WorldWideScience

Sample records for detailed kinetic mechanisms

  1. 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.

  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. 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.

  5. 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

    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......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...

  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. Validation and updating of detailed kinetic mechanisms: The case of ethane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Bonini, F.; Servida, A.; Morbidelli, M.; Carra, S. (Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata)

    1994-11-01

    The authors have investigated experimentally the oxidation of ethane in a perfectly stirred reactor in the temperature range 870--1,080 K and for fuel-air stoichiometric ratio ranging from 0.25 to 1.27. The concentrations of the main molecular species have been measured by probe sampling and GC analysis. These experimental results have been compared with predictions of three popular detailed kinetic mechanisms previously presented in the literature. A reasonable agreement between the experimental results and the model predictions has been found for almost all the species and the mechanisms. The only relevant exception is acetylene, which is greatly overpredicted by one of the mechanisms for all the investigated conditions. Parametric sensitivity analysis has been used for updating such a mechanism in order to improve the agreement with the experimental observations.

  8. 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.

  9. CFD Simulation of Propane Cracking Tube Using Detailed Radical Kinetic Mechanism

    Institute of Scientific and Technical Information of China (English)

    张楠; 邱彤; 陈丙珍

    2013-01-01

    In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous compu-tational fluid dynamics (CFD) model. The eddy-dissipation-concept (EDC) model is introduced to deal with turbu-lence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high as-pect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation op-timization aiming at high conversion and selectivity of pyrolysis process.

  10. 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.

  11. A Detailed Chemical Kinetic Reaction Mechanism for n-Alkane Hydrocarbons from n-Octane to n-Hexadecane

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-25

    Detailed chemical kinetic reaction mechanisms have been developed to describe the pyrolysis and oxidation of the n-alkanes, including n-octane (n-C{sub 8}H{sub 18}), n-nonane (n-C{sub 9}H{sub 20}), n-decane (n-C{sub 10}H{sub 22}), n-undecane (n-C{sub 11}H{sub 24}), n-dodecane (n-C{sub 12}H{sub 26}), n-tridecane (n-C{sub 13}H{sub 28}), n-tetradecane (n-C{sub 14}H{sub 30}), n-pentadecane (n-C{sub 15}H{sub 32}), and n-hexadecane (n-C{sub 16}H{sub 34}). These mechanisms include both high temperature and low temperature reaction pathways. The mechanisms are based on previous mechanisms for n-heptane, using the same reaction class mechanism construction developed initially for n-heptane. Individual reaction class rules are as simple as possible in order to focus on the parallelism between all of the n-alkane fuels included in the mechanisms, and there is an intent to develop these mechanisms further in the future to incorporate greater levels of accuracy and predictive capability. Several of these areas for improvement are identified and explained in detail. These mechanisms are validated through comparisons between computed and experimental data from as many different sources as possible. In addition, numerical experiments are carried out to examine features of n-alkane combustion in which the detailed mechanisms can be used to compare processes in all of the n-alkane fuels. The mechanisms for all of these n-alkanes are presented as a single detailed mechanism, which can be edited to produce efficient mechanisms for any of the n-alkanes included, and the entire mechanism, with supporting thermochemical and transport data, together with an explanatory glossary explaining notations and structural details, will be available on our web page when the paper is accepted for publication.

  12. A Detailed Chemical Kinetic Reaction Mechanism for n-Alkane Hydrocarbons From n-Octane to n-Hexadecane

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-02-08

    Detailed chemical kinetic reaction mechanisms have been developed to describe the pyrolysis and oxidation of nine n-alkanes larger than n-heptane, including n-octane (n-C{sub 8}H{sub 18}), n-nonane (n-C{sub 9}H{sub 20}), n-decane (n-C{sub 10}H{sub 22}), n-undecane (n-C{sub 11}H{sub 24}), n-dodecane (n-C{sub 12}H{sub 26}), n-tridecane (n-C{sub 13}H{sub 28}), n-tetradecane (n-C{sub 14}H{sub 30}), n-pentadecane (n-C{sub 15}H{sub 32}), and n-hexadecane (n-C{sub 16}H{sub 34}). These mechanisms include both high temperature and low temperature reaction pathways. The mechanisms are based on our previous mechanisms for the primary reference fuels n-heptane and iso-octane, using the reaction class mechanism construction first developed for n-heptane. Individual reaction class rules are as simple as possible in order to focus on the parallelism between all of the n-alkane fuels included in the mechanisms, and these mechanisms will be refined further in the future to incorporate greater levels of accuracy and predictive capability. These mechanisms are validated through extensive comparisons between computed and experimental data from a wide variety of different sources. In addition, numerical experiments are carried out to examine features of n-alkane combustion in which the detailed mechanisms can be used to compare reactivities of different n-alkane fuels. The mechanisms for all of these n-alkanes are presented as a single detailed mechanism, which can be edited to produce efficient mechanisms for any of the n-alkanes included, and the entire mechanism, with supporting thermochemical and transport data, together with an explanatory glossary explaining notations and structural details, will be available for download from our web page.

  13. Reduction of Large Detailed Chemical Kinetic Mechanisms for Autoignition Using Joint Analyses of Reaction Rates and Sensitivities

    Energy Technology Data Exchange (ETDEWEB)

    Saylam, A; Ribaucour, M; Pitz, W J; Minetti, R

    2006-11-29

    A new technique of reduction of detailed mechanisms for autoignition, which is based on two analysis methods is described. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n-heptane and iso-octane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n-heptane mechanism and by a factor of 16.7 for iso-octane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species.

  14. 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.

  15. A Detailed Chemical Kinetic Model for TNT

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K

    2005-01-13

    A detailed chemical kinetic mechanism for 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and soot formation during the destruction of munitions. The TNT mechanism treats only gas-phase reactions. Reactions for the decomposition of TNT and for the consumption of intermediate products formed from TNT are assembled based on information from the literature and on current understanding of aromatic chemistry. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reaction paths are developed based on similar paths for aromatic hydrocarbons. Reaction-rate constant expressions are estimated from the literature and from analogous reactions where the rate constants are available. The detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons. Computed results show the effect of oxygen concentration on the amount of soot precursors that are formed in the combustion of RDX and TNT mixtures in N{sub 2}/O{sub 2} mixtures.

  16. Role of hydrogen abstraction acetylene addition mechanisms in the formation of chlorinated naphthalenes. 2. Kinetic modeling and the detailed mechanism of ring closure.

    Science.gov (United States)

    McIntosh, Grant J; Russell, Douglas K

    2014-12-26

    The dominant formation mechanisms of chlorinated phenylacetylenes, naphthalenes, and phenylvinylacetylenes in relatively low pressure and temperature (∼40 Torr and 1000 K) pyrolysis systems are explored. Mechanism elucidation is achieved through a combination of theoretical and experimental techniques, the former employing a novel simplification of kinetic modeling which utilizes rate constants in a probabilistic framework. Contemporary formation schemes of the compounds of interest generally require successive additions of acetylene to phenyl radicals. As such, infrared laser powered homogeneous pyrolyses of dichloro- or trichloroethylene were perturbed with 1,2,4- or 1,2,3-trichlorobenzene. The resulting changes in product identities were compared with the major products expected from conventional pathways, aided by the results of our previous computational work. This analysis suggests that a Bittner-Howard growth mechanism, with a novel amendment to the conventional scheme made just prior to ring closure, describes the major products well. Expected products from a number of other potentially operative channels are shown to be incongruent with experiment, further supporting the role of Bittner-Howard channels as the unique pathway to naphthalene growth. A simple quantitative analysis which performs very well is achieved by considering the reaction scheme as a probability tree, with relative rate constants being cast as branching probabilities. This analysis describes all chlorinated phenylacetylene, naphthalene, and phenylvinylacetylene congeners. The scheme is then tested in a more general system, i.e., not enforcing a hydrogen abstraction/acetylene addition mechanism, by pyrolyzing mixtures of di- and trichloroethylene without the addition of an aromatic precursor. The model indicates that these mechanisms are still likely to be operative.

  17. CATALYTIC COMBUSTION OF METHANE OVER Pt/γ-Al2O3 IN MICRO-COMBUSTOR WITH DETAILED CHEMICAL KINETIC MECHANISMS

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2014-11-01

    Full Text Available Micro-scale catalytic combustion characteristics and heat transfer processes of preheated methane-air mixtures (φ = 0.4 in the plane channel were investigated numerically with detailed chemical kinetic mechanisms. The plane channel of length L = 10.0 mm, height H =1.0 mm and wall thickness δ = 0.1 mm, which inner horizontal surfaces contained Pt/γ-Al2O3 catalyst washcoat. The computational results indicate that the presence of the gas phase reactions extends mildly the micro-combustion stability limits at low and moderate inlet velocities due to the strong flames establishment, and have a more profound effect on extending the high-velocity blowout limits by allowing for additional heat release originating mainly from the incomplete CH4 gas phase oxidation in the plane channel. When the same mass flow rate (ρin × Vin is considered, the micro-combustion stability limits at p: 0.1 MPa are much narrower than at p: 0.6 MPa due to both gas phase and catalytic reaction activities decline with decreasing pressure. Catalytic micro-combustor can achieve stable combustion at low solid thermal conductivity ks < 0.1 W∙m-1•K-1, while the micro-combustion extinction limits reach their larger extent for the higher thermal conductivity ks = 20.0-100.0 W∙m-1•K-1. The existence of surface radiation heat transfers significantly effects on the micro-combustion stability limits and micro-combustors energy balance. Finally, gas phase combustion in catalytic micro-combustors can be sustained at the sub-millimeter scale (plane channel height of 0.25 mm.

  18. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

  19. Cleaner combustion developing detailed chemical kinetic models

    CERN Document Server

    Battin-Leclerc, Frédérique; Blurock, Edward

    2013-01-01

    This overview compiles the on-going research in Europe to enlarge and deepen the understanding of the reaction mechanisms and pathways associated with the combustion of an increased range of fuels. Focus is given to the formation of a large number of hazardous minor pollutants and the inability of current combustion models to predict the  formation of minor products such as alkenes, dienes, aromatics, aldehydes and soot nano-particles which have a deleterious impact on both the environment and on human health. Cleaner Combustion describes, at a fundamental level, the reactive chemistry of min

  20. 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.

  1. Prediction of Combustion Instability with Detailed Chemical Kinetics

    Science.gov (United States)

    2014-12-01

    public release; distribution is unlimited. 5 of 19 American Institute of Aeronautics and Astronautics (a1) LOP = 8.89cm (a2) LOP = 13.97cm (a3) LOP ...19.05cm (a) Global single step kinetics (b1) LOP = 8.89cm (b2) LOP = 13.97cm (b3) LOP = 19.05cm (b) Detailed, GRI-1.2 kinetics Figure 5: Pressure trace...American Institute of Aeronautics and Astronautics (a1) LOP = 8.89cm (a2) LOP = 13.97cm (a3) LOP = 19.05cm (a) Global single step kinetics (b1) LOP

  2. Towards cleaner combustion engines through groundbreaking detailed chemical kinetic models.

    Science.gov (United States)

    Battin-Leclerc, Frédérique; Blurock, Edward; Bounaceur, Roda; Fournet, René; Glaude, Pierre-Alexandre; Herbinet, Olivier; Sirjean, Baptiste; Warth, V

    2011-09-01

    In the context of limiting the environmental impact of transportation, this critical review discusses new directions which are being followed in the development of more predictive and more accurate detailed chemical kinetic models for the combustion of fuels. In the first part, the performance of current models, especially in terms of the prediction of pollutant formation, is evaluated. In the next parts, recent methods and ways to improve these models are described. An emphasis is given on the development of detailed models based on elementary reactions, on the production of the related thermochemical and kinetic parameters, and on the experimental techniques available to produce the data necessary to evaluate model predictions under well defined conditions (212 references). This journal is © The Royal Society of Chemistry 2011

  3. 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.

  4. Reduced chemical kinetic mechanisms for hydrocarbon fuels

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, C J; Cremer, M A; Heap, M P; Chen, J -Y; Westbrook, C K; Maurice, L Q

    1999-12-10

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, a variety of different reduced chemical kinetic mechanisms for ethylene and n-heptane have been generated. The reduced mechanisms have been compared to detailed chemistry calculations in simple homogeneous reactors and experiments. Reduced mechanisms for combustion of ethylene having as few as 10 species were found to give reasonable agreement with detailed chemistry over a range of stoichiometries and showed significant improvement over currently used global mechanisms. The performance of reduced mechanisms derived from a large detailed mechanism for n-heptane was compared to results from a reduced mechanism derived from a smaller semi-empirical mechanism. The semi-empirical mechanism was advantageous as a starting point for reduction for ignition delay, but not for PSR calculations. Reduced mechanisms with as few as 12 species gave excellent results for n-heptane/air PSR calculations but 16-25 or more species are needed to simulate n-heptane ignition delay.

  5. Application of Detailed Chemical Kinetics to Combustion Instability Modeling

    Science.gov (United States)

    2016-01-04

    under two different conditions corresponding to marginally stable and unstable operation in order to evaluate the performance of the chemical kinetics...instability is a complex interaction between acoustics and the heat release due to combustion.In rocket engines, which are acoustically compact, there is...and amplitudes remains a challenge. The present article is an attempt towards addressing such discrepancies by enhancing the chemical kinetics model

  6. Structured detailed opto-mechanical tolerance modeling

    Science.gov (United States)

    Swart, P. C.

    2016-02-01

    Opto-mechanical tolerancing is a complex art, which is often reduced to inadequate tabled data of allowable tilts and decentres. During the process the respective roles of optical- and mechanical designers can become entangled and a source of conflict. A framework of principles is introduced to guide the design team through these murky waters. From these principles the development of a catalogue of models, practices and past precedents are proposed. An example is presented to serve as illustration. The final result is a model, of opto-mechanical tolerances, which allows a structured flow of tolerances into optical performance prediction.

  7. Soot formation in a blast furnace - Prediction via a parametric study, using detailed kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nordstroem, T.; Kilpinen, P.; Hupa, M. [Aabo Akademi, Turku (Finland). Combustion Chemistry Group

    1996-12-31

    The objective of this work has been to investigate the soot formation in a blast furnace fired with heavy fuel oil, using detailed kinetic modelling. This work has been concentrated on parameter studies that could explain under which conditions soot is formed and how that formation could be avoided. The parameters investigated were temperature, pressure, stoichiometric ratio, pyrolysis gas composition and reactor model. The calculations were based on a reaction mechanism that consists of 100 species and 446 reactions including polyaromatic hydrocarbons (PAM) up to 7 aromatic rings SULA 2 Research Programme; 4 refs.

  8. Detailed Chemical Kinetic Modeling of Diesel Combustion with Oxygenated Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Curran, H J; Fisher, E M; Glaude, P-A; Marinov, N M; Pitz, W J; Westbrook, C K; Flynn, P F; Durrett, R P; zur Loye, A O; Akinyemi, O C; Dryer, F L

    2000-01-11

    Emission standards for diesel engines in vehicles have been steadily reduced in recent years, and a great deal of research and development effort has been focused on reducing particulate and nitrogen oxide emissions. One promising approach to reducing emissions involves the addition of oxygen to the fuel, generally by adding an oxygenated compound to the normal diesel fuel. Miyamoto et al. [1] showed experimentally that particulate levels can be significantly reduced by adding oxygenated species to the fuel. They found the Bosch smoke number (a measure of the particulate or soot levels in diesel exhaust) falls from about 55% for conventional diesel fuel to less than 1% when the oxygen content of the fuel is above about 25% by mass, as shown in Figure 1. It has been well established that addition of oxygenates to automotive fuel, including both diesel fuel as well as gasoline, reduces NOx and CO emissions by reducing flame temperatures. This is the basis for addition of oxygenates to produce reformulated gasoline in selected portions of the country. Of course, this is also accompanied by a slight reduction in fuel economy. A new overall picture of diesel combustion has been developed by Dec [2], in which laser diagnostic studies identified stages in diesel combustion that had not previously been recognized. These stages are summarized in Figure 2. The evolution of the diesel spray is shown, starting as a liquid jet that vaporizes and entrains hot air from the combustion chamber. This relatively steady process continues as long as fuel is being injected. In particular, Dec showed that the fuel spray vaporizes and mixes with air and products of earlier combustion to provide a region in which a gas phase, premixed fuel-rich ignition and burn occurs. The products of this ignition are then observed experimentally to lead rapidly to formation of soot particles, which subsequently are consumed in a diffusion flame. Recently, Flynn et al. [3] used a chemical kinetic and

  9. Combustion of n-heptane in a shock tube and in a stirred reactor: A detailed kinetic modeling study

    Energy Technology Data Exchange (ETDEWEB)

    Gaffuri, P.; Curran, H.J.; Pitz, W.J.; Westbrook, C.K.

    1995-04-13

    A detailed chemical kinetic reaction mechanism is used to study the oxidation of n-heptane under several classes of conditions. Experimental results from ignition behind reflected shock waves and in a rapid compression machine were used to develop and validate the reaction mechanism at relatively high temperatures, while data from a continuously stirred tank reactor (cstr) were used to refine the low temperature portions of the reaction mechanism. In addition to the detailed kinetic modeling, a global or lumped kinetic mechanism was used to study the same experimental results. The lumped model was able to identify key reactions and reaction paths that were most sensitive in each experimental regime and provide important guidance for the detailed modeling effort. In each set of experiments, a region of negative temperature coefficient (NTC) was observed. Variation in pressure from 5 to 40 bars were found to change the temperature range over which the NTC region occurred. Both the lumped and detailed kinetic models reproduced the measured results in each type of experiments, including the features of the NTC region, and the specific elementary reactions and reaction paths responsible for this behavior were identified and rate expressions for these reactions were determined.

  10. Experimental and detailed kinetic modeling study of PAH formation in laminar co-flow methane diffusion flames

    DEFF Research Database (Denmark)

    Cuoci, Alberto; Frassoldati, Alessio; Faravelli, Tiziano

    2013-01-01

    In the present paper, synchrotron VUV photoionization mass spectrometry is used to study the detailed chemistry of co-flow methane diffusion flames with different dilution ratios. The experimental results constitute a comprehensive characterization of species important for PAH and soot formation...... an original CFD code based on the operator-splitting technique, specifically conceived to handle large kinetic mechanisms. The detailed kinetic modeling was effectively used to describe and analyze the fuel consumption and the formation of PAH. Experimental measurements and numerical predictions were found...

  11. 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)

  12. Mechanisms and kinetics of coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, R M; Furlong, M W

    1981-05-01

    Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes, and asphaltenes. Experimental work was completed on a suite of bituminous coals, thus completing the initial phase of the coal reactivity study. Eleven of the 14 coals of the suite were successfully run in duplicate. Conversion to THF solubles was correlated well by pseudo-second order kinetics. The resulting kinetic rate constants correlated with H/C ratio, mean-max vitrinite reflectance, and a specially-defined fraction of reactive macerals. The data did not correlate well with O/C ratios of the parent coals. Computer-derived statistical fits of various kinetic models were limited in their effectiveness at fitting the experimental data. Experimental work on the first phase of the disposal catalyst studies was completed. Statistical significance testing of the experimental data showed: fractional conversion and yield of light hydrocarbon products increased with time; and mineral properties of the additives were more significant in increasing overall conversion than the additive surface areas. The relative effects of the additives are given.

  13. Detailed reduction of reaction mechanisms for flame modeling

    Science.gov (United States)

    Wang, Hai; Frenklach, Michael

    1991-01-01

    A method for reduction of detailed chemical reaction mechanisms, introduced earlier for ignition system, was extended to laminar premixed flames. The reduction is based on testing the reaction and reaction-enthalpy rates of the 'full' reaction mechanism using a zero-dimensional model with the flame temperature profile as a constraint. The technique is demonstrated with numerical tests performed on the mechanism of methane combustion.

  14. Two-dimensional numerical simulation of reactive flow in aero-engine combustor with detailed chemical kinetic mechanisms%详细反应机理的航空发动机二维燃烧流场计算

    Institute of Scientific and Technical Information of China (English)

    侯宽新; 刘勇; 赵坚行

    2009-01-01

    对某航空发动机主燃烧室简化模型进行了基于正庚烷(n-C_7H_(16))详细反应机理的燃烧流场数值模拟.在二维贴体坐标系下,计算过程采用了κ-ε双方程模型来预估湍流特性,用EDC(eddy dissipation concept)湍流燃烧模型预估反应速率,用PSR(perfectly stirred reactor)模型的方法处理复杂化学反应项,得出了基于详细反应机理的温度场、组分浓度场,验证了机理文件中反应的某些组分与特定自由基之间的关系,对比了总包反应EBU-SRK(eddy break up-simplified reaction kinetics)的温度场,结果基本相符.

  15. Benefits of detailed models of muscle activation and mechanics

    Science.gov (United States)

    Lehman, S. L.; Stark, L.

    1981-01-01

    Recent biophysical and physiological studies identified some of the detailed mechanisms involved in excitation-contraction coupling, muscle contraction, and deactivation. Mathematical models incorporating these mechanisms allow independent estimates of key parameters, direct interplay between basic muscle research and the study of motor control, and realistic model behaviors, some of which are not accessible to previous, simpler, models. The existence of previously unmodeled behaviors has important implications for strategies of motor control and identification of neural signals. New developments in the analysis of differential equations make the more detailed models feasible for simulation in realistic experimental situations.

  16. Kinetic partitioning mechanism of HDV ribozyme folding

    Science.gov (United States)

    Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing

    2014-01-01

    RNA folding kinetics is directly tied to RNA biological functions. We introduce here a new approach for predicting the folding kinetics of RNA secondary structure with pseudoknots. This approach is based on our previous established helix-based method for predicting the folding kinetics of RNA secondary structure. In this approach, the transition rates for an elementary step: (1) formation, (2) disruption of a helix stem, and (3) helix formation with concomitant partial melting of an incompatible helix, are calculated with the free energy landscape. The folding kinetics of the Hepatitis delta virus (HDV) ribozyme and the mutated sequences are studied with this method. The folding pathways are identified by recursive searching the states with high net flux-in(out) population starting from the native state. The theory results are in good agreement with that of the experiments. The results indicate that the bi-phasic folding kinetics for the wt HDV sequence is ascribed to the kinetic partitioning mechanism: Part of the population will quickly fold to the native state along the fast pathway, while another part of the population will fold along the slow pathway, in which the population is trapped in a non-native state. Single mutation not only changes the folding rate but also the folding pathway.

  17. Kinetic partitioning mechanism of HDV ribozyme folding

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing, E-mail: wbzhang@whu.edu.cn [Department of Physics, Wuhan University, Wuhan, Hubei 430072 (China)

    2014-01-14

    RNA folding kinetics is directly tied to RNA biological functions. We introduce here a new approach for predicting the folding kinetics of RNA secondary structure with pseudoknots. This approach is based on our previous established helix-based method for predicting the folding kinetics of RNA secondary structure. In this approach, the transition rates for an elementary step: (1) formation, (2) disruption of a helix stem, and (3) helix formation with concomitant partial melting of an incompatible helix, are calculated with the free energy landscape. The folding kinetics of the Hepatitis delta virus (HDV) ribozyme and the mutated sequences are studied with this method. The folding pathways are identified by recursive searching the states with high net flux-in(out) population starting from the native state. The theory results are in good agreement with that of the experiments. The results indicate that the bi-phasic folding kinetics for the wt HDV sequence is ascribed to the kinetic partitioning mechanism: Part of the population will quickly fold to the native state along the fast pathway, while another part of the population will fold along the slow pathway, in which the population is trapped in a non-native state. Single mutation not only changes the folding rate but also the folding pathway.

  18. Energy landscapes, folding mechanisms, and kinetics of RNA tetraloop hairpins.

    Science.gov (United States)

    Chakraborty, Debayan; Collepardo-Guevara, Rosana; Wales, David J

    2014-12-31

    RNA hairpins play a pivotal role in a diverse range of cellular functions, and are integral components of ribozymes, mRNA, and riboswitches. However, the mechanistic and kinetic details of RNA hairpin folding, which are key determinants of most of its biological functions, are poorly understood. In this work, we use the discrete path sampling (DPS) approach to explore the energy landscapes of two RNA tetraloop hairpins, and provide insights into their folding mechanisms and kinetics in atomistic detail. Our results show that the potential energy landscapes have a distinct funnel-like bias toward the folded hairpin state, consistent with efficient structure-seeking properties. Mechanistic and kinetic information is analyzed in terms of kinetic transition networks. We find microsecond folding times, consistent with temperature jump experiments, for hairpin folding initiated from relatively compact unfolded states. This process is essentially driven by an initial collapse, followed by rapid zippering of the helix stem in the final phase. Much lower folding rates are predicted when the folding is initiated from extended chains, which undergo longer excursions on the energy landscape before nucleation events can occur. Our work therefore explains recent experiments and coarse-grained simulations, where the folding kinetics exhibit precisely this dependency on the initial conditions.

  19. To acquire more detailed radiation drive by use of ``quasi-steady'' approximation in atomic kinetics

    Science.gov (United States)

    Ren, Guoli; Pei, Wenbing; Lan, Ke; Gu, Peijun; Li, Xin

    2012-10-01

    In current routine 2D simulation of hohlraum physics, we adopt the principal-quantum- number(n-level) average atom model(AAM) in NLTE plasma description. However, the detailed experimental frequency-dependant radiative drive differs from our n-level simulated drive, which reminds us the need of a more detailed atomic kinetics description. The orbital-quantum- number(nl-level) average atom model is a natural consideration, however the nl-level in-line calculation needs much more computational resource. By distinguishing the rapid bound-bound atomic processes from the relative slow bound-free atomic processes, we found a method to build up a more detailed bound electron distribution(nl-level even nlm-level) using in-line n-level calculated plasma conditions(temperature, density, and average ionization degree). We name this method ``quasi-steady approximation'' in atomic kinetics. Using this method, we re-build the nl-level bound electron distribution (Pnl), and acquire a new hohlraum radiative drive by post-processing. Comparison with the n-level post-processed hohlraum drive shows that we get an almost identical radiation flux but with more fine frequency-denpending spectrum structure which appears only in nl-level transition with same n number(n=0) .

  20. Modeling the Emission of CO from Wood Fires using Detailed Chemical Kinetics

    DEFF Research Database (Denmark)

    Dederichs, Anne

    Carbon monoxide is treated as one of the most common and dangerous of gases evolving in fires. Modeling the formation of the toxic gas CO from in fire enclosures using detailed chemical kinetics is the topic of this manuscript. A semi-empirical model is developed to study the formation of CO from......, 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....

  1. Detailed enzyme kinetics in terms of biochemical species: study of citrate synthase.

    Directory of Open Access Journals (Sweden)

    Daniel A Beard

    Full Text Available The compulsory-ordered ternary catalytic mechanism for two-substrate two-product enzymes is analyzed to account for binding of inhibitors to each of the four enzyme states and to maintain the relationship between the kinetic constants and the reaction equilibrium constant. The developed quasi-steady flux expression is applied to the analysis of data from citrate synthase to determine and parameterize a kinetic scheme in terms of biochemical species, in which the effects of pH, ionic strength, and cation binding to biochemical species are explicitly accounted for in the analysis of the data. This analysis provides a mechanistic model that is consistent with the data that have been used support competing hypotheses regarding the catalytic mechanism of this enzyme.

  2. Detailed kinetics of methylphenyldichlorosilane synthesis from methyldichlorosilane and chlorobenzene by gas phase condensation

    Institute of Scientific and Technical Information of China (English)

    Tong Liu; Tiefeng Wang; Yunlong Huang; Chao Wang; Jinfu Wang

    2015-01-01

    Methylphenyldichlorosilane (MPDS, CH3C6H5SiCl2) is an important silicone monomer for the synthesis of high-performance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C-Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.

  3. Kinetic study and mechanism of Niclosamide degradation

    Science.gov (United States)

    Zaazaa, Hala E.; Abdelrahman, Maha M.; Ali, Nouruddin W.; Magdy, Maimana A.; Abdelkawy, M.

