge state on the kinetics of the corrosion process were found. A thermodynamic analysis of the current-producing reactions in the cell was done and is included.

  3. In situ investigation of mesoporous silicon oxidation kinetics using infrared emittance spectroscopy.

    Science.gov (United States)

    Bardet, Benjamin; De Sousa Meneses, Domingos; Defforge, Thomas; Billoué, Jérôme; Gautier, Gaël

    2016-07-21

    In this paper, we study the thermal oxidation kinetics of mesoporous silicon layers, synthesized by electrochemical anodization, from 260 °C up to 1100 °C. A specific apparatus is employed to heat the mesoporous samples in air and to record at the same time their infrared emittance. Based on Bruggeman effective medium approximation, an optical model is set up to realistically approximate the dielectric function of the porous material with an emphasis on the surface chemistry and oxide content. A transition temperature of 600 °C is evidenced from data processing which gives evidence of two oxidation mechanisms with distinct kinetics. Between 260-600 °C, the oxidation is surface-limited with kinetics dependent on the hydrogen desorption rate. However, above 600 °C, the oxide growth is limited by oxygen diffusion through the existing oxide layer. A parabolic law is employed to fit the oxidation rate and to extract the high-temperature activation energy (EA = 1.5 eV). A precise control of the oxide growth can thus be achieved. PMID:27333267

  4. Nonlinear Stochastic Dynamics of Complex Systems, I: A Chemical Reaction Kinetic Perspective with Mesoscopic Nonequilibrium Thermodynamics

    CERN Document Server

    Qian, Hong

    2016-01-01

    We distinguish a mechanical representation of the world in terms of point masses with positions and momenta and the chemical representation of the world in terms of populations of different individuals, each with intrinsic stochasticity, but population wise with statistical rate laws in their syntheses, degradations, spatial diffusion, individual state transitions, and interactions. Such a formal kinetic system in a small volume $V$, like a single cell, can be rigorously treated in terms of a Markov process describing its nonlinear kinetics as well as nonequilibrium thermodynamics at a mesoscopic scale. We introduce notions such as open, driven chemical systems, entropy production, free energy dissipation, etc. Then in the macroscopic limit, we illustrate how two new "laws", in terms of a generalized free energy of the mesoscopic stochastic dynamics, emerge. Detailed balance and complex balance are two special classes of "simple" nonlinear kinetics. Phase transition is intrinsically related to multi-stability...

  5. Kinetic Modelling for the Assay of Nortriptyline Hydrochloride Using Potassium Permanganate as Oxidant

    OpenAIRE

    Rahman, Nafisur; Khan, Sumaiya

    2014-01-01

    Kinetic methods for accurate determination of nortriptyline hydrochloride have been described. The methods are based on the oxidation of nortriptyline hydrochloride with KMnO4 in acidic and basic media. In acidic medium, the decrease in absorbance at 525.5 nm and in basic medium, the increase in absorbance at 608.5 nm were measured as a function of time. The variables affecting the reactions were carefully investigated and optimised. Kinetic models such as initial rate, rate constant, variabl...

  6. Oxidation kinetics of reaction products formed in uranium metal corrosion

    International Nuclear Information System (INIS)

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O2 and Ar-20%O2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

  7. Kinetics studies of oxidation of niacinamide by alkaline potassium permanganate

    OpenAIRE

    Sandipsingh Gour; Sayyed Hussain; Mazahar Farooqui

    2012-01-01

    The oxidation of niacinamide in alkaline media is carried out using potassium permanganate as a oxiding agent. The reaction was monitored using UV-Visible spectrophotometer at 525 nm. It was found to be zero order with respect to oxidant,, fractional order with respect to hydrogen ion concentration and first order with respect to substrate. The thermodynamic parameters(were determinied . The average (?G#) was found to be 87.60 KJ/mol. The values ?S# was found to be -0.2132 K...

  8. Mechanistic and kinetic analysis of the oxidative dehydrogenation of ethane via novel supported alkali chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Universitaet Muenchen (Germany). Catalysis Research Center

    2013-11-01

    The oxidative dehydrogenation of ethane over advanced catalysts is promising to selectively produce ethylene, an essential building block for the chemical industry. In this way, ethane from shale gas can be efficiently valorized. Supported alkali chloride catalysts are investigated in this work. Essential feature of those materials is the presence of a solid core (magnesium oxide in part doped with Dy{sub 2}O{sub 3}) covered under reaction conditions with a molten alkali chloride shell. It is shown that especially the lowered melting point of eutectic mixtures of LiCl with other alkali/alkaline earth metals is the key to taylor highly efficient materials. Elucidating the ODH reaction mechanism is essential to understand the reactivity of this novel catalyst class and provides the basis for improving performances. Information about elementary steps and the rate determining step were extracted from kinetic measurements, both in steady state and in transient configuration. Furthermore, isotopic labelling studies were performed, i.e. SSITKA studies and temperature programmed isotopic exchange experiments. Step experiments showed a significant oxygen uptake by the catalysts. Retained oxygen reacted quantitatively with ethane at nearly 100% selectivity to ethylene and conversion rates were comparable with rates observed during steady state operation. Thus, chemically bound oxygen in the melt is the active and selective intermediate in the ODH. Therefore, it is required to consider an intermediate and the activation is concluded to relate to the oxygen dissociation. The total concentration of stored oxygen can be correlated to the steady-state activity, while the viscosity of the melts mainly influences the selectivity towards ethene. Properties of the solid core impact on the catalyst efficiency suggesting that the oxygen species forms at the interface between support and overlayer. The quantity of retained oxygen additionally depends on the properties of the chloride

  9. Research in chemical kinetics. Progress report, August 1, 1987--July 20, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, F.S.

    1996-09-01

    This paper describes chemical kinetics research in the following areas: reactions of thermalized tritium atoms with organo-tin compounds; studies on the hydrolysis of OCS and CS{sub 2}; thermal chlorine 38 reactions with 2,3-dichloro-hexafluoro-2-butene; and thermal T reactions with fluoroethylenes.

  10. Variable elimination in chemical reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We consider chemical reaction networks taken with mass-action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination...

  11. Reduced chemical kinetic mechanisms for NOx emission prediction in biomass combustion

    DEFF Research Database (Denmark)

    Houshfar, Ehsan; Skreiberg, Øyvind; Glarborg, Peter;

    2012-01-01

    reactions and chemical species, that is, 35 species and 198 reactions, corresponding to 72% reduction in the number of reactions and, therefore, improving the computational time considerably. Yet, the model based on the reduced mechanism predicts correctly concentrations of NOx and CO that are essentially...... parameters on NOx emission. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 219–231, 2012...

  12. Chemical kinetics study of hydrocarbon regeneration from organic matter in carbonate source rocks and its significance

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    In the comparison research of hydrocarbon regeneration, a low maturity carbonate source rock is heated to different temperatures in a gold tube to obtain a series of samples with different maturities. Then, the heated samples, before and after extraction, are subjected to Rock-Eval pyrolysis through a thermal simulation of hydrocarbon regeneration in order to inspect pyrolysis characteristics and probe into the characteristics of the chemical kinetics of each sample. The results indicate that, whether hy- drocarbon regeneration peak is delayed or advanced, the potential of hydrocarbon regeneration is closely related to the expulsion amount and breakdown maturity of primary hydrocarbon generation. After extraction, the average activation energy of artificially maturated samples increases with the in- creasing maturity, but the chemical kinetic properties of un-extracted samples decrease. The calibrated chemical kinetic models that describe extracted and un-extracted samples are applied to the Bohai Bay and the Songliao Basin, and the results indicate that the combination of the two models can explain some contradictory conclusions previously reported. These results also facilitate the quantitative evaluation of the amount of hydrocarbon regeneration by the chemical kinetic method.

  13. The Teaching and Learning of Chemical Kinetics Supported with MS Excel

    Science.gov (United States)

    Zain, Sharifuddin Md; Rahman, Noorsaadah Abdul; Chin, Lee Sui

    2013-01-01

    Students in 12 secondary schools in three states of Malaysia were taught to use worksheets on the chemical kinetics topic which had been pre-created using the MS Excel worksheets. After the teaching, an opinion survey of 612 Form Six students from these schools was conducted. The results showed that almost all the students felt that MS Excel…

  14. Chemical kinetics study of hydrocarbon regeneration from organic matter in carbonate source rocks and its significance

    Institute of Scientific and Technical Information of China (English)

    LU ShuangFang; ZHONG NingNing; XUE HaiTao; PAN ChangChun; LI JiJun; LI HongTao

    2007-01-01

    In the comparison research of hydrocarbon regeneration, a low maturity carbonate source rock is heated to different temperatures in a gold tube to obtain a series of samples with different maturities. Then, the heated samples, before and after extraction, are subjected to Rock-Eval pyrolysis through a thermal simulation of hydrocarbon regeneration in order to inspect pyrolysis characteristics and probe into the characteristics of the chemical kinetics of each sample. The results indicate that, whether hydrocarbon regeneration peak is delayed or advanced, the potential of hydrocarbon regeneration is closely related to the expulsion amount and breakdown maturity of primary hydrocarbon generation. After extraction, the average activation energy of artificially maturated samples increases with the in creasing maturity, but the chemical kinetic properties of un-extracted samples decrease. The calibrated chemical kinetic models that describe extracted and un-extracted samples are applied to the Bohai Bay and the Songliao Basin, and the results indicate that the combination of the two models can explain some contradictory conclusions previously reported. These results also facilitate the quantitative evaluation of the amount of hydrocarbon regeneration by the chemical kinetic method.

  15. Development and Validation of Chemical Kinetic Mechanism Reduction Scheme for Large-Scale Mechanisms

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin;

    2014-01-01

    This work is an extension to a previously reported work on chemical kinetic mechanism reduction scheme for large-scale mechanisms. Here, Perfectly Stirred Reactor (PSR) was added as a criterion of data source for mechanism reduction instead of using only auto-ignition condition. As a result, a...

  16. Designing and Evaluating an Evidence-Informed Instruction in Chemical Kinetics

    Science.gov (United States)

    Cakmakci, Gultekin; Aydogdu, Cemil

    2011-01-01

    We have investigated the effects of a teaching intervention based on evidence from educational theories and research data, on students' ideas in chemical kinetics. A quasi-experimental design was used to compare the outcomes for the intervention. The subjects of the study were 83 university first-year students, who were in two different classes in…

  17. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    NARCIS (Netherlands)

    Rao, Shodhan; Jayawardhana, Bayu; Schaft, Arjan van der

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we

  18. Planarization mechanism of alkaline copper CMP slurry based on chemical mechanical kinetics

    Institute of Scientific and Technical Information of China (English)

    Wang Shengli; Yin Kangda; Li Xiang; Yue Hongwei; Liu Yunling

    2013-01-01

    The planarization mechanism of alkaline copper slurry is studied in the chemical mechanical polishing (CMP) process from the perspective of chemical mechanical kinetics.Different from the international dominant acidic copper slurry,the copper slurry used in this research adopted the way of alkaline technology based on complexation.According to the passivation property of copper in alkaline conditions,the protection of copper film at the concave position on a copper pattern wafer surface can be achieved without the corrosion inhibitors such as benzotriazole (BTA),by which the problems caused by BTA can be avoided.Through the experiments and theories research,the chemical mechanical kinetics theory of copper removal in alkaline CMP conditions was proposed.Based on the chemical mechanical kinetics theory,the planarization mechanism of alkaline copper slurry was established.In alkaline CMP conditions,the complexation reaction between chelating agent and copper ions needs to break through the reaction barrier.The kinetic energy at the concave position should be lower than the complexation reaction barrier,which is the key to achieve planarization.

  19. Green chemicals : A Kinetic Study on the Conversion of Glucose to Levulinic Acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L.P.B.M.; Heeres, H.J.

    2006-01-01

    Levulinic acid has been identified as a promising green, biomass derived platform chemical. A kinetic study on one of the key steps in the conversion of biomass to levulinic acid, i.e., the acid catalysed decomposition of glucose to levulinic acid has been performed. The experiments were performed i

  20. Cooperative Learning Instruction for Conceptual Change in the Concepts of Chemical Kinetics

    Science.gov (United States)

    Kirik, Ozgecan Tastan; Boz, Yezdan

    2012-01-01

    Learning is a social event and so the students need learning environments that enable them to work with their peers so that they can learn through their interactions. This study discusses the effectiveness of cooperative learning compared to traditional instruction in terms of students' motivation and understanding of chemical kinetics in a high…

  1. Kinetics and mechanism of oxidation of chloramphenicol by 1-chlorobenzotriazole in acidic medium

    Indian Academy of Sciences (India)

    R C Hiremath; R V Jagadeesh; Puttaswamy; S M Mayanna

    2005-07-01

    Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with respect to [CAP]o. The fractional-order dependence of rate on [H+] suggests complex formation between CBT and H+. It fails to induce polymerization of acrylonitrile under the experimental conditions employed. Activation parameters are evaluated. The observed solvent isotope effect indicates the absence of hydride transfer during oxidation. Effects of dielectric constant and ionic strength of the medium on the reaction rate have been studied. Oxidation products are identified. A suitable reaction scheme is proposed and an appropriate rate law is deduced to account for the observed kinetic data.

  2. Kinetics of heterogeneous catalysis oxidation of carbon monoxide

    International Nuclear Information System (INIS)

    An irreversible kinetic surface-reaction model, based upon the reaction of carbon monoxide nd oxygen on a catalyst surface is investigated by means of Monte Carlo simulation. The adsorbed molecules/atoms on the surface undergo both first and second order kinetic phase transitions. The first order transition is found to occur at x/sub/co=x/sub/2=0.5255 with an error bar of 0.0003, where x/sub/co is the concentration of carbon monoxide in the gas phase. The time evolution of this catalytic reaction is studied both analytically and by computer simulation. Slightly above x/sub/2, the oxygen coverage relaxation time for the oxygen is found to diverage as the inverse of 3.54 times the absolute of the difference of x/sub/2 and x/sub/co. (orig./A.B.)

  3. Evaluation of the intrinsic photocatalytic oxidation kinetics of indoor air pollutants.

    Science.gov (United States)

    Salvadó-Estivill, Ignasi; Hargreaves, David M; Puma, Gianluca Li

    2007-03-15

    This paper presents a methodology for the evaluation of the intrinsic photocatalytic oxidation (PCO) kinetics of indoor air pollutants. It combines computational fluid dynamics (CFD) modeling of the fluid flow in the reactor with radiation field modeling and photocatalytic reaction kinetics to yield a rigorous model of a flat-plate, single-pass, flow-through photocatalytic reactor for indoor air purification. This method was applied to model the PCO of trichloroethylene (TCE) in humidified air and to derive kinetic parameters directly from kinetic data in an integral flow reactor. Steady-state PCO experiments of TCE over irradiated TiO2 (Degussa P25) thin films immobilized on glass supports were carried out at different radiation intensities, flow rates, and inlet substrate concentrations. The oxidation rate of TCE was found to be first-order on the incident photon flux and to follow a Langmuir-Hinshelwood type reaction kinetics rate law. Mass transfer resistances were observed at Reynolds numbers less than 46. Apparent quantum yields were found to be up to 0.97 mol Einstein(-1). A comparison of the model prediction with the experimental results in an integral reactor yielded pollutant-specific kinetic rate parameters which were independent of reactor geometry, radiation field, and fluid-dynamics. The kinetic parameters would,therefore, be more universally applicable to the design and scale-up of photocatalytic reactors for indoor air purification. PMID:17410801

  4. Structural evolution during the reduction of chemically derived graphene oxide.

    Science.gov (United States)

    Bagri, Akbar; Mattevi, Cecilia; Acik, Muge; Chabal, Yves J; Chhowalla, Manish; Shenoy, Vivek B

    2010-07-01

    The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed. PMID:20571578

  5. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670-773 K

  6. The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

    International Nuclear Information System (INIS)

    The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N→O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations

  7. Measured release kinetics of ruthenium from uranium oxides in air and steam

    International Nuclear Information System (INIS)

    The Canadian program on severe fuel damage includes investigation of the kinetics of oxidation of UO2 in both air and steam and the concurrent behaviour of the fission products. These studies are performed in support of fission-product release and transport-model development for postulated-accident and post-accident conditions in CANDU power reactors. In this paper, a summary of the experimental results obtained at the Chalk River Nuclear Laboratories is presented. The release characteristics and kinetics, their dependence on oxygen partial pressure, and the comparison with thermodynamic calculations for the different ruthenium oxides, are discussed

  8. Mutual sensitization of the oxidation of nitric oxide and a natural gas blend in a JSR at elevated pressure: experimental and detailed kinetic modeling study.

    Science.gov (United States)

    Dagaut, Philippe; Dayma, Guillaume

    2006-06-01

    The mutual sensitization of the oxidation of NO and a natural gas blend (methane-ethane 10:1) was studied experimentally in a fused silica jet-stirred reactor operating at 10 atm, over the temperature range 800-1160 K, from fuel-lean to fuel-rich conditions. Sonic quartz probe sampling followed by on-line FTIR analyses and off-line GC-TCD/FID analyses were used to measure the concentration profiles of the reactants, the stable intermediates, and the final products. A detailed chemical kinetic modeling of the present experiments was performed yielding an overall good agreement between the present data and this modeling. According to the proposed kinetic scheme, the mutual sensitization of the oxidation of this natural gas blend and NO proceeds through the NO to NO2 conversion by HO2, CH3O2, and C2H5O2. The detailed kinetic modeling showed that the conversion of NO to NO2 by CH3O2 and C2H5O2 is more important at low temperatures (ca. 820 K) than at higher temperatures where the reaction of NO with HO2 controls the NO to NO2 conversion. The production of OH resulting from the oxidation of NO by HO2, and the production of alkoxy radicals via RO2 + NO reactions promotes the oxidation of the fuel. A simplified reaction scheme was delineated: NO + HO2 --> NO2 + OH followed by OH + CH4 --> CH3 + H2O and OH + C2H6 --> C2H5 + H2O. At low-temperature, the reaction also proceeds via CH3 + O2 (+ M) --> CH3O2 (+ M); CH3O2 + NO --> CH3O + NO2 and C2H5 + O2 --> C2H5O2; C2H5O2 + NO --> C2H5O + NO2. At higher temperature, methoxy radicals are produced via the following mechanism: CH3 + NO2 --> CH3O + NO. The further reactions CH3O --> CH2O + H; CH2O + OH --> HCO + H2O; HCO + O2 --> HO2 + CO; and H + O2 + M --> HO2 + M complete the sequence. The proposed model indicates that the well-recognized difference of reactivity between methane and a natural gas blend is significantly reduced by addition of NO. The kinetic analyses indicate that in the NO-seeded conditions, the main production

  9. Chemical vapour deposition of metal oxides and phosphides.

    OpenAIRE

    Binions, R.

    2006-01-01

    This thesis investigates the deposition of thin films of main group metal phosphide and main group metal oxide compounds on glass substrates by the use of dual source atmospheric pressure chemical vapour deposition. Binary phosphide systems with tin, germanium, silicon, antimony, copper or boron have been examined. Binary oxide systems of gallium, antimony, tin or niobium have also been investigated. Additionally these systems were deposited on gas sensor substrates and evaluated as metal oxi...

  10. The initial oxidation of epsilon-Fesub2Nsub1-x: growth kinetics

    DEFF Research Database (Denmark)

    Graat, Peter C.J.; Somers, Marcel A. J.; Mittemeijer, Eric J.