    2014-11-01

    A spectrophotometric kinetic study of Niclosamide alkaline degradation as a function of drug concentration, alkaline concentration and temperature has been established utilizing double divisor-ratio spectra spectrophotometric method. The developed method allowed determination of Niclosamide in presence of its alkaline degradation products; namely; 2-chloro-4-nitro aniline (DEG I) and 5-chloro salicylic acid (DEG II) with characterization of its degradation mechanism. It was found that degradation kinetic of Niclosamide followed pseudo-first order under the established experimental conditions with a degradation rate constant (k) of 0.0829 mol/h and half life (t1/2) of 8.35 h. The overall degradation rate constant as a function of the temperature under the given conditions obeyed Arrhenius equation where the activation energy was calculated to be 3.41 kcal/mol.

  4. Construction and validation of a detailed kinetic model of glycolysis in Plasmodium falciparum.

    Science.gov (United States)

    Penkler, Gerald; du Toit, Francois; Adams, Waldo; Rautenbach, Marina; Palm, Daniel C; van Niekerk, David D; Snoep, Jacky L

    2015-04-01

    The enzymes in the Embden-Meyerhof-Parnas pathway of Plasmodium falciparum trophozoites were kinetically characterized and their integrated activities analyzed in a mathematical model. For validation of the model, we compared model predictions for steady-state fluxes and metabolite concentrations of the hexose phosphates with experimental values for intact parasites. The model, which is completely based on kinetic parameters that were measured for the individual enzymes, gives an accurate prediction of the steady-state fluxes and intermediate concentrations. This is the first detailed kinetic model for glucose metabolism in P. falciparum, one of the most prolific malaria-causing protozoa, and the high predictive power of the model makes it a strong tool for future drug target identification studies. The modelling workflow is transparent and reproducible, and completely documented in the SEEK platform, where all experimental data and model files are available for download. The mathematical models described in the present study have been submitted to the JWS Online Cellular Systems Modelling Database (http://jjj.bio.vu.nl/database/penkler). The investigation and complete experimental data set is available on SEEK (10.15490/seek.1. 56). © 2015 FEBS.

  5. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  6. Detailed surface reaction mechanism in a three-way catalyst.

    Science.gov (United States)

    Chatterjee, D; Deutschmann, O; Warnatz, J

    2001-01-01

    Monolithic three-way catalysts are applied to reduce the emission of combustion engines. The design of such a catalytic converter is a complex process involving the optimization of different physical and chemical parameters (in the simplest case, e.g., length, cell densities or metal coverage of the catalyst). Numerical simulation can be used as an effective tool for the investigation of the catalytic properties of a catalytic converter and for the prediction of the performance of the catalyst. To attain this goal, a two-dimensional flow-field description is coupled with a detailed surface reaction model (gas-phase reactions can be neglected in three-way catalysts). This surface reaction mechanism (with C3H6 taken as representative of unburnt hydrocarbons) was developed using sub-mechanisms recently developed for hydrogen, carbon monoxide and methane oxidation, literature values for C3H6 oxidation, and estimates for the remaining unknown reactions. Results of the simulation of a monolithic single channel are used to validate the surface reaction mechanism. The performance of the catalyst was simulated under lean, nearly stoichiometric and rich conditions. For these characteristic conditions, the oxidation of propene and carbon monoxide and the reduction of NO on a typical Pt/Rh coated three-way catalyst were simulated as a function of temperature. The numerically predicted conversion data are compared with experimentally measured data. The simulation further reveals the coupling between chemical reactions and transport processes within the monolithic channel.

  7. Mathematical modeling provides kinetic details of the human immune response to vaccination

    Directory of Open Access Journals (Sweden)

    Dustin eLe

    2015-01-01

    Full Text Available With major advances in experimental techniques to track antigen-specific immune responses many basic questions on the kinetics of virus-specific immunity in humans remain unanswered. To gain insights into kinetics of T and B cell responses in human volunteers we combine mathematical models and experimental data from recent studies employing vaccines against yellow fever and smallpox. Yellow fever virus-specific CD8 T cell population expanded slowly with the average doubling time of 2 days peaking 2.5 weeks post immunization. Interestingly, we found that the peak of the yellow fever-specific CD8 T cell response is determined by the rate of T cell proliferation and not by the precursor frequency of antigen-specific cells as has been suggested in several studies in mice. We also found that while the frequency of virus-specific T cells increases slowly, the slow increase can still accurately explain clearance of yellow fever virus in the blood. Our additional mathematical model describes well the kinetics of virus-specific antibody-secreting cell and antibody response to vaccinia virus in vaccinated individuals suggesting that most of antibodies in 3 months post immunization are derived from the population of circulating antibody-secreting cells. Taken together, our analysis provides novel insights into mechanisms by which live vaccines induce immunity to viral infections and highlight challenges of applying methods of mathematical modeling to the current, state-of-the-art yet limited immunological data.

  8. 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.

  9. Quasi-Dimensional Modeling of a CNG Fueled HCCI Engine Combustion Using Detailed Chemical Kinetic

    Directory of Open Access Journals (Sweden)

    Younes Bakhshan

    2013-01-01

    Full Text Available In this study, an in-house quasi dimensional code has been developed which simulates the intake, compression, combustion, expansion and exhaust strokes of a homogeneous charge compression ignition (HCCI engine. The compressed natural gas (CNG has been used as fuel. A detailed chemical kinetic scheme constituting of 310 and 1701 elementary equations developed by Bakhshan et al. has been applied for combustion modeling and heat release calculations. The zero-dimensional k-ε turbulence model has been used for calculation of heat transfer. The output results are the performance and pollutants emission and combustion characteristics in HCCI engines. Parametric studies have been conducted to discussing the effects of various parameters on performance and pollutants emission of these engines.

  10. A detailed kinetic study of Mox-1, a plasmid-encoded class C beta-lactamase.

    Science.gov (United States)

    Alba, Jimena; Bauvois, Cedric; Ishii, Yoshikazu; Galleni, Moreno; Masuda, Katsuyoshi; Ishiguro, Masaji; Ito, Masahiko; Frere, Jean-Marie; Yamaguchi, Keizo

    2003-08-29

    Surveys of beta-lactamases in different parts of the world show an important increase in class C beta-lactamases, thus the study of these enzymes is becoming an important issue. We created an overproduction system for Mox-1, a plasmid class C beta-lactamase, by cloning the gene encoding this enzyme, and placing it under the control of a T7 promoter, using vector pET 28a. The enzyme, purified by ion exchange chromatography, was used to obtain the molecular mass (38246), the N-terminal sequence (GEASPVDPLRPVV), and pI (8.9), and to perform a detailed kinetic study. Cephalotin was used as reporter substrate in the case of poor substrates. The kinetic study showed that benzylpenicillin, cephalotin, cefcapene and moxalactam were good substrates for Mox-1 (k(cat)/K(m) values >2.5 x 10(6) M(-1) s(-1)). On the other hand, ceftazidime and cefepime were poor substrates for this enzyme (K(m) values >200 microM). Clavulanic acid had no inhibitory effect on Mox-1 (K(m)=30.2 mM), however aztreonam behaved as an inhibitor of Mox-1 (K(i)=2.85 microM).

  11. Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

    KAUST Repository

    Rachidi, Mariam El

    2017-06-23

    Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

  12. Mechanism and kinetics of hydrated electron diffusion

    CERN Document Server

    Tay, Kafui A; Boutin, Anne; 10.1063/1.2964101

    2012-01-01

    Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps^{-1} at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ/mol. Through analysis of Arrhenius plots and the application of a simple random walk...

  13. 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

  14. 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.

  15. Numerical prediction of oblique detonation wave structures using detailed and reduced reaction mechanisms

    Science.gov (United States)

    Thaker, A. A.; Chelliah, H. K.

    1997-12-01

    Modelling of the structure and the limiting flow turning angles of an oblique detonation wave, established by a two-dimensional wedge, requires the implementation of detailed chemical kinetic models involving a large number of chemical species. In this paper, a method of reducing the computational effort involved in simulating such high-speed reacting flows by implementing a systematically reduced reaction mechanism is presented. For a hydrogen - air mixture, starting with an elementary mechanism having eight species in 12 reactions, three alternate four-step reduced reaction mechanisms are developed by introducing the steady-state approximation for the reaction intermediates HO2, O and OH, respectively. Additional reduction of the computational effort is achieved by introducing simplifications to the thermochemical data evaluations. The influence of the numerical grid used in predicting the induction process behind the shock is also investigated. Comparisons of the induction zone predicted by two-dimensional oblique detonation wave calculations with that of a static reactor model (with initial conditions of the gas mixture specified by those behind the nonreactive oblique shock wave) are also presented. The reasonably good agreement between the three four-step reduced mechanism predictions and the starting mechanism predictions indicates that further reduction to a two-step mechanism is feasible for the physical flow time scales (corresponding to inflow Mach numbers of 8 - 10) considered here, and needs to be pursued in the future.

  16. Kinetic analysis of the multistep aggregation mechanism of monoclonal antibodies.

    Science.gov (United States)

    Nicoud, Lucrèce; Arosio, Paolo; Sozo, Margaux; Yates, Andrew; Norrant, Edith; Morbidelli, Massimo

    2014-09-11

    We investigate by kinetic analysis the aggregation mechanism of two monoclonal antibodies belonging to the IgG1 and IgG2 subclass under thermal stress. For each IgG, we apply a combination of size exclusion chromatography and light scattering techniques to resolve the time evolution of the monomer, dimer, and trimer concentrations, as well as the average molecular weight and the average hydrodynamic radius of the aggregate distribution. By combining the detailed experimental characterization with a theoretical kinetic model based on population balance equations, we extract relevant information on the contribution of the individual elementary steps on the global aggregation process. The analysis shows that the two molecules follow different aggregation pathways under the same operating conditions. In particular, while the monomer depletion of the IgG1 is found to be rate-limited by monomeric conformational changes, bimolecular collision is identified as the rate-limiting step in the IgG2 aggregation process. The measurement of the microscopic rate constants by kinetic analysis allows the quantification of the protein-protein interaction potentials expressed in terms of the Fuchs stability ratio (W). It is found that the antibody solutions exhibit large W values, which are several orders of magnitude larger than the values computed in the frame of the DLVO theory. This indicates that, besides net electrostatic repulsion, additional effects delay the aggregation kinetics of the antibody solutions with respect to diffusion-limited conditions. These effects likely include the limited efficiency of the collision events due to the presence of a limited number of specific aggregation-prone patches on the heterogeneous protein surface, and the contribution of additional repulsive non-DLVO forces to the protein-protein interaction potential, such as hydration forces.

  17. A multipurpose reduced chemical-kinetic mechanism for methanol combustion

    Science.gov (United States)

    Fernández-Tarrazo, Eduardo; Sánchez-Sanz, Mario; Sánchez, Antonio L.; Williams, Forman A.

    2016-07-01

    A multipurpose reduced chemical-kinetic mechanism for methanol combustion comprising 8 overall reactions and 11 reacting chemical species is presented. The development starts by investigating the minimum set of elementary reactions needed to describe methanol combustion with reasonable accuracy over a range of conditions of temperature, pressure, and composition of interest in combustion. Starting from a 27-step mechanism that has been previously tested and found to give accurate predictions of ignition processes for these conditions, it is determined that the addition of 11 elementary reactions taken from its basis (San Diego) mechanism extends the validity of the description to premixed-flame propagation, strain-induced extinction of non-premixed flames, and equilibrium composition and temperatures, giving results that compare favourably with experimental measurements and also with computations using the 247-step detailed San Diego mechanism involving 50 reactive species. Specifically, premixed-flame propagation velocities and extinction strain rates for non-premixed counterflow flames calculated with the 38-step mechanism show departures from experimental measurements and detailed-chemistry computations that are roughly on the order of 10%, comparable with expected experimental uncertainties. Similar accuracy is found in comparisons of autoignition times over the range considered, except at very high temperatures, under which conditions the computations tend to overpredict induction times for all of the chemistry descriptions tested. From this 38-step mechanism, the simplification is continued by introducing steady-state approximations for the intermediate species CH3, CH4, HCO, CH3O, CH2OH, and O, leading to an 8-step reduced mechanism that provides satisfactory accuracy for all conditions tested. The flame computations indicate that thermal diffusion has a negligible influence on methanol combustion in all cases considered and that a mixture-average species

  18. KINETICS AND MECHANISMS OF NOx - CHAR REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Suuberg, E.M.

    1998-06-19

    This study was undertaken in order to improve understanding of several aspects of the NO-carbon reaction. This reaction is of practical importance in combustion systems, but its close examination also provides some fundamental insight into oxidizing gas-carbon reactions. As part of this study, a comprehensive literature review of earlier work on this reaction has been published (Aarna and Suuberg, Fuel, 1997, 76, 475-491). It has been thought for some time that the kinetics of the NO-carbon reaction are unusual, in that they often show a two-regime Arrhenius behavior. It has, however, turned out during this work that NO is not alone in this regard. In this laboratory, we also uncovered evidence of two kinetic regime behavior in CO{sub 2} gasification. In another laboratory, a former colleague has identified the same behavior in N{sub 2}O. The low temperature reaction regime always shows an activation energy which is lower than that in the high temperature regime, leaving little doubt that a shift in mechanism, as opposed to transport limitations, dictates the behavior. The activation energy of the low temperature regime of these reactions is typically less than 100 kJ/mol, and the activation energy of the high temperature regime is generally considerably in excess of this value. In this study, we have resolved some apparent inconsistencies in the explanation of the low temperature regime, whose rate has generally been ascribed to desorption-controlled processes. Part of the problem in characterization of the different temperature regimes is that they overlap to a high degree. It is difficult to probe the low temperature regime experimentally, because of slow relaxation of the surface oxides in that regime. Using careful experimental techniques, we were able to demonstrate that the low temperature regime is indeed characterized by zero order in NO, as it must be. A separate study is being carried out to model the behavior in this regime in NO and in other gases, and

  19. Chemical kinetic mechanism for the oxidation of paraffinic hydrocarbons needed for primary reference fuels

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J.

    1993-03-01

    A detailed chemical kinetic reaction mechanism is described which simulates the oxidation of the primary reference fuels n-heptane and iso-octane. The high temperature subset of these mechanisms is identified, and the extensions to deal with low temperature conditions are also explained. The algorithms used to assign reaction rates to elementary steps in the reaction mechanism are described, and the means of identifying the different chemical species and the relevant reactions are outlined. Finally, we show how interested kinetic modeling researchers can obtain copies of this reaction mechanism.

  20. Modelling The Photooxidation of Toluene: New Concepts For Developing and Validating Detailed Mechanisms

    Science.gov (United States)

    Wagner, V.; Jenkin, M. E.; Saunders, S.; Stanton, J.; Pilling, M. J.

    The photooxidation of aromatic hydrocarbons contributes significantly to the forma- tion of photochemical smog. The master chemical mechanism (MCM3) contains de- tailed mechanisms for a variety of aromatics, which represent the current understand- ing of the atmospheric photochemical oxidation of these compounds. The comparison of MCM3 simulations with smog chamber experiments have revealed large discrepan- cies, particular in the ozone concentration-time profiles, that suggests that these mech- anisms are not yet suitable for the application in atmospheric models. We will present a variety of tools that help to give a more quantitative understanding of the radical transformation and the breakdown of the carbon skeleton in the aromatic systems. The toluene mechanism is chosen as an example and the significant intermediates, which have most impact on ozone formation, are identified by sensitivity analysis. Further- more, with the aid of budget calculations, we investigate the effect of each of the major reaction channels on the global reactivity of the reaction system. The gathered infor- mation is then discussed in terms of validation concepts for detailed mechanisms with the aid of smog chamber experiments. In this way, we try to explore new concepts in which mechanism development becomes an interactive procedure between kinetic studies, chamber experiments and modelling.

  1. Quantum Chemical Studies on Detail Mechanism of Nitrosylation of NAMI-A-HSA Adduct.

    Science.gov (United States)

    Das, Dharitri; Mondal, Paritosh

    2015-08-20

    Hydrolysis of NAMI-A in NAMI-A-HSA (HSA = human serum albumin) and nitrosylation of hydrolyzed NAMI-A-HSA adduct have been studied in detail using density functional theory method. It has been observed that the chloride exchange reaction with water in the NAMI-A-HSA adduct follows an interchange dissociative mechanism passing through an unstable heptacoordinated activated complex. The computed free energy of activation (ΔG) and rate constant (k) for the hydrolysis process in aqueous medium are observed to be 24.85 kcal mol(-1) and 3.81 × 10(-6) s(-1), respectively. Nitrosylation of hydrolyzed NAMI-A-HSA adduct with nitric oxide is found to be thermodynamically more favorable with the incorporation of solvent effect and provides a detailed understanding related to the antimetastatic activity of the NAMI-A drug. This investigation shows that nitric oxide coordinates linearly to NAMI-A-HSA adduct leading to the reduction of ruthenium(III) to more active ruthenium(II), with the reduction potential of -2.32 V. Negative relative solvation and relative binding free energies suggest that the hydrolysis and nitrosylation reactions are found to be thermodynamically favorable and faster. Our computed results provide a detailed thermodynamics and kinetics which may be highly beneficial for understanding antimetastatic activity as well as the nitric oxide scavenging ability of NAMI-A.

  2. 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

  3. 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.

  4. RADICAL QUENCHING OF METHANE-AIR PREMIXED FLAME IN MICROREACTORS USING DETAILED CHEMICAL KINETICS

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2015-10-01

    Full Text Available The steady hetero-/homogeneous combustion of lean methane-air mixtures in plane channel-flow microreactors was investigated numerically to elucidate the effects of wall material and initial sticking coefficient on radical quenching. Simulations were performed with a two-dimensional numerical model employing detailed reaction mechanisms to examine the interaction between heterogeneous and homogeneous reactions on platinum, alumina, quartz and copper. Comparisons among wall materials revealed that the wall chemical effect plays a vital role in the distribution of OH* radical. Homogeneous reaction of methane over platinum is significantly inhibited due to the rapid depletion of reactants on catalytic surfaces, rather than the radical adsorption. The inhibition of radical quenching on the surface of alumina is most pronounced. As the microreactor is smaller than the critical dimension of 0.7 mm, the wall chemical effect on flame characteristics becomes of great importance.

  5. Thermal and mechanical analysis for the detailed model using submodel

    Energy Technology Data Exchange (ETDEWEB)

    Kuh, Jung Eui; Kang, Chul Hyung; Park, Jeong Hwa [Korea Atomic Energy Research Institute, Taejon (Korea)

    1999-11-01

    A very big model is required for the TM analysis for HLRW repository, and also very small size of mesh is needed to simulate precisely main parts of analysis, e.g., canister, buffer, etc. However, it is practically impossible due to high memory size and computing time. In this report, a submodel concept in ABAQUS is used to handle this difficulty. A submodel concept is the part interested only is performed detailed modelling and this result is used as a boundary condition of full scale model. To follow this kind of computation procedure temperature distribution in buffer and canister could be computed precisely. This approach can be applied to TM analysis of buffer and canister, or a finite size of repository. 12 refs., 28 figs., 9 tabs. (Author)

  6. Mechanical Details for Construction of a Dry Aerosol Deposition Device

    Science.gov (United States)

    2014-07-22

    DISTRIBUTION/AVAILABILITY STATEMENT 13. SUPPLEMENTARY NOTES 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: a. REPORT b. ABSTRACT...mechanism for rapid and highly reproducible loading of microorganisms onto surfaces. The DADD was tested with Bacillus atrophaeus spores and

  7. Fuel spray combustion of waste cooking oil and palm oil biodiesel: Direct photography and detailed chemical kinetics

    KAUST Repository

    Kuti, Olawole

    2013-10-14

    This paper studies the ignition processes of two biodiesel from two different feedstock sources, namely waste cooked oil (WCO) and palm oil (PO). They were investigated using the direct photography through high-speed video observations and detailed chemical kinetics. The detailed chemical kinetics modeling was carried out to complement data acquired using the high-speed video observations. For the high-speed video observations, an image intensifier combined with OH* filter connected to a high-speed video camera was used to obtain OH* chemiluminscence image near 313 nm. The OH* images were used to obtain the experimental ignition delay of the biodiesel fuels. For the high-speed video observations, experiments were done at an injection pressure of 100, 200 and 300 MPa using a 0.16 mm injector nozzle. Also a detailed chemical kinetics for the biodiesel fuels was carried out using ac chemical kinetics solver adopting a 0-D reactor model to obtain the chemical ignition delay of the combusting fuels. Equivalence ratios obtained from the experimental ignition delay were used for the detailed chemical kinetics analyses. The Politecnico di Milano\\'s thermochemical and reaction kinetic data were adopted to simulate the ignition processes of the biodiesels using the five fatty acid methyl esters (FAME) major components in the biodiesel fuels. From the high-speed video observations, it was observed that at increasing injection pressure, experimental ignition delay increased as a result of improvement in fuel and air mixing effects. Also the palm oil biodiesel has a shorter ignition delay compared to waste cooked oil biodiesel. This phenomenon could be attributed to the higher cetane number of palm biodiesel. The fuel spray ignition properties depend on both the physical ignition delay and chemical ignition delay. From the detailed chemical kinetic results it was observed that at the low temperature, high ambient pressure conditions reactivity increased as equivalent ratio

  8. Modelling cycle to cycle variations in an SI engine with detailed chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Etheridge, Jonathan; Mosbach, Sebastian; Kraft, Markus [Department of Chemical Engineering and Biotechnology, University of Cambridge (United Kingdom); Wu, Hao; Collings, Nick [Department of Engineering, University of Cambridge (United Kingdom)

    2011-01-15

    This paper presents experimental results and a new computational model that investigate cycle to cycle variations (CCV) in a spark ignition (SI) engine. An established stochastic reactor model (SRM) previously used to examine homogeneous charge compression ignition (HCCI) combustion has been extended by spark initiation, flame propagation and flame termination sub-models in order to simulate combustion in SI engines. The model contains a detailed chemical mechanism but relatively short computation times are achieved. The flame front is assumed to be spherical and centred at the spark location, and a pent roof and piston bowl geometry are accounted for. The model is validated by simulating the pressure profile and emissions from an iso-octane fuelled single cylinder research engine that showed low CCV. The effects of key parameters are investigated. Experimental results that show cycle to cycle fluctuations in a four-cylinder naturally aspirated gasoline fuelled SI engine are presented. The model is then coupled with GT-Power, a one-dimensional engine simulation tool, which is used to simulate the breathing events during a multi-cycle simulation. This allows an investigation of the cyclic fluctuations in peak pressure. The source and magnitude of nitric oxide (NO) emissions produced by different cycles are then investigated. It was found that faster burning cycles result in increased NO emissions compared with cycles that have a slower rate of combustion and that more is produced in the early stages of combustion compared with later in the cycle. The majority of NO was produced via the thermal mechanism just after combustion begins. (author)

  9. A Plan for the Development of the Spatial Kinetics and the Detailed Reactivity Model for a Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Y. M.; Jeong, H. Y.; Lee, Y. B.; Sim, Y. S

    2005-11-15

    The reactivity feedback effect of metallic fuel is determined by the fuel burnup characteristics, the configuration of core and fuel assembly, and the complicated interaction between the fuel assembly and core internal structures. Currently, a quite simple evaluation model is frequently applied for the calculation of reactivity feedback. The simple model usually induces some over-conservatism to compensate the simplification, which is an obstacle to take advantage of the positive characteristics of metallic fuel over the oxide fuel. Therefore, to develop a detailed reactivity feedback model and to remove the over-conservatism in the existing simple model would be the foundation to strengthen the economic and operational competitiveness of a liquid metal-cooled fast reactor. In the present study, the plan for the development of the detailed reactivity feedback model and the methodology to combine the spatial kinetics code with the thermal-hydraulic code have been set up, which are two prerequisites for the evaluation of the detailed reactivity feedback effect. The proposed detailed model is expected to be developed in short-term, thus, easily implemented in the SSC-K code. The development of the spatial kinetics code and the merging it to the detailed thermal-hydraulics code would be achieved in long-term, but finally minimize the uncertainty in the reactivity feedback evaluation by including the detailed thermal-hydraulic information in the reactivity calculation.

  10. Potential and kinetic shaping for control of underactuated mechanical systems

    OpenAIRE

    Bloch, Anthony M.; Leonard, Naomi Ehrich; Chang, Dong Eui; Marsden, Jerrold E.

    2000-01-01

    This paper combines techniques of potential shaping with those of kinetic shaping to produce some new methods for stabilization of mechanical control systems. As with each of the techniques themselves, our method employs energy methods and the LaSalle invariance principle. We give explicit criteria for asymptotic stabilization of equilibria of mechanical systems which, in the absence of controls, have a kinetic energy function that is invariant under an Abelian group.

  11. 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.

  12. Insights into Coupled Folding and Binding Mechanisms from Kinetic Studies.

    Science.gov (United States)

    Shammas, Sarah L; Crabtree, Michael D; Dahal, Liza; Wicky, Basile I M; Clarke, Jane

    2016-03-25

    Intrinsically disordered proteins (IDPs) are characterized by a lack of persistent structure. Since their identification more than a decade ago, many questions regarding their functional relevance and interaction mechanisms remain unanswered. Although most experiments have taken equilibrium and structural perspectives, fewer studies have investigated the kinetics of their interactions. Here we review and highlight the type of information that can be gained from kinetic studies. In particular, we show how kinetic studies of coupled folding and binding reactions, an important class of signaling event, are needed to determine mechanisms.

  13. Systems biology from micro-organisms to human metabolic diseases: the role of detailed kinetic models.

    Science.gov (United States)

    Bakker, Barbara M; van Eunen, Karen; Jeneson, Jeroen A L; van Riel, Natal A W; Bruggeman, Frank J; Teusink, Bas

    2010-10-01

    Human metabolic diseases are typically network diseases. This holds not only for multifactorial diseases, such as metabolic syndrome or Type 2 diabetes, but even when a single gene defect is the primary cause, where the adaptive response of the entire network determines the severity of disease. The latter may differ between individuals carrying the same mutation. Understanding the adaptive responses of human metabolism naturally requires a systems biology approach. Modelling of metabolic pathways in micro-organisms and some mammalian tissues has yielded many insights, qualitative as well as quantitative, into their control and regulation. Yet, even for a well-known pathway such as glycolysis, precise predictions of metabolite dynamics from experimentally determined enzyme kinetics have been only moderately successful. In the present review, we compare kinetic models of glycolysis in three cell types (African trypanosomes, yeast and skeletal muscle), evaluate their predictive power and identify limitations in our understanding. Although each of these models has its own merits and shortcomings, they also share common features. For example, in each case independently measured enzyme kinetic parameters were used as input. Based on these 'lessons from glycolysis', we will discuss how to make best use of kinetic computer models to advance our understanding of human metabolic diseases.

  14. Carbothermal reduction kinetics of mechanically activated chromite with graphite

    OpenAIRE

    Kenan Yıldız

    2011-01-01

    The carbothermal reduction kinetics of mechanically activated chromite with graphite under an argon atmosphere was investigated at temperatures between 1100 and 1400°C. Zhuravlev-Lesokhin-Tempelman (ZLT) method was used in the reduction kinetics for non-activated chromite and the activation energy was calculated as 401.7 kJ/mol. Solid-state diffusion method was used in the reduction kinetics for 60 min-activated chromite and the activation energy was calculated as 283.3 kJ/mol. This decrease ...

  15. Kinetic mechanism of streptomycin adenylyltransferase from a recombinant Escherichia coli.

    Science.gov (United States)

    Jana, Snehasis; Deb, J K

    2005-04-01

    Bacterial resistance to the aminoglycoside antibiotics is manifested primarily by enzymic modification of these drugs. One important mechanism of streptomycin modification is through ATP-dependent O-adenylation, catalyzed by streptomycin adenylyltransferase. Initial velocity patterns deduced from steady state kinetics indicate a sequential mechanism. Dead-end inhibition by tobramycin and neomycin is non-competitive versus streptomycin and uncompetitive versus ATP, indicative of ordered substrate binding where ATP binds first and then streptomycin. These results surmise that streptomycin adenylyltransferase follows an ordered, sequential kinetic mechanism in which one substrate (ATP) binds prior to the antibiotic and pyrophosphate is released prior to formation of AMP-streptomycin.

  16. Enzymatic hydrolysis of microcrystalline cellulose and pretreated wheat straw: a detailed comparison using convenient kinetic analysis.

    Science.gov (United States)

    Monschein, Mareike; Reisinger, Christoph; Nidetzky, Bernd

    2013-01-01

    Marked slow-down of soluble sugar production at low degree of substrate conversion limits the space-time yield of enzymatic hydrolysis of ligno-cellulosic materials. A simple set of kinetic descriptors was developed to compare reducing sugar release from pure crystalline cellulose (Avicel) and pretreated wheat straw by Trichoderma reesei cellulase at 50 °C. The focus was on the rate-retarding effect of maximum hydrolysis rate at reaction start (r(max)), limiting hydrolysis rate (r(lim)) at extended reaction time (24h), and substrate conversion, marking the transition between the r(max) and r(lim) kinetic regimes (C(trans)). At apparent saturation of substrate (12.2g cellulose/L) with enzyme, r(max) for pretreated wheat straw (~9.6g/L/h) surpassed that for Avicel by about 1.7-fold whereas their r(lim) were almost identical (~0.15 g/L/h). C(trans) roughly doubled as enzyme/substrate loading was increased from 3.8 to 75FPU/g, suggesting C(trans) to be a complex manifestation of cellulase-cellulose interaction, not an intrinsic substrate property. A low-temperature adsorption step preceding hydrolysis at 50 °C resulted in enhanced cellulase binding at reaction start without increasing r(max). C(trans) was higher for pretreated wheat straw (~30%) than for Avicel (~20%) under these conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Kinetic mechanism of indole-3-glycerol phosphate synthase.

    Science.gov (United States)

    Schlee, Sandra; Dietrich, Susanne; Kurćon, Tomasz; Delaney, Pamela; Goodey, Nina M; Sterner, Reinhard

    2013-01-08

    The (βα)(8)-barrel enzyme indole-3-glycerol phosphate synthase (IGPS) catalyzes the multistep transformation of 1-(o-carboxyphenylamino)-1-deoxyribulose 5-phosphate (CdRP) into indole-3-glycerol phosphate (IGP) in tryptophan biosynthesis. Mutagenesis data and crystal structure analysis of IGPS from Sulfolobus solfataricus (sIGPS) allowed for the formulation of a plausible chemical mechanism of the reaction, and molecular dynamics simulations suggested that flexibility of active site loops might be important for catalysis. Here we developed a method that uses extrinsic fluorophores attached to active site loops to connect the kinetic mechanism of sIGPS to structure and conformational motions. Specifically, we elucidated the kinetic mechanism of sIGPS and correlated individual steps in the mechanism to conformational motions of flexible loops. Pre-steady-state kinetic measurements of CdRP to IGP conversion monitoring changes in intrinsic tryptophan and IGP fluorescence provided a minimal three-step kinetic model in which fast substrate binding and chemical transformation are followed by slow product release. The role of sIGPS loop conformational motion during substrate binding and catalysis was examined via variants that were covalently labeled with fluorescent dyes at the N-terminal extension of the enzyme and mobile active site loop β1α1. Analysis of kinetic data monitoring dye fluorescence revealed a conformational change that follows substrate binding, suggesting an induced-fit-type binding mechanism for the substrate CdRP. Global fitting of all kinetic results obtained with wild-type sIGPS and the labeled variants was best accommodated by a four-step kinetic model. In this model, both the binding of CdRP and its on-enzyme conversion to IGP are accompanied by conformational transitions. The liberation of the product from the active site is the rate-limiting step of the overall reaction. Our results confirm the importance of flexible active loops for substrate

  18. Mechanisms and Kinetics of Diphthalocyanine Electrode Processes.

    Science.gov (United States)

    1983-07-01

    Science and Engineering, to be published by Pergamon Press in 1983. In condensed style, this paper describes electrochromic display devices and their...operating mechanisms and compares the electrochromic materials tungsten oxide, iridium oxide, n-heptyl viologen bromide, rare-earth diphthalocyanines...Scheme .. .. ... .... 14 E. Electrochromics .. .. ... ... ... ... . .. ..... 21 *F. Multicolor Electrochromic Display Technology .. .. ...... 22 S.IV

  19. Sensitivity of natural gas HCCI combustion to fuel and operating parameters using detailed kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Aceves, S; Dibble, R; Flowers, D; Smith, J R; Westbrook, C K

    1999-07-19

    This paper uses the HCT (Hydrodynamics, Chemistry and Transport) chemical kinetics code to analyze natural gas HCCI combustion in an engine. The HCT code has been modified to better represent the conditions existing inside an engine, including a wall heat transfer correlation. Combustion control and low power output per displacement remain as two of the biggest challenges to obtaining satisfactory performance out of an HCCI engine, and these are addressed in this paper. The paper considers the effect of natural gas composition on HCCI combustion, and then explores three control strategies for HCCI engines: DME (dimethyl ether) addition, intake heating and hot EGR addition. The results show that HCCI combustion is sensitive to natural gas composition, and an active control may be required to compensate for possible changes in composition. The three control strategies being considered have a significant effect in changing the combustion parameters for the engine, and should be able to control HCCI combustion.

  20. Interactions between polyphenols in thinned young apples and porcine pancreatic α-amylase: Inhibition, detailed kinetics and fluorescence quenching.

    Science.gov (United States)

    Sun, Lijun; Chen, Weiqi; Meng, Yonghong; Yang, Xingbin; Yuan, Li; Guo, Yurong

    2016-10-01

    Young apple polyphenols (YAP) and nine types of phenolic compounds were investigated regarding the inhibitory activity against porcine pancreatic α-amylase (PPA) in vitro. Tannic acid, chlorogenic acid and caffeic acid in YAP showed relatively high inhibition with the IC50 values of 0.30, 1.96 and 3.69mg/mL, respectively. A detailed kinetics of inhibition study revealed that YAP and tannic acid were competitive inhibitors of PPA, whereas chlorogenic acid and caffeic acid were mixed inhibitors, exhibiting both competitive and uncompetitive characteristics. The fluorescence of PPA could be significantly quenched by YAP and the three polyphenols, and their quenching constants were determined. The results showed that for the polyphenols investigated, the order of the apparent static quenching constants (KFQ) was in agreement with that of the reciprocal competitive inhibition constants (1/Kic) (tannic acid>chlorogenic acid>caffeic acid>epicatechin); both of the parameters were contrary to the order of the IC50 values. Thus, combining detailed kinetics and fluorescence quenching studies can be applied to characterise the interactions between polyphenols in young apples and α-amylase.

  1. Enzymatic hydrolysis of protein:mechanism and kinetic model

    Institute of Scientific and Technical Information of China (English)

    Qi Wei; He Zhimin

    2006-01-01

    The bioreaction mechanism and kinetic behavior of protein enzymatic hydrolysis for preparing active peptides were investigated to model and characterize the enzymatic hydrolysis curves.Taking into account single-substrate hydrolysis,enzyme inactivation and substrate or product inhibition,the reaction mechanism could be deduced from a series of experimental results carried out in a stirred tank reactor at different substrate concentrations,enzyme concentrations and temperatures based on M-M equation.An exponential equation dh/dt = aexp(-bh) was also established,where parameters a and b have different expressions according to different reaction mechanisms,and different values for different reaction systems.For BSA-trypsin model system,the regressive results agree with the experimental data,i.e.the average relative error was only 4.73%,and the reaction constants were determined as Km = 0.0748 g/L,Ks = 7.961 g/L,kd = 9.358/min,k2 =38.439/min,Ea= 64.826 kJ/mol,Ed= 80.031 kJ/mol in accordance with the proposed kinetic mode.The whole set of exponential kinetic equations can be used to model the bioreaction process of protein enzymatic hydrolysis,to calculate the thermodynamic and kinetic constants,and to optimize the operating parameters for bioreactor design.

  2. Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations

    CERN Document Server

    Sirjean, Baptiste; Ruiz-Lopez, M F; Fournet, Ren{é}

    2006-01-01

    This work reports a theoretical study of the gas phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data (\\delta H^0_f, S^0, C^0_p) for all the involved species have been obtained by means of isodesmic reactions. The contribution of hindered rotors has also been included. Activation barriers of each reaction have been analyzed to assess the 1 energetically most favorable pathways for the decomposition of biradicals. Rate constants have been derived for all elementary reactions using transition state theory at 1 atm and temperatures ranging from 600 to 2000 K. Global rate constant for the decomposition of the cyclic alkanes in molecular products have been calculated. Comparison between calculated and experimental results allowed to validate the ...

  3. Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations.

    Science.gov (United States)

    Sirjean, B; Glaude, P A; Ruiz-Lopez, M F; Fournet, R

    2006-11-23

    This work reports a theoretical study of the gas-phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data(DeltaHf(o), S(o), Cp(o)) for all the involved species have been obtained by means of isodesmic reactions. The contribution of hindered rotors has also been included. Activation barriers of each reaction have been analyzed to assess the energetically most favorable pathways for the decomposition of biradicals. Rate constants have been derived for all elementary reactions using transition-state theory at 1 atm and temperatures ranging from 600 to 2000 K. Global rate constant for the decomposition of the cyclic alkanes in molecular products have been calculated. Comparison between calculated and experimental results allowed us to validate the theoretical approach. An important result is that the rotational barriers between the conformers, which are usually neglected, are of importance in decomposition rate of the largest biradicals. Ring strain energies (RSE) in transition states for ring opening have been estimated and show that the main part of RSE contained in the cyclic reactants is removed upon the activation process.

  4. DETAILED CHEMICAL KINETIC MODELING OF ISO-OCTANE SI-HCCI TRANSITION

    Energy Technology Data Exchange (ETDEWEB)

    Havstad, M A; Aceves, S M; McNenly, M J; Piggott, W T; Edwards, K D; Wagner, R M; Daw, C S; Finney, C A

    2009-10-12

    The authors describe a CHEMKIN-based multi-zone model that simulates the expected combustion variations in a single-cylinder engine fueled with iso-octane as the engine transitions from spark-ignited (ST) combustion to homogeneous charge compression ignition (HCCI) combustion. The model includes a 63-species reaction mechanism and mass and energy balances for the cylinder and the exhaust flow. For this study they assumed that the SI-to-HCCI transition is implemented by means of increasing the internal exhaust gas recirculation (EGR) at constant engine speed. This transition scneario is consistent with that implemented in previously reported experimental measurements on an experimental engine equipped with variable valve actuation. They find that the model captures many of the important experimental trends, including stable SI combustion at low EGR ({approx} 0.10), a transition to highly unstable combustion at intermediate EGR, and finally stable HCCI combustion at very high EGR ({approx} 0.75). Remaining differences between the predicted and experimental instability patterns indicate that there is further room for model improvement.

  5. Construction and validation of detailed kinetic models for the combustion of gasoline surrogates; Construction et validation de modeles cinetiques detailles pour la combustion de melanges modeles des essences

    Energy Technology Data Exchange (ETDEWEB)

    Touchard, S.

    2005-10-15

    The irreversible reduction of oil resources, the CO{sub 2} emission control and the application of increasingly strict standards of pollutants emission lead the worldwide researchers to work to reduce the pollutants formation and to improve the engine yields, especially by using homogenous charge combustion of lean mixtures. The numerical simulation of fuel blends oxidation is an essential tool to study the influence of fuel formulation and motor conditions on auto-ignition and on pollutants emissions. The automatic generation helps to obtain detailed kinetic models, especially at low temperature, where the number of reactions quickly exceeds thousand. The main purpose of this study is the generation and the validation of detailed kinetic models for the oxidation of gasoline blends using the EXGAS software. This work has implied an improvement of computation rules for thermodynamic and kinetic data, those were validated by numerical simulation using CHEMKIN II softwares. A large part of this work has concerned the understanding of the low temperature oxidation chemistry of the C5 and larger alkenes. Low and high temperature mechanisms were proposed and validated for 1 pentene, 1-hexene, the binary mixtures containing 1 hexene/iso octane, 1 hexene/toluene, iso octane/toluene and the ternary mixture of 1 hexene/toluene/iso octane. Simulations were also done for propene, 1-butene and iso-octane with former models including the modifications proposed in this PhD work. If the generated models allowed us to simulate with a good agreement the auto-ignition delays of the studied molecules and blends, some uncertainties still remains for some reaction paths leading to the formation of cyclic products in the case of alkenes oxidation at low temperature. It would be also interesting to carry on this work for combustion models of gasoline blends at low temperature. (author)

  6. Fundamentally excited flow past a surface-mounted rib. Part II: Kinetic energy budget details

    Indian Academy of Sciences (India)

    P K Panigrahi

    2001-10-01

    This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence contributions after the reattachment region are from the large-scale structures contrary to the belief that mostly random turbulent structures are present after reattachment. The dissipation is not a small-scale phenomena only. It may result due to the interaction between large-scale structures. From the results of higher order moments, the outer edge of the shear layer is observed to be non-Gaussian in nature with significant deviation from the Gaussian skewness and flatness value. The kinetic energy budget results show positive intermodal production in the outer edge of the shear layer indicating the presence of back scattering. The non-Gaussian velocity distribution, ejection motions and back-scattering present in the outer shear layer may be conjectured to be correlated with each other.

  7. 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 re...

  8. Mechanism of protein kinetic stabilization by engineered disulfide crosslinks.

    Directory of Open Access Journals (Sweden)

    Inmaculada Sanchez-Romero

    Full Text Available The impact of disulfide bonds on protein stability goes beyond simple equilibrium thermodynamics effects associated with the conformational entropy of the unfolded state. Indeed, disulfide crosslinks may play a role in the prevention of dysfunctional association and strongly affect the rates of irreversible enzyme inactivation, highly relevant in biotechnological applications. While these kinetic-stability effects remain poorly understood, by analogy with proposed mechanisms for processes of protein aggregation and fibrillogenesis, we propose that they may be determined by the properties of sparsely-populated, partially-unfolded intermediates. Here we report the successful design, on the basis of high temperature molecular-dynamics simulations, of six thermodynamically and kinetically stabilized variants of phytase from Citrobacter braakii (a biotechnologically important enzyme with one, two or three engineered disulfides. Activity measurements and 3D crystal structure determination demonstrate that the engineered crosslinks do not cause dramatic alterations in the native structure. The inactivation kinetics for all the variants displays a strongly non-Arrhenius temperature dependence, with the time-scale for the irreversible denaturation process reaching a minimum at a given temperature within the range of the denaturation transition. We show this striking feature to be a signature of a key role played by a partially unfolded, intermediate state/ensemble. Energetic and mutational analyses confirm that the intermediate is highly unfolded (akin to a proposed critical intermediate in the misfolding of the prion protein, a result that explains the observed kinetic stabilization. Our results provide a rationale for the kinetic-stability consequences of disulfide-crosslink engineering and an experimental methodology to arrive at energetic/structural descriptions of the sparsely populated and elusive intermediates that play key roles in irreversible

  9. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2005-01-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  10. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2004-09-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature has been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  11. Kinetic modelling and mechanism of dye adsorption on unburned carbon

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S.B.; Li, H.T. [Curtin University of Technology, Perth, WA (Australia). Dept. of Chemical Engineering

    2007-07-01

    Textile dyeing processes are among the most environmentally unfriendly industrial processes by producing coloured wastewaters. The adsorption method using unburned carbon from coal combustion residue was studied for the decolourisation of typical acidic and basic dyes. It was discovered that the unburned carbon showed high adsorption capacity at 1.97 x 10{sup -4} and 5.27 x 10{sup -4} mol/g for Basic Violet 3 and Acid Black 1, respectively. The solution pH, particle size and temperature significantly influenced the adsorption capacity. Higher solution pH favoured the adsorption of basic dye while reduced the adsorption of acid dye. The adsorption of dye increased with increasing temperature but decreased with increasing particle size. Sorption kinetic data indicated that the adsorption kinetics followed the pseudo-second-order model. The adsorption mechanism consisted of two processes, external diffusion and intraparticle diffusion, and the external diffusion was the dominating process.

  12. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien

    2012-10-16

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines. © 2012 American Chemical Society.

  13. Reaction route graphs. III. Non-minimal kinetic mechanisms.

    Science.gov (United States)

    Fishtik, Ilie; Callaghan, Caitlin A; Datta, Ravindra

    2005-02-24

    The concept of reaction route (RR) graphs introduced recently by us for kinetic mechanisms that produce minimal graphs is extended to the problem of non-minimal kinetic mechanisms for the case of a single overall reaction (OR). A RR graph is said to be minimal if all of the stoichiometric numbers in all direct RRs of the mechanism are equal to +/-1 and non-minimal if at least one stoichiometric number in a direct RR is non-unity, e.g., equal to +/-2. For a given mechanism, four unique topological characteristics of RR graphs are defined and enumerated, namely, direct full routes (FRs), empty routes (ERs), intermediate nodes (INs), and terminal nodes (TNs). These are further utilized to construct the RR graphs. One algorithm involves viewing each IN as a central node in a RR sub-graph. As a result, the construction and enumeration of RR graphs are reduced to the problem of balancing the peripheral nodes in the RR sub-graphs according to the list of FRs, ERs, INs, and TNs. An alternate method involves using an independent set of RRs to draw the RR graph while satisfying the INs and TNs. Three examples are presented to illustrate the application of non-minimal RR graph theory.

  14. An MPI-CUDA approach for hypersonic flows with detailed state-to-state air kinetics using a GPU cluster

    Science.gov (United States)

    Bonelli, Francesco; Tuttafesta, Michele; Colonna, Gianpiero; Cutrone, Luigi; Pascazio, Giuseppe

    2017-10-01

    This paper describes the most advanced results obtained in the context of fluid dynamic simulations of high-enthalpy flows using detailed state-to-state air kinetics. Thermochemical non-equilibrium, typical of supersonic and hypersonic flows, was modeled by using both the accurate state-to-state approach and the multi-temperature model proposed by Park. The accuracy of the two thermochemical non-equilibrium models was assessed by comparing the results with experimental findings, showing better predictions provided by the state-to-state approach. To overcome the huge computational cost of the state-to-state model, a multiple-nodes GPU implementation, based on an MPI-CUDA approach, was employed and a comprehensive code performance analysis is presented. Both the pure MPI-CPU and the MPI-CUDA implementations exhibit excellent scalability performance. GPUs outperform CPUs computing especially when the state-to-state approach is employed, showing speed-ups, of the single GPU with respect to the single-core CPU, larger than 100 in both the case of one MPI process and multiple MPI process.

  15. Kinetics and mechanism of the oxidation of amaranth with hypochlorite.

    Science.gov (United States)

    Nadupalli, S; Koorbanally, N; Jonnalagadda, S B

    2011-07-14

    The reaction mechanism of the oxidation of Amaranth dye (2-hydroxy-1-(4-sulfonato-1-naphthylazo) naphthalene-3,6-disulfonate) with hypochlorite under varied pH conditions was elucidated by a kinetic approach. Under excess concentration of oxidant, the reaction followed pseudo-first-order kinetics with respect to Amaranth, and the oxidation was found to occur through two competitive reactions, initiated by hypochlorite and hypochlorous acid. The reaction order with respect to both OCl(-) ion and HOCl was unity. While the latter reaction was fast, the significance of the oxidation paths depended on the relative concentration of the two oxidizing species, which was dictated by the reaction pH. The role of the H(+) ion in the reaction was established. For the hypochlorite ion and hypochlorous acid facilitated reactions, the second-order rate coefficients were 1.9 and 23.2 M(-1) s(-1), respectively. The energy parameters were E(a) = 33.7 kJ mol(-1), ΔH(‡) = 31.2 kJ mol(-1) and ΔS(‡) = -190.6 J K(-1) mol(-1) for the OCl(-) ion-driven oxidation, and E(a) = 26.9 kJ mol(-1), ΔH(‡) = 24.3 kJ mol(-1) and ΔS(‡) = -222.8 J K(-1) mol(-1) for the reaction with HOCl-initiated oxidation. The major oxidation products for both the pathways were 3,4-dihydroxy naphthalene-2,7-disulfonic sodium salt (P(1)), dichloro-1,4-naphthoquione (P(2)) and naphtha(2,3)oxirene-2, 3-dione (P(3)). On the basis of the primary salt effect and other kinetic data, the rate law for the overall reaction and probable reaction mechanism was elucidated. The proposed mechanism was validated by simulations using Simkine-2.

  16. Kinetic mechanism of putrescine oxidase from Rhodococcus erythropolis.

    Science.gov (United States)

    Kopacz, Malgorzata M; Heuts, Dominic P H M; Fraaije, Marco W

    2014-10-01

    Putrescine oxidase from Rhodococcus erythropolis (PuO) is a flavin-containing amine oxidase from the monoamine oxidase family that performs oxidative deamination of aliphatic diamines. In this study we report pre-steady-state kinetic analyses of the enzyme with the use of single- and double-mixing stopped-flow spectroscopy and putrescine as a substrate. During the fast and irreversible reductive half-reaction no radical intermediates were observed, suggesting a direct hydride transfer from the substrate to the FAD. The rate constant of flavin reoxidation depends on the ligand binding; when the imine product was bound to the enzyme the rate constant was higher than with free enzyme species. Similar results were obtained with product-mimicking ligands and this indicates that a ternary complex is formed during catalysis. The obtained kinetic data were used together with steady-state rate equations derived for ping-pong, ordered sequential and bifurcated mechanisms to explore which mechanism is operative. The integrated analysis revealed that PuO employs a bifurcated mechanism due to comparable rate constants of product release from the reduced enzyme and reoxidation of the reduced enzyme-product complex.

  17. Kinetics and Mechanism of Bacterial Disinfection by Chlorine Dioxide1

    Science.gov (United States)

    Benarde, Melvin A.; Snow, W. Brewster; Olivieri, Vincent P.; Davidson, Burton

    1967-01-01

    Survival data are presented for a fecal strain of Escherichia coli exposed to three concentrations of chlorine dioxide at four temperatures. Chick's first-order reaction equation is generalized to a pseudo nth-order model. Nonlinear least squares curve-fitting of the survival data to the nth order model was performed on an analogue computer. The data were observed to follow fractional order kinetics with respect to survival concentration, with an apparent activation energy of 12,000 cal/mole. Initial experiments support the thesis that the mechanism of chlorine dioxide kill occurs via disruption of protein synthesis. Images Fig. 1 Fig. 2 Fig. 3 PMID:5339839

  18. Kinetic mechanism of the activation of human plasminogen by streptokinase.

    Science.gov (United States)

    Kosow, D P

    1975-10-07

    A method of determining the initial rate of plasminogen activation has been developed. The method has been used to investigate the mechanism of activation of human plasminogen by streptokinase. Plasmin formation follows saturation kinetics. Inhibition of plasmin formation by epsilon-aminocaproic acid is uncompetitive with a Ki of 0.6 mM. A model consistent with the data is that streptokinase induces a conformational change in the plasminogen molecule, producing an active center which cleaves an internal peptide bond to produce plasmin. Thus, streptokinase functions as a catalytic allosteric effector.

  19. Mechanism and kinetics analysis of AlN combustion synthesis

    Institute of Scientific and Technical Information of China (English)

    郑永挺; 张宇民; 赫晓东; 刘长青

    2004-01-01

    Mechanism of AlN combustion synthesis was studied by DSC analysis and "quenching" experiment of combustion wave. In preheating region, Al powder melted at 660 ℃ and became spherical because of surface tension. In reaction region, Al volatilized rapidly at 1 000 ℃ and Al vapor reacted with N2 to form AlN, which nucleated and grew on the surface of AlN formed precedently as a diluent. Based on the experiment analysis,kinetics equations and modeling were established. Analysis showed the dramatic effect of temperature, aluminum particle size and nitrogen pressure on the reaction speed.

  20. Evaluation of a Detailed Reaction Mechanism for Partial and Total Oxidation of C1 - C4 Alkanes

    OpenAIRE

    Quiceno González, Raúl

    2007-01-01

    In the present work a chemical kinetic mechanism was developed, suitable for modeling combustion and partial oxidation processes of C1 – C4 alkanes. The gas-phase kinetic mechanism describes intermediate and high temperature chemistry. Accordingly, the formation and evolution of important intermediate gas-phase species: Olefins and oxygenates were described in terms of different pathways typical at those temperature regimes. A previously developed mechanism suitable for high temperature condi...

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

    Science.gov (United States)

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

    2013-08-01

    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.

  2. 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.

  3. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  4. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  5. Mechanism and kinetics of 2-chlorophenol degradation in drinking water by photo-electrochemical synergic effect

    Institute of Scientific and Technical Information of China (English)

    SONG; Qiang; (宋; 强); QU; Jiuhui; (曲久辉)

    2003-01-01

    The synergic effect mechanism of photo-electrochemical oxidation is investigated in detail through reaction products and kinetics analysis in a photo-electric integral reactor with 2-chlorophenol (2-CP) as the model pollutant. A kinetics model is constructed for the combinatorial photo-electrochemical (CPE) degradation. A remarkable synergetic effect, which can significantly enhance the mineralization rate of the CPE process, is verified by the comparison of apparent kinetic constants. In the CPE process, complemental effects with multi-level and multi-pathway for pollutants degradation under our experimental conditions are speculated. It is proved that the degradation pathways are not only the simple summation of that of photolysis and electrolysis, but the formation of synergic effect through combination of several new acting approaches. The degradation efficiency is enhanced considerably by three factors, control of electrode poisoning by the UV irradiation, control of excitation and reaction trend of pollutants molecules by the UV irradiation, and control of activation effect and transfer trend by the oriented direct current (DC) electric field. An advanced oxidation system is set up through manifold of free radicals chain reactions in the CPE reactions, so that the aqueous organics can be mineralized fast and completely. It is proven by the kinetics analysis that the mineralization of organic pollutants is mainly attributed to the generation of very active hydroxyl radicals (OH@) in bulk solution from the CPE synergetic effect.

  6. Kinetic calculations and mechanism definition for reactions in an ammonium perchlorate flame

    Energy Technology Data Exchange (ETDEWEB)

    Ermolin, N.E.; Fomin, V.M.; Korobeinichev, O.P.; Tereshchenko, A.G.

    1982-09-01

    This article reports on detailed calculations on the reaction kinetics in APC flames on the basis of a wide set of possible reactions and experimental data on the initial composition of the gas mixture (gasification products from APC). The purpose is to select the most important reactions in this system by comparing the calculations on the kinetics with experimental data on the concentration profiles in APC flames. Discusses kinetic equations; rate constants as the reaction mechanism; results from kinetic calculations; and identification of major stages. A laminar flame such as that provided by ammonium perchlorate is described in general form by a system of differential equations that incorporate the transport of heat and matter in the presence of chemical reactions. APC is a system consisting of 4 elements (N,H,Cl and O). Points out that the scheme enables one to determine which reactions are responsible for producing the final products. Suggests that in the future one will be able to analyze experimental data on the reaction-rate profiles for stable components in order to determine either the atom and radical concentrations or the rate constants of the reactions involving them.

  7. Reaction kinetics, molecular action, and mechanisms of cellulolytic proteins.

    Science.gov (United States)

    Mosier, N S; Hall, P; Ladisch, C M; Ladisch, M R

    1999-01-01

    Cellulolytic proteins form a complex of enzymes that work together to depolymerize cellulose to the soluble products cellobiose and glucose. Fundamental studies on their molecular mechanisms have been facilitated by advances in molecular biology. These studies have shown homology between cellulases from different microorganisms, and common mechanisms between enzymes whose modes of action have sometimes been viewed as being different, as suggested by the distribution of soluble products. A more complete picture of the cellulolytic action of these proteins has emerged and combines the physical and chemical characteristics of solid cellulose substrates with the specialized structure and function of the cellulases that break it down. This chapter combines the fundamentals of cellulose structure with enzyme function in a manner that relates the cellulose binding and biochemical kinetics at the catalytic site of the proteins to the macroscopic behavior of cellulase enzyme systems.