    1999-01-01

    due to Fromhold and Cook wherein cation and electron currents in the growing oxide film are coupled. The effect of the nitrogen concentration in the iron-nitride substrate on the oxidation kinetics could be discussed in terms of this model and related to the morphology and phase constitution of the......The oxidation kinetics of epsilon-Fe2N1-x, subjected either to a sputter cleaning pretreatment or a sputter cleaning and an additional annealing pretreatment, at P-O2 = 1 x 10(-4) Pa and at temperatures ranging from 300 to 500 K, was investigated with ellipsometry. The initial oxidation rate of...... sputter cleaned + annealed epsilon-Fe2N1-x was observed to be lower than of sputter cleaned epsilon-Fe2N1-x, but upon prolonged oxidation sputter cleaned + annealed epsilon-Fe2N1-x attained a higher oxidation rate than sputter cleaned epsilon-Fe2N1-x. The oxidation kinetics was interpreted using the model...

  11. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    Science.gov (United States)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  12. Detailed Chemical Kinetic Reaction Mechanisms for Primary Reference Fuels for Diesel Cetane Number and Spark-Ignition Octane Number

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Mehl, M; Curran, H J

    2010-03-03

    For the first time, a detailed chemical kinetic reaction mechanism is developed for primary reference fuel mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethyl nonane for diesel cetane ratings. The mechanisms are constructed using existing rules for reaction pathways and rate expressions developed previously for the primary reference fuels for gasoline octane ratings, n-heptane and iso-octane. These reaction mechanisms are validated by comparisons between computed and experimental results for shock tube ignition and for oxidation under jet-stirred reactor conditions. The combined kinetic reaction mechanism contains the submechanisms for the primary reference fuels for diesel cetane ratings and submechanisms for the primary reference fuels for gasoline octane ratings, all in one integrated large kinetic reaction mechanism. Representative applications of this mechanism to two test problems are presented, one describing fuel/air autoignition variations with changes in fuel cetane numbers, and the other describing fuel combustion in a jet-stirred reactor environment with the fuel varying from pure 2,2,4,4,6,8,8-heptamethyl nonane (Cetane number of 15) to pure n-hexadecane (Cetane number of 100). The final reaction mechanism for the primary reference fuels for diesel fuel and gasoline is available on the web.

  13. Thermogravimetric Analysis of Modified Hematite by Methane (CH{sub 4}) for Chemical-Looping Combustion: A Global Kinetics Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Monazam, Esmail R; Breault, Ronald W; Siriwardane, Ranjani; Miller, Duane D

    2013-10-01

    Iron oxide (Fe{sub 2}O{sub 3}) or in its natural form (hematite) is a potential material to capture CO{sub 2} through the chemical-looping combustion (CLC) process. It is known that magnesium (Mg) is an effective methyl cleaving catalyst and as such it has been combined with hematite to assess any possible enhancement to the kinetic rate for the reduction of Fe{sub 2}O{sub 3} with methane. Therefore, in order to evaluate its effectiveness as a hematite additive, the behaviors of Mg-modified hematite samples (hematite –5% Mg(OH){sub 2}) have been analyzed with regard to assessing any enhancement to the kinetic rate process. The Mg-modified hematite was prepared by hydrothermal synthesis. The reactivity experiments were conducted in a thermogravimetric analyzer (TGA) using continuous stream of CH{sub 4} (5, 10, and 20%) at temperatures ranging from 700 to 825 {degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2}, H{sub 2}O, H{sub 2} and CO in the gaseous product. The kinetic data at reduction step obtained by isothermal experiments could be well fitted by two parallel rate equations. The modified hematite samples showed higher reactivity as compared to unmodified hematite samples during reduction at all investigated temperatures.

  14. Oxidation kinetics of zircaloy-4 in the temperature range correspondent to alpha phase

    International Nuclear Information System (INIS)

    Oxidation kinetics of Zry-4 in the alpha phase is isothermally studied in the temperature range from 6000 C to 8000 C, by continuous and discontinuous gravimetric methods. The total mass gain during the oxidation takes place by two distinct ways: oxide formation and solid solution formation. The first one has been studied by microscopy: the latter by microhardness. The oxygen diffusion coefficients in the zirconium are experimentally determined by microhardness measurements and are compared with those obtained by the oxide layer thickness and by oxygen mass in the oxide. The oxygen diffusion coefficients in the oxide are obtained too by oxide layer thickness and by oxygen diffusivities in the alpha phase and compared with literature. (author)

  15. Dissolution kinetics and thermodynamic analysis of vanadium trioxide during pressure oxidation

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The dissolution kinetics of vanadium trioxide in sulphuric acid-oxygen medium was examined. It was determined that the concentration of sulphuric acid and stirring speed above 800 r min 1 did not significantly affect vanadium extraction. The dissolution rate increased with increasing temperature and oxygen partial pressure, but decreased with increasing particle size. The dissolution kinetics was controlled by the chemical reaction at the surface with the estimated activation energy of 43.46 kJ·mol-1. The l...

  16. LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

    A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

  17. Minimal Curvature Trajectories: Riemannian Geometry Concepts for Model Reduction in Chemical Kinetics

    CERN Document Server

    Lebiedz, Dirk; Siehr, Jochen

    2009-01-01

    In dissipative ordinary differential equation systems different time scales cause anisotropic phase volume contraction along solution trajectories. Model reduction methods exploit this for simplifying chemical kinetics via a time scale separation into fast and slow modes. The aim is to approximate the system dynamics with a dimension-reduced model after eliminating the fast modes by enslaving them to the slow ones via computation of a slow attracting manifold. We present a novel method for computing approximations of such manifolds using trajectory-based optimization. We discuss Riemannian geometry concepts as a basis for suitable optimization criteria characterizing trajectories near slow attracting manifolds and thus provide insight into fundamental geometric properties of multiple time scale chemical kinetics. The optimization criteria correspond to a suitable mathematical formulation of "minimal relaxation" of chemical forces along reaction trajectories under given constraints. We present various geometri...

  18. Functional metal oxide coatings by molecule-based thermal and plasma chemical vapor deposition techniques.

    Science.gov (United States)

    Mathur, S; Ruegamer, T; Donia, N; Shen, H

    2008-05-01

    Deposition of thin films through vaccum processes plays an important role in industrial processing of decorative and functional coatings. Many metal oxides have been prepared as thin films using different techniques, however obtaining compositionally uniform phases with a control over grain size and distribution remains an enduring challenge. The difficulties are largely related to complex compositions of functional oxide materials, which makes a control over kinetics of nucleation and growth processes rather difficult to control thus resulting in non-uniform material and inhomogeneous grain size distribution. Application of tailor-made molecular precursors in low pressure or plasma-enhanced chemical vapor deposition (CVD) techniques offers a viable solution for overcoming thermodynamic impediments involved in thin film growth. In this paper molecule-based CVD of functional coatings is demonstrated for iron oxide (Fe2O3, Fe3O4), vanadium oxide (V2O5, VO2) and hafnium oxide (HfO2) phases followed by the characterization of their microstructural, compositional and functional properties which support the advantages of chemical design in simplifying deposition processes and optimizing functional behavior. PMID:18572690

  19. Kinetics studies of oxidation of niacinamide by alkaline potassium permanganate

    Directory of Open Access Journals (Sweden)

    Sandipsingh Gour

    2012-04-01

    Full Text Available The oxidation of niacinamide in alkaline media is carried out using potassium permanganate as a oxiding agent. The reaction was monitored using UV-Visible spectrophotometer at 525 nm. It was found to be zero order with respect to oxidant,, fractional order with respect to hydrogen ion concentration and first order with respect to substrate. The thermodynamic parameters(were determinied . The average (?G# was found to be 87.60 KJ/mol. The values ?S# was found to be -0.2132 KJ/mole and energy of activation was found to be 23.95 KJ/mole. A suitable mechanism is proposed based on the experimental conditions.

  20. Macro kinetics of uranium or rare earth oxides fluorination in vortex flows

    International Nuclear Information System (INIS)

    Highly efficient vortex-type apparatuses with low flow rates of fluorine and oxide solid phase are of great interest for preparation of uranium hexafluoride and rare earth fluorides from their oxides. For obtaining initial data on designing the apparatuses the fields of local rates of the solid phase particles in the vortex flow of a model apparatus 4.8x10-2 m in diameter are identified and numerical studies of macro kinetics of uranium oxide fluorination in fluorine vortex flow are conducted. It is shown that uranium oxide particles actually do not burn out in kinetic mode of the process, being largely burnt out in diffusion mode. About 60-70% of total time of the particle burning falls on the stage of quasistationary warming up of the mixture

  1. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    Science.gov (United States)

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. PMID:26426294

  2. Surface oxidation energetics and kinetics on MoS2 monolayer

    International Nuclear Information System (INIS)

    In this work, surface oxidation of monolayer MoS2 (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS2 shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS2 surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS2 surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS2 monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale

  3. Surface nanosegregation of the chemical composition of complex oxides

    International Nuclear Information System (INIS)

    A brief review of theoretical and experimental studies in the field of surface nanosegregation of chemical composition of oxides SrTiO3, LiNbO3, LiTaO3, Gd2(MoO4)3, KNbO3, PbFe0.5Nb0.5O3, induced by temperature and other factors, is provided. Results of experimental studies of the relevant oxide monocrystals by the methods of electron spectrometry and model presentations suggest diffusion mechanism of segregation. It proved possible to predict the character of changes in surface composition of the oxides on the basis of the models considered

  4. Incipient oxidation kinetics and residual stress of the oxide scale grown on Haynes 230 at high temperatures

    International Nuclear Information System (INIS)

    Highlights: ► Incipient oxidation kinetics of alloy 230 has been investigated by in situ thermogravimetry. ► A two-stage oxidation kinetics was observed; each stage followed Wagner's parabolic law. ► Cr2O3 and MnCr2O4 are mixed with each other and uniformly distributed throughout the scale. ► The intrinsic residual stresses of the scale are highly tensile, ranging from 648.9 to 1308.4 MPa. - Abstract: Incipient oxidation kinetics of alloy 230 in air in the temperature range of 850–1000 °C was investigated by in situ thermogravimetry. A two-stage oxidation kinetics was observed; each stage followed Wagner's parabolic law. The activation energies for the first and the second stages are 246.5 and 212.1 kJ/mol, respectively. Grazing incidence X-ray diffraction showed that two types of oxide phases existed: Cr2O3 and MnCr2O4. Cr2O3 was the dominated phase. Structural characterization revealed that Cr2O3 and MnCr2O4 are mixed with each other and uniformly distributed throughout the scale. The results of residual stress measurements showed that the intrinsic residual stresses of the scale are highly tensile, ranging from 648.9 to 1308.4 MPa. The stress state of alloy 230 near the scale/substrate was found to be tensile, which is opposite to the stress state in the oxide scale, such that the forces balanced.

  5. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才

    2004-01-01

    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  6. Mixed butanols addition to gasoline surrogates: Shock tube ignition delay time measurements and chemical kinetic modeling

    KAUST Repository

    AlRamadan, Abdullah S.

    2015-10-01

    The demand for fuels with high anti-knock quality has historically been rising, and will continue to increase with the development of downsized and turbocharged spark-ignition engines. Butanol isomers, such as 2-butanol and tert-butanol, have high octane ratings (RON of 105 and 107, respectively), and thus mixed butanols (68.8% by volume of 2-butanol and 31.2% by volume of tert-butanol) can be added to the conventional petroleum-derived gasoline fuels to improve octane performance. In the present work, the effect of mixed butanols addition to gasoline surrogates has been investigated in a high-pressure shock tube facility. The ignition delay times of mixed butanols stoichiometric mixtures were measured at 20 and 40bar over a temperature range of 800-1200K. Next, 10vol% and 20vol% of mixed butanols (MB) were blended with two different toluene/n-heptane/iso-octane (TPRF) fuel blends having octane ratings of RON 90/MON 81.7 and RON 84.6/MON 79.3. These MB/TPRF mixtures were investigated in the shock tube conditions similar to those mentioned above. A chemical kinetic model was developed to simulate the low- and high-temperature oxidation of mixed butanols and MB/TPRF blends. The proposed model is in good agreement with the experimental data with some deviations at low temperatures. The effect of mixed butanols addition to TPRFs is marginal when examining the ignition delay times at high temperatures. However, when extended to lower temperatures (T < 850K), the model shows that the mixed butanols addition to TPRFs causes the ignition delay times to increase and hence behaves like an octane booster at engine-like conditions. © 2015 The Combustion Institute.

  7. Combustion in Homogeneous Charge Compression Ignition Engines: Experiments and Detailed Chemical Kinetic Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Flowers, D L

    2002-06-07

    Homogeneous charge compression ignition (HCCI) engines are being considered as an alternative to diesel engines. The HCCI concept involves premixing fuel and air prior to induction into the cylinder (as is done in current spark-ignition engine) then igniting the fuel-air mixture through the compression process (as is done in current diesel engines). The combustion occurring in an HCCI engine is fundamentally different from a spark-ignition or Diesel engine in that the heat release occurs as a global autoignition process, as opposed to the turbulent flame propagation or mixing controlled combustion used in current engines. The advantage of this global autoignition is that the temperatures within the cylinder are uniformly low, yielding very low emissions of oxides of nitrogen (NO{sub x}, the chief precursors to photochemical smog). The inherent features of HCCI combustion allows for design of engines with efficiency comparable to, or potentially higher than, diesel engines. While HCCI engines have great potential, several technical barriers exist which currently prevent widespread commercialization of this technology. The most significant challenge is that the combustion timing cannot be controlled by typical in-cylinder means. Means of controlling combustion have been demonstrated, but a robust control methodology that is applicable to the entire range of operation has yet to be developed. This research focuses on understanding basic characteristics of controlling and operating HCCI engines. Experiments and detailed chemical kinetic simulations have been applied to the characterize some of the fundamental operational and design characteristics of HCCI engines. Experiments have been conducted on single and multi-cylinder engines to investigate general features of how combustion timing affects the performance and emissions of HCCI engines. Single-zone modeling has been used to characterize and compare the implementation of different control strategies. Multi

  8. Unzipping Kinetics of Duplex DNA Containing Oxidized Lesions in an α-Hemolysin Nanopore

    OpenAIRE

    Jin, Qian; Fleming, Aaron M.; Burrows, Cynthia J.; White, Henry S.

    2012-01-01

    The unzipping kinetics for lesion-containing DNA duplexes was studied in an α-hemolysin (α-HL) nanopore. The lesion of focus was the guanine two-electron oxidation product, 8-oxo-7,8-dihydroguanine (OG), and its further oxidation products, the hydantoins guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp). The voltage-driven unzipping of individual duplex DNA molecules with symmetrical overhangs was carried out by pulling one strand of the duplex through the α-HL channel using an electrica...

  9. Eco-friendly kinetic separation of trans-limonene and carvomenthene oxides

    Indian Academy of Sciences (India)

    S Chandrappa Santosh Kumar; Javagal Rangaswamy Manjunatha; Pullabhatla Srinivas; Bheemanakere Kemapaiah Bettadaiah

    2014-05-01

    Kinetic separation of trans-limonene oxide and trans-carvomenthene oxide was achieved in high yield by selective ring opening of their cis-epoxides in the presence of InCl3 catalyst in water. Catalytic activity of InCl3 was conserved up to 10 cycles. Nucleophilic addition of methanol in presence of InCl3 was also selective as cis-epoxides preferentially reacted leaving behind trans-epoxides, which were separated by fractional distillation.

  10. Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

    Science.gov (United States)

    Bansal, Narottam P.; Gamble, Eleanor A.

    2005-01-01

    Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

  11. Effects of alloy heat treatment on oxidation kinetics and scale morphology for Crofer 22 APU

    Science.gov (United States)

    Magdefrau, Neal J.; Chen, Lei; Sun, Ellen Y.; Aindow, Mark

    2013-11-01

    The effect of alloy heat treatment on the oxidation kinetics and oxide scale microstructure of Crofer 22 APU has been studied. Parabolic oxidation rate constants were measured for the as-received alloy and after pre-oxidation heat treatment in argon at 1050 °C for 1 and 4 h. The oxide scale microstructure was investigated using scanning electron microscopy, focused ion beam milling and transmission electron microscopy. It was found that the alloy forms a two-layer scale with a continuous chromia layer and a discontinuous MnCr2O4 overlayer. Two forms of internal oxides were also formed: subscale pockets of spinel and isolated TiOx precipitates in the underlying alloy. The pre-oxidation heat treatment had a profound effect on the grain size and morphology of the Cr2O3 and MnCr2O4 layers in the scale. The heat-treated samples exhibit a 3.5× lower parabolic oxidation rate constant than the as-received Crofer 22 APU. This improvement in oxidation resistance is attributed to the dramatic differences in the morphology of the oxide scale that forms during the earliest stages of oxidation (<5 h). The implications of these findings for oxidation mechanisms and long-term SOFC performance are discussed.

  12. Kinetics of carbon monoxide oxidation over modified supported CuO catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Loc, Luu Cam; Tri, Nguyen; Cuong, Hoang Tien; Thoang, Ho Si [Vietnam Academy of Science and Technology (VAST), Ho Chi Minh City (Viet Nam). Inst. of Chemical Technology; Agafonov, Yu.A.; Gaidai, N.A.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2013-11-01

    The following supported on {gamma}-Al{sub 2}O{sub 3} catalysts: 10(wt.)%CuO (CuAl), 10%CuO+10%Cr{sub 2}O{sub 3} (CuCrAl) and 10%CuO+20%CeO{sub 2} (CuCeAl) were under the investigation. Physico-chemical characteristics of the catalysts were determined by the methods of BET, X-ray Diffraction (XRD), and Temperature-Programmed Reduction (TPR). A strong interaction of copper with support in CuAl resulted in the formation of low active copper aluminates. The bi-oxide CuCrAl was more active than CuAl owing to the formation of high catalytically active spinel CuCr{sub 2}O{sub 4}. The fact of very high activity of the sample CuCeAl can be explained by the presence of the catalytically active form of CuO-CeO{sub 2}-Al{sub 2}O{sub 3}. The kinetics of CO total oxidation was studied in a gradientless flow-circulating system at the temperature range between 200 C and 270 C. The values of initial partial pressures of carbon monoxide (P{sup o}{sub CO}), oxygen (P{sup o}{sub O2}), and specially added carbon dioxide (P{sup o}{sub CO{sub 2}}) were varied in ranges (hPa): 10 / 45; 33 / 100, and 0 / 30, respectively. (orig.)

  13. Double-focusing mixing jet for XFEL study of chemical kinetics

    International Nuclear Information System (INIS)

    A novel method for time-resolved study of chemical kinetics using a windowless mixing jet at an X-ray free-electron laser (XFEL) is described and demonstrated. The short mixing time gives a time resolution of about 250 µs; the design introduces controllable delays after the initiation of a chemical reaction, allowing the possibility for detection of transient structures by an XFEL beam pulse. Applications may include time-resolved enzyme–substrate imaging or protein folding. Several liquid sample injection methods have been developed to satisfy the requirements for serial femtosecond X-ray nanocrystallography, which enables radiation-damage-free determination of molecular structure at room temperature. Time-resolved nanocrystallography would combine structure analysis with chemical kinetics by determining the structures of the transient states and chemical kinetic mechanisms simultaneously. A windowless liquid mixing jet device has been designed for this purpose. It achieves fast uniform mixing of substrates and enzymes in the jet within 250 µs, with an adjustable delay between mixing and probing by the X-ray free-electron laser beam of up to 1 s for each frame of a ‘movie’. The principle of the liquid mixing jet device is illustrated using numerical simulation, and experimental results are presented using a fluorescent dye

  14. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola

    2001-01-01

    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacu...

  15. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Henych, Jiří; Janos, P.; Skoumal, M.