  8. Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

    Science.gov (United States)

    Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

    2014-07-07

    An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

  9. MULTI-WORLD MECHANISM FOR MODELING EVOLUTIONARY DESIGN PROCESS FROM CONCEPTUAL DESIGN TO DETAILED DESIGN

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A multi-world mechanism is developed for modeling evolutionary design process from conceptual design to detailed design. In this mechanism, the evolutionary design database is represented by a sequence of worlds corresponding to the design descriptions at different design stages. In each world, only the differences with its ancestor world are recorded. When the design descriptions in one world are changed, these changes are then propagated to its descendant worlds automatically. Case study is conducted to show the effectiveness of this evolutionary design database model.

  10. Reduced kinetic mechanism of n-heptane oxidation in modeling polycyclic aromatic hydrocarbon formation in opposed-flow diffusion flames

    Institute of Scientific and Technical Information of China (English)

    Beijing ZHONG; Jun XI

    2008-01-01

    A reduced mechanism, which could couple with the multidimensional computational fluid dynamics code for quantitative description of a reacting flow, was developed for chemical kinetic modeling of polycyclic aro-matic hydrocarbon formation in an opposed-flow dif-fusion flame. The complete kinetic mechanism, which comprises 572 reactions and 108 species, was reduced to a simplified mechanism that includes only 83 reactions and 56 species through sensitivity analysis. The results computed via this reduced mechanism are nearly indistin-guishable from those via the detailed mechanism, which demonstrate that the model based on this reduced mech-anism can properly describe n-heptane oxidation chem-istry and quantitatively predict polycyclic aromatic hydrocarbon (such as benzene, naphthalene, phenan-threne and pyrene) formation in opposed-flow diffusion flames.

  11. Mechanics, thermodynamics, and kinetics of ligand binding to biopolymers.

    Science.gov (United States)

    Jarillo, Javier; Morín, José A; Beltrán-Heredia, Elena; Villaluenga, Juan P G; Ibarra, Borja; Cao, Francisco J

    2017-01-01

    Ligands binding to polymers regulate polymer functions by changing their physical and chemical properties. This ligand regulation plays a key role in many biological processes. We propose here a model to explain the mechanical, thermodynamic, and kinetic properties of the process of binding of small ligands to long biopolymers. These properties can now be measured at the single molecule level using force spectroscopy techniques. Our model performs an effective decomposition of the ligand-polymer system on its covered and uncovered regions, showing that the elastic properties of the ligand-polymer depend explicitly on the ligand coverage of the polymer (i.e., the fraction of the polymer covered by the ligand). The equilibrium coverage that minimizes the free energy of the ligand-polymer system is computed as a function of the applied force. We show how ligands tune the mechanical properties of a polymer, in particular its length and stiffness, in a force dependent manner. In addition, it is shown how ligand binding can be regulated applying mechanical tension on the polymer. Moreover, the binding kinetics study shows that, in the case where the ligand binds and organizes the polymer in different modes, the binding process can present transient shortening or lengthening of the polymer, caused by changes in the relative coverage by the different ligand modes. Our model will be useful to understand ligand-binding regulation of biological processes, such as the metabolism of nucleic acid. In particular, this model allows estimating the coverage fraction and the ligand mode characteristics from the force extension curves of a ligand-polymer system.

  12. Complete kinetic mechanism for recycling of the bacterial ribosome.

    Science.gov (United States)

    Borg, Anneli; Pavlov, Michael; Ehrenberg, Måns

    2016-01-01

    How EF-G and RRF act together to split a post-termination ribosomal complex into its subunits has remained obscure. Here, using stopped-flow experiments with Rayleigh light scattering detection and quench-flow experiments with radio-detection of GTP hydrolysis, we have clarified the kinetic mechanism of ribosome recycling and obtained precise estimates of its kinetic parameters. Ribosome splitting requires that EF-G binds to an already RRF-containing ribosome. EF-G binding to RRF-free ribosomes induces futile rounds of GTP hydrolysis and inhibits ribosome splitting, implying that while RRF is purely an activator of recycling, EF-G acts as both activator and competitive inhibitor of RRF in recycling of the post-termination ribosome. The ribosome splitting rate and the number of GTPs consumed per splitting event depend strongly on the free concentrations of EF-G and RRF. The maximal recycling rate, here estimated as 25 sec(-1), is approached at very high concentrations of EF-G and RRF with RRF in high excess over EF-G. The present in vitro results, suggesting an in vivo ribosome recycling rate of ∼5 sec(-1), are discussed in the perspective of rapidly growing bacterial cells.

  13. Kinetics mechanism of microwave sintering in ceramic materials

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Based on the traditional sintering model incorporating the characteristic of microwave sintering, the ionic conductance diffusion mechanism in microwave sintering was studied. A flat-ball model was presented to describe the kinetics process in microwave sintering, and was applied to the sintering process of TZP and ZrO2-Al2O3 ceramics. The results indicate that the shrinkage rate of materials in microwave sintering is proportional to t2/3 and r-4/3, respectively, where t is the sintering time and r is the particle radius. Whereas, the shrinkage rate of materials in conventional sintering is proportional to sintering time t2/5. Our model suggests that microwave sintering is faster than conventional sintering, which shows a good agreement with the experimental observation in sintering process of TZP and ZrO2-Al2O3.

  14. Sonolytic degradation of dimethoate: kinetics, mechanisms and toxic intermediates controlling.

    Science.gov (United States)

    Yao, Juan-Juan; Hoffmann, Michael R; Gao, Nai-Yun; Zhang, Zhi; Li, Lei

    2011-11-15

    The sonolytic degradation of aqueous solutions of dimethoate, O,O-dimethyl S-[2-(methylamino)-2-oxoethyl]dithiophosphate, was examined. Optimal degradation rates were obtained at 619 kHz for continuous sonolysis and 406 kHz for pulse sonolysis. The primary pathways for degradation include hydroxyl radical oxidation, hydrolysis and pyrolysis on collapsing cavitation bubble interfaces. Reaction mechanisms coupled with the corresponding kinetic models are proposed to reproduce the observed concentration versus time profiles for dimethoate, omethoate and N-(methyl) mercaptoacetamide during sonolysis. The oxidation and hydrolysis of dimethoate and omethoate occurred at the water-bubble interface was the rate-determining step for sonolytic overall degradation of dimethoate. More than 90% toxicity of dimethoate was reduced within 45 min ultrasonic irradiation. Ferrous ion at micro molar level can significantly enhance the sonolytic degradation of dimethoate and effectively reduce the yields of toxic intermediate omethoate.

  15. A Skeletal, Gas Phase, Finite Rate, Chemical Kinetics Mechanism for Modeling the Deflagration of Ammonium Perchlorate - Hydroxyl-Terminated Polybutadiene Composite Propellants

    Science.gov (United States)

    2016-04-01

    expressions that sensitivity analyses indicated were important. Addressing this issue through the application of computational - chemistry -based methods...Lin MC. Computational studies on the kinetics and mechanisms for NH3 reactions with ClOx (x = 0 - 4) radicals. Journal of Physical Chemistry A...ABSTRACT A (full) detailed, gas-phase, finite-rate chemical kinetics mechanism for representing the combustion- chemistry -associated ammonium

  16. Kinetics and mechanism of dye adsorption on WO3 nanoparticles

    Science.gov (United States)

    Adhikari, Sangeeta; Mandal, Sandip; Sarkar, Debasish; Kim, Do-Heyoung; Madras, Giridhar

    2017-10-01

    Monoclinic WO3 nanoparticles were synthesized by a simple acid catalyzed co-precipitation reaction. Spherical particles with average size ∼55 nm were confirmed from electron microscopy followed by functional, structural and optical characterizations. The adsorption of methylene blue was examined by using WO3 nanoparticles and the capacity was higher than most of the reported studies. The effect of pH and material loading on adsorption was determined. The mechanism of adsorption was examined by XPS and a detailed explanation of surface phenomena was proposed. Regeneration study was carried and a high stability of heat treated WO3 towards adsorption of methylene blue was observed.

  17. Proton-pumping mechanism of cytochrome c oxidase: A kinetic master-equation approach

    Science.gov (United States)

    Kim, Young C.; Hummer, Gerhard

    2011-01-01

    Cytochrome c oxidase (CcO) is an efficient energy transducer that reduces oxygen to water and converts the released chemical energy into an electrochemical membrane potential. As a true proton pump, CcO translocates protons across the membrane against this potential. Based on a wealth of experiments and calculations, an increasingly detailed picture of the reaction intermediates in the redox cycle has emerged. However, the fundamental mechanism of proton pumping coupled to redox chemistry remains largely unresolved. Here we examine and extend a kinetic master-equation approach to gain insight into redox-coupled proton pumping in CcO. Basic principles of the CcO proton pump emerge from an analysis of the simplest kinetic models that retain essential elements of the experimentally determined structure, energetics, and kinetics, and that satisfy fundamental physical principles. The master-equation models allow us to address the question of how pumping can be achieved in a system in which all reaction steps are reversible. Whereas proton pumping does not require the direct modulation of microscopic reaction barriers, such kinetic gating greatly increases the pumping efficiency. Further efficiency gains can be achieved by partially decoupling the proton uptake pathway from the ative-site region. Such a mechanism is consistent with the proposed Glu valve, in which the side chain of a key glutamic acid shuttles between the D channel and the active-site region. We also show that the models predict only small proton leaks even in the absence of turnover. The design principles identified here for CcO provide a blueprint for novel biology-inspired fuel cells, and the master-equation formulation should prove useful also for other molecular machines. PMID:21946020

  18. Proton-pumping mechanism of cytochrome c oxidase: a kinetic master-equation approach.

    Science.gov (United States)

    Kim, Young C; Hummer, Gerhard

    2012-04-01

    Cytochrome c oxidase is an efficient energy transducer that reduces oxygen to water and converts the released chemical energy into an electrochemical membrane potential. As a true proton pump, cytochrome c oxidase translocates protons across the membrane against this potential. Based on a wealth of experiments and calculations, an increasingly detailed picture of the reaction intermediates in the redox cycle has emerged. However, the fundamental mechanism of proton pumping coupled to redox chemistry remains largely unresolved. Here we examine and extend a kinetic master-equation approach to gain insight into redox-coupled proton pumping in cytochrome c oxidase. Basic principles of the cytochrome c oxidase proton pump emerge from an analysis of the simplest kinetic models that retain essential elements of the experimentally determined structure, energetics, and kinetics, and that satisfy fundamental physical principles. The master-equation models allow us to address the question of how pumping can be achieved in a system in which all reaction steps are reversible. Whereas proton pumping does not require the direct modulation of microscopic reaction barriers, such kinetic gating greatly increases the pumping efficiency. Further efficiency gains can be achieved by partially decoupling the proton uptake pathway from the active-site region. Such a mechanism is consistent with the proposed Glu valve, in which the side chain of a key glutamic acid shuttles between the D channel and the active-site region. We also show that the models predict only small proton leaks even in the absence of turnover. The design principles identified here for cytochrome c oxidase provide a blueprint for novel biology-inspired fuel cells, and the master-equation formulation should prove useful also for other molecular machines. .

  19. Kinetics and mechanism of Dionaea muscipula trap closing.

    Science.gov (United States)

    Volkov, Alexander G; Adesina, Tejumade; Markin, Vladislav S; Jovanov, Emil

    2008-02-01

    The Venus flytrap (Dionaea muscipula) possesses an active trapping mechanism to capture insects with one of the most rapid movements in the plant kingdom, as described by Darwin. This article presents a detailed experimental investigation of trap closure by mechanical and electrical stimuli and the mechanism of this process. Trap closure consists of three distinctive phases: a silent phase with no observable movement; an accelerated movement of the lobes; and the relaxation of the lobes in their closed state, resulting in a new equilibrium. Uncouplers and blockers of membrane channels were used to investigate the mechanisms of different phases of closing. Uncouplers increased trap closure delay and significantly decreased the speed of trap closure. Ion channel blockers and aquaporin inhibitors increased time of closing. Transmission of a single electrical charge between a lobe and the midrib causes closure of the trap and induces an electrical signal propagating between both lobes and midrib. The Venus flytrap can accumulate small subthreshold charges, and when the threshold value is reached, the trap closes. Repeated application of smaller charges demonstrates the summation of stimuli. The cumulative character of electrical stimuli points to the existence of electrical memory in the Venus flytrap. The observed fast movement can be explained by the hydroelastic curvature model without invoking buckling instability. The new hydroelastic curvature mechanism provides an accurate description of the authors' experimental data.

  20. Database of atomistic reaction mechanisms with application to kinetic Monte Carlo.

    Science.gov (United States)

    Terrell, Rye; Welborn, Matthew; Chill, Samuel T; Henkelman, Graeme

    2012-07-07

    Kinetic Monte Carlo is a method used to model the state-to-state kinetics of atomic systems when all reaction mechanisms and rates are known a priori. Adaptive versions of this algorithm use saddle searches from each visited state so that unexpected and complex reaction mechanisms can also be included. Here, we describe how calculated reaction mechanisms can be stored concisely in a kinetic database and subsequently reused to reduce the computational cost of such simulations. As all accessible reaction mechanisms available in a system are contained in the database, the cost of the adaptive algorithm is reduced towards that of standard kinetic Monte Carlo.

  1. Mechanism of controlled release kinetics from medical devices

    Directory of Open Access Journals (Sweden)

    A. Raval

    2010-06-01

    Full Text Available Utilization of biodegradable polymers for controlled drug delivery has gained immense attention in the pharmaceutical and medical device industry to administer various drugs, proteins and other bio-molecules both systematically and locally to cure several diseases. The efficacy and toxicity of this local therapeutics depends upon drug release kinetics, which will further decide drug deposition, distribution, and retention at the target site. Drug Eluting Stent (DES presently possesses clinical importance as an alternative to Coronary Artery Bypass Grafting due to the ease of the procedure and comparable safety and efficacy. Many models have been developed to describe the drug delivery from polymeric carriers based on the different mechanisms which control the release phenomenon from DES. Advanced characterization techniques facilitate an understanding of the complexities behind design and related drug release behavior of drug eluting stents, which aids in the development of improved future drug eluting systems. This review discusses different drug release mechanisms, engineering principles, mathematical models and current trends that are proposed for drug-polymer coated medical devices such as cardiovascular stents and different analytical methods currently utilized to probe diverse characteristics of drug eluting devices.

  2. A steady-state kinetic analysis of the prolyl-4-hydroxylase mechanism.

    Science.gov (United States)

    Soskel, N T; Kuby, S A

    1981-01-01

    Published kinetic data by Kivirikko, et al. on the prolyl-4-hydroxylase reaction have been re-evaluated using the overall steady-state velocity equation in the forward and reverse directions for an ordered ter ter kinetic mechanism. Qualitatively, the published data for prolyl-4-hydroxylase appear to fit the predicted patterns for this kinetic mechanism. More kinetic data are needed to confirm these results and to quantitate the kinetic parameters but, tentatively, the order of substrate addition would appear to be alpha-ketoglutarate, oxygen, and peptide; and the order of product release would be hydroxylated peptide (or collagen), carbon dioxide, and succinate.

  3. Mechanical-Kinetic Modeling of a Molecular Walker from a Modular Design Principle

    Science.gov (United States)

    Hou, Ruizheng; Loh, Iong Ying; Li, Hongrong; Wang, Zhisong

    2017-02-01

    Artificial molecular walkers beyond burnt-bridge designs are complex nanomachines that potentially replicate biological walkers in mechanisms and functionalities. Improving the man-made walkers up to performance for widespread applications remains difficult, largely because their biomimetic design principles involve entangled kinetic and mechanical effects to complicate the link between a walker's construction and ultimate performance. Here, a synergic mechanical-kinetic model is developed for a recently reported DNA bipedal walker, which is based on a modular design principle, potentially enabling many directional walkers driven by a length-switching engine. The model reproduces the experimental data of the walker, and identifies its performance-limiting factors. The model also captures features common to the underlying design principle, including counterintuitive performance-construction relations that are explained by detailed balance, entropy production, and bias cancellation. While indicating a low directional fidelity for the present walker, the model suggests the possibility of improving the fidelity above 90% by a more powerful engine, which may be an improved version of the present engine or an entirely new engine motif, thanks to the flexible design principle. The model is readily adaptable to aid these experimental developments towards high-performance molecular walkers.

  4. DNA-Binding Kinetics Determines the Mechanism of Noise-Induced Switching in Gene Networks.

    Science.gov (United States)

    Tse, Margaret J; Chu, Brian K; Roy, Mahua; Read, Elizabeth L

    2015-10-20

    Gene regulatory networks are multistable dynamical systems in which attractor states represent cell phenotypes. Spontaneous, noise-induced transitions between these states are thought to underlie critical cellular processes, including cell developmental fate decisions, phenotypic plasticity in fluctuating environments, and carcinogenesis. As such, there is increasing interest in the development of theoretical and computational approaches that can shed light on the dynamics of these stochastic state transitions in multistable gene networks. We applied a numerical rare-event sampling algorithm to study transition paths of spontaneous noise-induced switching for a ubiquitous gene regulatory network motif, the bistable toggle switch, in which two mutually repressive genes compete for dominant expression. We find that the method can efficiently uncover detailed switching mechanisms that involve fluctuations both in occupancies of DNA regulatory sites and copy numbers of protein products. In addition, we show that the rate parameters governing binding and unbinding of regulatory proteins to DNA strongly influence the switching mechanism. In a regime of slow DNA-binding/unbinding kinetics, spontaneous switching occurs relatively frequently and is driven primarily by fluctuations in DNA-site occupancies. In contrast, in a regime of fast DNA-binding/unbinding kinetics, switching occurs rarely and is driven by fluctuations in levels of expressed protein. Our results demonstrate how spontaneous cell phenotype transitions involve collective behavior of both regulatory proteins and DNA. Computational approaches capable of simulating dynamics over many system variables are thus well suited to exploring dynamic mechanisms in gene networks.

  5. Simple Numerical Method for Kinetical Investigation of Planar Mechanical Systems with Two Degrees of Freedom

    Directory of Open Access Journals (Sweden)

    István Bíró

    2016-01-01

    Full Text Available The aim of this article is to demonstrate the application of a simple numerical method which is suitable for motion analysis of different mechanical systems. For mechanical engineer students it is important task. Mechanical systems consisting of rigid bodies are linked to each other by different constraints. Kinematical and kinetical analysis of them leads to integration of second order differential equations. In this way the kinematical functions of parts of mechanical systems can be determined. Degrees of freedom of the mechanical system increase as a result of built-in elastic parts. Numerical methods can be applied to solve such problems. The simple numerical method will be demonstrated in MS Excel by author by the aid of two examples. MS Excel is a quite useful tool for mechanical engineers because easy to use it and details can be seen moreover failures can be noticed. Some parts of results obtained by using the numerical method were checked by analytical way. The published method can be used in higher education for mechanical engineer students.

  6. Mechanism and kinetics of the NOCO reaction on Rh

    Science.gov (United States)

    Zhdanov, V. P.; Kasemo, B.

    During the past 15 years, the NOCO reaction on Rh has attracted considerable attention of the researchers working in academic and applied surface science. The practical importance of this reaction is connected with its relevance for environmental chemistry. From the point of view of academic studies, the NOCO reaction on Rh is of interest because it represents one of the simplest examples from the class of catalytic reactions occurring via decomposition of adsorbed species. At present, the detailed kinetic data for this reaction are available both for single-crystal and supported Rh, at ultrahigh vacuum (UHV) conditions and also at realistic pressures. For this reason, the NOCO reaction on Rh has become one of the major testing platforms for a microscopic, surface-science based approach to heterogeneous catalysis. The present review shows how far the progress in this field has come. In particular, the review describes in detail the evolution of the ideas for the mechanism of the reaction and also presents the data for the elementary reaction steps, obtained primarily on Rh(1 1 1) at UHV conditions. Then, the possibility of using these data for simulation of the reaction kinetics at moderate pressures, P NO ⋍ P CO ⋍ 0.01 bar, is discussed. The technological aspects of application of Rh in the automotive exhaust systems are surveyed as well, but only briefly.

  7. Mutant IDH1 enhances the production of 2-hydroxyglutarate due to its kinetic mechanism.

    Science.gov (United States)

    Rendina, Alan R; Pietrak, Beth; Smallwood, Angela; Zhao, Huizhen; Qi, Hongwei; Quinn, Chad; Adams, Nicholas D; Concha, Nestor; Duraiswami, Chaya; Thrall, Sara H; Sweitzer, Sharon; Schwartz, Benjamin

    2013-07-02

    The human, cytosolic enzyme isocitrate dehydrogenase 1 (IDH1) reversibly converts isocitrate to α-ketoglutarate (αKG). Cancer-associated somatic mutations in IDH1 result in a loss of this normal function but a gain in a new or neomorphic ability to convert αKG to the oncometabolite 2-hydroxyglutarate (2HG). To improve our understanding of the basis for this phenomenon, we have conducted a detailed kinetic study of wild-type IDH1 as well as the known 2HG-producing clinical R132H and G97D mutants and mechanistic Y139D and (newly described) G97N mutants. In the reductive direction of the normal reaction (αKG to isocitrate), dead-end inhibition studies suggest that wild-type IDH1 goes through a random sequential mechanism, similar to previous reports on related mammalian IDH enzymes. However, analogous experiments studying the reductive neomorphic reaction (αKG to 2HG) with the mutant forms of IDH1 are more consistent with an ordered sequential mechanism, with NADPH binding before αKG. This result was further confirmed by primary kinetic isotope effects for which saturating with αKG greatly reduced the observed isotope effect on (D)(V/K)NADPH. For the mutant IDH1 enzyme, the change in mechanism was consistently associated with reduced efficiencies in the use of αKG as a substrate and enhanced efficiencies using NADPH as a substrate. We propose that the sum of these kinetic changes allows the mutant IDH1 enzymes to reductively trap αKG directly into 2HG, rather than allowing it to react with carbon dioxide and form isocitrate, as occurs in the wild-type enzyme.

  8. 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.

  9. Analysis of the kinetic mechanism of recombinant human isoprenylcysteine carboxylmethyltransferase (Icmt

    Directory of Open Access Journals (Sweden)

    Baron Rudi A

    2004-12-01

    Full Text Available Abstract Background Isoprenylcysteine carboxyl methyltransferase (Icmt is the third of three enzymes that posttranslationally modify proteins that contain C-terminal CaaX motifs. The processing of CaaX proteins through this so-called prenylation pathway via a route initiated by addition of an isoprenoid lipid is required for both membrane targeting and function of the proteins. The involvement of many CaaX proteins such as Ras GTPases in oncogenesis and other aberrant proliferative disorders has led to the targeting of the enzymes involved in their processing for therapeutic development, necessitating a detailed understanding of the mechanisms of the enzymes. Results In this study, we have investigated the kinetic mechanism of recombinant human Icmt. In the reaction catalyzed by Icmt, S-adenosyl-L-methionine (AdoMet provides the methyl group that is transferred to the second substrate, the C-terminal isoprenylated cysteine residue of a CaaX protein, thereby generating a C-terminal prenylcysteine methyl ester on the protein. To facilitate the kinetic analysis of Icmt, we synthesized a new small molecule substrate of the enzyme, biotin-S-farnesyl-L-cysteine (BFC. Initial kinetic analysis of Icmt suggested a sequential mechanism for the enzyme that was further analyzed using a dead end competitive inhibitor, S-farnesylthioacetic acid (FTA. Inhibition by FTA was competitive with respect to BFC and uncompetitive with respect to AdoMet, indicating an ordered mechanism with SAM binding first. To investigate the order of product dissociation, product inhibition studies were undertaken with S-adenosyl-L-homocysteine (AdoHcy and the N-acetyl-S-farnesyl-L-cysteine methylester (AFCME. This analysis indicated that AdoHcy is a competitive inhibitor with respect to AdoMet, while AFCME shows a noncompetitive inhibition with respect to BFC and a mixed-type inhibition with respect to AdoMet. These studies established that AdoHcy is the final product released, and

  10. 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.

  11. Unraveling protein folding mechanism by analyzing the hierarchy of models with increasing level of detail

    Science.gov (United States)

    Hayashi, Tomohiko; Yasuda, Satoshi; Škrbić, Tatjana; Giacometti, Achille; Kinoshita, Masahiro

    2017-09-01

    Taking protein G with 56 residues for a case study, we investigate the mechanism of protein folding. In addition to its native structure possessing α-helix and β-sheet contents of 27% and 39%, respectively, we construct a number of misfolded decoys with a wide variety of α-helix and β-sheet contents. We then consider a hierarchy of 8 different models with increasing level of detail in terms of the number of entropic and energetic physical factors incorporated. The polyatomic structure is always taken into account, but the side chains are removed in half of the models. The solvent is formed by either neutral hard spheres or water molecules. Protein intramolecular hydrogen bonds (H-bonds) and protein-solvent H-bonds (the latter is present only in water) are accounted for or not, depending on the model considered. We then apply a physics-based free-energy function (FEF) corresponding to each model and investigate which structures are most stabilized. This special approach taken on a step-by-step basis enables us to clarify the role of each physical factor in contributing to the structural stability and separately elucidate its effect. Depending on the model employed, significantly different structures such as very compact configurations with no secondary structures and configurations of associated α-helices are optimally stabilized. The native structure can be identified as that with lowest FEF only when the most detailed model is employed. This result is significant for at least the two reasons: The most detailed model considered here is able to capture the fundamental aspects of protein folding notwithstanding its simplicity; and it is shown that the native structure is stabilized by a complex interplay of minimal multiple factors that must be all included in the description. In the absence of even a single of these factors, the protein is likely to be driven towards a different, more stable state.

  12. Preliminary study on mechanics-based rainfall kinetic energy

    Directory of Open Access Journals (Sweden)

    Yuan Jiuqin Ms.

    2014-09-01

    Full Text Available A raindrop impact power observation system was employed to observe the real-time raindrop impact power during a rainfall event and to analyze the corresponding rainfall characteristics. The experiments were conducted at different simulated rainfall intensities. As rainfall intensity increased, the observed impact power increased linearly indicating the power observation system would be satisfactory for characterizing rainfall erosivity. Momentum is the product of mass and velocity (Momentum=MV, which is related to the observed impact power value. Since there is no significant difference between momentum and impact power, observed impact power can represent momentum for different rainfall intensities. The relationship between momentum and the observed impact power provides a convenient way to calculate rainfall kinetic energy. The value of rainfall kinetic energy based on the observed impact power was higher than the classic rainfall kinetic energy. The rainfall impact power based kinetic energy and the classic rainfall kinetic energy showed linear correlation, which indicates that the raindrop impact power observation system can characterize rainfall kinetic energy. The article establishes a preliminary way to calculate rainfall kinetic energy by using the real-time observed momentum, providing a foundation for replacing the traditional methods for estimating kinetic energy of rainstorms.

  13. 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.

  14. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

  15. Complete protein-protein association kinetics in atomic detail revealed by molecular dynamics simulations and Markov modelling

    Science.gov (United States)

    Plattner, Nuria; Doerr, Stefan; de Fabritiis, Gianni; Noé, Frank

    2017-10-01

    Protein-protein association is fundamental to many life processes. However, a microscopic model describing the structures and kinetics during association and dissociation is lacking on account of the long lifetimes of associated states, which have prevented efficient sampling by direct molecular dynamics (MD) simulations. Here we demonstrate protein-protein association and dissociation in atomistic resolution for the ribonuclease barnase and its inhibitor barstar by combining adaptive high-throughput MD simulations and hidden Markov modelling. The model reveals experimentally consistent intermediate structures, energetics and kinetics on timescales from microseconds to hours. A variety of flexibly attached intermediates and misbound states funnel down to a transition state and a native basin consisting of the loosely bound near-native state and the tightly bound crystallographic state. These results offer a deeper level of insight into macromolecular recognition and our approach opens the door for understanding and manipulating a wide range of macromolecular association processes.

  16. Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

    Directory of Open Access Journals (Sweden)

    V. Wagner

    2003-01-01

    Full Text Available Toluene photooxidation is chosen as an example to examine how simulations of smog-chamber experiments can be used to unravel shortcomings in detailed mechanisms and to provide information on complex reaction systems that will be crucial for the design of future validation experiments. The mechanism used in this study is extracted from the Master Chemical Mechanism Version 3 (MCM v3 and has been updated with new modules for cresol and g-dicarbonyl chemistry. Model simulations are carried out for a toluene-NOx experiment undertaken at the European Photoreactor (EUPHORE. The comparison of the simulation with the experimental data reveals two fundamental shortcomings in the mechanism: OH production is too low by about 80%, and the ozone concentration at the end of the experiment is over-predicted by 55%. The radical budget was analysed to identify the key intermediates governing the radical transformation in the toluene system. Ring-opening products, particularly conjugated g-dicarbonyls, were identified as dominant radical sources in the early stages of the experiment. The analysis of the time evolution of radical production points to a missing OH source that peaks when the system reaches highest reactivity. First generation products are also of major importance for the ozone production in the system. The analysis of the radical budget suggests two options to explain the concurrent under-prediction of OH and over-prediction of ozone in the model: 1 missing oxidation processes that produce or regenerate OH without or with little NO to NO2 conversion or 2 NO3 chemistry that sequesters reactive nitrogen oxides into stable nitrogen compounds and at the same time produces peroxy radicals. Sensitivity analysis was employed to identify significant contributors to ozone production and it is shown how this technique, in combination with ozone isopleth plots, can be used for the design of validation experiments.

  17. Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

    CERN Document Server

    Sosso, Gabriele C; Donadio, Davide; Tribello, Gareth A; Michaelides, Angelos

    2016-01-01

    Most ice in nature forms thanks to impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is twenty orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong 2D character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed.

  18. Study on the kinetic mechanisms of copper vapor lasers with hydrogen-neon admixtures

    Science.gov (United States)

    Cheng, Cheng; Sun, Wei

    1997-02-01

    The kinetic mechanisms of copper vapor lasers with hydrogen-neon admixtures are studied in detail with a computational model. (i) The copper particle density increases as the wall temperature rises after adding hydrogen into neon buffer gas, and de-population of the laser lower levels is enhanced during the interpulse period owing to a larger thermal diffusion loss from the tube center to the wall. (ii) The power dissipated by the thyratron or current through it decreases with increasing frequency of the momentum-transfer collision of electrons, i.e. the input power into the laser tube increases. On the other hand, the plasma electron temperature and electron density decrease as the electron energy is depleted through the impact excitation of the vibration levels of hydrogen, which makes the population of the laser upper levels restrained.

  19. Development and validation of a generic reduced chemical kinetic mechanism for CFD spray combustion modelling of biodiesel fuels

    DEFF Research Database (Denmark)

    Cheng, Xinwei; Ng, Hoon Kiat; Ho, Jee Hou

    2015-01-01

    In this reported work, a generic reduced biodiesel chemical kinetic mechanism, with components of methyl decanoate (C11H22O2, MD), methyl-9-decenoate (C11H20O2, MD9D) and n-heptane (C7H16) was built to represent the methyl esters of coconut, palm, rapeseed and soybean. The reduced biodiesel...... and detailed mechanism predictions, for each zero-dimensional (0D) auto-ignition and extinction process using CHEMKIN-PRO. Maximum percentage errors of less than 40.0% were recorded when the predicted ignition delay (ID) periods for coconut, palm, rapeseed and soybean methyl esters were compared to those...

  20. A detailed look at the reaction mechanisms of substituted carbenes with water.

    Science.gov (United States)

    Gómez, Sara; Guerra, Doris; López, José G; Toro-Labbé, Alejandro; Restrepo, Albeiro

    2013-03-07

    Two competitive reaction mechanisms for the gas-phase chemical transformation of singlet chlorocarbene into chloromethanol in the presence of one and two water molecules are examined in detail. An analysis of bond orders and bond order derivatives as well as of properties of bond critical points in the electron densities along the intrinsic reaction coordinates (IRCs for intermediates → transition state (TS) → products) suggests that, from the perspective of bond breaking/formation, both reactions should be considered to be highly nonsynchronous, concerted processes. Both transition states are early, resembling the intermediates, yielding rate constants whose magnitudes are mostly influenced by structural changes and to a lesser degree by bond breaking/formation. For the case of one water molecule, most of the energy in the reactants region of the IRC is used for structural changes, while the transition state region encompasses the majority of electron activity, except for the formation of the C-O bond, which extends well into the products region. In the case of two water molecules, very little electron flux and comparatively less work required for structural changes is noticed in the reactants region, leading to an earlier transition state and therefore to a smaller activation energy and to a larger rate constant. This, together with evidence gathered from other sources, allows us to provide plausible explanations for the observed difference in rate constants.

  1. Detailed analysis of the cell-inactivation mechanism by accelerated protons and light ions

    Energy Technology Data Exchange (ETDEWEB)

    Kundrat, Pavel [Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, CZ-182 21 Praha 8 (Czech Republic)

    2006-03-07

    A detailed study of the biological effects of diverse quality radiations, addressing their biophysical interpretation, is presented. Published survival data for V79 cells irradiated by monoenergetic protons, helium-3, carbon and oxygen ions and for CHO cells irradiated by carbon ions have been analysed using the probabilistic two-stage model of cell inactivation. Three different classes of DNA damage formed by traversing particles have been distinguished, namely severe single-track lesions which might lead to cell inactivation directly, less severe lesions where cell inactivation is caused by their combinations and lesions of negligible severity that can be repaired easily. Probabilities of single ions forming these lesions have been assessed in dependence on their linear energy transfer (LET) values. Damage induction probabilities increase with atomic number and LET. While combined lesions play a crucial role at lower LET values, single-track damage dominates in high-LET regions. The yields of single-track lethal lesions for protons have been compared with Monte Carlo estimates of complex DNA lesions, indicating that lethal events correlate well with complex DNA double-strand breaks. The decrease in the single-track damage probability for protons of LET above approximately 30 keV {mu}m{sup -1}, suggested by limited experimental evidence, is discussed, together with the consequent differences in the mechanisms of biological effects between protons and heavier ions. Applications of the results in hadrontherapy treatment planning are outlined.

  2. Active mechanics reveal molecular-scale force kinetics in living oocytes

    CERN Document Server

    Ahmed, Wylie W; Almonacid, Maria; Bussonnier, Matthias; Verlhac, Marie-Helene; Gov, Nir S; Visco, Paolo; van Wijland, Frederic; Betz, Timo

    2015-01-01

    Unlike traditional materials, living cells actively generate forces at the molecular scale that change their structure and mechanical properties. This nonequilibrium activity is essential for cellular function, and drives processes such as cell division. Single molecule studies have uncovered the detailed force kinetics of isolated motor proteins in-vitro, however their behavior in-vivo has been elusive due to the complex environment inside the cell. Here, we quantify active force generation in living oocytes using in-vivo optical trapping and laser interferometry of endogenous vesicles. We integrate an experimental and theoretical framework to connect mesoscopic measurements of nonequilibrium properties to the underlying molecular-scale force kinetics. Our results show that force generation by myosin-V drives the cytoplasmic-skeleton out-of-equilibrium (at frequencies below 300 Hz) and actively softens the environment. In vivo myosin-V activity generates a force of $F \\sim 0.4$ pN, with a power-stroke of len...

  3. Mechanism and Kinetic Parameters of Thermal Decomposition of Cobalt Dichloride Hexahydrate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The thermal decomposition of the cobalt dichloride hexahydrate and its kinetics were studied by TG and DTG technique under the non-isothermal condition with nitrogen atnosphere.The non-isothermal kinetic data and kinetic parameters were evaluated by means of integral and differential methods.The most probable mechanism functions of the thermal decomposition reaction for the first stage are:f(α)=(1-α)2 and g(α)=(1-α)-1-1.

  4. The quantum mechanics based on a general kinetic energy

    CERN Document Server

    Wei, Yuchuan

    2016-01-01

    In this paper, we introduce the Schrodinger equation with a general kinetic energy operator. The conservation law is proved and the probability continuity equation is deducted in a general sense. Examples with a Hermitian kinetic energy operator include the standard Schrodinger equation, the relativistic Schrodinger equation, the fractional Schrodinger equation, the Dirac equation, and the deformed Schrodinger equation. We reveal that the Klein-Gordon equation has a hidden non-Hermitian kinetic energy operator. The probability continuity equation with sources indicates that there exists a different way of probability transportation, which is probability teleportation. An average formula is deducted from the relativistic Schrodinger equation, the Dirac equation, and the K-G equation.

  5. Renormalizing the kinetic energy operator in elementary quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, F A B [Faculdade de Medicina, Universidade de Sao Paulo e LIM 01-HCFMUSP, 05405-000 Sao Paulo (Brazil); Amaku, M [Faculdade de Medicina Veterinaria e Zootecnia, Universidade de Sao Paulo, 05508-970 Sao Paulo (Brazil)], E-mail: coutinho@dim.fm.usp.br

    2009-09-15

    In this paper, we consider solutions to the three-dimensional Schroedinger equation of the form {psi}(r) = u(r)/r, where u(0) {ne} 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly cancelling the kinetic energy divergence. This renormalization procedure produces a self-adjoint Hamiltonian. We solve some problems with this new Hamiltonian to illustrate its usefulness.

  6. Detailed insights into the retention mechanism of caffeine metabolites on the amide stationary phase in hydrophilic interaction chromatography.

    Science.gov (United States)

    Guo, Yong; Shah, Rajan

    2016-09-09

    The amide phase was investigated using a wide range of acetonitrile content in the mobile phase in both the HILIC and RPLC modes. Using caffeine metabolites as the model compounds, the retention, thermodynamic and kinetic data was obtained under various mobile phase conditions and supported the previous postulation that there might be a transition of the predominant retention mechanism in relation to the acetonitrile content in HILIC. On the amide phase, hydrophilic partitioning seemed to be the predominant retention mechanism below 85% acetonitrile; and a different retention mechanism (presumably surface adsorption) made more and more significant contributions to the overall retention when the acetonitrile content reached above 85%. This study also provided more direct evidences to explain the effect of salt concentration on the retention of non-charged solutes in HILIC. In addition, the retention, thermodynamic and kinetic data suggest that the amide phase behaved very differently from the conventional C18 phase in the RPLC mode.

  7. Miniature free-piston homogeneous charge compression ignition engine-compressor concept - Part II: modeling HCCI combustion in small scales with detailed homogeneous gas phase chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Aichlmayr, H.T.; Kittelson, D.B.; Zachariah, M.R. [The University of Minnesota, Minneapolis (United States). Departments of Mechanical Engineering and Chemistry

    2002-10-01

    Operational maps for crankshaft-equipped miniature homogeneous charge compression ignition engines are established using performance estimation, detailed chemical kinetics, and diffusion models for heat transfer and radical loss. In this study, radical loss was found to be insignificant. In contrast, heat transfer was found to be increasingly significant for 10, 1, and 0.1 W engines, respectively. Also, temperature-pressure trajectories and ignition delay time maps are used to explore relationships between engine operational parameters and HCCI. Lastly, effects of engine operating conditions and design on the indicated fuel conversion efficiency are investigated. (author)

  8. A Comparison of Kinetic Energy and Momentum in Special Relativity and Classical Mechanics

    Science.gov (United States)

    Riggs, Peter J.

    2016-01-01

    Kinetic energy and momentum are indispensable dynamical quantities in both the special theory of relativity and in classical mechanics. Although momentum and kinetic energy are central to understanding dynamics, the differences between their relativistic and classical notions have not always received adequate treatment in undergraduate teaching.…

  9. A Comparison of Kinetic Energy and Momentum in Special Relativity and Classical Mechanics

    Science.gov (United States)

    Riggs, Peter J.

    2016-01-01

    Kinetic energy and momentum are indispensable dynamical quantities in both the special theory of relativity and in classical mechanics. Although momentum and kinetic energy are central to understanding dynamics, the differences between their relativistic and classical notions have not always received adequate treatment in undergraduate teaching.…

  10. Renormalizing the Kinetic Energy Operator in Elementary Quantum Mechanics

    Science.gov (United States)

    Coutinho, F. A. B.; Amaku, M.

    2009-01-01

    In this paper, we consider solutions to the three-dimensional Schrodinger equation of the form [psi](r) = u(r)/r, where u(0) [is not equal to] 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly…

  11. Renormalizing the Kinetic Energy Operator in Elementary Quantum Mechanics

    Science.gov (United States)

    Coutinho, F. A. B.; Amaku, M.

    2009-01-01

    In this paper, we consider solutions to the three-dimensional Schrodinger equation of the form [psi](r) = u(r)/r, where u(0) [is not equal to] 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly…

  12. Kinetic mechanism of putrescine oxidase from Rhodococcus erythropolis

    NARCIS (Netherlands)

    Kopacz, Malgorzata; Heuts, Dominic P. H. M.; Fraaije, Marco W.

    2014-01-01

    Putrescine oxidase from Rhodococcus erythropolis (PuO) is a flavin-containing amine oxidase from the monoamine oxidase family that performs oxidative deamination of aliphatic diamines. In this study we report pre-steady-state kinetic analyses of the enzyme with the use of single-and double-mixing st

  13. Kinetic mechanism of putrescine oxidase from Rhodococcus erythropolis

    NARCIS (Netherlands)

    Kopacz, Malgorzata; Heuts, Dominic P. H. M.; Fraaije, Marco W.

    2014-01-01

    Putrescine oxidase from Rhodococcus erythropolis (PuO) is a flavin-containing amine oxidase from the monoamine oxidase family that performs oxidative deamination of aliphatic diamines. In this study we report pre-steady-state kinetic analyses of the enzyme with the use of single-and double-mixing

  14. Crystal structure and kinetic mechanism of aminoglycoside phosphotransferase-2″-IVa

    Science.gov (United States)

    Toth, Marta; Frase, Hilary; Antunes, Nuno Tiago; Smith, Clyde A; Vakulenko, Sergei B

    2010-01-01

    Acquired resistance to aminoglycoside antibiotics primarily results from deactivation by three families of aminoglycoside-modifying enzymes. Here, we report the kinetic mechanism and structure of the aminoglycoside phosphotransferase 2″-IVa (APH(2″)-IVa), an enzyme responsible for resistance to aminoglycoside antibiotics in clinical enterococcal and staphylococcal isolates. The enzyme operates via a Bi-Bi sequential mechanism in which the two substrates (ATP or GTP and an aminoglycoside) bind in a random manner. The APH(2″)-IVa enzyme phosphorylates various 4,6-disubstituted aminoglycoside antibiotics with catalytic efficiencies (kcat/Km) of 1.5 × 103 to 1.2 × 106 (M−1 s−1). The enzyme uses both ATP and GTP as the phosphate source, an extremely rare occurrence in the phosphotransferase and protein kinase enzymes. Based on an analysis of the APH(2″)-IVa structure, two overlapping binding templates specifically tuned for hydrogen bonding to either ATP or GTP have been identified and described. A detailed understanding of the structure and mechanism of the GTP-utilizing phosphotransferases is crucial for the development of either novel aminoglycosides or, more importantly, GTP-based enzyme inhibitors which would not be expected to interfere with crucial ATP-dependent enzymes. PMID:20556826

  15. Global investigation of potential energy surfaces for the pyrolysis of C(1)-C(3) hydrocarbons: toward the development of detailed kinetic models from first principles.

    Science.gov (United States)

    Ryazantsev, Mikhail N; Jamal, Adeel; Maeda, Satoshi; Morokuma, Keiji

    2015-11-07

    Detailed kinetic models (DKMs) are the most fundamental "bottom-up" approaches to computational investigation of the pyrolysis and oxidation of fuels. The weakest points of existing DKMs are incomplete information about the reaction types that can be involved in the potential energy surfaces (PESs) in pyrolysis and oxidation processes. Also, the computational thermodynamic parameters available in the literature vary widely with the level of theory employed. More sophisticated models require improvement both in our knowledge of the type of the reactions involved and the consistency of thermodynamic and kinetic parameters. In this paper, we aim to address these issues by developing ab initio models that can be used to describe early stages of pyrolysis of C1-C3 hydrocarbons. We applied a recently developed global reaction route mapping (GRRM) strategy to systematically investigate the PES of the pyrolysis of C1-C3 hydrocarbons at a consistent level of theory. The reactions are classified into 14 reaction types. The critical points on the PES for all reactions in the network are calculated at the highly accurate UCCSD(T)-F12b/cc-pVTZ//UM06-2X/cc-pVTZ level of theory. The data reported in this paper can be used for first principle calculations of kinetic constants and for a subsequent study on modeling the evolution of the species from the reaction network of the pyrolysis and oxidation of C1-C3 hydrocarbons.

  16. Kinetic mechanism for low-pressure oxygen/methane ignition and combustion

    Science.gov (United States)

    Slavinskaya, N. A.; Wiegand, M.; Starcke, J. H.; Riedel, U.; Haidn, O. J.; Suslov, D.

    2013-03-01

    It is known that during a launch of a rocket, the interaction of the exhaust gases of rocket engines with the atmosphere causes a local depletion of the ozone layer. In order to study these chemical processes in detail, a chemical reaction mechanism of the methane oxidation appropriate for high- and low-pressure conditions and a chemical reactor network to reproduce operating conditions in rocket engines and in the environment have been developed. An earlier developed detailed chemical kinetic model for the high-pressure CH4/O2 combustion has been improved for the low pressure and low temperature methane combustion and augmented with a submodel for NOx formation. The main model improvements are related to the pressure depending reactions. The model has been validated for operating conditions of 0.02 jet. Simulations performed have shown that the exhaust gases of a methane/oxygen propelled liquid rocket engine contain high amounts of active radicals, which can influence the formation of nitrogen compounds and consume ozone in the atmosphere.

  17. Compact Kinetic Mechanisms for Petroleum-Derived and Alternative Aviation Fuels Project

    Data.gov (United States)

    National Aeronautics and Space Administration — To be useful for computational combustor design and analysis using tools like the National Combustion Code (NCC), low-dimensional chemical kinetic mechanisms for...

  18. Kinetic regulation mechanism of pbuE riboswitch

    Science.gov (United States)

    Gong, Sha; Wang, Yujie; Zhang, Wenbing

    2015-01-01

    Riboswitches are RNA residue segments located in untranslated regions of messenger RNAs. These folded segments directly bind ligands through shape complementarity and specific interactions in cells and alter the expression of genes at the transcriptional or translational level through conformation change. Using the recently developed systematic helix-based computational method to predict the cotranscription folding kinetics, we theoretically studied the cotranscription folding behavior of the Bacillus subtilis pbuE riboswitch in the absence and presence of the ligand. The ligand concentration, the transcription speed, and the transcription pausing are incorporated into the method. The results are in good agreement with the experimental results. We find that there are no obvious misfolded structures formed during the transcription and the formation of the ligand bound state is rate-limited by the association of the ligand and the RNA. For this kinetically driven riboswitch, the ligand concentration, the transcription speed, and the transcription pausing are coupled to perform regulatory activity.

  19. Degradation kinetics and mechanisms of phenolin photo-Fenton process

    Institute of Scientific and Technical Information of China (English)

    何锋; 雷乐成

    2004-01-01

    Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD: while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.

  20. Chlorine dioxide oxidation of Escherichia coli in water - A study of the disinfection kinetics and mechanism.

    Science.gov (United States)

    Ofori, Isaac; Maddila, Suresh; Lin, Johnson; Jonnalagadda, Sreekantha B

    2017-06-07

    This study investigated the kinetics and mechanism of chlorine dioxide (ClO2) inactivation of a Gram-negative bacteria Escherichia coli (ATCC 35218) in oxidant demand free (ODF) water in detail as a function of disinfectant concentration (0.5-5.0 mg/L), water pH (6.5-8.5), temperature variations (4-37°C) and bacterial density (10(5)-10(7) cfu/mL). The effects of ClO2 on bacterial cell morphology, outer membrane permeability, cytoplasmic membrane disruption and intracellular enzymatic activity were also studied to elucidate the mechanism of action on the cells. Increasing temperature and disinfectant concentration were proportional to the rate of cell killing, but efficacy was found to be significantly subdued at 0.5 mg/L and less dependent on the bacterial density. The bactericidal efficiency was higher at alkaline pH of 8 or above as compared to neutral and slightly acidic pH of 7 and 6.5 respectively. The disinfection kinetic curves followed a biphasic pattern of rapid inactivation within the initial 2 min which were followed by a tailing even in the presence of residual biocide. The curves were adequately described by the Cavg Hom model. Transmission Electron Microscopy images of the bacteria cells exposed to lethal concentrations of ClO2 indicated very little observable morphological damage to the outer membranes of the cells. ClO2 however was found to increase the permeability of the outer and cytoplasmic membranes leading to the leakage of membrane components such as 260 nm absorbing materials and inhibiting the activity of the intracellular enzyme β-D-galactosidase. It is suggested that the disruption of the cytoplasmic membrane and subsequent efflux of intracellular components result in the inactivation of the Gram-negative bacteria.

  1. Light induced oxidative water splitting in photosynthesis: energetics, kinetics and mechanism.

    Science.gov (United States)

    Renger, Gernot

    2011-01-01

    The essential steps of photosynthetic water splitting take place in Photosystem II (PSII) and comprise three different reaction sequences: (i) light induced formation of the radical pair P680(+)Q(A)(-), (ii) P680(+) driven oxidative water splitting into O(2) and four protons, and (iii) two step plastoquinone reduction to plastoquinol by Q(A)(-). This mini-review briefly summarizes our state of knowledge on energetics, kinetics and mechanism of oxidative water splitting. Essential features of the two types of reactions involved are described: (a) P680(+) reduction by the redox active tyrosine Y(z) and (b) sequence of oxidation steps induced by Y(z)(ox) in the water-oxidizing complex (WOC). The rate of the former reaction is limited by the non-adiabatic electron transfer (NET) step and the multi-phase kinetics shown to originate from a sequence of relaxation processes. In marked contrast, the rate of the stepwise oxidation by Y(z)(ox) of the WOC up to the redox level S(3) is not limited by NET but by trigger reactions which probably comprise proton shifts and/or conformational changes. The overall rate of the final reaction sequence leading to formation and release of O(2) is assumed to be limited by the electron transfer step from the S(3) state of WOC to Y(z)(ox) due to involvement of an endergonic redox equilibrium. Currently discussed controversial ideas on possible pathways are briefly outlined. Several crucial points of the mechanism of oxidative water splitting, like O-O bond formation, role of local proton shift(s), details of hydrogen bonding, are still not clarified and remain a challenging topic of future research.

  2. Kinetics and mechanism of the chlorine dioxide-trithionate reaction.

    Science.gov (United States)

    Cseko, György; Horváth, Attila K

    2012-03-22

    The trithionate-chlorine dioxide reaction has been studied spectrophotometrically in a slightly acidic medium at 25.0 ± 0.1 °C in acetate/acetic acid buffer monitoring the decay of chlorine dioxide at constant ionic strength (I = 0.5 M) adjusted by sodium perchlorate. We found that under our experimental conditions two limiting stoichiometries exist and the pH, the concentration of the reactants, and even the concentration of chloride ion affects the actual stoichiometry of the reaction that can be augmented by an appropriate linear combination of these limiting processes. It is also shown that although the formal kinetic order of trithionate is strictly one that of chlorine dioxide varies between 1 and 2, depending on the actual chlorine dioxide excess and the pH. Moreover, the otherwise sluggish chloride ion, which is also a product of the reaction, slightly accelerates the initial rate of chlorine dioxide consumption and may therefore act as an autocatalyst. In addition to that, overshoot-undershoot behavior is also observed in the [(·)ClO(2)]-time curves in the presence of chloride ion at chlorine dioxide excess. On the basis of the experiments, a 13-step kinetic model with 6 fitted kinetic parameter is proposed by nonlinear parameter estimation. © 2012 American Chemical Society

  3. Development of multi-component diesel surrogate fuel models – Part I: Validation of reduced mechanisms of diesel fuel constituents in 0-D kinetic simulations

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Pang, Kar Mun; Ng, Hoon Kiat

    2016-01-01

    In the present work, development and validation of reduced chemical kinetic mechanisms for several different hydrocarbons are performed. These hydrocarbons are potential representative for practical diesel fuel constituents. n-Hexadecane (HXN), 2,2,4,4,6,8,8-heptamethylnonane (HMN), cyclohexane...... (CHX) and toluene are selected to represent straight-alkane, branched-alkane, cyclo-alkane and aromatic compounds in the diesel fuel. A five-stage chemical kinetic mechanism reduction scheme formulated in the previous work is applied to develop the reduced HMN and CHX models based on their respective...... developed fuel constituent reduced mechanisms, together with the formerly derived reduced HXN mechanism are comprehensively validated in zero-dimensional chemical kinetic simulations under a wide range of shock tube and jet-stirred reactor (JSR) conditions. Well agreement between the reduced and detailed...

  4. New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms.

    Science.gov (United States)

    Ji, Yuefei; Dong, Changxun; Kong, Deyang; Lu, Junhe

    2015-03-21

    The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides.

  5. Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

    Science.gov (United States)

    Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

    2016-06-02

    The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

  6. ATS-6 engineering performance report. Volume:Program and systems summaries: Mechanical and thermal details

    Science.gov (United States)

    Wales, R. O. (Editor)

    1981-01-01

    The overall mission and spacecraft systems, testing, and operations are summarized. The mechanical subsystems are reviewed, encompassing mechanical design requirements; separation and deployment mechanisms; design and performance evaluation; and the television camera reflector monitor. Thermal control and contamination are discussed in terms of thermal control subsystems, design validation, subsystems performance, the advanced flight experiment, and the quartz-crystal microbalance contamination monitor.

  7. Detailed spectroscopic, thermodynamic, and kinetic studies on the protolytic equilibria of Fe(III)cydta and the activation of hydrogen peroxide.

    Science.gov (United States)

    Brausam, Ariane; Maigut, Joachim; Meier, Roland; Szilágyi, Petra A; Buschmann, Hans-Jürgen; Massa, Werner; Homonnay, Zoltán; van Eldik, Rudi

    2009-08-17

    .1 cm(3) mol(-1). A detailed kinetic study of the effect of the buffer, temperature, and pressure on the reaction of hydrogen peroxide with [Fe(III)(cydta)(H(2)O)](-) was performed using stopped-flow techniques. The reaction was found to consist of two steps and resulted in the formation of a purple Fe(III) side-on-bound peroxo complex [Fe(III)(cydta)(eta(2)-O(2))](3-). The peroxo complex and its degradation products were characterized using Mossbauer spectroscopy. Formation of the purple peroxo complex is only observable above a pH of 9.5. Both reaction steps are affected by specific and general acid catalysis. Two different buffer systems were used to clarify the role of general acid catalysis in these reactions. Mechanistic descriptions and a comparison between the edta and cydta systems are presented. The first reaction step reveals an element of reversibility, which is evident over the whole studied pH range. The positive volume of activation for the forward reaction and the positive entropy of activation for the backward reaction suggest a dissociative interchange mechanism for the reversible end-on binding of hydrogen peroxide to [Fe(III)(cydta)(H(2)O)](-). Deprotonation of the end-on-bound hydroperoxo complex leads to the formation of a seven-coordinate side-on-bound peroxo complex [Fe(III)(cydta)(eta(2)-O(2))](3-), where one carboxylate arm is detached. [Fe(III)(cydta)(eta(2)-O(2))](3-) can be reached by two different pathways, of which one is catalyzed by a base and the other by deprotonated hydrogen peroxide. For both pathways, a small negative volume and entropy of activation was observed, suggesting an associative interchange mechanism for the ring-closure step to the side-on-bound peroxo complex. For the second reaction step, no element of reversibility was found.

  8. Kinetics of coal combustion: Part 3, Mechanisms and kinetics of char combustion

    Energy Technology Data Exchange (ETDEWEB)

    Gavalas, G. R.; Flagan, R. C. [California Inst. of Tech., Pasadena, CA (USA)

    1988-09-01

    This report summarizes a three-year research program aimed at developing this level of understanding of char combustion through a combination of detailed analysis of chars as produced during devolatilization and as they evolve during oxidation, and theoretical studies of the porous microstructures and of pore diffusion and reaction within the coal particles. A small number of coals have been studied in detail, namely a HVA bituminous (PSOC 1451), a sub-bituminous (PSOC 1488), and a lignite (PSOC 1443). Chars have been generated from size-classified samples of these coals by pyrolysis in an inert atmosphere in a drop tube furnace. The chars were then characterized both chemically and physically. Subsequent oxidation studies were performed on these chars. 42 refs., 54 figs., 4 tabs.