    2016-01-01

    Roč. 236, č. 2016 (2016), s. 239-259. ISSN 0179-5953 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : chemical warfare agent * metal nanoparticle * unique surface-chemistry * mesoporous manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 3.744, year: 2014

  16. Dissolution kinetics of spent petroleum catalyst using sulfur oxidizing acidophilic microorganisms.

    Science.gov (United States)

    Mishra, Debaraj; Ahn, Jong G; Kim, Dong J; Roychaudhury, G; Ralph, David E

    2009-08-15

    Bioleaching studies of spent petroleum catalyst were carried out using sulfur oxidizing, Acidithiobacillus species. Leaching studies were carried out in two-stage, in the first stage bacteria were grown and culture filtrate was used in the second stage for leaching purpose. XRD analysis of spent petroleum catalyst showed oxides of V, Fe and Al and sulfides of Mo and Ni. The leaching kinetics followed dual rate, initial faster followed by slower rate and equilibrium could be achieved within 7 days. The leaching rate of Ni and V were high compared to Mo. The low Mo leaching rate may be either due to formation of impervious sulfur layer or refractoriness of sulfides or both. The leaching kinetics followed 1st order rate. Using leaching kinetics, rate equations for dissolution process for different metal ions were evaluated. The rate determining step observed to be pore diffusion controlled. PMID:19286311

  17. Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

    Science.gov (United States)

    Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

    2016-05-01

    The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

  18. Self-limited kinetics of electron doping in correlated oxides

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jikun, E-mail: jikunchen@seas.harvard.edu; Zhou, You; Jiang, Jun; Shi, Jian; Ramanathan, Shriram [School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 (United States); Middey, Srimanta; Chakhalian, Jak [Department of Physics, University of Arkansas, Fayetteville, Arkansas 72701 (United States); Chen, Nuofu [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Source, North China Electric Power University, Beijing 102206 (China); Chen, Lidong; Shi, Xun [CAS Key Laboratory of Materials for Energy Conversion, Shanghai institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Döbeli, Max [Laboratory of Ion Beam Physics, ETH Zurich, Zurich 8093 (Switzerland)

    2015-07-20

    Electron doping by hydrogenation can reversibly modify the electrical properties of complex oxides. We show that in order to realize large, fast, and reversible response to hydrogen, it is important to consider both the electron configuration on the transition metal 3d orbitals, as well as the thermodynamic stability in nickelates. Specifically, large doping-induced resistivity modulations ranging several orders of magnitude change are only observed for rare earth nickelates with small ionic radii on the A-site, in which case both electron correlation effects and the meta-stability of Ni{sup 3+} are important considerations. Charge doping via metastable incorporation of ionic dopants is of relevance to correlated oxide-based devices where advancing approaches to modify the ground state electronic properties is an important problem.

  19. Kinetic parameters of nitrous oxide production and reduction during denitrification in pasture soils

    Czech Academy of Sciences Publication Activity Database

    Čuhel, Jiří; Šimek, Miloslav

    Braunschweig : Bba - Federal Biological Research Centre for Agriculture and Forestry, 2007. s. 160. [Symposium on Bacterial Genetics and Ecology. BAGECO 9. Microbial Community Networks /9./. 23.06.2007-27.06.2007, Wernigerode] Institutional research plan: CEZ:AV0Z60660521 Keywords : kinetic parameters * nitrous oxide production * denitrification in pasture soils Subject RIV: EH - Ecology, Behaviour

  20. Mechanism and kinetics of the oxidation of synthetic alpha-NiS

    Directory of Open Access Journals (Sweden)

    BOYAN BOYANOV

    2008-02-01

    Full Text Available The results of an investigation of the mechanism and kinetics of the oxidation process of synthetic a-NiS are presented in this paper. The mechanism of a-NiS oxidation was investigated based on the comparative analysis of DTA–TG–DTG and XRD results, as well as the constructed phase stability diagrams (PSD for the Ni–S–O system. The kinetic investigations of the oxidation process were performed under isothermal conditions (temperature range 823–1073 K. The obtained degrees of desulfurization were used in the calculation process according to the Sharp model and the kinetic parameters, including the activation energies and the rate constants of the characteristic reactions, for the oxidation of a-NiS were determined. These results enabled the formulation of a kinetic equation for the desulfurization process: ‑ln(1−a = k1t = 27.89 exp(–9860/Tt, with an activation energy of 82±4 kJ mol-1, for the first stage of the process and –ln (1 − a = k2t = 1.177 exp(–4810/Tt, with an activation energy of 40±2 kJ mol-1, for the second stage.

  1. Enzyme catalyzed oxidative gelation of sugar beet pectin: Kinetics and rheology

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

    2012-01-01

    Sugar beet pectin (SBP) is a marginally utilized co-processing product from sugar production from sugar beets. In this study, the kinetics of oxidative gelation of SBP, taking place via enzyme catalyzed cross-linking of ferulic acid moieties (FA), was studied using small angle oscillatory measure...

  2. Ferrate promoted oxidative cleavage of sulfonamides: Kinetics and product formation under acidic conditions

    Science.gov (United States)

    Sulfonamide-based antibiotics are often detected in surface waters and secondary wastewater effluents and pose an eminent threat for the development of antibiotic resistance bacteria and genes in aquatic environment. This paper presents the kinetics and stoichiometry of the oxid...

  3. Nitrite-Driven Nitrous Oxide Production Under Aerobic Soil Conditions: Kinetics and Biochemical Controls

    Science.gov (United States)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

  4. Kinetic if Phenol Oxidation by the Yeast Candida tropicalis

    Czech Academy of Sciences Publication Activity Database

    Prell, Aleš; Páca, J.; Komárková, E.; Stiborová, M.; Sobotka, Miroslav; Kujan, Petr

    Tatrianské Matriare, 2002, s. 45. [International Conference of Slovak Society of Chemical Engineering /29./. Tatranské Matliare (SK), 27.05.2002-31.05.2002] Institutional research plan: CEZ:AV0Z5020903 Keywords : biodegradation * phenol * candida tropicalis Subject RIV: EE - Microbiology, Virology

  5. Study of the oxidation kinetics of the nickel-molybdenum alloy

    International Nuclear Information System (INIS)

    This research thesis reports the study of the oxidation of a nickel-molybdenum alloy in the high-nickel-content part of this alloy. After a bibliographical study on the both metals, the author proposes a physical model based on observed phenomena and based on experimental results. Based on a thermodynamic study, the author compares the stability of the different oxides which may be formed, and reports a prediction of oxides obtained on the alloy during oxidation. Qualitative and quantitative studies have been performed by scanning electron microscopy coupled with electronic microprobe analysis to investigate morphological characteristics on oxidation films. A kinetic study by thermogravimetry shows a decrease of the alloy oxidation rate with respect to that of pure nickel at temperatures lower than 800 degrees C. This result is interpreted by the intervention of two opposed diffusion phenomena which act against each other

  6. Kinetics and mechanism of the oxidation of some -hydroxy acids by hexamethylenetetramine-bromine

    Indian Academy of Sciences (India)

    Dimple Garg; Seema Kothari

    2004-11-01

    The oxidation of lactic acid, mandelic acid and ten monosubstituted mandelic acids by hexamethylenetetramine-bromine (HABR) in glacial acetic acid, leads to the formation of the corresponding oxoacid. The reaction is first order with respect to each of the hydroxy acids and HABR. It is proposed that HABR itself is the reactive oxidizing species. The oxidation of -deuteriomandelic acid exhibits the presence of a substantial kinetic isotope effect (/ = 5.91 at 298 K). The rates of oxidation of the substituted mandelic acids show excellent correlation with Brown’s + values. The reaction constants are negative. The oxidation exhibits an extensive cross conjugation between the electron-donating substituent and the reaction centre in the transition state. A mechanism involving transfer of a hydride ion from the acid to the oxidant is postulated.

  7. Chemical Composition of Seed Oil from Roselle (Hibiscus sabdariffa L. and the Kinetics of Degradation of the Oil During Heating

    Directory of Open Access Journals (Sweden)

    G. Bouanga-Kalou

    2011-03-01

    Full Text Available The aim of the study was to investigate the chemical composition and the kinetics of degradation of roselle seed oil during heating. The seed is a good source of oil (23.27%. The physical properties of the oil extracts showed the state to be liquid at room temperature and indicated that the oil had refractive index, 1.4652; the peroxide value, 3.15 (meq O2/kg oil; free fatty acid, 0.82%; iodine value, 97.78%; saponification value, 198.45 and viscosity, 15.15 (mPa.s at 25ºC. Gas liquid chromatography technique has been developed for identification and quantitative determination of total unsaturated and saturated fatty acids shows that the crude oil had 73.4 and 26.57%, respectively. DSC indicates the presence of two components in oil extracted. The first peak at low melting point appears at -20.53°C ΔHf = +3.00 J/g and the second peak appears to - 2.17ºC ΔHf = +0.49 J/g. The degradation kinetic of the oil was also investigated. The thermal oxidation of the double bonds of the oil showed a first-order thermal oxidation kinetic and the Arrhenius plot yielded a straight line with a slope equivalent to activation energy of 9.041 KJ/mol.There is the possibility of considering the seed as feed supplement and its oil for industrial application.

  8. Thermal oxidation kinetics and oxide scale adhesion of Fe-15Cr alloys as a function of their silicon content

    International Nuclear Information System (INIS)

    Three types of Fe-15Cr alloys, containing 0, 0.5 and 1 wt.% Si, were studied between 850 and 950 deg. C in terms of oxidation kinetics, oxide spallation and oxide adhesion energy. The oxidation kinetics in Ar-15% O2 were found to be parabolic, exhibiting non-monotonic evolution of the parabolic rate constant with increasing Si content, with a minimum value for 0.5% Si. Chromia scale spallation on cooling was quantified as a function of oxide thickness, showing again non-monotonic behaviour, with no spallation for the Si-free alloy, up to a scale thickness of 2.7 μm, and maximum spallation for the 0.5% Si alloy. Room temperature tensile testing in a scanning electron microscope chamber was used to quantify oxide adhesion. Interfacial fracture energy values derived from these experiments were shown to be in the range 20-80 J m-2, with the respective values in good agreement with the observation of spallation during cooling

  9. Study of oxide and α-Zr(O) growth kinetics from high temperature steam oxidation of Zircaloy-4 cladding

    Science.gov (United States)

    Sawarn, Tapan K.; Banerjee, Suparna; Samanta, Akanksha; Rath, B. N.; Kumar, Sunil

    2015-12-01

    Oxidation kinetics of Zircaloy-4 cladding of fuel pins of Indian pressurized heavy water reactors (IPHWRs) under a simulated loss of coolant accident (LOCA) condition was investigated. The kinetic rate constants for the oxide and oxygen stabilized α-Zr phase growth were established from the isothermal metal-steam reaction at high temperatures (900-1200 °C) with soaking periods in the range of 60-900 s. Oxide and α-Zr(O) layer thickness were measured to derive the respective growth rates. The observed rates obeyed a parabolic law and Arrhenius expressions of rate constants were established. Percentage equivalent clad reacted (%ECR) was calculated using Baker-Just equation. Hydrogen estimation was carried out on the oxidized samples using inert gas fusion technique. The hydrogen pick up was found to be in the range 10-30 ppm. The measured values of oxide and α-Zr(O) layer thickness were compared with the results obtained using OXYCON, an indigenously developed model. The model predicts the oxide growth reasonably well but under predicts the α-Zr(O) growth significantly at thickness values higher than 80 μm.

  10. Radiation-chemical oxidation of adamantylideneadamantane with dioxetane formation

    International Nuclear Information System (INIS)

    Liquid-phase radiation-chemical oxidation of adamantylideneadamantane with 1,2-dioxetane formation is studied. Gamma-irradiation is carried out with the doses up to 17.2 kGy, the dose rate being 1.2 Gy/s. It is shown that the main chance of radiation-chemical oxidation of this alkene is radical expoxidation. One of the sources of radical generation in acetone is the process of oxygen quenching the triplet acetone. In the presence of intermediaries passing excitation to dissolved oxygene in solvents with high yield of excited states generation 1O2 is produced, and alkene is oxidized to dioxetane. Therewith, the epoxide yield is decreased, the dioxetane and epoxide yield ratio is defined by competition between reactions of O2 and intermediaries leading to 1O2 or radical products

  11. Nonlinear effects in infrared action spectroscopy of silicon and vanadium oxide clusters: experiment and kinetic modeling.

    Science.gov (United States)

    Calvo, Florent; Li, Yejun; Kiawi, Denis M; Bakker, Joost M; Parneix, Pascal; Janssens, Ewald

    2015-10-21

    For structural assignment of gas phase compounds, infrared action spectra are usually compared to computed linear absorption spectra. However, action spectroscopy is highly nonlinear owing to the necessary transfer of the excitation energy and its subsequent redistribution leading to statistical ionization or dissociation. Here, we examine by joint experiment and dedicated modeling how such nonlinear effects affect the spectroscopic features in the case of selected inorganic clusters. Vibrational spectra of neutral silicon clusters are recorded by tunable IR-UV two-color ionization while IR spectra for cationic vanadium oxide clusters are obtained by IR multiphoton absorption followed by dissociation of the bare cluster or of its complex with Xe. Our kinetic modeling accounts for vibrational anharmonicities, for the laser interaction through photon absorption and stimulated emission rates, as well as for the relevant ionization or dissociation rates, all based on input parameters from quantum chemical calculations. Comparison of the measured and calculated spectra indicates an overall agreement as far as trends are concerned, except for the photodissociation of the V3O7(+)-Xe messenger complex, for which anharmonicities are too large and poorly captured by the perturbative anharmonic model. In all systems studied, nonlinear effects are essentially manifested by variations in the intensities as well as spectral broadenings. Differences in some band positions originate from inaccuracies of the quantum chemical data rather than specific nonlinear effects. The simulations further yield information on the average number of photons absorbed, which is otherwise unaccessible information: several to several tens of photons need to be absorbed to observe a band through dissociation, while three to five photons can be sufficient for detection of a band via IR-UV ionization. PMID:26208251

  12. Kinetics and Reaction Mechanisms of High-Temperature Flash Oxidation of Molybdenite

    Science.gov (United States)

    Wilkomirsky, Igor; Otero, Alfonso; Balladares, Eduardo

    2010-02-01

    The kinetics and reaction mechanism of the flash oxidation of +35/-53 μm molybdenite particles in air, as well as in 25, 50, and 100 pct oxygen higher than 800 K, has been investigated using a stagnant gas reactor and a laminar flow reactor coupled to a fast-response, two-wavelength pyrometer. The changes in the morphology and in the chemical composition of partially reacted particles were also investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA), and electron microprobe. High-speed photography was also used to characterize the particle combustion phenomena. The effects of oxygen concentration and gas temperature on ignition and peak combustion temperatures were studied. The experimental results indicate that MoS2 goes through a process of ignition/combustion with the formation of gaseous MoO3 and SO2 with no evidence of formation of a molten phase, although the reacting molybdenite particles reach temperatures much higher than their melting temperature. This effect may be a result of the combustion of gaseous sulfur from partial decomposition of molybdenite to Mo2S3 under a high gas temperature and 100 pct oxygen. In some cases, the partial fragmentation and distortion of particles also takes place. The transformation can be approximated to the unreacted core model with chemical control and with activation energy of 104.0 ± 4 kJ/mol at the actual temperature of the reacting particles. The reaction was found to be first order with respect to the oxygen concentration. The rate constant calculated at the actual temperatures of the reacting particles shows a good agreement with kinetic data obtained at lower temperatures. The ignition temperature of molybdenite shows an inverse relationship with the gas temperature and oxygen content, with the lowest ignition temperature of 1120 K for 100 pct oxygen. Increasing the oxygen content from 21 to 100 pct increases the particle combustion temperature from 1600 K

  13. Kinetics and Mechanism of Nanostructures in Oxidation of Si1-xGex Alloys

    Institute of Scientific and Technical Information of China (English)

    黄伟其; 蔡绍洪

    2002-01-01

    We investigate the oxidation behaviour of Si1-xGex alloys (x = 0.05, 0.15, and 0.25). The oxidation of SiGe flms with different compositions was carried out in O2 (dry) atmosphere at 800, 900 and 1000°C, respectively,for various lengths of time. The thickness and property of the nanoparticle and nanolayer in oxide films and germanium segregation in oxidation of SiGe alloys are measured by using a high precision ellipsometer. The results are in good agreement with the Rutherford backscattering spectrometry, profile dektak instrument and high-resolution scanning transmission electron microscopy. We found that the Ge content in the oxide layer increases with the Ge content in SiGe alloys, and that the Ge content in the oxide film decreases with the increasing oxidation temperature and time. Rejection of Ge results in piling up of Ge at the interface between the growing SiO2 and the remaining SiGe, which forms a nanometre Ge-rich layer. Substantial interdiffusion of Si and Ge takes place in the remaining SiGe, which leads to the complicated distribution of Ge segregation. We find a nanometre cap layer over the oxide film after fast oxidation, in which there are many Ge nanoparticles.We analyse the kinetics and mechanism of the nanostructure of the oxide and Ge segregation in oxidation of Si1- x Gex alloys.

  14. Kinetics of oxidation of nickel(II) aza macrocycles by peroxydisulphate in aqueous media

    Indian Academy of Sciences (India)

    J Lalitham; V R Vijayaraghavan

    2000-10-01

    The kinetics of the oxidation of nickel (II) hexaaza and nickel (II) pentaaza macrocycles by the peroxydisulphate anion, S2O8 2-, were studied in aqueous media. Effect of H on reaction rate was also studied. The rate increases with increase of S2OO8 2- concentration. Rates are almost independent of acid between H 4 and 2, giving overall a relatively simple second-order rate law followed by oxidation within the ion pair solvent shell. Using rate = +1/2 d[Ni(L)3+]/dt = k[Ni(L)2+][S2O8 2-], oxidation rate constants were determined.

  15. Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

    Science.gov (United States)

    Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

    2016-02-01

    Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

  16. Accelerating finite-rate chemical kinetics with coprocessors: comparing vectorization methods on GPUs, MICs, and CPUs

    CERN Document Server

    Stone, Christopher P

    2016-01-01

    Efficient ordinary differential equation solvers for chemical kinetics must take into account the available thread and instruction-level parallelism of the underlying hardware, especially on many-core coprocessors, as well as the numerical efficiency. A stiff Rosenbrock and nonstiff Runge-Kutta solver are implemented using the single instruction, multiple thread (SIMT) and single instruction, multiple data (SIMD) paradigms with OpenCL. The performances of these parallel implementations were measured with three chemical kinetic models across several multicore and many-core platforms. Two runtime benchmarks were conducted to clearly determine any performance advantage offered by either method: evaluating the right-hand-side source terms in parallel, and integrating a series of constant-pressure homogeneous reactors using the Rosenbrock and Runge-Kutta solvers. The right-hand-side evaluations with SIMD parallelism on the host multicore Xeon CPU and many-core Xeon Phi co-processor performed approximately three ti...