  9. Remote toehold: a mechanism for flexible control of DNA hybridization kinetics.

    Science.gov (United States)

    Genot, Anthony J; Zhang, David Yu; Bath, Jonathan; Turberfield, Andrew J

    2011-02-23

    Hybridization of DNA strands can be used to build molecular devices, and control of the kinetics of DNA hybridization is a crucial element in the design and construction of functional and autonomous devices. Toehold-mediated strand displacement has proved to be a powerful mechanism that allows programmable control of DNA hybridization. So far, attempts to control hybridization kinetics have mainly focused on the length and binding strength of toehold sequences. Here we show that insertion of a spacer between the toehold and displacement domains provides additional control: modulation of the nature and length of the spacer can be used to control strand-displacement rates over at least 3 orders of magnitude. We apply this mechanism to operate displacement reactions in potentially useful kinetic regimes: the kinetic proofreading and concentration-robust regimes.

  10. 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

  11. CSP-based chemical kinetics mechanisms simplification strategy for non-premixed combustion: An application to hybrid rocket propulsion

    KAUST Repository

    Ciottoli, Pietro P.

    2017-08-14

    A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics mechanism for hydrocarbon combustion. This mechanism is used for predictions of the oxidation of butadiene, the primary HTPB pyrolysis product. A Computational Singular Perturbation (CSP) based simplification strategy for non-premixed combustion is proposed. The simplification algorithm is fed with the steady-solutions of classical flamelet equations, these being representative of the non-premixed nature of the combustion processes characterizing a hybrid rocket combustion chamber. The adopted flamelet steady-state solutions are obtained employing pure butadiene and gaseous oxygen as fuel and oxidizer boundary conditions, respectively, for a range of imposed values of strain rate and background pressure. Three simplified chemical mechanisms, each comprising less than 20 species, are obtained for three different pressure values, 3, 17, and 36 bar, selected in accordance with an experimental test campaign of lab-scale hybrid rocket static firings. Finally, a comprehensive strategy is shown to provide simplified mechanisms capable of reproducing the main flame features in the whole pressure range considered.

  12. Reduced and Validated Kinetic Mechanisms for Hydrogen-CO-sir Combustion in Gas Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Yiguang Ju; Frederick Dryer

    2009-02-07

    Rigorous experimental, theoretical, and numerical investigation of various issues relevant to the development of reduced, validated kinetic mechanisms for synthetic gas combustion in gas turbines was carried out - including the construction of new radiation models for combusting flows, improvement of flame speed measurement techniques, measurements and chemical kinetic analysis of H{sub 2}/CO/CO{sub 2}/O{sub 2}/diluent mixtures, revision of the H{sub 2}/O{sub 2} kinetic model to improve flame speed prediction capabilities, and development of a multi-time scale algorithm to improve computational efficiency in reacting flow simulations.

  13. Curing kinetics, mechanism and chemorheological behavior of methanol etherified amino/novolac epoxy systems

    OpenAIRE

    S. F. Zhao; G.P. Zhang; Sun, R; C.P. Wong

    2014-01-01

    The curing kinetics and mechanism of epoxy novolac resin (DEN) and modified epoxy novolac resin (MDEN) with methanol etherified amino resin were studied by means of differential scanning calorimetry (DSC), Fourier transforminfrared (FT-IR) spectroscopy and chemorheological analysis. Their kinetics parameters and models of the curing were examined utilizing isoconversional methods, Flynn-Wall-Ozawa and Friedman methods. For the DEN mixture, its average activation energy (Ea) was 71.05 kJ/mol a...

  14. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms

    OpenAIRE

    Cui, You-Wei; Li,Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    2016-01-01

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM...

  15. Kinetics and Structure of Refractory Compounds and AlloysObtained by Mechanical Alloying

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Refractory compounds are material with interesting properties for structural applications. However, the processing of such material is a great challenge because of their high melting temperature and limited ductility. Mechanical alloying is a novel technique of producing refractory compounds with specific properties. Kinetical and structural peculiarities of refractory compounds and alloys obtained by mechanical alloying are discussed.

  16. Mechanisms, kinetics, impurities and defects: consequences in macromolecular crystallization

    OpenAIRE

    McPherson, Alexander; Kuznetsov, Yurii G

    2014-01-01

    New imaging techniques, particularly AFM, permitted the elucidation of the mechanisms for protein and virus crystal growth. They have also allowed direct visualization of crystal defect structure and the consequences of impurity incorporation.

  17. Catalytic oxidation ofS(IV) on activated carbon in aqueous suspension: kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brodzinsky, R.

    1981-02-01

    Activated carbon and combustion produced soot particles have been studied for their catalytic effect on the oxidation of aqueous sulfur(IV) species. Detailed kinetic studies of the reaction were performed on three different activated carbons and on a soot collected in a highway tunnel. Combustion produced soots were tested for their catalytic behavior and found to be similar to the activated carbons. The reaction rate was found to be linearly dependent on the concentration of carbon particles in the solution. The rate was found to follow a Langmuir adsorption isotherm for its dependence on oxygen and the product of two adsorption isotherms for S(IV). The reaction is independent of the pH of the solution when the pH is below 7.6. The reaction does not occur when the pH is above 7.6. The three aqueous S(IV) species are catalyzed in their oxidation by the carbon particles in a similar manner. Activation energies for the reactions on the different carbons are all about 8.5 kcal/mole. A possible four-step reaction mechanism is proposed. It consists of the adsorption of a dissolved oxygen molecule onto the carbon surface, followed by the adsorption of two S(IV) molecules or ions. These are oxidized on the surface to sulfate, which desorbs from the surface, regenerating the catalytically active site.

  18. In vitro kinetic analysis of oligofructose consumption by Bacteroides and Bifidobacterium spp. indicates different degradation mechanisms.

    Science.gov (United States)

    Van der Meulen, Roel; Makras, Lefteris; Verbrugghe, Kristof; Adriany, Tom; De Vuyst, Luc

    2006-02-01

    The growth of pure cultures of Bacteroides thetaiotaomicron LMG 11262 and Bacteroides fragilis LMG 10263 on fructose and oligofructose was examined and compared to that of Bifidobacterium longum BB536 through in vitro laboratory fermentations. Gas chromatography (GC) analysis was used to determine the different fractions of oligofructose and their degradation during the fermentation process. Both B. thetaiotaomicron LMG 11262 and B. fragilis LMG 10263 were able to grow on oligofructose as fast as on fructose, succinic acid being the major metabolite produced by both strains. B. longum BB536 grew slower on oligofructose than on fructose. Acetic acid and lactic acid were the main metabolites produced when fructose was used as the sole energy source. Increased amounts of formic acid and ethanol were produced when oligofructose was used as an energy source at the cost of lactic acid. Detailed kinetic analysis revealed a preferential metabolism of the short oligofructose fractions (e.g., F2 and F3) for B. longum BB536. After depletion of the short fractions, the larger oligofructose fractions (e.g., F4, GF4, F5, GF5, and F6) were metabolized, too. Both Bacteroides strains did not display such a preferential metabolism and degraded all oligofructose fractions simultaneously, transiently increasing the fructose concentration in the medium. This suggests a different mechanism for oligofructose breakdown between the strain of Bifidobacterium and both strains of Bacteroides, which helps to explain the bifidogenic nature of inulin-type fructans.

  19. Kinetics and mechanism of dimethoate chlorination during drinking water treatment.

    Science.gov (United States)

    Tian, Fang; Liu, Wenjun; Guo, Guang; Qiang, Zhimin; Zhang, Can

    2014-05-01

    Dimethoate (DMT), a commonly used organophosphorus pesticide, is of great concern because of its toxicity and potentially harmful effects on water sources. The elimination of DMT as well as the toxicity and persistence of the byproducts formed during DMT degradation is most important for the safety of drinking water. This study first determined the reaction kinetics of DMT with free chlorine (FC) under typical water treatment conditions. The reaction between DMT and FC proceeded rapidly, exhibiting first-order with respect to each reactant. The degradation of DMT by FC was highly pH dependent, and the pseudo-first-order rate constant decreased obviously from 0.13 to 0.02 s(-1) with an increase in pH from 7.0 to 8.3. Bromide ion accelerated the reaction by acting as a catalyst, and the accelerated reaction rate was linearly proportional to the bromide concentration. As a ubiquitous component in natural waters, humic acid also increased the reaction rate. However, the presence of ammonium inhibited the degradation of DMT due to its rapid converting FC to chloramines. Omethoate (OMT) was identified as an important byproduct of DMT chlorination, but only accounted for ca. 28% of the DMT degraded; and other two organic byproducts were also identified. The acute toxicity of DMT solution increased after treatment with FC due to the formation of more toxic byproducts (e.g. OMT).

  20. Exterior beam-column joint study with non-conventional reinforcement detailing using mechanical anchorage under reversal loading

    Indian Academy of Sciences (India)

    S Rajagopal; S Prabavathy

    2014-10-01

    Reinforced concrete structures beam-column joints are the most critical regions in seismic prone areas. Proper reinforcement anchorage is essential to enhance the performance of the joints. An attempt has been made to appraise the performance of the anchorages and joints. The anchorages are detailed as per ACI-352 (mechanical anchorages), ACI-318 (conventional bent hooks) and IS-456 (conventional full anchorage). The joints are detailed without confinement in group-I and with additional X-cross bar in group-II. To assess the seismic performance, the specimens are assembled into two groups of three specimens each and were tested under reversal loading, The specimen with T-type mechanical anchorage (Headed bar) and T-type mechanical anchorage combination with X-cross bar exhibited significant improvement in seismic performance: load-displacement capacity, displacement ductility, stiffness degradation, controlled crack capacity in the joint shear panel and also reduced congestion of reinforcement in joint core.

  1. A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

    Science.gov (United States)

    Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

    2016-09-29

    The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

  2. Three autocatalysts and self-inhibition in a single reaction: a detailed mechanism of the chlorite-tetrathionate reaction.

    Science.gov (United States)

    Horváth, Attila K; Nagypál, István; Epstein, Irving R

    2006-11-27

    The chlorite-tetrathionate reaction has been studied spectrophotometrically in the pH range of 4.65-5.35 at T = 25.0 +/- 0.2 degrees C with an ionic strength of 0.5 M, adjusted with sodium acetate as a buffer component. The reaction is unique in that it demonstrates autocatalysis with respect to the hydrogen and chloride ion products and the key intermediate, HOCl. The thermodynamically most-favorable stoichiometry, 2S(4)O(6)2- + 7ClO2- + 6H2O --> 8SO(4)2- + 7Cl- + 12H+, is not found. Under our experimental conditions, chlorine dioxide, the chlorate ion, or both are detected in appreciable amounts among the products. Initial rate studies reveal that the formation of chlorine dioxide varies in an unusual way, with the chlorite ion acting as a self-inhibitor. The reaction is supercatalytic (i.e., second order with respect to autocatalyst H+). The autocatalytic behavior with respect to Cl- comes from chloride catalysis of the chlorite-hypochlorous acid and hypochlorous acid-tetrathionate subsystems. A detailed kinetic study and a model that explains this unusual kinetic behavior are presented.

  3. Kinetic process of mechanical alloying in Fe50Cu50

    DEFF Research Database (Denmark)

    Huang, J.Y.; Jiang, Jianzhong; Yasuda, H.

    1998-01-01

    It is shown that mechanical alloying in the immiscible Fe-Cu system is governed by the atomic shear event and shear-induced diffusion process. We found that an alpha-to-gamma phase transformation, as evidenced by the Nishiyama-Wasserman orientation relationship, occurs by simultaneous shearing...... structures, until a complete fee Fe-Cu solid solution is formed. The results provide significant insight into the understanding of recent experiments showing that chemical mixing of immiscible elements can bd induced by mechanical alloying. [S0163-1829(98)51342-2]....

  4. Cell mechanics and stress: from molecular details to the 'universal cell reaction' and hormesis.

    Science.gov (United States)

    Agutter, Paul S

    2007-04-01

    The 'universal cell reaction' (UCR), a coordinated biphasic response to external (noxious and other) stimuli observed in all living cells, was described by Nasonov and his colleagues in the mid-20th century. This work has received no attention from cell biologists in the West, but the UCR merits serious consideration. Although it is non-specific, it is likely to be underpinned by precise mechanisms and, if these mechanisms were characterized and their relationship to the UCR elucidated, then our understanding of the integration of cellular function could be improved. As a step towards identifying such mechanisms, I review some recent advances in understanding cell mechanics and the stress response and I suggest potentially testable hypotheses. There is a particular need for time-course studies of cellular responses to different stimulus doses or intensities. I also suggest a correspondence with hormesis; re-investigation of the UCR using modern biophysical and molecular-biological techniques might throw light on this much-discussed phenomenon.

  5. Reaction kinetics and mechanism of magnetic field effects in cryptochrome

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing sixth sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically...

  6. Students' Misconceptions about Heat Transfer Mechanisms and Elementary Kinetic Theory

    Science.gov (United States)

    Pathare, S. R.; Pradhan, H. C.

    2010-01-01

    Heat and thermodynamics is a conceptually rich area of undergraduate physics. In the Indian context in particular there has been little work done in this area from the point of view of misconceptions. This prompted us to undertake a study in this area. We present a study of students' misconceptions about heat transfer mechanisms, i.e. conduction,…

  7. nonlinear kinetics and mechanism of nile blue reaction

    African Journals Online (AJOL)

    Prof. S.B. Jonnalagadda

    under varied oxidative and reducing media is pivotal in their applications as ... communication, we report the complex mechanism of the reaction between nile blue ... Both the instruments were interfaced for data storage and have ..... The authors acknowledge the financial support received from the University of Durban-.

  8. Derivation of a quantitative minimal model from a detailed elementary-step mechanism supported by mathematical coupling analysis

    Science.gov (United States)

    Shaik, O. S.; Kammerer, J.; Gorecki, J.; Lebiedz, D.

    2005-12-01

    Accurate experimental data increasingly allow the development of detailed elementary-step mechanisms for complex chemical and biochemical reaction systems. Model reduction techniques are widely applied to obtain representations in lower-dimensional phase space which are more suitable for mathematical analysis, efficient numerical simulation, and model-based control tasks. Here, we exploit a recently implemented numerical algorithm for error-controlled computation of the minimum dimension required for a still accurate reduced mechanism based on automatic time scale decomposition and relaxation of fast modes. We determine species contributions to the active (slow) dynamical modes of the reaction system and exploit this information in combination with quasi-steady-state and partial-equilibrium approximations for explicit model reduction of a novel detailed chemical mechanism for the Ru-catalyzed light-sensitive Belousov-Zhabotinsky reaction. The existence of a minimum dimension of seven is demonstrated to be mandatory for the reduced model to show good quantitative consistency with the full model in numerical simulations. We derive such a maximally reduced seven-variable model from the detailed elementary-step mechanism and demonstrate that it reproduces quantitatively accurately the dynamical features of the full model within a given accuracy tolerance.

  9. Kinetics and mechanism of removal of methylene blue by adsorption onto perlite.

    Science.gov (United States)

    Doğan, Mehmet; Alkan, Mahir; Türkyilmaz, Aydin; Ozdemir, Yasemin

    2004-06-18

    The kinetics and mechanism of methylene blue adsorption on perlite have been studied. The effects of various experimental parameters, such as initial dye concentration, temperature and pH on the adsorption rate were investigated. Adsorption measurements show that the process is very fast and physical in nature. The extent of the dye removal increased with increase in the initial concentration of the dye and the initial pH and temperature of solution. Adsorption data were modelled using the first and second-order kinetic equations, mass transfer and intra-particle diffusion models. It was shown that the second-order kinetic equation could best describe the sorption kinetics. The diffusion coefficient, D, was found to increase when the initial dye concentration, pH and temperature were raised. Thermodynamic activation parameters, such as DeltaG*, DeltaS* and DeltaH*, were calculated.

  10. Kinetics and mechanism of the adsorption of methylene blue onto ACFs

    Institute of Scientific and Technical Information of China (English)

    YANG Zhi-yuan

    2008-01-01

    The kinetics and mechanism of methylene blue (MB) adsorption onto activated carbon fibers (ACFs) have been studied.The effects of various experimental parameters, such as the initial MB concentration and the ACF mass, on the adsorption rate were investigated. Equilibrium data were fit well by a Freundlich isotherm equation. Adsorption measurements show that the process is very fast. The adsorption data were modeled using first- and second-order kinetic equations and intra-particle diffusion models. It was found that the first-order kinetic equation could best describe the adsorption kinetics. The adsorption process was found to be complex and controlled by both surface and pore diffusion with surface diffusion at the earlier stages, followed by pore diffusion at the later stages. The thermodynamic parameters △G0, △S0 and △H0, have been calculated. The thermodynamics of the MB-ACF system indicate that the adsorption process is spontaneous.

  11. Cholesterol increases kinetic, energetic, and mechanical stability of the human β2-adrenergic receptor

    DEFF Research Database (Denmark)

    Zocher, Michael; Zhang, Cheng; Rasmussen, Søren Gøgsig Faarup;

    2012-01-01

    the kinetic, energetic, and mechanical stability of almost every structural segment at sufficient magnitude to alter the structure and functional relationship of β(2)AR. One exception was the structural core segment of β(2)AR, which establishes multiple ligand binding sites, and its properties were...... to quantify the mechanical strength and flexibility, conformational variability, and kinetic and energetic stability of structural segments stabilizing the human β(2)-adrenergic receptor (β(2)AR) in the absence and presence of the cholesterol analog cholesteryl hemisuccinate (CHS). CHS considerably increased...

  12. A two-dimensional modeling of solid oxide fuel cell button cells with detailed electrochemistry mechanism

    Science.gov (United States)

    Li, Jingde; Bai, Zhengyu; Croiset, Eric

    2016-11-01

    A two-dimensional model of nickel/yttria-stabilized zirconia (Ni/YSZ) solid oxide fuel cell (SOFC) was developed for a button cell system. The model integrates the detailed catalytic, electrochemical elementary reactions with ionic/electronic conduction and multiple gas transport processes in SOFC. The model is validated using published experimental data for H2-H2O fuel gas under different cell sizes and operating conditions. The distributions of gas/surface phase species concentration and current density were predicted and the effects of operating temperature, fuel gas composition and fuel channel tube design on the cell performance were studied. The results show that the electrochemical reaction processes occurs mainly within a 20 μm distance from the anode/electrolyte interface and that the Ni catalyst surface is covered mainly by H(s). For the chamber channel design, the calculations show that the tube chamber should have a diameter no smaller than the cathode electrode to obtain the best SOFC performance.

  13. Reaction kinetics and mechanism of magnetic field effects in cryptochrome

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing sixth sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically...... sensitive radical pair reactions occurring in the retina, the light-sensitive part of animal eyes. A photoreceptor, cryptochrome, has been suggested to endow birds with magnetoreceptive abilities as the protein has been shown to exhibit the biophysical properties required for an animal magnetoreceptor...

  14. Detailed theoretical investigation of excited-state intramolecular proton transfer mechanism of a new chromophore II

    Science.gov (United States)

    Cui, Yanling; Li, Yafei; Dai, Yumei; Verpoort, Francis; Song, Peng; Xia, Lixin

    2016-02-01

    In the present work, TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II [Sensors and Actuators B: Chemical. 202 (2014) 1190]. The calculated absorption and fluorescence spectra agree well with experimental results. In addition, two types of II configurations are found in the first excited state (S1), which can be ascribed to the ESIPT reaction. Based on analysis of the calculated infrared (IR) spectra of O-H stretching vibration as well as the hydrogen bonding energies, the strengthening of the hydrogen bond in the S1 state has been confirmed. The frontier molecular orbitals (MOs), Hirshfeld charge distribution and the Natural bond orbital (NBO) have also been analyzed, which displays the tendency of the ESIPT process. Finally, potential energy curves of the S0 and S1 states were constructed, demonstrating that the ESIPT reaction can be facilitated based on the photo-excitation.

  15. Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kalay, Ilkay [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    research on the behaviors of glass forming alloys. Further motivation arising from the application of this system as a basis for many BMGs and ACC materials; the Cu-Zr system warrants this attention and offers great potential for the development of new materials. However, the prediction and control of microstructural evolution during devitrification remains challenging because of the complex devitrification behavior of the Cu-Zr binary alloy which is arising from the competition of metastable and stable phases and diversity of crystal structures. This dissertation details a systematic fundamental investigation into the mechanisms and kinetics of the various crystallization transformation processes involved in the overall devitrification response of Cu-Zr and Cu-Zr-Al glasses. Various isothermal and nonisothermal treatments are employed, and the structural response is characterized using bulk X-ray and thermal analysis methods as well as nanoscale microscopic analysis methods, revealing structural and chemical details down to the atomic-scale. By carefully combining techniques such as differential scanning calorimetry (DSC), in-situ synchrotron high energy X-ray diffraction (HEXRD), and transmission electron microscopy (TEM) to quantify the characterization transformations, this research has uncovered numerous details concerning the atomistic mechanisms of crystallization and has provided much new understanding related to the dominant phases, the overall reaction sequences, and the rate-controlling mechanisms. As such this work represents a substantial step forward in understanding these transformations and provides a clear framework for further progress toward ultimate application of controlled devitrification processing for the production of new materials with remarkable properties.

  16. Detailed monitoring of two biogas plants and mechanical solid-liquid separation of fermentation residues.

    Science.gov (United States)

    Bauer, Alexander; Mayr, Herwig; Hopfner-Sixt, Katharina; Amon, Thomas

    2009-06-01

    The Austrian "green electricity act" (Okostromgesetz) has led to an increase in biogas power plant size and consequently to an increased use of biomass. A biogas power plant with a generating capacity of 500 kW(el) consumes up to 38,000 kg of biomass per day. 260 ha of cropland is required to produce this mass. The high water content of biomass necessitates a high transport volume for energy crops and fermentation residues. The transport and application of fermentation residues to farmland is the last step in this logistic chain. The use of fermentation residues as fertilizer closes the nutrient cycle and is a central element in the efficient use of biomass for power production. Treatment of fermentation residues by separation into liquid and solid phases may be a solution to the transport problem. This paper presents detailed results from the monitoring of two biogas plants and from the analysis of the separation of fermentation residues. Furthermore, two different separator technologies for the separation of fermentation residues of biogas plants were analyzed. The examined biogas plants correspond to the current technological state of the art and have designs developed specifically for the utilization of energy crops. The hydraulic retention time ranged between 45.0 and 83.7 days. The specific methane yields were 0.40-0.43 m(3)N CH(4) per kg VS. The volume loads ranged between 3.69 and 4.00 kg VS/m(3). The degree of degradation was between 77.3% and 82.14%. The screw extractor separator was better suited for biogas slurry separation than the rotary screen separator. The screw extractor separator exhibited a high throughput and good separation efficiency. The efficiency of slurry separation depended on the dry matter content of the fermentation residue. The higher the dry matter content, the higher the proportion of solid phase after separation. In this project, we found that the fermentation residues could be divided into 79.2% fluid phase with a dry matter

  17. Mechanism and kinetics for scavenging superoxide anion by progesterone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The chemical reaction of progesterone with superoxide anion in 0.1 mol/L NaHCO3 medium is studied by polarography. Differing from the indirect inhibition of generation by synthesized glucocorticoids in mechanism, the function that progesterone scavenges is ascribed to that directly oxidizes the C == C double bond conjugated with the carbonyl moiety of progesterone molecule to a free radical, and then is reduced to H2O2. The result obtained in this work gives new evidence for biomedical research. The equation of rate constant of the oxidization reaction is de-duced, and the apparent rate constant obtained is 308 L·mol-1·s-1.

  18. Understanding the mechanical properties of DNA origami tiles and controlling the kinetics of their folding and unfolding reconfiguration.

    Science.gov (United States)

    Chen, Haorong; Weng, Te-Wei; Riccitelli, Molly M; Cui, Yi; Irudayaraj, Joseph; Choi, Jong Hyun

    2014-05-14

    DNA origami represents a class of highly programmable macromolecules that can go through conformational changes in response to external signals. Here we show that a two-dimensional origami rectangle can be effectively folded into a short, cylindrical tube by connecting the two opposite edges through the hybridization of linker strands and that this process can be efficiently reversed via toehold-mediated strand displacement. The reconfiguration kinetics was experimentally studied as a function of incubation temperature, initial origami concentration, missing staples, and origami geometry. A kinetic model was developed by introducing the j factor to describe the reaction rates in the cyclization process. We found that the cyclization efficiency (j factor) increases sharply with temperature and depends strongly on the structural flexibility and geometry. A simple mechanical model was used to correlate the observed cyclization efficiency with origami structure details. The mechanical analysis suggests two sources of the energy barrier for DNA origami folding: overcoming global twisting and bending the structure into a circular conformation. It also provides the first semiquantitative estimation of the rigidity of DNA interhelix crossovers, an essential element in structural DNA nanotechnology. This work demonstrates efficient DNA origami reconfiguration, advances our understanding of the dynamics and mechanical properties of self-assembled DNA structures, and should be valuable to the field of DNA nanotechnology.

  19. Kinetics and mechanism of the mercury(II)-assisted hydrolysis of methyl iodide.

    Science.gov (United States)

    Celo, Valbona; Scott, Susannah L

    2005-04-01

    The kinetics and mechanism of the reaction of aqueous Hg(II) with methyl iodide have been investigated. The overall reaction is best described as Hg(II)-assisted hydrolysis, resulting in quantitative formation of methanol and, in the presence of excess methyl iodide, ultimately, HgI2 via the intermediate HgI+. The kinetics are biexponential when methyl iodide is in excess. At 25 degrees C, the acceleration provided by Hg2+ is 7.5 times greater than that caused by HgI+, while assistance of hydrolysis was not observed for HgI2. Thus, the reactions are not catalytic in Hg(II). The kinetics are consistent with an SN2-M+ mechanism involving electrophilic attack at iodide. As expected, methylation of mercury is not a reaction pathway; traces of methylmercury(II) are artifacts of the extraction/preconcentration procedure used for methylmercury analysis.

  20. Aggregation kinetics of single-walled carbon nanotubes investigated using mechanically wrapped multinuclear complexes: probing the tube-tube repulsive barrier.

    Science.gov (United States)

    Ameen, Anjail A; Giordano, Andrea N; Alston, Jeffrey R; Forney, Michael W; Herring, Natalie P; Kobayashi, Shiho; Ridlen, Shawn G; Subaran, Sarah S; Younts, Thomas J; Poler, J C

    2014-03-28

    The rational design of supraparticle assemblies requires a detailed understanding of directed assembly processes. The stability of dispersions of nanoscale materials, like single-walled carbon nanotubes (SWCNTs), is still not fully understood, nor are the mechanisms of aggregation and assembly. A detailed balance of attractive van der Waals type interactions with various repulsive barrier mechanisms is needed to control the assembly of industrially viable and functional hybrid-nanoscale supraparticles. We report a detailed study of SWCNT dispersion stability and aggregation kinetics as a function of the nature of the coagulant used in various solvent systems. We explore three classes of coagulants that vary in charge, size, shape, solvation energy, and the ability to bind to the SWCNTs. We use these kinetic data to assess the tube-solvent-coagulant-tube interactions. We compare the relative contributions from two types of repulsive barriers. We find that tube-mediated structured solvent around the SWCNTs does not sufficiently describe our measured kinetic data. A DLVO type, electrical double layer repulsion is used to rationalize our observations. The data presented in this paper require a more detailed theoretical understanding of the physico-chemical environment near nanoparticle surfaces such as aggregating SWCNTs.

  1. On the estimation of cooperativity in ion channel kinetics: activation free energy and kinetic mechanism of Shaker K+ channel.