  17. A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations.

    Science.gov (United States)

    Nguyen, Thanh Lam; Stanton, John F

    2015-07-16

    In the field of chemical kinetics, the solution of a two-dimensional master equation that depends explicitly on both total internal energy (E) and total angular momentum (J) is a challenging problem. In this work, a weak-E/fixed-J collisional model (i.e., weak-collisional internal energy relaxation/free-collisional angular momentum relaxation) is used along with the steady-state approach to solve the resulting (simplified) two-dimensional (E,J)-grained master equation. The corresponding solutions give thermal rate constants and product branching ratios as functions of both temperature and pressure. We also have developed a program that can be used to predict and analyze experimental chemical kinetics results. This expedient technique, when combined with highly accurate potential energy surfaces, is cable of providing results that may be meaningfully compared to experiments. The reaction of singlet oxygen with methane proceeding through vibrationally excited methanol is used as an illustrative example. PMID:25815602

  18. Electrode Kinetics and Gas Conversion in Solid Oxide Cells

    OpenAIRE

    Njodzefon, Jean-Claude; Hjelm, Johan; Graves, Christopher R.; Weber, André

    2015-01-01

    Fastoxid brændselsceller (SOFC) omdanner brint, kulmonoxid og kulbrinteholdige brændstoffer (direkte) til elektricitet med meget høje virkningsgrader og har demonstreret næsten tilsvarende resultater, når de drives i omvendt tilstand, som en fast oxid elektrolysecelle (SOEC). I dette tilfælde lagres elektrisk (og termiske) energi som kemisk energi i reaktionsprodukterne. Til dette formål tilsættes cellerne med damp (H2O elektrolyse), kuldioxid (CO2 elektrolyse) eller en blanding af begge dele...

  19. Influence of hydrogen oxidation kinetics on hydrogen environment embrittlement

    Science.gov (United States)

    Walter, R. J.; Kendig, M. W.; Meisels, A. P.

    1992-01-01

    Results are presented from experiments performed to determine the roles of hydrogen absorption and hydrogen electron transfer on the susceptibility of Fe- and Ni-base alloys to ambient-temperature hydroen embrittlement. An apparent independence is noted between hydrogen environment embrittlement and internal hydrogen embrittlement. The experiments were performed on Inconel 718, Incoloy 903, and A286. The electrochemical results obtained indicate that Inconel 718 either adsorbs hydrogen more rapidly and/or the electrochemical oxidation of the adsorbed hydrogen occurred more rapidly than in the other two materials.

  20. Kinetic study of pyrite oxidation in basic carbonate solutions

    International Nuclear Information System (INIS)

    The general goal of this experimental study was to find ways to control the unwanted oxidation of pyrite during the in situ leaching of uranium ores. The authors investigated the effect of particle size, leaching pH, flow rate, total carbonate concentration, and cation type of column leaching rates. The work appears to be the first dealing with pyrite leaching in test columns at high pH in which the identity and percentages of the various eluted sulfur compounds was measured. The most interesting of the experimental observations was the ultimate ceasing of the pyrite reaction when using an ammonia leachant

  1. Characteristics of SME biodiesel-fueled diesel particle emissions and the kinetics of oxidation.

    Science.gov (United States)

    Jung, Heejung; Kittelson, David B; Zachariah, Michael R

    2006-08-15

    Biodiesel is one of the most promising alternative diesel fuels. As diesel emission regulations have become more stringent, the diesel particulate filter (DPF) has become an essential part of the aftertreatment system. Knowledge of kinetics of exhaust particle oxidation for alternative diesel fuels is useful in estimating the change in regeneration behavior of a DPF with such fuels. This study examines the characteristics of diesel particulate emissions as well as kinetics of particle oxidation using a 1996 John Deere T04045TF250 off-highway engine and 100% soy methyl ester (SME) biodiesel (B100) as fuel. Compared to standard D2 fuel, this B100 reduced particle size, number, and volume in the accumulation mode where most of the particle mass is found. At 75% load, number decreased by 38%, DGN decreased from 80 to 62 nm, and volume decreased by 82%. Part of this decrease is likely associated with the fact that the particles were more easily oxidized. Arrhenius parameters for the biodiesel fuel showed a 2-3times greater frequency factor and approximately 6 times higher oxidation rate compared to regular diesel fuel in the range of 700-825 degrees C. The faster oxidation kinetics should facilitate regeneration when used with a DPF. PMID:16955891

  2. Kinetic Analysis of the Anodic Carbon Oxidation Mechanism in a Molten Carbonate Medium

    International Nuclear Information System (INIS)

    The oxidation mechanism for carbon in a carbonate melt was modelled using an electrochemical kinetic approach. Through the Butler-Volmer equation for electrode kinetics, a series of expressions was derived assuming each step of the proposed carbon oxidation mechanism is in turn the rate determining step (RDS). Through the derived expressions the transfer coefficient and Tafel slope were calculated for each possible RDS of the proposed mechanism and these were compared with real data collected on carbon based electrodes including graphite and coal. It was established that the RDS of the electrochemical oxidation process is dependent on both the carbon type and the potential region of oxidation. The simplified kinetic analysis suggested that the RDS in the main oxidation region is likely to be the first or second electron transfer on a graphite electrode surface, which occurs following initial adsorption of an oxygen anion to an active carbon site. This is contrary to previous suggestions that adsorption of the second anion to the carbon surface will be rate determining. It was further shown that use of a coal based carbon introduces a change in mechanism with an additional reaction region where a different mechanism is proposed to be operating

  3. Kinetic modeling of low temperature oxidation of copper nanoparticles by O2

    International Nuclear Information System (INIS)

    Highlights: • Low temperature oxidation of copper nanoparticles resulted in hollow Cu2O particles. • A mechanism is proposed to explain the outward growth of Cu2O. • The reaction involves simultaneously growth and nucleation processes of Cu2O. • Adsorption is the rate determining step below the slowdown of the reaction. • A kinetic model is proposed and confronted to the experimental data. - Abstract: The mechanism and kinetics of copper nanoparticles oxidation at low temperature were investigated using thermogravimetry (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal and isobaric studies of the oxidation reaction were carried out at various temperatures. It was found that working under an oxygen partial pressure of 1 kPa in the temperature range 125–145 °C leads to reaction where nucleation of the oxide phase is in competition with its growth. The study of the dependency of the growth rate on the oxygen partial pressure under 10 kPa has shown the adsorption of oxygen at the surface of the oxide to be the rate-determining step. A mechanism and a kinetic model have been established to interpret the experimental curves

  4. Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burchell, Timothy D [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert [Univ. of Tennessee, Knoxville, TN (United States)

    2015-05-01

    This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetime of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.

  5. Kinetics and mechanism of oxidation of aliphatic alcohols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Manju Baghmar; Pradeep K Sharma

    2001-04-01

    Oxidation of nine primary aliphatic alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the polymerization of acrylonitrile. Tetrabutylammonium chloride has no effect on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The oxidation of [1,1-2H2]ethanol exhibits a substantial kinetic isotope effect. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The reaction is susceptible to both polar and steric effects of substituents. A mechanism involving transfer of a hydride ion in the ratedetermining step has been proposed.

  6. Feasibility of Reduced Chemical Kinetic Mechanisms of Methane in Internal Combustion Engine Simulations

    Science.gov (United States)

    Ennetta, Ridha; Said, Rachid

    2008-09-01

    Three reduced chemical kinetic mechanisms of methane combustion were tested and compared with the standard detailed scheme GriMech 3.0., using the internal combustion engine (ICE) model of Chemkin 4.02 [1]. This study shows acceptable concordances in the prediction of temperature and main species profiles. But reduced schemes were incapables to predict all polluant emissions in an internal combustion engine.

  7. Nonlinear Stochastic Dynamics of Complex Systems, I: A Chemical Reaction Kinetic Perspective with Mesoscopic Nonequilibrium Thermodynamics

    OpenAIRE

    Qian, Hong

    2016-01-01

    We distinguish a mechanical representation of the world in terms of point masses with positions and momenta and the chemical representation of the world in terms of populations of different individuals, each with intrinsic stochasticity, but population wise with statistical rate laws in their syntheses, degradations, spatial diffusion, individual state transitions, and interactions. Such a formal kinetic system in a small volume $V$, like a single cell, can be rigorously treated in terms of a...

  8. Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition

    OpenAIRE

    Ma, Teng; Ren, Wencai; Zhang, Xiuyun; Liu, Zhibo; Gao, Yang; Yin, Li-Chang; Ma, Xiu-Liang; Ding, Feng; Cheng, Hui-Ming

    2013-01-01

    Controlled synthesis of wafer-sized single crystalline high-quality graphene is a great challenge of graphene growth by chemical vapor deposition because of the complicated kinetics at edges that govern the growth process. Here we report the synthesis of single-crystal graphene domains with tunable edges from zigzag to armchair via a growth–etching–regrowth process. Both growth and etching of graphene are strongly dependent on the edge structure. This growth/etching behavior is well explained...

  9. A kinetic model for chemical reactions without barriers : transport coefficients and eigenmodes

    OpenAIRE

    Alves, Giselle M.; Marques Júnior, Wilson; Soares, A. J.; Kremer, Gilberto M.

    2011-01-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solution of the Boltzmann equation is determined through an expansion in Sonine polyn...

  10. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    OpenAIRE

    Rao, Shodhan; Jayawardhana, Bayu; der Schaft, Arjan van

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we can characterize the space of equilibrium points and provide simple dynamical analysis on the state space modulo the space of equilibrium points.

  11. On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

    OpenAIRE

    der Schaft, Arjan van; Rao, Shodhan; Jayawardhana, Bayu

    2011-01-01

    Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the same time the structure of the complex graph and the stoichiometry of the network, and which admits a direct thermodynamical interpretation. This formulation allows us to easily characterize the set ...

  12. Accuracy and precision of protein–ligand interaction kinetics determined from chemical shift titrations

    International Nuclear Information System (INIS)

    NMR-monitored chemical shift titrations for the study of weak protein–ligand interactions represent a rich source of information regarding thermodynamic parameters such as dissociation constants (KD) in the micro- to millimolar range, populations for the free and ligand-bound states, and the kinetics of interconversion between states, which are typically within the fast exchange regime on the NMR timescale. We recently developed two chemical shift titration methods wherein co-variation of the total protein and ligand concentrations gives increased precision for the KD value of a 1:1 protein–ligand interaction (Markin and Spyracopoulos in J Biomol NMR 53: 125–138, 2012). In this study, we demonstrate that classical line shape analysis applied to a single set of 1H–15N 2D HSQC NMR spectra acquired using precise protein–ligand chemical shift titration methods we developed, produces accurate and precise kinetic parameters such as the off-rate (koff). For experimentally determined kinetics in the fast exchange regime on the NMR timescale, koff ∼ 3,000 s−1 in this work, the accuracy of classical line shape analysis was determined to be better than 5 % by conducting quantum mechanical NMR simulations of the chemical shift titration methods with the magnetic resonance toolkit GAMMA. Using Monte Carlo simulations, the experimental precision for koff from line shape analysis of NMR spectra was determined to be 13 %, in agreement with the theoretical precision of 12 % from line shape analysis of the GAMMA simulations in the presence of noise and protein concentration errors. In addition, GAMMA simulations were employed to demonstrate that line shape analysis has the potential to provide reasonably accurate and precise koff values over a wide range, from 100 to 15,000 s−1. The validity of line shape analysis for koff values approaching intermediate exchange (∼100 s−1), may be facilitated by more accurate KD measurements from NMR-monitored chemical shift

  13. Measurement and chemical kinetic model predictions of detonation cell size in methanol-oxygen mixtures

    Science.gov (United States)

    Eaton, R.; Zhang, B.; Bergthorson, J. M.; Ng, H. D.

    2012-03-01

    In this study, detonation cell sizes of methanol-oxygen mixtures are experimentally measured at different initial pressures and compositions. Good agreement is found between the experiment data and predictions based on the chemical length scales obtained from a detailed chemical kinetic model. To assess the detonation sensitivity in methanol-oxygen mixtures, the results are compared with those of hydrogen-oxygen and methane-oxygen mixtures. Based on the cell size comparison, it is shown that methanol-oxygen is more detonation sensitive than methane-oxygen but less sensitive than hydrogen-oxygen.

  14. Modeling the Emission of CO from Wood Fires using Detailed Chemical Kinetics

    DEFF Research Database (Denmark)

    Dederichs, Anne

    birch wood using detailed chemical kinetics on the combustion of pyrolysis gas from birch wood. The composition of the pyrolysis gas is taken from the experiment by Zanzi and coworkers. The numerical model applies a counter flow configuration involving 84 chemical species and 804 reactions. Hence......, the model separately treats the process of pyrolysis and combustion. For under ventilated conditions and at high temperatures during pyrolysis it is found that the process of pyrolysation strongly influences the formation of CO in fire. CO2 follows the same trend....

  15. Effects of chemical kinetics and starting material regeneration on the efficiency of an iodine laser amplifier

    International Nuclear Information System (INIS)

    A model of the chemical kinetics occurring in an iodine laser amplifier is presented and used to calculate the degree to which the starting material is consumed as a result of laser operation. The cost of purchasing new starting material is estimated and shown to be prohibitive. A scheme for regenerating the starting material from the species present in the amplifier after lasing is proposed. It is shown that the estimated efficiency of this chemical regeneration process is appreciably higher than the projected optimum efficiency of the pumping process

  16. Effects of chemical kinetics and starting material regeneration on the efficiency of an iodine laser amplifier

    Energy Technology Data Exchange (ETDEWEB)

    Fisk, G.A.

    1977-05-01

    A model of the chemical kinetics occurring in an iodine laser amplifier is presented and used to calculate the degree to which the starting material is consumed as a result of laser operation. The cost of purchasing new starting material is estimated and shown to be prohibitive. A scheme for regenerating the starting material from the species present in the amplifier after lasing is proposed. It is shown that the estimated efficiency of this chemical regeneration process is appreciably higher than the projected optimum efficiency of the pumping process.

  17. Numerical Simulation of a Reacting Vortex Ring Using Detailed Chemical Kinetics

    Science.gov (United States)

    Safta, C.; Madnia, C. K.

    1999-11-01

    A DNS study is conducted to examine the laminar flame-vortex interactions in a reacting vortex ring using `realistic' chemical kinetics. The set of equations solved is the compressible multi-species reacting flow equations comprising conservation of mass, linear momentum, energy, and species mass fractions. Transport properties for pure species were evaluated using thermo-molecular databases provided by the Chemkin library.(R.J. Kee et al.,) SANDIA Report, SAND86-8246, 1994. The mixture average formulation was used to evaluate the transport properties for the mixture. Methane combustion was simulated using GRI-Mech v1.2 kinetic model. The vortex ring was generated by a brief discharge of fuel through a round orifice which enters a quiescent ambient with the chemical composition of air. By adjusting the ratio of the ambient and fuel temperatures, the ignition delay time was controlled. The detailed kinetic mechanism will be examined to determine the ignition paths for this unsteady configuration. Time dependent correlations between fundamental parameters such as stoichiometry, heat release rate, hydrodynamic and chemical variables will be investigated to find the most appropriate flame observables for unsteady methane diffusion flames.

  18. Thermodynamics and kinetics of apoazurin folding under macromolecular crowding effect and chemical interference

    Science.gov (United States)

    Zegarra, Fabio; Cheung, Margaret

    2013-03-01

    Proteins fold in a cellular milieu crowded by different kinds of macromolecules. They exert volume exclusion impacting protein folding processes in vivo. Folding processes, however, has been studied by chemical denaturation under in vitro conditions. The impact of the two factors as an attempt to advance the understanding of folding mechanism in vivo is not understood. Here, we investigate the folding mechanisms of apoazurin affected by the macromolecular crowding and chemical interference by using coarse-grained molecular simulations. Crowding agents are modeled as hard-spheres and the chemical denaturation effects are implemented into an energy function of the side chain and backbone interactions. Protein folding stability, mechanism, and kinetics rates of apoazurin under chemical interference and macromolecular crowding conditions are being investigated. Supported by NSF, Molecular & Cellular Biosciences (MCB0919974).

  19. Dependence of Heterogeneous OH Kinetics with Biomass Burning Aerosol Proxies on Oxidant Concentration and Relative Humidity

    Science.gov (United States)

    Slade, J. H.; Knopf, D. A.

    2013-12-01

    Chemical transformations of aerosol particles by heterogeneous reactions with trace gases such as OH radicals can influence particle physicochemical properties and lifetime, affect cloud formation, light scattering, and human health. Furthermore, OH oxidation can result in degradation of particle mass by volatilization reactions, altering the budget of volatile organic compounds (VOCs). However, the reactive uptake coefficient (γ) and particle oxidation degree can vary depending on several factors including oxidant concentration and relative humidity (RH). While RH can influence the extent of dissociation/ionization, it can also affect particle phase and thus oxidant diffusivity. Only one study so far has investigated the effect of RH on the rate of OH uptake to organic surfaces; however, the underlying processes affecting OH reactivity with organic aerosol under humidified conditions still remains elusive. Here, we determine the effect of RH on OH reactivity with laboratory-generated biomass burning aerosol (BBA) surrogate particles: levoglucosan and 4-methyl-5-nitrocatechol. The effect of OH concentration on γ for three common BBA molecular markers (levoglucosan, abietic acid, and nitroguaiacol) under dry conditions was investigated from [OH]≈107-1011 molecule cm-3, covering both [OH] in biomass burning plumes and [OH] commonly used in particle aging studies. Furthermore, key VOC reaction products and their production pathways resulting from BBA volatilization by OH were identified. OH radicals are produced using a microwave induced plasma (MIP) of H2 in He or Ar followed by reaction with O2, or by photolysis of O3 in the presence of H2O. A cylindrical rotating wall flow-tube reactor and fast-flow aerosol flow reactor are used for conducting kinetic studies. OH is detected using a Chemical Ionization Mass Spectrometer (CIMS) and a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) is employed for VOC analysis. γ decreases from 0.2-0.5 at

  20. Kinetics of oxidation of tryptophan by sodium hypochlorite

    International Nuclear Information System (INIS)

    The oxidation of tryptophan to 3-indoleacetaldehyde with sodium hypochlorite was investigated with 14C labelled DL-tryptophan. The reaction was performed under pseudo first order conditions. From the pH dependence of the reaction it was concluded that only the unprotonated tryptophan is converted to the aldehyde. The activation energy is 35 +- 2.2 (SE) kJ x mol-1 as derived from the Arrhenius plot. Variing the pH between 8.5 and 11.0 and the temperature in the range from 298 K to 318 K did not alter the selectivity of the reaction as confirmed by TLC of the product (purity >= 90%). A possible reaction mechanism is proposed. (orig.)

  1. Kinetics of oxidative coupling of methane: Bridging the gap between comprehension and description

    Institute of Scientific and Technical Information of China (English)

    M. Yu. Sinev; Z.T. Fattakhova; V.I. Lomonosov; Yu. A. Gordienko

    2009-01-01

    The development of notions about the mechanism of the oxidative coupling of methane (OCM) over oxide catalysts and corresponding progress in its kinetic description are reviewed and discussed. The latter becomes essential at the stage of scaling up and optimization of the process in pilot and industrial reactors. It is demonstrated that the main achievements in the development of kinetic models can be reached by combining the approaches conventionally used in homo-geneous gas-phase kinetics and in heterogeneous catalysis. In partic-ular,some important features of the OCM process can be described if several elementary reactions of free radical species (formation and transformation) with surface active sites are included into the detailed scheme of methane oxidation in gas. However,some important fea-tures,such as a non-additive character of the reciprocal influence of methane and ethane in the case of their simultaneous presence in the reaction mixture,cannot yet be described and comprehended in the framework of schemes developed so far. Possible ways towards an advanced kinetic model,accounting the main principles of catalyst functioning (redox nature of active sites) and pathways of product formation (via free radicals) are traced.

  2. Kinetics and mechanism of the oxidation of substituted benzylamines by cetyltrimethylammonium permanganate

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; László Kótai; Kalyan K Banerji

    2003-04-01

    Oxidation of meta- and para-substituted benzylamines by cetyltrimethylammonium permanganate (CTAP) to the corresponding aldimines is first order with respect to both the amine and CTAP. Oxidation of deuteriated benzylamine (PhCD2NH2) exhibited the presence of a substantial kinetic isotope effect (/ = 5.60 at 293 K). This confirmed the cleavage of an -C-H bond in the ratedetermining step. Correlation analyses of the rates of oxidation of 19 monosubstituted benzylamines were performed with various single and multiparametric equations. The rates of the oxidation showed excellent correlations in terms of Yukawa-Tsuno and Brown’s equations. The polar reaction constants are negative. The oxidation exhibited an extensive cross-conjugation, in the transition state, between the electron-donating substituents and the reaction centre. A mechanism involving a hydride-ion transfer from the amine to CTAP in the rate-determining step has been proposed.

  3. Kinetics and Mechanism of Oxidation of Phenyl Acetic Acid and Dl-Mandelic Acid by Permanganate in Acid Medium

    OpenAIRE

    B. Syama Sundar; P.S.Radhakrishna murti

    2014-01-01

    Kinetics of oxidation of phenyl acetic acid and DL- Mandelic acid by potassium permanganate in aqueous acetic acid and perchloric acid mixture reveals that the kinetic orders are first order in oxidant, first order in H+ and zero order in substrate for phenyl acetic acid. DL-Mandelic acid exhibits first order in oxidant and zero order in substrate. The results are rationalised by a mechanism involving intermediate formation of mandelic acid in case of Phenyl acetic acid and ester formation wi...

  4. On Validity of Linear Phenomenological Nonequilibrium Thermodynamics Equations in Chemical Kinetics

    International Nuclear Information System (INIS)

    The chemical equilibrium state is treated as a fundamental ''reference frame'' in description of chemical reaction. In a definition of reactive absolute activities for components in chemical reaction the difference of chemical potential and its value in the equilibrium is used. The chemical reaction rate is shown to be proportional to the force Xnew defined as the difference of reactive absolute activities of reactants and products. The force Xnew is shown to be equivalent to the force following from chemical kinetics equations and compared with the reduced affinity X as well as with the force of Ross and Mazur XRM = 1 - exp(-X). The force Xnew coincides with X and XRM near to the chemical equilibrium state. A range of the molar fraction of product, in which a difference between the forces Xnew and X is relatively small, is larger than it would be for the forces XRM and X. It means that for some chemical reactions the formalism of linear nonequilibrium thermodynamics can be used in wider ranges than usually expected. Particular analysis is presented for simple reactions. (author)

  5. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    Science.gov (United States)

    Adamovich, Igor V; Li, Ting; Lempert, Walter R

    2015-08-13

    This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N2 vibrational energy transfer, reactions of excited electronic species of N2, O2, N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N2 vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H2-air, CH4-air and C2H4-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C3H8-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C3H8-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H2-air, CH4-air and C2H4-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate 'conventional' chemistry mechanism

  6. Kinetics of bromide catalysed oxidation of dextrose by cerium (IV) in aqueous sulphuric acid solution

    International Nuclear Information System (INIS)

    Kinetics of bromide catalysed oxidation of dextrose by CeIV in aqueous sulphuric acid medium show first order dependence each in dextrose and cerium(IV). The reaction rate decreases on increasing the concentration of hydrogen ion. The increase in [HSO4-] or [SO42-] decreases the rate. The bromide ion shows positive catalytic effect on the reaction rate. The value of activation energy has been calculated and a suitable mechanism confirming to the kinetic data is proposed. (author). 3 refs., 3 tabs

  7. Kinetics and mechanisms of thermal oxidation reactions of sewage sludge in heterogenous phase

    International Nuclear Information System (INIS)

    In this paper a waste water purification plant sludge was analyzed. The organic fraction was characterized by the total organic carbon content, cyclohexane extractions, and thermal desorptions in nitrogen and air flow. The inorganic fraction was analyzed by water leaching. FT-IR spectroscopy, thermogravimetric analysis, and scanning electron microscopy/energy dispersion X-ray analysis. Batch kinetic studies of the thermal oxidation were performed in air, in the 250-5000 C temperature range. At each kinetic time the organic reagents concentration decrease was determined with a lump parameter: the organic carbon content. The experimental data were fitted with a sum of two exponentials. Thermodynamic and activation parameters were also calculated

  8. Kinetics and Mechanistic Study of Permanganate Oxidation of Fluorenone Hydrazone in Alkaline Medium

    OpenAIRE

    Fawzy, Ahmed; Saleh A. Ahmed; Althagafi, Ismail I.; Morad, Moataz H.; Khairou, Khalid S

    2016-01-01

    The oxidation kinetics of fluorenone hydrazone (FH) using potassium permanganate in alkaline medium were measured at a constant ionic strength of 0.1 mol dm−3 and at 25°C using UV/VIS spectrophotometer. A first-order kinetics has been monitored in the reaction of FH with respect to [permanganate]. Less-than-unit order dependence of the reaction on [FH] and [OH−] was revealed. No pronounced effect on the reaction rate by increasing ionic strength was recorded. Intervention of free radicals was...

  9. A Kinetic Study on the Oxidation of Indole by Peroxomonosulphate in Acetonitrile Solvent

    International Nuclear Information System (INIS)

    Kinetics of oxidation of indole by peroxomonosulphate (PMS) in aqueous acetonitrile medium has been investigated. The reaction follows a total second order, first order each with respect to [Indole] and [PMS]. The rate of the reaction was not affected by added [H+]. Variation of ionic strength (μ) had no influence on the rate. Increase of percentage of acetonitrile decreased the rate. Absence of any polymerization indicated a nonradical pathway. Activation and thermodynamic parameters have bee n computed. A suitable kinetic scheme based on these observations is proposed. The reactivity of PMS towards Indole was found to be higher than that with peroxodisulphate

  10. Use of Mg-Al oxide for boron removal from an aqueous solution in rotation: Kinetics and equilibrium studies.

    Science.gov (United States)

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2016-01-01

    Mg-Al oxide prepared through the thermal treatment of [Formula: see text] intercalated Mg-Al layered double hydroxides (CO3·Mg-Al LDH) was found to remove boron (B) from an aqueous solution. B was removed by the rehydration of Mg-Al oxide accompanied by combination with [Formula: see text] . When using twice the stoichiometric quantity of Mg-Al oxide for Mg/Al = 4, the residual concentration of B dropped from 100 to 2.8 mg/L in 480 min, and for Mg/Al = 2, it decreased from 100 to 2.5 mg/L in 240 min. In both cases, the residual concentration of B was highlighted to be lower than the current Japanese effluent standards (10 mg/L). The removal of B can be explained by way of pseudo-first-order reaction kinetics. The apparent activation energy of 63.5 kJ mol(-1), calculated from the Arrhenius plot indicating that a chemical reaction dominates the removal of B by Mg-Al oxide (Mg/Al = 2). The adsorption of B acts upon a Langmuir-type phenomena. The maximum adsorption (qm) and equilibrium adsorption constants (KL) were 7.4 mmol g(-1) and 1.9 × 10(3), respectively, for Mg-Al oxide (Mg/Al = 2). [Formula: see text] in B(OH)4·Mg-Al LDH produced by the removal of B was observed to undergo anion exchange with [Formula: see text] in solution. Following regeneration, the Mg-Al oxide maintained the ability to remove B from an aqueous solution. This study has clarified the possibility of recycling Mg-Al oxide for B removal. PMID:26454072

  11. Electronic polarizability, optical properties and chemical bonding of oxide glasses

    International Nuclear Information System (INIS)

    Full text: The current status of the polarizability approach to glass science has been considered. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of the electronic ion polarizability, αo2.(n0) as well as of the average single bond strength, BMo, as basic parameters of linear and nonlinear optical properties of oxide glasses has been emphasized. More acidic glasses possess large BMo (450-350 kJ/mol) which means participation of an average oxide ion in more covalent M-BO (bridging oxygen) bonds such as P-O, Si-O, and Ge-O. The decrease of BM0 could be attributed to formation of M-NBO (non-bridging oxygen) or other bonds with increased ionicity such as La-O, Pb-O, etc. The smallest values of BM0 at about 250 kJ/mol have been obtained for basic tellurite and bismuthate glasses. It has been assumed that these values could be associated with the presence of Te-NBO, Te-BO, and Bi-BO chemical bonds with large ionic contribution. The results obtained probably provide a good basis for prediction of the type of bonding in oxide glasses based on refractive index as well as for prediction of new nonlinear optical materials

  12. Chemically reduced graphene oxide for ammonia detection at room temperature.

    Science.gov (United States)

    Ghosh, Ruma; Midya, Anupam; Santra, Sumita; Ray, Samit K; Guha, Prasanta K

    2013-08-14

    Chemically reduced graphene oxide (RGO) has recently attracted growing interest in the area of chemical sensors because of its high electrical conductivity and chemically active defect sites. This paper reports the synthesis of chemically reduced GO using NaBH4 and its performance for ammonia detection at room temperature. The sensing layer was synthesized on a ceramic substrate containing platinum electrodes. The effect of the reduction time of graphene oxide (GO) was explored to optimize the response, recovery, and response time. The RGO film was characterized electrically and also with atomic force microscopy and X-ray photoelectron spectroscopy. The sensor response was found to lie between 5.5% at 200 ppm (parts per million) and 23% at 2800 ppm of ammonia, and also resistance recovered quickly without any application of heat (for lower concentrations of ammonia). The sensor was exposed to different vapors and found to be selective toward ammonia. We believe such chemically reduced GO could potentially be used to manufacture a new generation of low-power portable ammonia sensors. PMID:23856001

  13. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    International Nuclear Information System (INIS)

    Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO2 at mild conditions (pH 4-9 and 22 oC). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg2+ or Ca2+. Experimental results of TTC indicate that MnO2 promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO2 generate little iso-OTC, but occur mainly at the A ring's dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO2, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines. - Highlights: → Tetracyclines transform rapidly by MnO2 to yield complicated products. → Isomerized, (hydr)oxygenated and N-demethylated products are formed. → Transformation product structures may suggest lowered antibacterial activity. - The complex transformation pathways of three popular tetracycline antibiotics (tetracycline, oxytetracycline and chlorotetracycline) with MnO2 under environmental conditions are systematically evaluated and elucidated.

  14. Kinetics of low-temperature CO oxidation on Au(111)

    Science.gov (United States)

    Thuening, Theodore; Walker, Joshua; Adams, Heather; Furlong, Octavio; Tysoe, Wilfred T.

    2016-06-01

    The oxidation of carbon monoxide on oxygen-modified Au(111) surfaces is studied using a combination of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). TPD reveals that CO desorbs in two states with the low-temperature state have a peak temperature between ~ 130 and 150 K, and the higher-temperature state having a peak temperature that varies from ~ 175 to ~ 220 K depending on the initial oxygen and CO coverages. Infrared spectroscopy indicates that the low-temperature CO desorption state is predominantly associated with CO adsorbed on Auδ + sites, while the higher-temperature states are due to CO on Au0 sites. No additional vibrational features are detected indicating that CO reacts directly with adsorbed atomic oxygen on gold to form CO2. Estimates of the activation energy for CO2 formation suggest that they are in the same range and found for supported gold catalysts at reaction temperature below ~ 300 K.

  15. Theoretical kinetic study of the low temperature oxidation of ethanol

    CERN Document Server

    Fournet, René; Bounaceur, Roda; Molière, Michel

    2009-01-01

    In order to improve the understanding of the low temperature combustion of ethanol, high-level ab initio calculations were performed for elementary reactions involving hydroxyethylperoxy radicals. These radicals come from the addition of hydroxethyl radicals (?CH3CHOH and ?CH2CH2OH) on oxygen molecule. Unimolecular reactions involving hydroxyethylperoxy radicals and their radical products were studied at the CBS-QB3 level of theory. The results allowed to highlight the principal ways of decomposition of these radicals. Calculations of potential energy surfaces showed that the principal channels lead to the formation of HO2 radicals which can be considered, at low temperature, as slightly reactive. However, in the case of CH3CH(OOH)O? radicals, a route of decomposition yields H atom and formic peracid, which is a branching agent that can strongly enhance the reactivity of ethanol in low temperature oxidation. In addition to these analyses, high-pressure limit rate constants were derived in the temperature rang...

  16. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    Energy Technology Data Exchange (ETDEWEB)

    Chen Wanru [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Huang, Ching-Hua, E-mail: ching-hua.huang@ce.gatech.edu [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States)

    2011-05-15

    Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO{sub 2} at mild conditions (pH 4-9 and 22 {sup o}C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg{sup 2+} or Ca{sup 2+}. Experimental results of TTC indicate that MnO{sub 2} promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO{sub 2} generate little iso-OTC, but occur mainly at the A ring's dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO{sub 2}, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines. - Highlights: > Tetracyclines transform rapidly by MnO{sub 2} to yield complicated products. > Isomerized, (hydr)oxygenated and N-demethylated products are formed. > Transformation product structures may suggest lowered antibacterial activity. - The complex transformation pathways of three popular tetracycline antibiotics (tetracycline, oxytetracycline and chlorotetracycline) with MnO{sub 2} under environmental conditions are systematically evaluated and elucidated.

  17. Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

    International Nuclear Information System (INIS)

    Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N2-saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO2 system by changing the reaction atmospheres.

  18. Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Wang, Zhaohui, E-mail: zhaohuiwang@dhu.edu.cn [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Liu, Jianshe, E-mail: liujianshe@dhu.edu.cn [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer Sequential photocatalytic reduction-oxidation degradation of TBBPA was firstly examined. Black-Right-Pointing-Pointer Different atmospheres were found to have significant effect on debromination reaction. Black-Right-Pointing-Pointer A possible sequential photocatalytic reduction-oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC-MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N{sub 2}-saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO{sub 2} system by changing the reaction atmospheres.

  19. Structure and chemical properties of molybdenum oxide thin films

    International Nuclear Information System (INIS)

    Molybdenum oxide (MoO3) exhibits interesting structural, chemical, electrical, and optical properties, which are dependent on the growth conditions and the fabrication technique. In the present work, MoO3 films were produced by pulsed-laser deposition and dc magnetron sputtering under varying conditions of growth temperature (Ts) and oxygen pressure (pO2). The effect of growth conditions on the structure and chemical properties of MoO3 films was examined using x-ray diffraction, reflection high-energy electron diffraction, x-ray photoelectron spectroscopy, and infrared spectroscopic measurements. The analyses indicate that the microstructure of Mo oxide films is sensitive to Ts and pO2. The growth conditions were optimized to produce stoichiometric and highly textured polycrystalline MoO3 films. A comparison of the microstructure of MoO3 films grown using pulsed-laser deposition and sputtering methods is also presented

  20. Investigation of the kinetics of internal oxidation of Cu-Fe-alloys with the help of Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Homogeneous and supersaturated Cu Fe mixed crystals are oxidated at an oxygen partial pressure which lies below the decomposition pressure of the copper oxides. With the help of Moessbauer spectroscopy, it is possible to track the kinetics of each iron state during internal oxidation. Corrosion products are magnetite, wuestite, and delafossite. The appearance of these compounds depends on the composition of the mixed crystal, the oxidation temperature and the oxidation time. (orig.)

  1. Chemical Liquid Phase Deposition of Thin Aluminum Oxide Films

    OpenAIRE

    Sun, Jie; Sun, Yingchun

    2007-01-01

    Thin aluminum oxide films were deposited by a new and simple physicochemical method called chemical liquid phase deposition (CLD) on semiconductor materials. Aluminum sulfate with crystallized water and sodium bicarbonate were used as precursors for film growth, and the control of the system pH value played an important role in this experiment. The growth rate is 12 nm/h at room temperature. Post-growth annealing not only densifies and purifies the films, but results in film crystallization a...

  2. Isomer-Specific Biodegradation and Chemical Oxidation of Nonylphenol

    OpenAIRE

    Lu, Zhijiang

    2014-01-01

    Nonylphenol (NP), a well-known environmental estrogen with numerous isomers, is commonly treated as a single compound in the evaluation of its environmental occurrence, fate and transport, treatment removal and toxicity. Recent studies showed that NP isomers exhibited different estrogenicity and biodegradability. However, at present little systematic information is available on its isomer-specific biodegradation and chemical oxidation under natural and engineered conditions.We comprehensively...

  3. Chemical evolution. XL - Clay-mediated oxidation of diaminomaleonitrile

    Science.gov (United States)

    Ferris, J. P.; Hagan, W. J., Jr.; Alwis, K. W.; Mccrea, J.

    1982-01-01

    The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.

  4. The Development of Metal Oxide Chemical Sensing Nanostructures

    Science.gov (United States)

    Hunter, G. W.; VanderWal,R. L.; Xu, J. C.; Evans, L. J.; Berger, G. M.; Kulis, M. J.

    2008-01-01

    This paper discusses sensor development based on metal oxide nanostructures and microsystems technology. While nanostructures such as nanowires show significant potential as enabling materials for chemical sensors, a number of significant technical challenges remain. This paper discusses development to address each of these technical barriers: 1) Improved contact and integration of the nanostructured materials with microsystems in a sensor structure; 2) Control of nanostructure crystallinity to allow control of the detection mechanism; and 3) Widening the range of gases that can be detected by fabricating multiple nanostructured materials. A sensor structure composed of three nanostructured oxides aligned on a single microsensor has been fabricated and tested. Results of this testing are discussed and future development approaches are suggested. It is concluded that while this work lays the foundation for further development, these are the beginning steps towards realization of repeatable, controlled sensor systems using oxide based nanostructures.

  5. Catalytic aerobic oxidation of bio-renewable chemicals

    DEFF Research Database (Denmark)

    Gorbanev, Yury

    This thesis covers the investigation of new catalytic systems for the aerobic oxidation of chemicals derived from bio-renewable sources. The effects of different factors and conditions on the reactions were examined. The employed catalysts were characterized by physisorption measurements, SEM, TEM......, EDS, XRF and other methods. Supported gold and ruthenium hydroxide catalyst systems were explored for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDA), a potential polymer building block for the plastic industry, or its dimethyl ester (FDMC). High product...... selectivities and yields were obtained under optimized conditions. Heterogeneous catalysts consisting of Au nanoparticles on different supports were shown to efficiently oxidize HMF to FDA or FDMC in water or methanol, respectively. Additionally, the reaction conditions were shown to be adjustable...

  6. Gas-Kinetic Navier-Stokes Solver for Hypersonic Flows in Thermal and Chemical Non-Equilibrium Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR project proposes to develop a gas-kinetic Navier-Stokes solver for simulation of hypersonic flows in thermal and chemical non-equilibrium. The...

  7. A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Z; Pitz, W J; Fournet, R; Glaude, P; Battin-Leclerc, F

    2009-12-18

    An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene, decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C{sub 4} + C{sub 2} species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C{sub 6}H{sub 4}CH{sub 3} radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C{sub 6}H{sub 4}CH{sub 3} radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

  8. Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere

    International Nuclear Information System (INIS)

    Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6–311 + G(3df,2p)//MPWB1K/6–31 + G(d,p) level. The study shows that H abstraction reaction from the CH3 group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH3O)2POOH (P1), CCl3CHOHPOOH(OCH3) (P2), CH3OPO2 (P3), CCl3COPO(OCH3)2 (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200–800 K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study. - Highlights: ► The H-abstracted reaction and OH addition reaction are favorable channels. ► The Arrhenius formulas of rate constants with the temperature are fitted. ► The rate constants of TCF relative to OH radical is 4.95 × 10−15 cm3 molecule−1 s−1.