    Science.gov (United States)

    Banerjee, Kinshuk; Das, Biswajit; Gangopadhyay, Gautam

    2013-04-28

    In this paper, we have explored generic criteria of cooperative behavior in ion channel kinetics treating it on the same footing with multistate receptor-ligand binding in a compact theoretical framework. We have shown that the characterization of cooperativity of ion channels in terms of the Hill coefficient violates the standard Hill criteria defined for allosteric cooperativity of ligand binding. To resolve the issue, an alternative measure of cooperativity is proposed here in terms of the cooperativity index that sets a unified criteria for both the systems. More importantly, for ion channel this index can be very useful to describe the cooperative kinetics as it can be readily determined from the experimentally measured ionic current combined with theoretical modelling. We have analyzed the correlation between the voltage value and slope of the voltage-activation curve at the half-activation point and consequently determined the standard free energy of activation of the ion channel using two well-established mechanisms of cooperativity, namely, Koshland-Nemethy-Filmer (KNF) and Monod-Wyman-Changeux (MWC) models. Comparison of the theoretical results for both the models with appropriate experimental data of mutational perturbation of Shaker K(+) channel supports the experimental fact that the KNF model is more suitable to describe the cooperative behavior of this class of ion channels, whereas the performance of the MWC model is unsatisfactory. We have also estimated the mechanistic performance through standard free energy of channel activation for both the models and proposed a possible functional disadvantage in the MWC scheme.

  2. Scaling the sandbox: New insights from detailed mechanical testing and quantitative comparison to nature

    Science.gov (United States)

    Ritter, Malte C.; Leever, Karen; Rosenau, Matthias; Oncken, Onno

    2016-04-01

    Analogue sandbox experiments are an important tool to understand tectonic deformation. In combination with modern imaging techniques they provide a spatio-temporal resolution no other method can achieve. The downside is that information on stress distribution within the sandbox model is not readily available, which is the reason for most experiments to date being interpreted kinematically only. However, with the advent of reliable force sensors with a suitable dynamic range the dynamic evolution of sandbox models becomes available for analysis, offering new insights into the transient evolution of tectonic systems. The interpretation of sandbox dynamics and its transfer to natural systems requires a much stricter scaling approach than usually considered. In particular it requires that not only the strength of the model material, but also its transient strength evolution, i.e. its weakening, be properly scaled to that of the natural prototype. No such scaling of transient strength exists up to now. Furthermore, published mechanical test data have mostly been obtained under normal load conditions not representative for analogue experiments. To derive a scaling of transient strength we therefore measured and analysed two standard analogue model materials (quartz sand and glass microbeads) using ring-shear tests at low normal loads similar to common analogue experiments. We find that strain weakening under these conditions ( 1 kPa) only. We show that this basically restricts proper scaling of transient strength of the tested materials to crustal scale models, with a length scaling factor of (nature/model) = 106. For this scale range we quantitatively compare the model materials' transient strength evolution both laboratory measurements of natural rocks and to estimates for the earth' crust. Accounting for lithostatic and hydrostatic conditions, respectively, we find that proper dynamic scaling - also of transient properties - is achieved in either case.

  3. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an

  4. 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 techni...

  5. Kinetic mechanism of vanillyl-alcohol oxidase with short-chain 4-alkylphenols

    NARCIS (Netherlands)

    Fraaije, Marco W.; Heuvel, Robert H.H. van den; Roelofs, Jules C.A.A.; Berkel, Willem J.H. van

    1998-01-01

    The kinetic mechanism of vanillyl-alcohol oxidase with 4-methylphenol, 4-ethylphenol, 4-propylphenol and their Cα-deuterated analogs has been studied at pH 7.5 and 25°C. Conversion of 4-methylphenol is extremely slow (0.005 s-1) while the enzyme is largely in the reduced form during turnover.

  6. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the Indol- Phos–Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows a

  7. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an

  8. A Review of the Mechanism and Kinetics of Electrochemical Hydrogen Entry and Degradation of Metallic Systems

    Science.gov (United States)

    1990-01-01

    Acad. Tokyo, Japan 15: 39- 26. Frumkin, A. N., Slygin, A., 1953. Acta Physicochim. URSS 3: 791- 27. Vetter, K. J. 1967. Electrochemical Kinetics...CA 93940 China Lake, CA 93555 A-TN: Mechanical Engineering ATTN: Library Department 1 Naval Air Systems Command NASA Washington, DC 20360 Lewis

  9. Kinetics and Mechanisms of Ciprofloxacin Oxidation on Hematite Surfaces.

    Science.gov (United States)

    Martin, Sébastien; Shchukarev, Andrey; Hanna, Khalil; Boily, Jean-François

    2015-10-20

    Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment.

  10. Coupling between chemical kinetics and mechanics that is both nonlinear and compatible with thermodynamics.

    Science.gov (United States)

    Klika, Václav; Grmela, Miroslav

    2013-01-01

    Motivated by biological applications (e.g., bone tissue development and regeneration) we investigate coupling between mesoscopic mechanics and chemical kinetics. Governing equations of both dynamical systems are first written in a form expressing manifestly their compatibility with microscopic mechanics and thermodynamics. The same form is then required from governing equations of the coupled dynamics. The main result of the paper is an admissible form of the coupled dynamics.

  11. Detailed mechanisms of (1)H spin-lattice relaxation in ammonium dihydrogen phosphate confirmed by magic angle spinning.

    Science.gov (United States)

    Hayashi, Shigenobu; Jimura, Keiko

    2017-07-08

    Mechanisms of the (1)H spin-lattice relaxation in NH4H2PO4 were studied in detail by use of the effect of magic angle spinning on the relaxation. The acid and the ammonium protons have different relaxation times at the spinning rates higher than 10 kHz due to suppression of spin diffusion between the two kinds of protons. The intrinsic relaxation times not affected by the spin diffusion and the spin-diffusion assisted relaxation times were evaluated separately, taking into consideration temperature dependence. Both mechanisms contribute to the (1)H relaxation of the acid protons comparatively. The spin-diffusion assisted relaxation mechanism was suppressed to the level lower than the experimental errors at the spinning rate of 30 kHz. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. The combustion chemistry of a fuel tracer: Measured flame speeds and ignition delays and a detailed chemical kinetic model for the oxidation of acetone

    Energy Technology Data Exchange (ETDEWEB)

    Pichon, S.; Black, G.; Simmie, J.M.; Curran, H.J. [Combustion Chemistry Centre, National University of Ireland, Galway (Ireland); Chaumeix, N.; Yahyaoui, M. [Institut de Combustion Aerothermique Reactivite et Environnement, CNRS, Orleans (France); Donohue, R. [Information Technology, National University of Ireland, Galway (Ireland)

    2009-02-15

    Acetone ignition delay and stretch-free laminar flame speed measurements have been carried out and a kinetic model has been developed to simulate these and literature data for acetone and for ketene, which was found to be an important intermediate in its oxidation. The mechanism has been based on one originally devised for dimethyl ether and modified through validation of the hydrogen, carbon monoxide and methane sub-mechanisms. Acetone oxidation in argon was studied behind reflected shock waves in the temperature range 1340-1930 K, at 1 atm and at equivalence ratios of 0.5, 1 and 2; it is also shown that the addition of up to 15% acetone to a stoichiometric n-heptane mixture has no effect on the measured ignition delay times. Flame speeds at 298 K and 1 atm of pure acetone in air were measured in a spherical bomb; a maximum flame speed of {proportional_to}35 cm s{sup -1} at {phi}=1.15 is indicated. (author)

  13. Sulfate radical-based oxidation of fluoroquinolone antibiotics: Kinetics, mechanisms and effects of natural water matrices.

    Science.gov (United States)

    Jiang, Canlan; Ji, Yuefei; Shi, Yuanyuan; Chen, Jifei; Cai, Tianming

    2016-12-01

    Widespread occurrence of fluoroquinolone antibiotics (FQs) in surface water, groundwater, soil and sediment has been reported and their remediation is essentially needed. Sulfate radical (SO4(-)) based advanced oxidation processes (SR-AOPs) are promising technologies for soil and groundwater remediation. In this study, the degradation kinetics, mechanisms, and effects of natural water matrices on heat-activated persulfate (PS) oxidation of FQs were systematically investigated. Experimental results clearly demonstrated that 92% of CIP was removed within 180 min (pH = 7, 60 °C). Higher temperature and lower pH facilitated the degradation of ciprofloxacin (CIP). The piperazine moiety of CIP was identified as the reactive site for SO4(-) attack by comparison with substructural analogs, flumequine (FLU) and 1-(2-fluorophenyl) piperazine (FPP). A comparison of the degradation of CIP, norfloxacin (NOR), enrofloxacin (ENR) and ofloxacin (OFL) confirmed that the presence of cyclopropane ring also influence the degradation of FQs. Water matrix significantly influenced the degradation of CIP and ENR, and the degradation rate followed the order of Milli-Q water (pH = 7) > groundwater > artificial seawater > artificial surface water > lake water. Degradation products of CIP in different water matrix were enriched by solid phase extraction (SPE) and then analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). Detailed transformation pathways of CIP were proposed and were compared with respect to different water matrices. Four transformation pathways including stepwise piperazine ring oxidation, OH/F substitution, hydroxylation, and cyclopropane ring cleavage were proposed for CIP degradation. Results clearly show that the water matrix influenced the degradation of FQs appreciably, a phenomenon that should be taken into consideration when applying SR-AOPs for remediation of soil and groundwater contaminated by

  14. Afterglow kinetics and storage mechanism in CaF{sub 2}:Mn (TLD-400)

    Energy Technology Data Exchange (ETDEWEB)

    Danilkin, M. [Faculty of Physics and Chemistry, University of Tartu, Taehe 4, 51010 Tartu (Estonia)], E-mail: danilkin@ut.ee; Lust, A.; Ratas, A.; Seeman, V.; Kerikmaee, M. [Faculty of Physics and Chemistry, University of Tartu, Taehe 4, 51010 Tartu (Estonia)

    2008-02-15

    Thermoluminescence (TL) of CaF{sub 2}:Mn and the isothermal afterglow curves were studied after a pre-annealing of irradiated samples. Afterglow kinetics can be easily approximated with two exponents. A simple kinetic model is suggested. The TL main peak activation energy (1.597 eV) is very close to the dissociation energy of F{sub 2} molecule (1.606 eV) and exceeds the thermal decay activation energies of all the other intrinsic defects previously known in CaF{sub 2}. A mechanism of energy storage and release is discussed.

  15. Self-organized evolution of mechanism kinetic scheme based on axiomatic design

    Institute of Scientific and Technical Information of China (English)

    Feng Yixiong; Tan Jianrong; Wei Zhe; Hao He

    2007-01-01

    The self-organized evolution technology of the mechanism kinetic scheme based on axiomatic design is presented.This technology tries to express the constraints between kinetic mechanisms briefly in a semantic form which is more familiar to the designers.Though the mapping process between the kinetic chain unit and the unit instance,the evolution from abstract unit to concrete engineering instance is achieved.The subdivision of unit coupling semantics is studied.and the evolution of semantics is finished.Also.the semantic constraints evolution of unit coupling semantics is described.The product structure models with function and assembly meanings are constructed based on the kinematic chain unit and unit coupling.It provides a basis to realize the inheritance and transfer of constraint information from conceptual design to design for assembly(DFA).As the engineering practice result shows,the method Can help the engineers express their design intension more clearly and naturally in a high semantic level.And the automation,recursion and visualization of the mechanism kinetic scheme design are realized.

  16. Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate: methyl propanoate radicals with oxygen molecule.

    Science.gov (United States)

    Le, Xuan T; Mai, Tam V T; Ratkiewicz, Artur; Huynh, Lam K

    2015-04-23

    This paper presents a computational study on the low-temperature mechanism and kinetics of the reaction between molecular oxygen and alkyl radicals of methyl propanoate (MP), which plays an important role in low-temperature oxidation and/or autoignition processes of the title fuel. Their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The potential energy surfaces of the reactions between three primary MP radicals and molecular oxygen, namely, C(•)H2CH2COOCH3 + O2, CH3C(•)HCOOCH3 + O2, and CH3CH2COOC(•)H2 + O2, were constructed using the accurate composite CBS-QB3 method. Thermodynamic properties of all species as well as high-pressure rate constants of all reaction channels were derived with explicit corrections for tunneling and hindered internal rotations. Our calculation results are in good agreement with a limited number of scattered data in the literature. Furthermore, pressure- and temperature-dependent rate constants for all reaction channels on the multiwell-multichannel potential energy surfaces were computed with the quantum Rice-Ramsperger-Kassel (QRRK) and the modified strong collision (MSC) theories. This procedure resulted in a thermodynamically consistent detailed kinetic submechanism for low-temperature oxidation governed by the title process. A simplified mechanism, which consists of important reactions, is also suggested for low-temperature combustion at engine-like conditions.

  17. 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.

  18. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman

    2015-07-01

    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

  19. 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.

  20. The Kinetic Reaction Mechanism of the Vibrio cholerae Sodium-dependent NADH Dehydrogenase*♦

    Science.gov (United States)

    Tuz, Karina; Mezic, Katherine G.; Xu, Tianhao; Barquera, Blanca; Juárez, Oscar

    2015-01-01

    The sodium-dependent NADH dehydrogenase (Na+-NQR) is the main ion transporter in Vibrio cholerae. Its activity is linked to the operation of the respiratory chain and is essential for the development of the pathogenic phenotype. Previous studies have described different aspects of the enzyme, including the electron transfer pathways, sodium pumping structures, cofactor and subunit composition, among others. However, the mechanism of the enzyme remains to be completely elucidated. In this work, we have studied the kinetic mechanism of Na+-NQR with the use of steady state kinetics and stopped flow analysis. Na+-NQR follows a hexa-uni ping-pong mechanism, in which NADH acts as the first substrate, reacts with the enzyme, and the oxidized NAD leaves the catalytic site. In this conformation, the enzyme is able to capture two sodium ions and transport them to the external side of the membrane. In the last step, ubiquinone is bound and reduced, and ubiquinol is released. Our data also demonstrate that the catalytic cycle involves two redox states, the three- and five-electron reduced forms. A model that gathers all available information is proposed to explain the kinetic mechanism of Na+-NQR. This model provides a background to understand the current structural and functional information. PMID:26004776

  1. Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction of Dinitroglycoluril

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Feng-Qi(赵凤起); HU,Rong-Zu(胡荣祖); CHEN,Pei(陈沛); LUO,Yang(罗阳); GAO,Sheng-Li(高胜利); SONG,Ji-Rong(宋纪蓉); SHI,Qi-Zhen(史启祯)

    2004-01-01

    Under linear temperature increase condition, the thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of the title compound have been studied by means of DSC and IR. The initial stage of the mechanism was proposed. The empirical kinetic model function in differential form, apparent activation energy and pre-exponential constant of the exothermic decomposition reaction are α 0.526, 207.0 kJ·mol-1 and 1018.49 s-1, respectively. The critical temperature of thermal explosion of the compound is 252.87 ℃. The values of △S≠, △H≠ and △G≠ of the reaction are 128.4 J·mol-1·K-1, 218.9 kJ·mol-1 and 152.7 kJ·mol-1, respectively.

  2. Kinetic behavior of the general modifier mechanism of Botts and Morales with non-equilibrium binding

    CERN Document Server

    Jia, Chen; Qian, Min-Ping; Jiang, Da-Quan; Zhang, Yu-Ping

    2010-01-01

    In this paper, we thoroughly investigate the kinetic behavior of the general modifier mechanism of Botts and Morales at both equilibrium steady state assuming equilibrium substrate- and modifier-binding steps and non-equilibrium steady state (NESS) without assuming equilibrium binding steps. We introduce the net flux into discussion and propose a method which gains a strong advantage over early approaches involving King-Atman method and even the numerical computations in dealing with the cyclic reaction systems. Using this new approach, the expression of product rate at NESS gives clear biophysical significance. Moreover, we classify the kinetic behavior of the modifier into three categories, namely hyperbolic behavior, bell-shaped behavior, and switching behavior. It turns out that a modifier cannot be regarded as overall activator or inhibitor when the reaction system is not at equilibrium. The switching-behaved modifier may convert between activator and inhibitor via the general modifier mechanism when the...

  3. Kinetics and mechanism of the oxidative bromination of o-xylene in solution

    Energy Technology Data Exchange (ETDEWEB)

    Dorfman, Ya.A.; Emel' yanova, V.S.; Efremenko, I.G.; Doroshkevich, D.M.; Korolev, A.V.

    1988-07-01

    The kinetics of oxidative bromination of aromatic compounds have been studied in HNO/sub 3/-HBr-H/sub 2/SO/sub 4/-H/sub 2/O-O/sub 2/ solution. A kinetic equation which describes the results was derived for P/sub O/sub 2// > 5 /times/ 10/sup 4/ Pa. The equation parameters were determined at a temperature of 323 K. Quantum mechanical CNDO calculations were carried out in order to study the nature of the reactive intermediates involved: NO/sub 2/ NO(OH)/sup +/, N(OH)/sub 2//sup 2 +/, NO(OH)Br, and N(OH)/sub 2/Br/sup +/. A mechanism has been proposed to account for the oxidative bromination of aromatic compounds in HNO/sub 3/-H/sub 2/SO/sub 4/-HBr-O/sub 2/-H/sub 2/ solution.

  4. Adsorption mechanism of malachite green onto activated phosphate rock: a kinetics and theoretical study

    Directory of Open Access Journals (Sweden)

    LABIDI Nouar Sofiane

    2016-08-01

    Full Text Available Adsorption kinetics of malachite green onto Algerian activated phosphate rock was studied for better removal of the dye from wastewater. The prepared sorbent displayed à good surface area of 42.2 m²/g. The adsorption process appeared to be of physisorption nature and it took less than 60 min to get equilibrium whereas the kinetics indicated that the adsorption is likely a second order reaction which is further proved with the high R2 value. The intraparticle diffusion model confirms an adsorption mechanism limited on two steps, i.e., (1 surface adsorption, and (2 pore diffusion with a diffusion parameter of Di=10-18 cm2 s-1. Besides, semi-empirical theoretical calculations provide a new insight into adsorption mechanism as a principle of hydrogen bonding and ionic interaction.

  5. Aftershock mechanisms from the 2010 Mw 8.8 Maule, Chile earthquake: detailed analysis using full waveform inversion

    Science.gov (United States)

    Rietbrock, A.; Hicks, S. P.; Chagas, B.; Detzel, H. A.

    2014-12-01

    Since the earthquake rupture process is extremely heterogeneous, it is vital to understand how structural variations in the overriding plate and downgoing slab may control slip style along the subduction megathrust. The large-scale 3-D geometry of subduction plate boundaries is rapidly becoming well understood; however, the nature of any finer-scale structure along the plate interface remains elusive. A detailed study of earthquake source mechanisms along a megathrust region can shed light on the nature of fine-scale structures along the megathrust. The Mw 8.8 Maule earthquake that struck central Chile in 2010 is the sixth largest earthquake ever recorded. Following the earthquake, there was an international deployment of seismic stations in the rupture area, making this one of the best datasets of an aftershock sequence following a large earthquake. This dataset provides a unique opportunity to perform a detailed study of megathrust earthquake source mechanisms. Based on a high-resolution 3-D velocity model and robust earthquake locations [Hicks et al., 2014], we calculate regional moment tensors using the ISOLA software package [Sokos & Zahradnik, 2008]. We incorporate accelerometer recordings, important for constraining solutions of large earthquakes in the overriding plate. We also validate the robustness of our solutions by assessing the consistency of mechanisms with P-wave polarities observed at both onshore and offshore seismic stations, and compare them to already published solutions. We find that accurate earthquake locations are vital for the fine-scale interpretation of focal mechanisms, particularly for offshore events. Our results show that most moment tensor solutions with thrusting mechanisms have a nodal plane dipping parallel to the subducting plate interface. Interestingly, we also find earthquakes with normal faulting mechanisms lying along to the megathrust plate interface in the south of the rupture area. This finding suggests that megathrust

  6. Simulations of Magnetic Reconnection - Kinetic Mechanisms Underlying the Fluid Description of Ions

    Science.gov (United States)

    Aunai, icolas; Belmont, Gerard; Smets, Roch

    2012-01-01

    Because of its ability to transfer the energy stored in magnetic field together with the breaking of the flux freezing constraint, magnetic reconnection is considered as one of the most important phenomena in plasma physics. When it happens in a collision less environment such as the terrestrial magnetosphere, it should a priori be modelled with in the framework of kinetic physics. The evidence of kinetic features has incidentally for a long time, been shown by researchers with the help of both numerical simulations and satellite observations. However, most of our understanding of the process comes from the more intuitive fluid interpretation with simple closure hypothesis which do not include kinetic effects. To what extent are these two separate descriptions of the same phenomenon related? What is the role of kinetic effects in the averaged/fluid dynamics of reconnection? This thesis addresses these questions for the proton population in the particular case of anti parallel merging with the help of 2D Hybrid simulations. We show that one can not assume, as is usually done, that the acceleration of the proton flow is only due to the Laplace force. Our results show, for symmetric and asymmetric connection, the importance of the pressure force, opposed to the electric one on the separatrices, in the decoupling region. In the symmetric case, we emphasize the kinetic origin of this force by analyzing the proton distribution functions and explain their structure by studying the underlying particle dynamics. Protons, as individual particles, are shown to bounce in the electric potential well created by the Hall effect. The spatial divergence of this well results in a mixing in phase space responsible for the observed structure of the pressure tensor. A detailed energy budget analysis confirms the role of the pressure force for the acceleration; but, contrary to what is sometimes assumed, it also reveals that the major part of the incoming Poynting flux is transferred to

  7. Kinetics and mechanism of the oxidation process of two-component Fe-Al alloys

    Science.gov (United States)

    Przewlocka, H.; Siedlecka, J.

    1982-01-01

    The oxidation process of two-component Fe-Al alloys containing up to 7.2% Al and from 18 to 30% Al was studied. Kinetic measurements were conducted using the isothermal gravimetric method in the range of 1073-1223 K and 1073-1373 K for 50 hours. The methods used in studies of the mechanism of oxidation included: X-ray microanalysis, X-ray structural analysis, metallographic analysis and marker tests.

  8. The kinetics and mechanism of the substitution of benzylideneacetone by azadienes in the irontricarbonylbenzylideneacetone complex

    OpenAIRE

    Squizani, F; E. Stein(INFN Turin); VICHI, EJS

    1996-01-01

    The kinetics of the substitution reactions of benzylideneacetone (bda) by the azadienes 2,2'-bipyridine (bipy), 2-acetylpyridineanil (apa), and diacetyldianil (dad), in the Fe(bda)(CO)(3) complex was performed in toluene in the temperature range between 40 and 55 degrees C. The results of this study showed that the mechanism of the reactions with bipy and dad - which are symmetric ligands, aromatic and aliphatic, respectively - involves two parallel reaction paths, one being dissociative and ...

  9. The kinetic mechanism of wild-type and mutant mouse dihydrofolate reductases.

    Science.gov (United States)

    Thillet, J; Adams, J A; Benkovic, S J

    1990-05-29

    A kinetic mechanism is presented for mouse dihydrofolate reductase that predicts all the steady-state parameters and full time-course kinetics. This mechanism was derived from association and dissociation rate constants and pre-steady-state transients by using stopped-flow fluorescence and absorbance measurements. The major features of this kinetic mechanism are as follows: (1) the two native enzyme conformers, E1 and E2, bind ligands with varying affinities although only one conformer, E1, can support catalysis in the forward direction, (2) tetrahydrofolate dissociation is the rate-limiting step under steady-state turnover at low pH, and (3) the pH-independent rate of hydride transfer from NADPH to dihydrofolate is fast (khyd = 9000 s-1) and favorable (Keq = 100). The overall mechanism is similar in form to the Escherichia coli kinetic scheme (Fierke et al., 1987), although several differences are observed: (1) substrates and products predominantly bind the same form of the E. coli enzyme, and (2) the hydride transfer rate from NADPH to either folate or dihydrofolate is considerably faster for the mouse enzyme. The role of Glu-30 (Asp-27 in E. coli) in mouse DHFR has also been examined by using site-directed mutagenesis as a potential source of these differences. While aspartic acid is strictly conserved in all bacterial DHFRs, glutamic acid is conserved in all known eucaryotes. The two major effects of substituting Asp for Glu-30 in the mouse enzyme are (1) a decreased rate of folate reduction and (2) an increased rate of hydride transfer from NADPH to dihydrofolate.(ABSTRACT TRUNCATED AT 250 WORDS)

  10. 基于详细反应机理的富燃多孔燃烧制氢的计算流体力学模拟%Determination of Hydrogen Production from Rich Filtration Combustion with Detailed Kinetics Based CFD Method

    Institute of Scientific and Technical Information of China (English)

    李国能; 周昊; 钱欣平; 岑可法

    2008-01-01

    Computational fluid dynamics (CFD) combined with detailed chemical kinetics was employed to model the filtration combustion of a mixture of methane/air in a packed bed of uniform 3 nun diameter alumina spherical particles. The standard k-ε turbulence model and a methane oxidation mechanism with 23 species and 39 elemental reactions were used. Various equivalence ratios (1.47, 1.88, 2.12 and 2.35) were studied. The numerical results showed good agreement with the experimental data. For ultra-rich mixtures, the combustion temperature exceeds the adiabatic value by hundreds of centigrade degrees. Syngas (hydrogen and carbon monoxide) can be obtained up to a mole fraction of 23%. The numerical results also showed that the combination of CFD with detailed chemical kinetics gives good performance for modeling the pseudo-homogeneous flames of methane in porous media.

  11. Adsorption mechanism of malachite green onto activated phosphate rock: a kinetics and theoretical study

    Directory of Open Access Journals (Sweden)

    Nouar Sofiane Labidi

    2016-07-01

    Full Text Available Original Research Adsorption mechanism of malachite green onto activated phosphate rock: a kinetics and theoretical study Nouar Sofiane Labidi* , Nour Elhouda Kacemi AuthorAffiliations Department of Materials Sciences, Institute of Science and Technologies. University Centre of Tamanrasset, Algeria GrantInformation Get PDF Get XML Export Share Abstract Adsorption kinetics of malachite green onto the Algerian activated phosphate rock was studied for better removal of the dye from wastewater. The prepared sorbent displayed à good surface area of 42.2 m²/g. The adsorption process appeared to be of physisorption nature and it took less than 60 min to get equilibrium whereas the kinetics indicated that the adsorption is likely a second order reaction, which is further proved with the high R2 value. The intraparticle diffusion model confirms an adsorption mechanism limited on two steps, i.e., (1 surface adsorption, and (2 pore diffusion with a diffusion parameter of Di=10-18 cm2 /s. Besides, semi-empirical theoretical calculations provide a new insight into adsorption mechanism as a principle of hydrogen bonding and ionic interaction.

  12. Ejecta Cloud from a Kinetic Impact on the Secondary of a Binary Asteroid: I. Mechanical Environment and Dynamic Model

    CERN Document Server

    Yu, Yang; Schwartz, Stephen R; Naidu, Shantanu P; Benner, Lance A M

    2016-01-01

    An understanding of the post-impact dynamics of ejecta clouds are crucial to the planning of a kinetic impact mission to an asteroid, and also has great implications for the history of planetary formation. The purpose of this article to track the evolution of ejecta produced by AIDA mission, which targets for kinetic impact the secondary of near-Earth binary asteroid 65803 Didymos on 2022, and to feedback essential informations to AIDA's ongoing phase-A study. We present a detailed dynamic model for the simulation of an ejecta cloud from a binary asteroid that synthesizes all relevant forces based on a previous analysis of the mechanical environment. We apply our method to gain insight into the expected response of Didymos to the AIDA impact, including the subsequent evolution of debris and dust. The crater scaling relations from laboratory experiments are employed to approximate the distributions of ejecta mass and launching speed. The size composition of fragments is modeled with a power law fitted from obs...

  13. RESEARCH OF KINETIC AND DIFFUSIVE MECHANISMS IN THE ADSORPTION OF Cu (II IN SUGAR CANE BAGASSE ASH

    Directory of Open Access Journals (Sweden)

    Julio Omar Prieto García

    2016-10-01

    Full Text Available In this paper a kinetic and diffusive study regarding adsorption of ions Cu (II on a sample of sugar cane bagasse ash is made. The results show that the second-order kinetic model better adjusts the experimental data than the Elovich and first-order kinetic model. The diffusive mechanism study shows that the diffusion in the liquid pellicle and in the micro-pores of the adsorbent prevail in the adsorption phenomenon.