  9. Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Yuan; Zhang, Chenxi; Yang, Wenbo; Hu, Jingtian [Environment Research Institute, Shandong University, Jinan 250100 (China); Sun, Xiaomin, E-mail: sxmwch@sdu.edu.cn [Environment Research Institute, Shandong University, Jinan 250100 (China); State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy Of Science, Lanzhou 730000 (China)

    2012-03-01

    Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311 + G(3df,2p)//MPWB1K/6-31 + G(d,p) level. The study shows that H abstraction reaction from the CH{sub 3} group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH{sub 3}O){sub 2}POOH (P1), CCl{sub 3}CHOHPOOH(OCH{sub 3}) (P2), CH{sub 3}OPO{sub 2} (P3), CCl{sub 3}COPO(OCH{sub 3}){sub 2} (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800 K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study. - Highlights: Black-Right-Pointing-Pointer The H-abstracted reaction and OH addition reaction are favorable channels. Black-Right-Pointing-Pointer The Arrhenius formulas of rate constants with the temperature are fitted. Black-Right-Pointing-Pointer The rate constants of TCF relative to OH radical is 4.95 Multiplication-Sign 10{sup -15} cm{sup 3} molecule{sup -1} s{sup -1}.

  10. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rau, M.S.; Gennero de Chialvo, M.R. [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina); Chialvo, A.C., E-mail: achialvo@fiq.unl.edu.a [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina)

    2010-07-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H{sub 2}SO{sub 4} solution at different rotation rates ({omega}). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on {omega}{sup 1/2}. On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

  11. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    Science.gov (United States)

    Li, Tiejun; Lin, Feng

    2016-04-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis-Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes.

  12. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate

    Indian Academy of Sciences (India)

    G P Panigrahi; Jagannath Panda

    2000-12-01

    Kinetics of oxidation of N-methyl and N-ethyl aniline by peroxomono-phosphoric acid (PMPA) in aqueous and 5% (v/v) acetonitrile medium respectively have been studied in presence of anionic micelles of sodium lauryl sulphate (SLS) at different H. Oxidation rate of both the substrates increases up to a certain [SLS] much below the critical micellar concentration (cmc) after which the rate is retarded. Kinetic data have been used to compute the binding constants of both substrate and oxidant with the micelle. A scheme explaining the kinetic data has been proposed.

  13. Oxidation kinetics of common Kilka (Clupeonella cultiventris caspia) oil in presence of bene oils' unsaponifiable matter.

    Science.gov (United States)

    Pazhouhanmehr, Samaneh; Farhoosh, Reza; Sharif, Ali; Esmaeilzadeh Kenari, Reza

    2016-01-01

    The oxidation mechanisms and kinetics of the purified common Kilka (Clupeonella cultiventris caspia) triacylglycerols (PKO) as affected by 1-1.5% (w/w) of unsaponifiable matters of bene kernel (UKO) and hull (UHO) oils were studied and compared with that of 100 mg/kg of butylated hydroxytoluene (BHT) and α-tocopherol in the Rancimat test at 50-70 °C. There were good correlations between the oxidative stability index (OSI) and time required to reach a 50%-increase in PV (t50). The frequency factor (A) and activation energy (Ea) were correlated well with the values of entropy and enthalpy, respectively. The values of free energy of activation (ΔG(++)) could describe the values of t50 or OSI well. Kinetic data indicated that the UKO with higher contents of tocopherols and tocotrienols, and terpenoid compounds was more effective than the UHO on the PKO stability. PMID:26213034

  14. Oxidation of Chalcones by Morpholinium Chlorochromate with Oxalic Acid as Catalyst: Kinetic and Mechanistic Study

    Directory of Open Access Journals (Sweden)

    K. Rajalakshmi

    2013-01-01

    Full Text Available The kinetics of oxidation of chalcones by morpholinium chlorochromate (MCC has been studied in 55% acetic acid-water (v/v medium. The reaction showed unit order dependence each with respect to oxidant and catalyst and fractional order with respect to substrate and H+ ion. Increased ionic strength has no effect on the reaction rate. In the case of substituted chalcones, the order with respect to substrate varies depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the reaction rate while the electron releasing substituents enhance the rate of the reaction. From the kinetic data obtained, the activation parameters have been calculated and a suitable mechanism has been proposed.

  15. An experimental and kinetic modelling study of the oxidation of the four isomers of butanol

    CERN Document Server

    Moss, J T; Oehlschlaeger, M A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; 10.1021/jp806464p

    2008-01-01

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition delay times. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock tube measurements. Reaction flux and sensitivity analysis indicate that the consumpti...

  16. Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes

    International Nuclear Information System (INIS)

    Kinetic studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (ρ- X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and ( ρ-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin

  17. A wide range kinetic modeling study of pyrolysis and oxidation of methyl butanoate and methyl decanoate. Note I: Lumped kinetic model of methyl butanoate and small methyl esters

    International Nuclear Information System (INIS)

    A lumped kinetic model of methyl butanoate pyrolysis and oxidation is presented and discussed in this work. The hierarchical approach first required the development and validation of sub-mechanisms of small esters such as methyl formate, methyl acrylate and methyl crotonate. A broad-ranging validation of the whole kinetic scheme of methyl butanoate oxidation was then carried out through comparisons with experimental data obtained in shock tube devices, plug flow and jet stirred reactors, rapid compression machines and premixed laminar flames. A detailed analysis of laminar flame speeds complements and extends this kinetic study. The lumped model predicts a wide range of experiments well, thus constituting a flexible and reliable kinetic scheme despite the reduced number of species involved. Moreover, this lumped approach and the proposed model lay the foundation for an extension to biodiesel fuel modeling.

  18. Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

    Directory of Open Access Journals (Sweden)

    Madi Abilev

    2015-03-01

    Full Text Available Oxidation of unsymmetrical dimethylhydrazine (UDMH during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of chemical oxidants in respect to main metabolites of UDMH – 1-formyl-2,2-dimethylhydrazine, dimethylaminoacetontrile, N-nitrosodimethylamine and 1-methyl-1H-1,2,4-triazole. Experiments on chemical oxidation by Fenton's reagent, potassium permanganate and sodium nitrite were conducted. Quantitative determination was performed by HPLC. Oxidation products were identified by gas chromatography-mass spectrometry in combination with solid-phase microextraction. 1-Formyl-2,2-dimethylhydrazine was completely oxidized by Fenton's reagent with formation of formaldehyde N-formyl-N-methyl-hydrazone, 1,4-dihydro-1,4-dimethyl-5H-tetrazol-5-one by the action of potassium permanganate and N-methyl-N-nitro-methanamine in the presence of sodium nitrite. Oxidation of 1-formyl-2,2-dimethylhydrazine also resulted in formation of N-nitrosodimethylamine. Oxidation of dimethylaminoacetontrile proceeded with formation of hydroxyacetonitrile, dimethylformamide and 1,2,5-trimethylpyrrole. After 30 days, dimethylaminoacetontrile was not detected in the presence of Fenton’s reagent and potassium permanganate, but it’s concentration in samples with sodium nitrite was 77.3 mg/L. In the presence of Fenton’s reagent, potassium permanganate and sodium nitrite after 30 days, N-nitrosodimethylamine concentration decreased by 85, 80 and 50%, respectively. In control sample, N-nitrosodimethylamine concentration decreased by 50%, indicating that sodium nitrite has no effect of on N-nitrosodimethylamine concentration. Only Fenton's reagent allowed to reduce the concentration of 1-methyl-1H-1,2,4-triazole to 50% in 30 days. In the presence of other oxidants, 1-methyl-1H-1,2,4-triazole

  19. On the effect of pre-oxidation on the nitriding kinetics

    DEFF Research Database (Denmark)

    Friehling, Peter Bernhard; Somers, Marcel A. J.

    2000-01-01

    The oxidation of ferritic surfaces prior to gaseous nitriding has been reported to lead to improved uniformity of the compound layer thickness and enhanced nitriding kinetics. The present work considers the nucleation and growth of a model compound layer on pure iron and, using previous...... experimental and theoretical work reported in the literature, puts forward two hypotheses to explain the effects of pre-oxidation on compound layer formation. It is proposed that the nucleation of iron nitrides is enhanced by the presence of an iron-oxide layer and that the growth of an iron-nitride layer...... proceeds faster after pre-oxidation, due to a higher nitrogen content in the part of the compound layer closest to the surface....

  20. Leaching Kinetics of Zinc from Metal Oxide Varistors (MOVs with Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Youngjin Kim

    2016-08-01

    Full Text Available The leaching kinetics of zinc from zinc oxide-based metal oxide varistors (MOVs was investigated in H2SO4 at atmospheric pressure. Kinetics experiments were carried out at various agitation speeds, particle sizes, initial H2SO4 concentrations, and reaction temperatures. It was determined that the leaching rate of zinc was independent of agitation speed above 300 rpm and also independent of particle size below 105 μm, whereas it dramatically increased with an increasing H2SO4 concentration. Except for when the H2SO4 concentration was varied, the m-values were almost constant at varying agitation speeds (m-values: 0.554–0.579, particle sizes (m-values: 0.507–0.560 and reaction temperature (m-values: 0.530–0.560 conditions. All of the m-values in these experiments were found to be below 0.580. Therefore, it is proposed that the extraction of zinc is a diffusion-controlled reaction. The leaching kinetics followed the D3 kinetic equation with a rate-controlling diffusion step through the ash layers, and the corresponding apparent activation energy was calculated as 20.7 kJ/mol in the temperature range of 313 K to 353 K.

  1. Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

    Science.gov (United States)

    Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

    2014-09-01

    Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. PMID:24997929

  2. Evaluation and Development of Chemical Kinetic Mechanism Reduction Scheme for Biodiesel and Diesel Fuel Surrogates

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin;

    2013-01-01

    The aim of this study is to evaluate the existing chemical kinetic mechanism reduction techniques. From here, an appropriate reduction scheme was developed to create compact yet comprehensive surrogate models for both diesel and biodiesel fuels for diesel engine applications. The reduction......-dimensional computational fluid dynamics (CFD) study. A new reduction scheme was therefore formulated. A 68-species mechanism for biodiesel surrogate and a 49-species mechanism for diesel surrogate were successfully derived from the respective detailed mechanisms. An overall 97% reduction in species number and......-hexadecane mechanism is expected to be a better representative of surrogate component for various transportation fuels such as biodiesel. Additionally, it can be applied to predict the reactivity of other n-alkane or interchange with one another for kinetic and CFD simulations....

  3. Oxidation hardening kinetics of the rheological function G'/('/G') in asphalts

    KAUST Repository

    Juristyarini, Pramitha

    2011-07-29

    The authors used 9 asphalts oxidized at various temperatures and pressures to determine the hardening kinetics for the DSR function, an easily measured and meaningful surrogate for 15C ductility that relates well to age-related binder deterioration. For each asphalt, there is a rapid initial period that slows to a constant rate period. This constant rate period can be represented by carbonyl formation (oxidation) rate times a hardening susceptibility (HS). For the DSR function and viscosity, the HS and initial jump were pressure-but not temperature-dependent. The DSR function initial jump was relatively higher than the viscosity initial jump. © 2011 Taylor & Francis Group, LLC.

  4. Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

    International Nuclear Information System (INIS)

    The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H+. A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given. (Author)

  5. Mechanistic Investigation of Oxidation of Phenylpropanolamine with N-Bromobenzenesulfonamide in Alkaline Medium: A Kinetic Approach

    OpenAIRE

    Prasad, Ningegowda; Mohana, Kikkeri N.

    2008-01-01

    The kinetics of oxidation of phenylpropanolamine (PPA) with sodium N-bromobenzenesulfonamide or bromamine-B (BAB) has been investigated in alkaline medium at 308 K. The oxidation reaction obeys the rate law, – d[BAB]/dt = k [BAB] [PPA]x [OH-], where x is less than unity. The variation of ionic strength of the medium, addition of the reduction product, benzenesulfonamide, and chloride ion had no pronounced effect on the reaction rate. Decrease of dielectric permittivity of the medium by increa...

  6. Kinetics and mechanism of the selective oxidation of primary aliphatic alcohols under phase transfer catalysis

    Directory of Open Access Journals (Sweden)

    K. Bijudas

    2014-03-01

    Full Text Available Kinetics of the oxidation of primary aliphatic alcohols has been carried out using phase transferred monochromate in benzene. Tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB are used as phase transfer catalysts (PT catalyst. The reaction shows first order dependence on both [alcohol] and [monochromate ion]. The oxidation leads to the formation of corresponding aldehyde and no traces of carboxylic acid has been detected. The reaction mixture failed to induce the polymerization of added acrylonitrile which rules out the presence radical intermediates in the reaction. Various thermodynamic parameters have been evaluated and a suitable mechanism has been proposed.

  7. Oxidation kinetics of high strength low alloy steels at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Talekar, Anjali [Materials Science and Engineering, Chemical and Metallurgical Engineering Department, MS 388, University of Nevada, 1664 North Virginia Street, Reno, NV 89557 (United States); Chandra, Dhanesh [Materials Science and Engineering, Chemical and Metallurgical Engineering Department, MS 388, University of Nevada, 1664 North Virginia Street, Reno, NV 89557 (United States)], E-mail: dchandra@unr.edu; Chellappa, Raja [Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road, Washington, DC 20015 (United States); Daemen, Jaak [Mining Engineering Department, University of Nevada, Reno, NV 89557 (United States); Tamura, Nobumichi; Kunz, Martin [Advanced Light Source, Lawrence Berkeley National Laboratories, MS 2R0222, Berkeley, CA 94720 (United States)

    2008-10-15

    High strength low alloy (HSLA) steels are candidate Rockbolt materials for use as underground roof supports at Yucca Mountain nuclear waste repository. Oxidation kinetics of International Rollforms Split Set Friction Rock Stabilizers (SS46), and Swellex Mn24 steels have been determined by temperature modulated thermogravimetry at temperatures ranging between 600 and 900 deg. C in pure oxygen atmosphere for 100 hr. The imposed sinusoidal temperature modulations ({+-}5 deg. C for a period of 1 cycle per 200 s) on the isothermal temperature did not have any noticeable effect on the weight gain characteristics during oxidation. Weight gain data on the steels indicate two distinct regions with different oxidation profiles, where a definite change in rates of oxidation is observed: a first oxidation regime where the steels followed a rate law y = kt{sup 0.40-0.63} (changing index of rate law depending upon steel and temperature) and a second stage oxidation regime that follows the parabolic law. The results of characterization of the oxide films using SEM/EDAX, X-ray diffraction and Synchrotron white beam X-ray microdiffraction are presented. The oxidation data of the steels presented here is expected to be useful for characterizing those steels for use in underground rock bolt system and as roof support for the DOE proposed Yucca Mountain Nuclear Waste Repository. To the best of our knowledge this is the first time thermogravimetric studies of this kind have been done on these steels.

  8. Wear and isothermal oxidation kinetics of nitrided TiAl based alloys

    Institute of Scientific and Technical Information of China (English)

    赵斌; 吴建生; 孙坚

    2002-01-01

    Gas nitridation of TiAl based alloys in an ammonia atmosphere was c arried out. The evaluation of the surface wear resistance was performed to compare with those of the non-nitrided alloys. It is concluded that high temperature nitridation raised wear resistance of TiAl based alloys markedly. The tribol ogical behaviors of the nitrided alloys were also discussed. The oxidation kinetics of the nitrided TiAl based alloys were investigated at 800~1000 ℃ in hot air. It is concluded that nitridation is detrimental to the oxidation resistance of TiAl based alloys under the present conditions. The nitrided alloys exhibit increased oxidizing rate with the prolongation of nitridation time at 800 ℃. However, alloys nitrided at 940 ℃ for 50 hdisplay a sign of better oxidat ion resistance than the other nitrided alloys at more severe oxidizing conditions. The parabolic rate law is considered as the basis of the data processing and interpretation of the mass gainvs time data. As a comparison with it, attempts were made to fit the data with the power law. The oxidation kinetic parameter kn, kp and n were measured and the trends were discussed.

  9. Kinetics of the electrochemical oxidation of 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum

    Science.gov (United States)

    Vedenyapina, M. D.; Simakova, A. P.; Platonov, M. M.; Terent'ev, A. O.; Skundin, A. M.; Vedenyapin, A. A.

    2013-03-01

    The electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane (1,2,4,5-tetraoxane) from 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum electrode in a cell with separated and unseparated cathode and anode space in an aprotic solvent is conducted. The kinetics of electrochemical oxidation of 1,1-bis(hydroperoxy)-4-methylcyclohexane is studied. The current yield of the reaction is determined.

  10. Kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium

    International Nuclear Information System (INIS)

    The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed. Hammett acidity function (H0) and Bunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechansim is proposed. (Author)

  11. Kinetics of uranium (4) oxidation by oxygen in NaCl-2CsCl melt

    International Nuclear Information System (INIS)

    Using the spectrophotometric method the dependence of the rate of uranium (4) oxidation by the molecular oxygen in NaCl-2CsCl melt upon the value of the specific interface, uranium (4) concentration, the partial pressure of oxygen and chlorine the gas reagent composition and upon the temperature has been found. The kinetic scheme for the reaction in which the interaction of the molecular oxygen with chlorine anions at the melt surface is a slow phase has been proposed

  12. Cost and Performance Assessment of In-situ Chemical Oxidation for Intermittent and Continuous Oxidant Injection

    Science.gov (United States)

    Kim, U.; Parker, J.; Borden, R. C.

    2015-12-01

    In situ chemical oxidation (ISCO) is a popular remediation technology that involves injection of chemical oxidant into groundwater to destroy dissolved and non-aqueous liquid phase contaminants. Depending on site conditions, oxidant can be injected into the contaminated subsurface periodically (intermittently) or continuously. A common approach is to intermittently inject oxidant into a network of wells over a period long enough to emplace oxidant over a target treatment volume (referred to ISCO-int). The injection phase is followed by a passive phase when the oxidant is allowed to react with contaminants and natural oxygen demand (NOD) and to migrate under natural hydraulic gradients. This process may be repeated multiple times until termination criteria are met. Recently, some practitioners have adopted an alternative approach in which oxidant is injected continuously with extraction wells recovering unreacted oxidant to recycle with additional makeup oxidant to maintain its constant concentration (referred to ISCO-cont). Each method has certain advantages and disadvantages. This study numerically evaluates those two ISCO practices in terms of remediation costs and performance based on multiple equi-probable parameter sets. Stochastic cost optimization toolbox (SCOToolkit) is used for this purpose. SCOToolkit is an integrated semi-analytical model for contaminant transport and remediation (e.g., thermal source treatment, ISCO, electron donor injections, permeable reactive barriers) enabling inverse solution and Monte Carlo simulations. Four different aquifer settings, slow and fast Darcy velocities combined with low and high NOD conditions, are used for the evaluation. Preliminary results showed that ISCO-cont is effective for a full scale application without large investment while ISCO-int is more efficient to utilize oxidant in well-characterized sites. Pros and cons of each approach are discussed for the practical use of ISCO for various site conditions.

  13. Time-dependent postirradiation oxidative chemical changes in dehydrated egg products

    International Nuclear Information System (INIS)

    Radiation-induced oxidative chemical changes in whole egg and egg yolk powder were followed in time after irradiation as a function of dose, dose rate, and storage atmosphere. In evacuated samples of whole egg powder the decay of lipid hydroperoxides (LOOH) was pseudo-first order (kappa = 0.088 day-1), while carotenoids did not decay at all. In the presence of air both lipid hydroperoxides and carotenoids decayed during postirradiation storage. The decay of LOOH could be treated by dispersive kinetics with the measure of dispersion, alpha = 0.51 +/- 0.05, independent of dose, and the effective lifetime tau inversely related to dose. The decay of carotenoids could also be treated by dispersive kinetics, with the values of alpha decreasing with increasing dose. The effective lifetimes of carotenoids did not depend on dose in samples irradiated in vacuum. In samples irradiated and stored in air the effective lifetimes decreased with dose, faster in egg yolk than in whole egg powder. The complex nature of postirradiation kinetics in solid food systems is discussed

  14. A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

    Directory of Open Access Journals (Sweden)

    James Bland

    2013-12-01

    Full Text Available The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM. The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C2H4, followed by dissociation of o-QM to the C6H6 isomers benzene and fulvene (+ CO. At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

  15. Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 1; Oxidation Kinetics

    Science.gov (United States)

    Raj, S. V.

    2008-01-01

    The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

  16. Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

    Science.gov (United States)

    Raj. Sai V.

    2008-01-01

    The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

  17. Kinetics and Mechanistic Study of Permanganate Oxidation of Fluorenone Hydrazone in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Ahmed Fawzy

    2016-01-01

    Full Text Available The oxidation kinetics of fluorenone hydrazone (FH using potassium permanganate in alkaline medium were measured at a constant ionic strength of 0.1 mol dm−3 and at 25°C using UV/VIS spectrophotometer. A first-order kinetics has been monitored in the reaction of FH with respect to [permanganate]. Less-than-unit order dependence of the reaction on [FH] and [OH−] was revealed. No pronounced effect on the reaction rate by increasing ionic strength was recorded. Intervention of free radicals was observed in the reaction. The reaction mechanism describing the kinetic results was illustrated which involves formation of 1 : 1 intermediate complex between fluorenone hydrazones and the active species of permanganate. 9H-Fluorenone as the corresponding ketone was found to be the final oxidation product of fluorenone hydrazone as confirmed by GC/MS analysis and FT-IR spectroscopy. The expression rate law for the oxidation reaction was deduced. The reaction constants and mechanism have been evaluated. The activation parameters associated with the rate-limiting step of the reaction, along with the thermodynamic quantities of the equilibrium constants, have been calculated and discussed.

  18. Chemical Kinetic Simulation of the Combustion of Bio-based Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Ashen, Ms. Refuyat [Oak Ridge High School; Cushman, Ms. Katherine C. [Oak Ridge High School

    2007-10-01

    Due to environmental and economic issues, there has been an increased interest in the use of alternative fuels. However, before widespread use of biofuels is feasible, the compatibility of these fuels with specific engines needs to be examined. More accurate models of the chemical combustion of alternative fuels in Homogeneous Charge Compression Ignition (HCCI) engines are necessary, and this project evaluates the performance of emissions models and uses the information gathered to study the chemical kinetics involved. The computer simulations for each alternative fuel were executed using the Chemkin chemical kinetics program, and results from the runs were compared with data gathered from an actual engine that was run under similar conditions. A new heat transfer mechanism was added to the existing model's subroutine, and simulations were then conducted using the heat transfer mechanism. Results from the simulation proved to be accurate when compared with the data taken from the actual engine. The addition of heat transfer produced more realistic temperature and pressure data for biodiesel when biodiesel's combustion was simulated in an HCCI engine. The addition of the heat transfer mechanism essentially lowered the peak pressures and peak temperatures during combustion of all fuels simulated in this project.

  19. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    KAUST Repository

    Bisetti, Fabrizio

    2012-06-01

    Recent trends in hydrocarbon fuel research indicate that the number of species and reactions in chemical kinetic mechanisms is rapidly increasing in an effort to provide predictive capabilities for fuels of practical interest. In order to cope with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix. The components of the approach are described in detail and applied to the ignition of stoichiometric methane-air and iso-octane-air mixtures, here described by two widely adopted chemical kinetic mechanisms. The approach is found to be robust even at relatively large time steps and the global error displays a nominal third-order convergence. The performance of the approach is improved by utilising an adaptive algorithm for the selection of the Krylov subspace size, which guarantees an approximation to the matrix exponential within user-defined error tolerance. The Krylov projection of the Jacobian matrix onto a low-dimensional space is interpreted as a local model reduction with a well-defined error control strategy. Finally, the performance of the approach is discussed with regard to the optimal selection of the parameters governing the accuracy of its individual components. © 2012 Copyright Taylor and Francis Group, LLC.

  20. Melting behavior of typical thermoplastic materials – An experimental and chemical kinetics study

    International Nuclear Information System (INIS)

    Highlights: • A new medium-scale melting and pyrolysis experiment instrument for thermoplastics was designed. • The thermal hazard induced by melting and dripping of thermoplastics was studied. • The medium-scale experimental results on the thermoplastics pyrolysis suggest some limit for TGA tests. -- Abstract: A medium-scale melting experiment rig was designed and constructed in this study. A detailed experimental study was conducted on the melting behavior and the chemical kinetic characteristics of three typical thermoplastic materials, including polypropylene (PP), polyethylene (PE) and polystyrene (PS). It is observed that the thermal decomposition of the thermoplastic materials mainly consists of three stages: the initial heating stage, the melting-dominated stage and the gasification-dominated stage. Melting of the materials examined takes place within a certain temperature range. The melting temperature of PS is the lowest, moreover, it takes the shortest time to be completely liquefied. To quantitatively represent the chemical kinetics, an nth-order reaction model was employed to interpret the thermal decomposition behavior of the materials. The calculated reaction order is largely in accordance with the small-scale thermal gravimetric analysis (TGA). The small difference between the results and TGA data suggests that there are some limitations in the small-scale experiments in simulating the behavior of thermoplastic materials in a thermal hazard. Therefore, investigating the thermal physical and chemical properties of the thermoplastic materials and their thermal hazard prevention in medium or large-scale experiments is necessary for the fire safety considerations of polymer materials

  1. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics.

    Science.gov (United States)

    Bazant, Martin Z

    2013-05-21

    Advances in the fields of catalysis and electrochemical energy conversion often involve nanoparticles, which can have kinetics surprisingly different from the bulk material. Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create variations that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend not only on the order parameter but also on its gradients at phase boundaries. Reaction-driven phase transformations are common in electrochemistry, when charge transfer is accompanied by ion intercalation or deposition in a solid phase. Examples abound in Li-ion, metal-air, and lead-acid batteries, as well as metal electrodeposition-dissolution. Despite complex thermodynamics, however, the standard kinetic model is the Butler-Volmer equation, based on a dilute solution approximation. The Marcus theory of charge transfer likewise considers isolated reactants and neglects elastic stress, configurational entropy, and other nonidealities in condensed phases. The limitations of existing theories recently became apparent for the Li-ion battery material LixFePO4 (LFP). It has a strong tendency to separate into Li-rich and Li-poor solid phases, which scientists believe limits its performance. Chemists first modeled phase separation in LFP as an isotropic "shrinking core" within each particle, but experiments later revealed striped phase boundaries on the active crystal facet. This raised the question: What is the reaction rate at a surface undergoing a phase transformation? Meanwhile, dramatic rate enhancement was attained with LFP nanoparticles, and classical battery models could not predict the roles of phase separation and surface modification. In this Account, I present a general theory of chemical kinetics, developed over

  2. Kinetics of plastoquinol oxidation by the Q-cycle in leaves.

    Science.gov (United States)

    Laisk, Agu; Oja, Vello; Eichelmann, Hillar

    2016-06-01

    Electrochromic shift measurements confirmed that the Q-cycle operated in sunflower leaves. The slow temporarily increasing post-pulse phase was recorded, when ATP synthase was inactivated in the dark and plastoquinol (PQH2) oxidation was initiated by a short pulse of far-red light (FRL). During illumination by red light, the Q-cycle-supported proton arrival at the lumen and departure via ATP synthase were simultaneous, precluding extreme build-up of the membrane potential. To investigate the kinetics of the Q-cycle, less than one PQH2 per cytochrome b6f (Cyt b6f) were reduced by illuminating the leaf with strong light pulses or single-turnover Xe flashes. The post-pulse rate of oxidation of these PQH2 molecules was recorded via the rate of reduction of plastocyanin (PC(+)) and P700(+), monitored at 810 and 950nm. The PSII-reduced PQH2 molecules were oxidized with multi-phase overall kinetics, τd=1, τp=5.6 and τs=16 ms (22 °C). We conclude that τd characterizes PSII processes and diffusion, τp is the bifurcated oxidation of the primary quinol and τs is the Q-cycle-involving reduction of the secondary quinol at the n-site, its transport to the p-site, and bifurcated oxidation there. The extraordinary slow kinetics of the Q-cycle may be related to the still unsolved mechanism of the "photosynthetic control." PMID:27056771

  3. Sample Handling and Chemical Kinetics in an Acoustically Levitated Drop Microreactor

    Science.gov (United States)

    2009-01-01

    Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container’s surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor. PMID:19769373

  4. The Statistical Evolution of Multiple Generations of Oxidation Products in the Photochemical Aging of Chemically Reduced Organic Aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Kevin R.; Smith, Jared D.; Kessler, Sean; Kroll, Jesse H.

    2011-10-03

    The heterogeneous reaction of hydroxyl radicals (OH) with squalane and bis(2-ethylhexyl) sebacate (BES) particles are used as model systems to examine how distributions of reactionproducts evolve during the oxidation of chemically reduced organic aerosol. A kinetic model of multigenerational chemistry, which is compared to previously measured (squalane) and new(BES) experimental data, reveals that it is the statistical mixtures of different generations of oxidation products that control the average particle mass and elemental composition during thereaction. The model suggests that more highly oxidized reaction products, although initially formed with low probability, play a large role in the production of gas phase reaction products.In general, these results highlight the importance of considering atmospheric oxidation as a statistical process, further suggesting that the underlying distribution of molecules could playimportant roles in aerosol formation as well as in the evolution of key physicochemical properties such as volatility and hygroscopicity.

  5. Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers

    KAUST Repository

    Bugler, John

    2015-07-16

    © 2015 American Chemical Society. This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the first- and second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight- and branched-chained alkanes.

  6. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    Science.gov (United States)

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting. PMID:27147197

  7. High temperature X-ray diffraction study of the oxidation products and kinetics of uranium-plutonium mixed oxides.

    Science.gov (United States)

    Strach, Michal; Belin, Renaud C; Richaud, Jean-Christophe; Rogez, Jacques

    2014-12-15

    The oxidation products and kinetics of two sets of mixed uranium-plutonium dioxides containing 14%, 24%, 35%, 46%, 54%, and 62% plutonium treated in air were studied by means of in situ X-ray diffraction (XRD) from 300 to 1773 K every 100 K. The first set consisted of samples annealed 2 weeks before performing the experiments. The second one consisted of powdered samples that sustained self-irradiation damage. Results were compared with chosen literature data and kinetic models established for UO2. The obtained diffraction patterns were used to determine the temperature of the hexagonal M3O8 (M for metal) phase formation, which was found to increase with Pu content. The maximum observed amount of the hexagonal phase in wt % was found to decrease with Pu addition. We conclude that plutonium stabilizes the cubic phases during oxidation, but the hexagonal phase was observed even for the compositions with 62 mol % Pu. The results indicate that self-irradiation defects have a slight impact on the kinetics of oxidation and the lattice parameter even after the phase transformation. It was concluded that the lattice constant of the high oxygen phase was unaffected by the changes in the overall O/M when it was in equilibrium with small quantities of M3O8. We propose that the observed changes in the high oxygen cubic phase lattice parameter are a result of either cation migration or an increase in the miscibility of oxygen in this phase. The solubility of Pu in the hexagonal phase was estimated to be below 14 mol % even at elevated temperatures. PMID:25412433

  8. An improved model to evaluate the oxidation kinetics of uranium dioxide during dry storage

    International Nuclear Information System (INIS)

    During dry air storage, the oxidation of the spent fuel in case of cladding and container failure (accidental scenario) could be detrimental for further handling of the spent fuel rod and for the safety of the facilities. Recently, the phase transition sequence during the first step of parabolic oxidation kinetic has been challenged again and two well-distinguished intermediate products, U4O9 and U3O7 have been identified. Moreover, these observations have shown that the three phases (UO2, U4O9 and U3O7) occur together. Starting from a previous model of grain oxidation based on finite difference approach, a new model, describing the parabolic oxidation kinetic, has been developed based on the oxygen atom diffusion. This model allows in one hand to take into account the occurrence of the three phases and in another hand to describe accurately the plateau behaviour. A comparison between the model and literature data obtained on non-irradiated powders has been carried out and shows that this model can describe the weight gain evolution as a function of time for different temperatures. The diffusion coefficients of oxygen in the two phases (U4O9 and U3O7) were obtained by fitting the model results to experimental data. The comparison with the values given in literature is quite good

  9. Kinetics and mechanisms of Co(II) EDTA oxidation by pyrolusite

    International Nuclear Information System (INIS)

    Monitoring and restoration activities at low-level radioactive waste disposal sites have identified complicated mixtures of inorganic and organic contaminants in soil and groundwater. Metallic contaminants are generally complexed with various chelating agents and organic acids which alter the geochemical behavior of the contaminants in subsurface media. The objective of this study was to provide an improved understanding of the geochemical processes controlling the subsurface transport of radioactive 60Co complexed with ethylenediaminetetraacetic acid (EDTA). Specifically, we investigated the kinetics and mechanisms of Co(II) EDTA2- oxidation to Co(III)EDTA- by the soil mineral pyrolusite β-MnO2. A column displacement technique was utilized to investigate Co(II)EDTA2- to Co(III)EDTA-. The oxidation of Co(II)EDTA2- appeared to involve the reduction of Mn(IV) to both an aqueous Mn2+ species and a theorized Mn(III)-oxide solid phase. The redox reaction was catalytic since the reduction products were gradually reoxidized in the presence of dissolved O2 to form a Mn (IV)-oxide phase. Oxidation of surface-bound Mn2+ and the theorized Mn(III)-oxide was slow relative to Co(II)EDTA2- oxidation, and a reversible loss in the oxidative ability of the β-MnO occurred when exposed to Co(II)EDTA2-. The reduction in catalytic activity of the MnO2 was not the result of direct surface poisoning by Mn2+, but rather was believed to result from the formation of an intermediate Mn(III)-oxide solid phase whose oxidative potential was significantly less than MnO2 was dependent on the rate of MnO2 surface regeneration. The environmental implications of this redox reaction are pronounced, since any Co(III) EDTA- produced is extremely stable, and this enhances the persistence and transport of 60Co in subsurface environments. 52 refs., 7 figs

  10. Oxide Transformation in Cr-Mn-Prealloyed Sintered Steels: Thermodynamic and Kinetic Aspects

    Science.gov (United States)

    Hryha, Eduard; Nyborg, Lars

    2014-04-01

    The main obstacle for utilization of Cr and Mn as alloying elements in powder metallurgy is their high oxygen affinity leading to oxidation risk during powder manufacturing, handling, and especially during further consolidation. Despite the high purity of the commercially available Cr- and Mn-prealloyed iron powder grades, the risk of stable oxide formation during the sintering process remains. Thermodynamic and kinetic simulation of the oxide formation/transformation on the former powder surface during heating and sintering stages using thermodynamic modeling tools (Thermo-Calc and HSC Chemistry) was performed. Simulation is based on the results from the analysis of amount, morphology, and composition of the oxide phases inside the inter-particle necks in the specimens from interrupted sintering trials utilizing advanced analysis tools (HRSEM + EDX and XPS). The effect of the processing parameters, such as sintering atmosphere composition, temperature profile as well as graphite addition on the possible scenarios of oxide reduction/formation/transformation for Fe-Cr-Mn-C powder systems, was evaluated. Results indicate that oxide transformation occurs in accordance with the thermodynamic stability of oxides as follows: Fe2O3 → FeO → Fe2MnO4 → Cr2FeO4 → Cr2O3 → MnCr2O4 → MnO/MnSiO x → SiO2. Spinel MnCr2O4 was identified as the most stable oxide phase at applied sintering conditions up to 1393 K (1120 °C). Controlled conditions during the heating stage minimize the formation of stable oxide products and produce oxide-free sintered parts.

  11. High-Pressure Turbulent Flame Speeds and Chemical Kinetics of Syngas Blends with and without Impurities

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, Eric; Mathieu, Olivier; Morones, Anibal; Ravi, Sankar; Keesee, Charles; Hargis, Joshua; Vivanco, Jose

    2014-12-01

    This Topical Report documents the first year of the project, from October 1, 2013 through September 30, 2014. Efforts for this project included experiments to characterize the atmospheric-pressure turbulent flame speed vessel over a range of operating conditions (fan speeds and turbulent length scales). To this end, a new LDV system was acquired and set up for the detailed characterization of the turbulence field. Much progress was made in the area of impurity kinetics, which included a numerical study of the effect of impurities such as NO2, NO, H2S, and NH3 on ignition delay times and laminar flame speeds of syngas blends at engine conditions. Experiments included a series of laminar flame speed measurements for syngas (CO/H2) blends with various levels of CH4 and C2H6 addition, and the results were compared to the chemical kinetics model of NUI Galway. Also, a final NOx kinetics mechanism including ammonia was assembled, and a journal paper was written and is now in press. Overall, three journal papers and six conference papers related to this project were published this year. Finally, much progress was made on the design of the new high-pressure turbulent flame speed facility. An overall design that includes a venting system was decided upon, and the detailed design is in progress.

  12. Multi-level Monte Carlo for stochastically modeled chemical kinetic systems

    CERN Document Server

    Anderson, David F

    2011-01-01

    A chemical reaction network involves multiple reactions and species. The simplest stochastic models of such networks treat the system as a continuous time Markov chain with the state being the number of molecules of each species and with reactions modeled as possible transitions of the chain. While there are methods that generate exact sample paths of the Markov chain, their computational cost scales linearly with the number of reaction events. Therefore, such methods become computationally intense for even moderately sized systems. This drawback is greatly exacerbated when such simulations are performed in conjunction with Monte Carlo techniques, as is the norm, which require the generation of many paths. We show how to extend a recently proposed multi-level Monte Carlo approach to this stochastic chemical kinetic setting, lowering the computational complexity needed to compute expected values of functions of the state of the system to a specified accuracy. The extension is non-trivial and a novel coupling o...

  13. Chemical vapor deposition coatings for oxidation protection of titanium alloys

    Science.gov (United States)

    Cunnington, G. R.; Robinson, J. C.; Clark, R. K.

    1991-01-01

    Results of an experimental investigation of the oxidation protection afforded to Ti-14Al-21Nb and Ti-14Al-23Nb-2V titanium aluminides and Ti-17Mo-3Al-3Nb titanium alloy by aluminum-boron-silicon and boron-silicon coatings are presented. These coatings are applied by a combination of physical vapor deposition (PVD) and chemical vapor deposition (CVD) processes. The former is for the application of aluminum, and the latter is for codeposition of boron and silicon. Coating thickness is in the range of 2 to 7 microns, and coating weights are 0.6 to 2.0 mg/sq cm. Oxidation testing was performed in air at temperatures to 1255 K in both static and hypersonic flow environments. The degree of oxidation protection provided by the coatings is determined from weight change measurements made during the testing and post test compositional analyses. Temperature-dependent total normal emittance data are also presented for four coating/substrate combinations. Both types of coatings provided excellent oxidation protection for the exposure conditions of this investigation. Total normal emittances were greater than 0.80 in all cases.

  14. The effect of substrate orientation on the kinetics of ultra-thin oxide-film growth on Al single crystals

    International Nuclear Information System (INIS)

    The kinetics of ultra-thin (O2=1x10-4Pa was investigated by real-time in situ spectroscopic ellipsometry. It follows that the oxide-film growth kinetics depends strongly on the parent metal substrate orientation. On Al{1 0 0} and Al{1 1 0}, the growth kinetics can be subdivided into an initial, very fast oxidation stage and a subsequent very slow oxidation stage, which is characterized by the occurrence of a near-limiting oxide-film thickness that increases with increasing temperature. On Al{1 1 1}, the initial, very fast growth rate decreases more gradually with increasing oxidation time and an unexpected decrease of oxide-film thickness, for an oxidation time of 6000 s, with increasing temperature up to 475 K is observed. The rate-limiting step(s) and mechanism(s) of the oxidation process were identified by a quantitative model description of the oxide-film growth kinetics on the basis of coupled currents of electrons (by both tunneling and thermionic emission) and cations under influence of a surface-charge field. It followed that the unexpected decrease of the oxide-film thickness with increasing temperature on Al{1 1 1} is due to a slow increase of the (relatively low) activation energy barrier for cation transport in combination with a constant kinetic potential due to the surface-charge field within the amorphous oxide-film regime (up to T ≤ 450 K). For Al{1 0 0} and Al{1 1 0}, the energy barrier for cation transport, as well as the kinetic potential, increase with increasing temperature due to, as compared to Al{1 1 1}, a more gradual amorphous-to-crystalline transition, which already starts at lower temperatures T < 400 K

  15. Kinetics of titanium and zirconium oxides dissolution in cryolite-alumina melt

    International Nuclear Information System (INIS)

    Data on kinetics of dissolution of titanium and zirconium oxides in cryolite-alumina melt were obtained. Temperature dependences of dissolution rate of titanium and zirconium oxides in pure cryolite were studied as well. The apparent activation energy of dissolution process (Esub(p)), determined according to the slope of straigh lines in lg(V/ωsup(1/2))-1/T coordinates, equals consequently 115kJ/mol for TiO2 and 144.6 kJ/mol for ZrO2. The activation energy of alumina dissolution equals 88kJ/mol. Such difference means that the process of titanium and zirconium oxide dissolution in cryolite is rather impeded, as compared to alumina. This fact can be related with the formation of fluoride and oxyfluoride complexes, which transport from dissolution zone proceeds with considerable energetic difficulties, as compared to alumina dissolution

  16. Kinetics and mechanism of N-chlorosaccharin oxidation of malic acid

    Directory of Open Access Journals (Sweden)

    Sanjay Kumar Singh

    2010-12-01

    Full Text Available Kinetic study of N-chlorosaccharin (NCSA oxidation of malic acid (MA in aqueous acetic acid medium in presence of perchloric acid has been investigated. The reactions exhibit first-order dependency in oxidant and HClO4 while order varies from one to zero in substrate. The reactions are acid catalyzed and retarded by the addition of saccharin, a byproduct of reaction. The rate of oxidation decreases with decrease in dielectric constant of the medium. The effect of temperature on the reaction has been investigated in the temperature range 313-333 K. The stochiometric studies revealed 1:1 mole ratio. Various thermodynamic parameters have been computed and a possible operative mechanism is proposed.

  17. Kinetics of oxidation and dissolution of uranium dioxide in aqueous acid solutions

    International Nuclear Information System (INIS)

    The oxidation and dissolution of UO2 has been studied using electrochemical methods with an UO2 rotating disc electrode in acidic (pH 3) and non-complexing (trifluoromethanesulfonate: 0.1 mol L−1 NaCF3SO3) media. The effect of the experimental parameters such as scan rate (v) and rotation rate (ω) on the electrochemical signal has been studied. The rotation rate of the electrode does not influence the resulting signal, which indicates that only a charge transfer is involved in the UO2 oxidation kinetic. However, scan rate variations show different reactions involved in the UO2 oxidation. Linear sweep voltammetry and cyclic voltammetry coupled to X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) measurements suggest two successive electrochemical reactions with an exchange of one electron for each of them and the formation of one intermediate species of U(V).

  18. Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate

    Indian Academy of Sciences (India)

    Sonu Saraswat; Vinita Sharma; K K Banerji

    2003-02-01

    Oxidation of nine aliphatic primary alcohols by quinolinium bromochromate (QBC) in dimethylsulphoxide leads to the formation of the corresponding aldehydes. The reaction is first order with respect to both QBC and the alcohol. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: obs = + [H+]. The oxidation of [1,1-2H2]ethanol (MeCD2OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analysed using Taft’s and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  19. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface

    Science.gov (United States)

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-01

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  20. Kinetics and mechanism of the oxidation of some neutral and acidic -amino acids by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

    The oxidation of eleven amino acids by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid results in the formation of the corresponding carbonyl compounds and ammonia. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with some of the amino acids while others exhibit second-order dependence. It failed to induce polymerization of acrylonitrile. The effect of solvent composition indicate that the rate of reaction increases with increase in the polarity of the medium. Addition of tetrabutylammonium chloride has no effect on the rate of oxidation. Addition of bromide ion causes decrease in the oxidation rate but only to a limiting value. The reaction is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  1. Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

    International Nuclear Information System (INIS)

    The purpose of this work is to develop modified resorcinol-formaldehyde (R-F) resin with enhanced chemical/oxidative stability in conditions typically encountered in the remediation of radioactive waste tanks. R-F resin is a regenerable organic ion-exchanger developed at Savannah River Technology Center that is being considered for use in the selective removal of radioactive cesium from alkaline waste tank supernates at both the Hanford and Savannah River sites

  2. Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

    Energy Technology Data Exchange (ETDEWEB)

    Hubler, T. [Pacific Northwest National Laboratory, Richland, WA (United States)

    1996-10-01

    The purpose of this work is to develop modified resorcinol-formaldehyde (R-F) resin with enhanced chemical/oxidative stability in conditions typically encountered in the remediation of radioactive waste tanks. R-F resin is a regenerable organic ion-exchanger developed at Savannah River Technology Center that is being considered for use in the selective removal of radioactive cesium from alkaline waste tank supernates at both the Hanford and Savannah River sites.

  3. Elementary reaction schemes for physical and chemical vapor deposition of transition metal oxides on silicon for high-k gate dielectric applications

    Science.gov (United States)

    Niu, D.; Ashcraft, R. W.; Kelly, M. J.; Chambers, J. J.; Klein, T. M.; Parsons, G. N.

    2002-05-01

    This article describes the kinetics of reactions that result in substrate consumption during formation of ultrathin transition metal oxides on silicon. Yttrium silicate films (˜40 Å) with an equivalent silicon dioxide thickness of ˜11 Å are demonstrated by physical vapor deposition (PVD) routes. Interface reactions that occur during deposition and during postdeposition treatment are observed and compared for PVD and chemical vapor deposition (CVD) yttrium oxides and CVD aluminum-oxide systems. Silicon diffusion, metal-silicon bond formation, and reactions involving hydroxides are proposed as critical processes in interface layer formation. For PVD of yttrium silicate, oxidation is thermally activated with an effective barrier of 0.3 eV, consistent with the oxidation of silicide being the rate-limited step. For CVD aluminum oxide, interface oxidation is consistent with a process limited by silicon diffusion into the deposited oxide layer.

  4. Thermogravimetric study of chemical compatibility of graphite with metal oxides

    International Nuclear Information System (INIS)

    Graphite and graphite mixtures with metal oxides are studied in conditions of nonisothermal heating to 1000 deg C using the methods of thermodynamic and gravimetric analyses. Chemical compatibility of graphite with Al2O3, CaO, SiO2, MgO, Fe2O3, TiO2, Na2O, K2O in the compositions considered is established. A decrease in the sample mass observed on the gravimetric curves in the presence of admixtures does not exceed the same value in pure graphite samples in specified conditions

  5. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola

    2001-01-01

    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo...... and solvated reaction profiles, as expected. In the solvents investigated (CH2Cl2 and MeOH), the most favorable mechanism is addition of peroxide anion to a fluorosilane (starting material or formed in situ), followed by a concerted migration and dissociation of hydroxide anion. In the gas phase, and...

  6. Chemical oxidation of phenolic acids by soil iron and manganese oxides

    International Nuclear Information System (INIS)

    The oxidation of six phenolic acids by soil Fe and Mn oxides was demonstrated by changes in phenolic acid extractability from soil with time, by production of Fe(II) and soluble Mn from the oxidation reaction, by quantitative recoveries of added phenolic acids from soil pretreated with dithionite-citrate to remove Fe and Mn oxides, and by the reactivity of phenolic acids in the presence of pure Mn and Fe oxides. The reactivities of phenolic acids were associated with the structures of the chemicals. Increasing methoxy substitution on the aromatic ring increased reactivity, and cinnamic acid derivatives were more reactive than benzoic acid derivatives. Oxidation products of 14C labeled ferulic acid were sorbed to MnO2 within minutes and were unextractable by organic solvents unless the mineral was pretreated with 6 M HCl or 0.5 M NaOH. The oxidation rate of ferulic acid by MnO2 approached zero after four days even with a surplus of reactants

  7. Reversible solid oxide fuel cells (R-SOFCs) with chemically stable proton-conducting oxides

    KAUST Repository

    Bi, Lei

    2015-07-01

    Proton-conducting oxides offer a promising way of lowering the working temperature of solid oxide cells to the intermediate temperate range (500 to 700. °C) due to their better ionic conductivity. In addition, the application of proton-conducting oxides in both solid oxide fuel cells (SOFCs) and sold oxide electrolysis cells (SOECs) provides unique advantages compared with the use of conventional oxygen-ion conducting conductors, including the formation of water at the air electrode site. Since the discovery of proton conduction in some oxides about 30. years ago, the development of proton-conducting oxides in SOFCs and SOECs (the reverse mode of SOFCs) has gained increased attention. This paper briefly summarizes the development in the recent years of R-SOFCs with proton-conducting electrolytes, focusing on discussing the importance of adopting chemically stable materials in both fuel cell and electrolysis modes. The development of electrode materials for proton-conducting R-SOFCs is also discussed. © 2015 Elsevier B.V.

  8. Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

    International Nuclear Information System (INIS)

    Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide – carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size ∼7 nm and ∼95 m2/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO2 thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors

  9. Chemical Bond Analysis of Single Crystal Growth of Magnesium Oxide

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Starting from the crystallographic structure of magnesium oxide (MgO), both the chemical bond model of solids and Pauling's third rule (polyhedral sharing rule) were employed to quantitatively analyze the chemical bonding structure of constituent atoms and single crystal growth. Our analytical results show that MgO single crystals prefer to grow along the direction and the growth rate of the {100} plane is the slowest one. Therefore, the results show that the {100} plane of MgO crystals can be the ultimate morphology face, which is in a good agreement with our previous experimental results. The study indicate that the structure analysis is an effective tool to control the single-crystal growth.

  10. Textured indium tin oxide thin films by chemical solution deposition and rapid thermal processing

    International Nuclear Information System (INIS)

    The microstructure of state-of-the-art chemical solution deposited indium tin oxide thin films typically consists of small randomly oriented grains, high porosity and poor homogeneity. The present study demonstrates how the thin film microstructure can be improved significantly by tailoring the precursor solutions and deposition conditions to be kinetically and thermodynamically favorable for generation of homogeneous textured thin films. This is explained by the occurrence of a single heterogeneous nucleation mechanism. The as-deposited thin films, crystallized at 800 deg. C, have a high apparent density, based on a refractive index of ∼ 1.98 determined by single wavelength ellipsometry at 633 nm. The microstructure of the films consists of columnar grains with preferred orientation as determined by X-ray diffraction and transmission electron microscopy. The resistivity, measured by the four point probe method, is ∼ 2 x 10-3 Ω cm prior to post-deposition treatments

  11. Kinetic and thermodynamic studies on biosorption of Cu(Ⅱ) by chemically modified orange peel

    Institute of Scientific and Technical Information of China (English)

    FENG Ning-chuan; GUO Xue-yi; LIANG Sha

    2009-01-01

    Cu(H) biosorption by orange peel that was chemically modified with sodium hydroxide and calcium chloride was investigated. The effects of temperature, contact time, initial concentration of metal ions and pH on the biosorption of Cu( II) ions were assessed. Thermodynamic parameters including change of free energy(△G~Θ), enthalpy (△H~Θ) and entropy(△S~Θ) during the biosorption were determined. The results show that the biosorption process of Cu( II) ions by chemically treated orange peel is feasible, spontaneous and exothermic under studied conditions. Equilibrium is well described by Langmuir equation with the maximum biosorption capacity(q_m) for Cu( II) as 72.73 mg/g and kinetics is found to fit pseudo-second order type biosorption kinetics. As the temperature increases from 16 ℃ to 60 ℃, copper biosorption decreases. The loaded biosorbent is regenerated using HC1 solution for repeatedly use for five times with little loss of biosorption capacity.

  12. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    Science.gov (United States)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  13. Potentiostatic Oxide Growth Kinetics on Ni-Cr and Co-Cr Alloys: Potential and pH Dependences

    International Nuclear Information System (INIS)

    Oxide growth kinetics on the Ni-Cr-Fe alloy Inconel 600 and the Co-Cr alloy Stellite 6 under potentiostatic polarization have been investigated by current measurements augmented by ex-situ surface analyses. The results reveal a mechanism for metal oxidation and oxide formation that is common to both alloys. The reaction thermodynamics for the oxidation of a metal determine whether a certain metal oxidation can or cannot occur. However, the metal oxidation proceeds via two competing pathways, oxide formation and metal ion dissolution. At pH 10.6 where the solubilities of FeII, NiII or CoII species are near their minima, oxide formation is favoured over metal ion dissolution. As the oxide grows, the rate of metal oxidation decreases with time due to an increase in the electrochemical potential barrier. The oxide formation occurs sequentially; the conversion of the preformed Cr2O3 film to chromite (FeCr2O4 or CoCr2O4) proceeds before the next layers of Fe3O4/NiFe2O4 and NiO/Ni(OH)2 grow on Inconel 600, or CoO/Co(OH)2 grows on Stellite 6. The effect of a different EAPP is to limit the oxidation sequence. The pH does not directly affect the driving force for metal oxidation but it strongly influences the relative rates of oxide formation and metal dissolution, thereby affecting metal oxidation kinetics

  14. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    International Nuclear Information System (INIS)

    Bulk oxygen exchange rate kinetics on CeO2 at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO2 powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10−2 s−1 with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO2, suggesting that oxygen exchange on PuO2 may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on 238PuO2 oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO2 at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO2 powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO2 exchange rates appear similar to the rates observed on PuO2 at 1000 °C

  15. Determination of thermoluminescence kinetic parameters of terbium-doped zirconium oxide

    International Nuclear Information System (INIS)

    In recent years considerable importance has been attached to zirconium oxide doped with rare earth (ZrO2 : RE) thin films due to their desirable characteristics for use in UV dosimetry. In our laboratories we have developed a method to prepare ZrO2 : RE thin films. Dosimetric characteristics of these materials have been reported previously (Azorin et al., Radiat. Meas. 29 (1998) 315; Radiat. Prot. Dosim. 85 (1999) 317) and results of these have stimulated continued development and analysis of the thermoluminescence mechanism. Two important parameters to be determined in TL studies are the activation energy (E) and the frequency factor (s). This paper presents the results of determining kinetic parameters of terbium-doped zirconium oxide (ZrO2 : Tb) thin films, exposed to 260 nm UV light, using the Lushchik (Sov. Phys. JETF 3 (1956) 390) and Chen (J. Appl. Phys. 40 (1969) 570; J. Electrochem. Soc. 166 (1969) 1254) methods. Kinetic analysis of the glow curve shows second order kinetics for both the first and second glow peaks. (author)

  16. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    International Nuclear Information System (INIS)

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N2-5% H2 gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal

  17. Simple and Efficient Synthesis of Iron Oxide-Coated Silica Gel Adsorbents for Arsenic Removal: Adsorption Isotherms and Kinetic Study

    International Nuclear Information System (INIS)

    Iron oxide (ferrihydrite, hematite, and magnetite) coated silica gels were prepared using a low-cost, easily-scalable and straightforward method as the adsorbent material for arsenic removal application. Adsorption of the anionic form of arsenic oxyacids, arsenite (AsO2-) and arsenate (AsO4-3), onto hematite coated silica gel was fitted against non-linear 3-parameter-model Sips isotherm and 2-parameter-model Langmuir and Freundlich isotherm. Adsorption kinetics of arsenic could be well described by pseudo-second-order kinetic model and value of adsorption energy derived from non-linear Dubinin-Radushkevich isotherm suggests chemical adsorption. Although arsenic adsorption process was not affected by the presence of sulfate, chloride, and nitrate anions, as expected, bicarbonate and silicate gave moderate negative effects while the presence of phosphate anions significantly inhibited adsorption process of both arsenite and arsenate. When the actual efficiency to remove arsenic was tested against 1 L of artificial arsenic-contaminated groundwater (0.6 mg/L) in the presence competing anions, the reasonable amount (20 g) of hematite coated silica gel could reduce arsenic concentration to below the WHO permissible safety limit of drinking water of 10 μg/L without adjusting pH and temperature, which would be highly advantageous for practical field application

  18. Kinetics of thermal decomposition of nano magnesium oxide catalyzed ammonium perchlorate

    International Nuclear Information System (INIS)

    Arrhenius kinetic parameters of ammonium perchlorate (AP) catalyzed with nano-sized magnesium oxide (MgO) has been determined in this work. Nano particles of MgO with an average size of approximately 20 to 30 nm have been used to catalyze the AP. The particles were characterized using Scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques before mixing with AP. Simultaneous Thermal Analysis (STA) shows that MgO nanoparticles have a strong catalytic effect on the thermal decomposition of ammonium perchlorate. The addition of MgO nano particles reduces the two stage decomposition of ammonium perchlorate to a single stage. Arrhenius kinetic parameters of pure and the catalyzed AP have been calculated using non isothermal kinetic approach based on Kissinger method. The comparison of the thermal behavior and kinetic parameters of pure and catalyzed AP has also been carried out to elucidate the reaction mechanism. The results show that the activation energy of the catalyzed AP has increased from 138.1 kJ/mole to 159.1kJ/mole. The rate of reaction, however, has increased in the catalyzed AP showing that it has become more reactive by the addition of MgO nano particles. The enthalpy of activation has increased by 16 percent in the catalyzed AP. (author)

  19. Numerical kinetic model including equilibrium and rate equations for chemical reactions of actinide elements

    International Nuclear Information System (INIS)

    Numerical simulation method was examined for chemical reactions of actinide elements U, Pu, Np, and Tc etc. in an aqueous nitric acid solution. It is known that the numerical calculation for the Purex process with chemical reactions and liquid flow becomes stiff, because time constant for the chemical reactions is two to three order of magnitude smaller due to the very fast reactions than that of mass transfer or of reaching distribution equilibrium. Recently in order to increase a time step Δt the partial equilibrium (P.E.) model, in which some very fast reactions are treated by the equilibrium law whereas other reactions are by the rate law, has been proposed. In the present study concentration change of the solutes in an aqueous solution with 30 chemical reactions, of which 4 are expressed by equilibrium equations, has been calculated. Description of the P.E. model and the comparison of the results and cpu time between the kinetic and the P.E. models are given. (author)

  20. Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

    Energy Technology Data Exchange (ETDEWEB)

    Hubler, T.L. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The goal of this task is to develop modified resorcinol-formaldehyde (R-F) resin to improve the chemical/oxidative stability of the resin. R-F resin is a regenerable organic ion-exchange resin that is selective for cesium ion in highly alkaline, high ionic-strength solutions. R-F resin tends to undergo chemical degradation, reducing its ability to remove cesium ion from waste solutions; the mechanistic details of these decomposition reactions are currently unknown. The approach used for this task is chemical modification of the resin structure, particularly the resorcinol ring unit of the polymer resin. This approach is based on prior characterization studies conducted at Pacific Northwest National Laboratory (PNNL) that indicated the facile chemical degradation of the resin is oxidation of the resorcinol ring to the para-quinone structure, with subsequent loss of ion-exchange sites for cesium ion. R-F resin represents an important alternative to current radiocesium remediation technology for tank wastes at both the Hanford and Savannah River sites, particularly if regenerable resins are needed.