  14. Anti-Inflammatory Applications of Melittin, a Major Component of Bee Venom: Detailed Mechanism of Action and Adverse Effects

    Directory of Open Access Journals (Sweden)

    Gihyun Lee

    2016-05-01

    Full Text Available Inflammation is a pervasive phenomenon triggered by the innate and adaptive immune systems to maintain homeostasis. The phenomenon normally leads to recovery from infection and healing, but when not properly phased, inflammation may cause immune disorders. Bee venom is a toxin that bees use for their protection from enemies. However, for centuries it has been used in the Orient as an anti-inflammatory medicine for the treatment of chronic inflammatory diseases. Bee venom and its major component, melittin, are potential means of reducing excessive immune responses and provide new alternatives for the control of inflammatory diseases. Recent experimental studies show that the biological functions of melittin could be applied for therapeutic use in vitro and in vivo. Reports verifying the therapeutic effects of melittin are accumulating in the literature, but the cellular mechanism(s of the anti-inflammatory effects of melittin are not fully elucidated. In the present study, we review the current knowledge on the therapeutic effects of melittin and its detailed mechanisms of action against several inflammatory diseases including skin inflammation, neuroinflammation, atherosclerosis, arthritis and liver inflammation, its adverse effects as well as future prospects regarding the use of melittin.

  15. Mechanisms and Kinetics of Environmentally Assisted Cracking: Current Status, Issues, and Suggestions for Further Work

    Science.gov (United States)

    Lynch, S. P.

    2013-03-01

    Mechanisms and kinetics of metal-induced embrittlement, hydrogen-embrittlement, and stress-corrosion cracking are discussed, and long-standing controversies are addressed by reviewing critical observations. Recommendations are also made regarding further work (including repetition of previous work using more advanced measurement and characterisation techniques) that should be carried out in order to resolve some of the contentious issues. The evidence to date suggests that adsorption-based mechanisms, involving weakening of substrate interatomic bonds so that dislocation emission or decohesion is facilitated, accounts for embrittlement in many systems. Embrittling adsorbed species include some metal atoms, hydrogen, and complex ions produced by de-alloying. Other viable mechanisms of embrittlement include those based on (1) dissolution of anodic grain-boundary regions, and (2) decohesion at grain boundaries owing to segregated hydrogen and impurities. The hydrogen-enhanced localised-plasticity mechanism, based on solute hydrogen facilitating dislocation activity in the plastic zone ahead of cracks, makes a contribution in some cases, but is relatively unimportant compared with these other mechanisms for most fracture modes. The film-induced cleavage mechanism, proposed especially for stress-corrosion cracking in systems involving de-alloying at crack tips, is questionable on numerous grounds, and is probably not viable. Rate-controlling processes for environmentally assisted cracking are not well established, except for solid-metal induced embrittlement where surface self-diffusion of embrittling atoms to crack tips controls cracking kinetics. In some systems, adsorption kinetics are probably rate-controlling for liquid-metal embrittlement, hydrogen-environment embrittlement, and stress-corrosion cracking. In other cases, rate-controlling processes could include the rate of anodic or cathodic reactions at and behind crack tips (responsible for producing embrittling

  16. Mechanisms of starch digestion by α-amylase-Structural basis for kinetic properties.

    Science.gov (United States)

    Dhital, Sushil; Warren, Frederick J; Butterworth, Peter J; Ellis, Peter R; Gidley, Michael J

    2017-03-24

    Recent studies of the mechanisms determining the rate and extent of starch digestion by α-amylase are reviewed in the light of current widely-used classifications for (a) the proportions of rapidly-digestible (RDS), slowly-digestible (SDS), and resistant starch (RS) based on in vitro digestibility, and (b) the types of resistant starch (RS 1,2,3,4…) based on physical and/or chemical form. Based on methodological advances and new mechanistic insights, it is proposed that both classification systems should be modified. Kinetic analysis of digestion profiles provides a robust set of parameters that should replace the classification of starch as a combination of RDS, SDS, and RS from a single enzyme digestion experiment. This should involve determination of the minimum number of kinetic processes needed to describe the full digestion profile, together with the proportion of starch involved in each process, and the kinetic properties of each process. The current classification of resistant starch types as RS1,2,3,4 should be replaced by one which recognizes the essential kinetic nature of RS (enzyme digestion rate vs. small intestinal passage rate), and that there are two fundamental origins for resistance based on (i) rate-determining access/binding of enzyme to substrate and (ii) rate-determining conversion of substrate to product once bound.

  17. Transformation of ferrihydrite to hematite: an in situ investigation on the kinetics and mechanisms

    OpenAIRE

    H. P. Vu; S. Shaw; Liane G. Benning

    2008-01-01

    The kinetics and mechanisms of the transformation of 2-line ferrihydrite (FH) to hematite (HM), in the presence of Pb at elevated temperatures and high pH condition, were elucidated using synchrotron-based, in situ energy dispersive X-ray diffraction (EDXRD). The time-resolved diffraction data indicated that HM crystallization occurred via a two-stage process. Based on the EDXRD data, combined with high-resolution electron microscopic images, an aqueous-aided 2D growth mechanism is proposed f...

  18. Development of Detailed and Reduced Kinetics Mechanisms for Surrogates of Petroleum-Derived and Synthetic Jet Fuels

    Science.gov (United States)

    2014-12-04

    nitrogen are introduced into an opposed jet annular mixing nozzle at the inlet to the quartz reactor tube. A water-cooled, borosilicate glass-lined...where it is rapidly mixed with synthetic air in the opposed jet annular mixing nozzle. Further dilution with nitrogen is used to limit temperature...the 700 K temperature sample point. Figure 3 presents the key linear alkenes measured during n-PCH oxidation. In addition to ethene, propene, and

  19. Development of Detailed and Reduced Kinetics Mechanisms for Surrogates of Petroleum-Derived and Synthetic Jet Fuels

    Science.gov (United States)

    2011-02-28

    chromatography . All flow rates and data acquisition are computer controlled via a PC with LabVIEW software. The temperature range of the present...the majority of the n- dodecane has decomposed , the residual absorption signal is dominated by the decomposition products with the highest absorption...be assured, in principle, by systematic studies of individual rate coefficients. However, the inherent uncertainties in the rate data leave a

  20. Dissolution Condensation Mechanism of Stress Corrosion Cracking in Liquid Metals: Driving Force and Crack Kinetics

    Science.gov (United States)

    Glickman, Evgeny E.

    2011-02-01

    Stress corrosion cracking (SCC) in aqueous solution is driven by exothermic reactions of metal oxidation. This stimulus, as well as classical mechanisms of SCC, does not apply to SCC in liquid metals (LMs). In the framework of the dissolution-condensation mechanism (DCM), we analyzed the driving force and crack kinetics for this nonelectrochemical mode of SCC that is loosely called "liquid metal embrittlement" (LME). According to DCM, a stress-induced increase in chemical potential at the crack tip acts as the driving force for out-of-the-tip diffusion mass transfer that is fast because diffusion in LMs is very fast and surface energy at the solid-liquid interface is small. In this article, we review two versions of DCM mechanism, discuss the major physics behind them, and develop DCM further. The refined mechanism is applied then to the experimental data on crack velocity V vs stress intensity factor, the activation energy of LME, and alloying effects. It is concluded that DCM provides a good conceptual framework for analysis of a unified kinetic mechanism of LME and may also contribute to SCC in aqueous solutions.

  1. Kinetics and reaction mechanism of yeast alcohol dehydrogenase with long-chain primary alcohols.

    Science.gov (United States)

    Schöpp, W; Aurich, H

    1976-01-01

    Kinetic studies of yeast alcohol dehydrogenase with NAD+ and ethanol, hexanol or decanol as substrates invariably result in non-linear Lineweaver-Burk plots if the alcohol is the variable substrate. The kinetic coefficients determined from secondary plots are consistent with an 'equilibrium random-order' mechanism for extremely low alcohol concentrations and for all alcohols, the transformation of the ternary complexes being the rate-limiting step of the reaction. This mechanism also applies to long-chain substrates at high concentrations, whereas the rate of the ethanol-NAD+ reaction at high ethanol concentrations is determined by the dissociation of the enzyme-NADH complex. The dissociation constants for the enzyme-NAD+ complex and for the enzyme-alcohol complexes obtained from the kinetic quotients satisfactorily correspond to the dissociation constants obtained by use of other techniques. It is suggested that the non-linear curves may be attributed to a structural change in the enzyme itself, caused by the alcohol. PMID:183740

  2. Structural and kinetic insights into the mechanism of 5-hydroxyisourate hydrolase from Klebsiella pneumoniae

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Ealick, Steven E., E-mail: see3@cornell.edu [Cornell University, Ithaca, NY 14853-1301 (United States)

    2011-08-01

    The crystal structure of 5-hydroxyisourate hydrolase from K. pneumoniae and the steady-state kinetic parameters of the native enzyme as well as several mutants provide insights into the catalytic mechanism of this enzyme and the possible roles of the active-site residues. The stereospecific oxidative degradation of uric acid to (S)-allantoin has recently been demonstrated to proceed via two unstable intermediates and requires three separate enzymatic reactions. The second step of this reaction, the conversion of 5-hydroxyisourate (HIU) to 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline, is catalyzed by HIU hydrolase (HIUH). The high-resolution crystal structure of HIUH from the opportunistic pathogen Klebsiella pneumoniae (KpHIUH) has been determined. KpHIUH is a homotetrameric protein that, based on sequence and structural similarity, belongs to the transthyretin-related protein family. In addition, the steady-state kinetic parameters for this enzyme and four active-site mutants have been measured. These data provide valuable insight into the functional roles of the active-site residues. Based upon the structural and kinetic data, a mechanism is proposed for the KpHIUH-catalyzed reaction.

  3. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Directory of Open Access Journals (Sweden)

    Sokić M.

    2012-01-01

    Full Text Available Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time on the leaching degree of zinc were investigated and kinetic analysis of the process was accomplished. With temperature increasing from 60 to 90°C, the zinc leaching increased from 25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model indicated that the diffusion through the product layer was the rate-controlling step during the sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range 60-90°C. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

  4. Mechanical disassembly of single virus particles reveals kinetic intermediates predicted by theory.

    Science.gov (United States)

    Castellanos, Milagros; Pérez, Rebeca; Carrillo, Pablo J P; de Pablo, Pedro J; Mateu, Mauricio G

    2012-06-06

    New experimental approaches are required to detect the elusive transient intermediates predicted by simulations of virus assembly or disassembly. Here, an atomic force microscope (AFM) was used to mechanically induce partial disassembly of single icosahedral T=1 capsids and virions of the minute virus of mice. The kinetic intermediates formed were imaged by AFM. The results revealed that induced disassembly of single minute-virus-of-mice particles is frequently initiated by loss of one of the 20 equivalent capsomers (trimers of capsid protein subunits) leading to a stable, nearly complete particle that does not readily lose further capsomers. With lower frequency, a fairly stable, three-fourths-complete capsid lacking one pentamer of capsomers and a free, stable pentamer were obtained. The intermediates most frequently identified (capsids missing one capsomer, capsids missing one pentamer of capsomers, and free pentamers of capsomers) had been predicted in theoretical studies of reversible capsid assembly based on thermodynamic-kinetic models, molecular dynamics, or oligomerization energies. We conclude that mechanical manipulation and imaging of simple virus particles by AFM can be used to experimentally identify kinetic intermediates predicted by simulations of assembly or disassembly. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  5. Transport in semiconductor nanowire superlattices described by coupled quantum mechanical and kinetic models.

    Science.gov (United States)

    Alvaro, M; Bonilla, L L; Carretero, M; Melnik, R V N; Prabhakar, S

    2013-08-21

    In this paper we develop a kinetic model for the analysis of semiconductor superlattices, accounting for quantum effects. The model consists of a Boltzmann-Poisson type system of equations with simplified Bhatnagar-Gross-Krook collisions, obtained from the general time-dependent Schrödinger-Poisson model using Wigner functions. This system for superlattice transport is supplemented by the quantum mechanical part of the model based on the Ben-Daniel-Duke form of the Schrödinger equation for a cylindrical superlattice of finite radius. The resulting energy spectrum is used to characterize the Fermi-Dirac distribution that appears in the Bhatnagar-Gross-Krook collision, thereby coupling the quantum mechanical and kinetic parts of the model. The kinetic model uses the dispersion relation obtained by the generalized Kronig-Penney method, and allows us to estimate radii of quantum wire superlattices that have the same miniband widths as in experiments. It also allows us to determine more accurately the time-dependent characteristics of superlattices, in particular their current density. Results, for several experimentally grown superlattices, are discussed in the context of self-sustained coherent oscillations of the current density which are important in an increasing range of current and potential applications.

  6. The chemical mechanism of nitrogenase: calculated details of the intramolecular mechanism for hydrogenation of eta(2)-N(2) on FeMo-co to NH(3).

    Science.gov (United States)

    Dance, Ian

    2008-11-21

    Using density functional calculations, a complete chemical mechanism has been developed for the reaction N(2) + 6e(-) + 6H(+)--> 2NH(3) catalyzed by the Fe(7)MoS(9)N(c)(homocitrate) cofactor (FeMo-co) of the enzyme nitrogenase. The mechanism is based on previous descriptions of the generation of H atoms on FeMo-co by proton relay through a protein path terminating in water molecule 679, and preserves the model (which explains much biochemical data) for vectorial migration of H atoms to two S atoms and two Fe atoms of FeMo-co. After calculation of the energy profiles for the many possible sequences of steps in which these H atoms are transferred to N(2) and its hydrogenated intermediates, a favourable pathway to 2NH(3) was developed. Transition states and activation potential energies for the 21 step mechanism are presented, together with results for some alternative branches. The mechanism develops logically from the eta(2)-coordination of N(2) at the endo position of one Fe atom of prehydrogenated FeMo-co, consistent with the previous kinetic-mechanistic scheme of Thorneley and Lowe, and passes through bound N(2)H(2) and N(2)H(4) intermediates. This mechanism is different from others in the literature because it uses a single replenishable path for serial supply of protons which become H atoms on FeMo-co, migrating to become S-H and Fe-H donors to N(2) and to the intermediates that follow. The new paradigm for the chemical catalysis is that hydrogenation of N(2) and intermediates is intramolecular and does not involve direct protonation from surrounding residues which appear to be unable to provide a replenishable supply of 6H(+). Many steps in this intramolecular hydrogenation are expected to be enhanced by H tunneling.

  7. Structural and kinetic insights into the mechanism of 5-hydroxyisourate hydrolase from Klebsiella pneumoniae

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Ealick, Steven E. (Cornell)

    2011-07-19

    The stereospecific oxidative degradation of uric acid to (S)-allantoin has recently been demonstrated to proceed via two unstable intermediates and requires three separate enzymatic reactions. The second step of this reaction, the conversion of 5-hydroxyisourate (HIU) to 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline, is catalyzed by HIU hydrolase (HIUH). The high-resolution crystal structure of HIUH from the opportunistic pathogen Klebsiella pneumoniae (KpHIUH) has been determined. KpHIUH is a homotetrameric protein that, based on sequence and structural similarity, belongs to the transthyretin-related protein family. In addition, the steady-state kinetic parameters for this enzyme and four active-site mutants have been measured. These data provide valuable insight into the functional roles of the active-site residues. Based upon the structural and kinetic data, a mechanism is proposed for the KpHIUH-catalyzed reaction.

  8. 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.

  9. Kinetics and Mechanism of the Oxidation of Menthol by Potassium Bromate in Acidic Solution

    Directory of Open Access Journals (Sweden)

    Ravikant na

    2014-06-01

    Full Text Available No suitable method is available for the estimation of menthol, hence in all kinetic results reported in this chapter, menthol was in excess over potassium bromate and the stoichiometry was also determined under the experimental conditions where menthol (substrate was in excess over potassium bromate (oxidant. Present study was focused on the analysis of kinetics and mechanism of oxidation of neomenthol by potassium bromate in acidic medium. For oxidizing neomenthol, potassium bromate stock solution (5.0×10─2 mol. dm─3 was prepared by dissolving exactly weighed quantity of potassium bromate in doubly distilled water. The suitable reaction mixtures were prepared and left at 313 K for over 24 hours to ensure complete oxidation of neomenthol. The unreacted potassium bromate was determined iodometrically and the results indicate that one mole of potassium bromate is consumed for every three moles of neomenthol and leads to the formation of menthone (ketone.

  10. Kinetics and mechanism of the anilino lysis of O-ethyl phenyl phosphonochloridothioic in acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Hoque, Md. Ehtesham Ul; Lee, Hai Whang [Inha Univ., Incheon (Korea, Republic of)

    2012-04-15

    The nucleophilic substitution reactions of O-ethyl phenyl phosphonochloridothioic with substituted anilines (XC{sub 6}H{sub 4}NH{sub 2}) and deuterated anilines (XC{sub 6}H{sub 4}ND{sub 2}) are kinetically investigated in acetonitrile at 55.0 .deg. C. The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE (k{sub H}/k{sub D} = 0.93) to a primary normal DKIE (k{sub H}/k{sub D} = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to front side attack. A concerted S{sub N}2 mechanism is proposed. A trigonal bipyramidal TS is proposed for a backside attack while a hydrogen-bonded, four-center-type TS is proposed for a front side attack.

  11. Oxidation of glycylglycine by ferricyanide in acid medium: Kinetics and mechanism

    Directory of Open Access Journals (Sweden)

    Krishna K. Yerneni

    2015-12-01

    Full Text Available The oxidative degradation of glycylglycine (GlyGly to formic acid, ammonium ion, and carbon dioxide occurs when it reacts with ferricyanide in acid medium, which has been studied spectrophotometrically at 303 nm at constant temperature. Kinetic runs have been performed under a pseudo-first-order condition of [GlyGly]0 >> [ferricyanide]0. The experimental rate law obtained for the redox reaction is: rate = kı [$ \\text{Fe(CN}^{3 - }_{6} $] [GlyGly]x [H+]y[Pd(II]0, where x and y are fractional orders. Effects of ionic strength and dielectric constant are also investigated. Activation parameters have been evaluated using Arrhenius and Eyring plots. A probable mechanism has been proposed and the derived rate law is consistent with the kinetic data.

  12. Mechanism and Kinetics of Thermal Decomposition of MgCl2 × 6H2O

    Science.gov (United States)

    Huang, Qiong-Zhu; Lu, Gui-Min; Wang, Jin; Yu, Jian-Guo

    2010-10-01

    The reaction mechanism and kinetic behavior of thermal decomposition of MgCl2 × 6H2O were studied by thermal gravimetric analysis. The results showed that the thermal decomposition process of MgCl2 × 6H2O could be divided into six stages. In the first two stages, four crystalline waters were lost. The dehydration and hydrolysis coexisted during the third and fourth stages. The fifth stage corresponded to the evaporation of 0.3 crystalline waters, and one molecular hydrogen chloride was eliminated in the last stage. The kinetic analysis of the thermal decomposition process was performed using the Doyle, Coats-Redfern, and Malek methods. The results suggested that the mechanisms of six stages were two-dimensional phase boundary mechanism, three-dimensional phase boundary mechanism, nucleation and nuclei growth mechanism (Avrami-Erofeev equation n = 3), two-dimensional phase boundary mechanism, three-dimensional diffusion mechanism (cylinder and G-B equation), and nucleation and nuclei growth mechanism (Avrami-Erofeev equation n = 1), respectively. The apparent active energies of six stages were 66.8 kJ × mol-1, 138.0 kJ × mol-1, 77.2 kJ × mol-1, 135.6 kJ × mol-1, 77.4 kJ × mol-1, and 92.2 kJ × mol-1, respectively. The frequency factors were 3.6 × 109 s-1, 8.8 × 1017 s-1, 4.6 × 109 s-1, 3.0 × 1014 s-1, 78.6 s-1, and 1.2 × 103 s-1, respectively.

  13. Interaction of lipoprotein lipase with p-nitrophenyl N-alkylcarbamates: kinetics, mechanism, and analogy to the acylenzyme mechanism.

    Science.gov (United States)

    Shin, H C; Quinn, D M

    1992-01-28

    The interaction of lipoprotein lipase with p-nitrophenyl N-alkylcarbamates [PNPOC(=O)-NHCnH2n+1; n = 4, 8, and 12] proceeds by the three-stage mechanism shown below. After reversible [formula: see text] formation of the enzyme-carbamate complex (EC), rapid carbamylation (kc) precedes slow decarbamylation. Therefore, in short-term assays (less than or equal to 30 min) of lipoprotein lipase catalyzed hydrolysis of p-nitrophenyl butyrate, activity is rapidly lost. The inhibition by p-nitrophenyl N-butylcarbamate follows saturation kinetics, which allows determination of Kc = 5.4 +/- 0.9 microM and kc = (4.9 +/- 0.7) x 10(-2)s-1. Saturation kinetics are not observed for the longer inhibitors p-nitrophenyl N-octylcarbamate and p-nitrophenyl N-dodecylcarbamate. Rather, plots of the pseudo-first-order rate constant for activity loss versus inhibitor concentration are concave upward, consistent with inhibitor binding to two sites on the enzyme. The inhibition phase is sufficiently rapid that p-nitrophenyl N-octylcarbamate can be used to titrate enzyme active sites. On the other hand, long-term assays (greater than 5 h) show sequential inhibition and activity return phases, and from the activity return phase kd is calculated. The long-term activity time course is accurately simulated by Runge-Kutta integration of the differential equations for the three-stage mechanism. These approaches have been used to characterize the kinetics of interaction of the enzyme with the carbamate inhibitors.(ABSTRACT TRUNCATED AT 250 WORDS)

  14. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-02-15

    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

  15. Curing Kinetics, Mechanical Properties and Thermal Stability of Epoxy/Graphene Nanoplatelets (GNPs) Powder Coatings

    Institute of Scientific and Technical Information of China (English)

    ZHI Maoyong; HUANG Wanxia

    2016-01-01

    Epoxy/graphene nanoplatelets (GNPs) powder coatings were fabricated using ultrasonic pre-dispersion of GNPs and melt-blend extrusion method. The isothermal curing kinetics of epoxy/GNPs powder coating were monitored by means of real-time Fourier transform infrared spectroscopy (FT-IR) with a heating cell. The mechanical properties of the epoxy/GNPs cured coatings had been investigated, by evaluating their fracture surfaces with ifeld-emission scanning electron microscopy (FE-SEM) after three-point-bending tests. The thermal stability of the epoxy/GNPs cured coatings was studied by thermo-gravimetric analysis (TGA). The isothermal curing kinetics result showed that the GNPs would not affect the autocatalytic reaction mechanism, but the loading of GNPs below 1.0 wt % additive played a prompting role in the curing of the epoxy/GNPs powder coatings. The fracture strain, fracture toughness and impact resistance of the epoxy/GNPs cured coatings increased dramatically at low levels of GNPs loading (1 wt %), indicating that the GNPs could improve the toughness of the epoxy/GNPs powder coatings. Furthermore, from FE-SEM studies of the fracture surfaces, the possible toughening mechanisms of the epoxy/GNPs cured coatings were proposed. TGA result showed that the incorporation of GNPs improved the thermal stability of the cured coatings. Hence, the GNPs modiifed epoxy can be an efifcient approach to toughen epoxy powder coating along with improving their thermal stability.

  16. Kinetic theory approach to modeling of cellular repair mechanisms under genome stress.

    Directory of Open Access Journals (Sweden)

    Jinpeng Qi

    Full Text Available Under acute perturbations from outer environment, a normal cell can trigger cellular self-defense mechanism in response to genome stress. To investigate the kinetics of cellular self-repair process at single cell level further, a model of DNA damage generating and repair is proposed under acute Ion Radiation (IR by using mathematical framework of kinetic theory of active particles (KTAP. Firstly, we focus on illustrating the profile of Cellular Repair System (CRS instituted by two sub-populations, each of which is made up of the active particles with different discrete states. Then, we implement the mathematical framework of cellular self-repair mechanism, and illustrate the dynamic processes of Double Strand Breaks (DSBs and Repair Protein (RP generating, DSB-protein complexes (DSBCs synthesizing, and toxins accumulating. Finally, we roughly analyze the capability of cellular self-repair mechanism, cellular activity of transferring DNA damage, and genome stability, especially the different fates of a certain cell before and after the time thresholds of IR perturbations that a cell can tolerate maximally under different IR perturbation circumstances.

  17. Kinetics and Mechanisms of Cadmium Carbonate Heteroepitaxial Growth at the Calcite (101¯4) Surface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10-14) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  18. Kinetics and mechanisms of cadmium carbonate heteroepitaxial growth at the calcite (10 1bar 4) surface

    Science.gov (United States)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10 1bar 4) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  19. Kinetics and mechanism of the thermal decomposition of unsaturated aldehydes: benzaldehyde, 2-butenal, and 2-furaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Grela, M.A.; Colussi, A.J.

    1986-01-30

    The thermal unimolecular decomposition of benzaldehyde (BA), crotonaldehyde (CA), and furfural (FA) have been investigated in a flow reactor at very low pressures by modulated beam mass spectrometry above 1040 K. Each reaction proceeds by a different mechanism. Whereas BA decomposes by C(O)-H bond fission CA readily undergoes decarbonylation to propene via a three-center transition-state reaction. FA decomposition into vinylketene and CO involves ring opening followed by H-atom transfer in the resulting biradical. Overall high-pressure Arrhenius parameters for the three reactions are derived from kinetic data. 26 references, 4 figures, 1 table.

  20. Kinetics and Mechanism of Oxidation of L-Cystine by Hexacyanoferrate(III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Annapurna Nowduri

    2009-01-01

    Full Text Available Kinetics of oxidation of L-cystine by hexacyanoferrate(III was studied in alkaline medium at 30 °C. The reaction was followed spectrophotometrically at λmax = 420 nm. The reaction was found to be first order dependence each on [HCF(III] and [cystine]. It was found that the rate of the reaction increases with increase in [OH-]. The oxidation product of the reaction was found to be cysteic acid. A plausible mechanism has been proposed to account for the experimental results.

  1. Kinetics and Mechanism of Oxidation of Some Diols by Dihydroxydiperiodatoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHAN, Jin-Huan; LI, Sheng-Min; HUO, Shu-Ying; SHEN, Shi-Gang; SUN, Han-Wen

    2006-01-01

    The kinetics of oxidation of ethylene glycol and 1,3-butylene glycol by dihydroxydiperiodatoargentate(Ⅲ) in alkaline medium have been studied by spectrophotometry in the range of 298.2-318.2 K. It is shown that the reaction was first order with respect to each reductant and Ag(Ⅲ), and kobs increased with an increase of [OH-]. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between complex and reductants was proposed, which could be applied to explain all experimental phenomena, and the activation parameters of the ratedetermining step have been also calculated.

  2. Tribological, Thermal, and Kinetic Characterization of 300-mm Copper Chemical Mechanical Planarization Process

    Science.gov (United States)

    Jiao, Yubo; Adi Sampurno, Yasa; Zhuang, Yun; Wei, Xiaomin; Meled, Anand; Philipossian, Ara

    2011-05-01

    In this study, the tribological, thermal, and kinetic attributes of 300-mm copper chemical mechanical planarization were characterized for two different pads. The coefficient of friction (COF) ranged from 0.39 to 0.59 for the D100 pad, indicating that boundary lubrication was the dominant tribological mechanism. In comparison, COF decreased sharply from 0.55 to 0.03 for the IC1000 pad, indicating that the tribological mechanism transitioned rapidly from boundary lubrication to partial lubrication. Consequently, the D100 pad exhibited higher pad temperatures and removal rates than the IC1000 pad. A two-step modified Langmuir-Hinshelwood model was used to simulate copper removal rates as well as chemical and mechanical rate constants. The simulated copper removal rates agreed very well with experimental data and the model successfully captured the non-Prestonian behavior. The simulated chemical rate to mechanical rate constant ratios indicated that the IC1000 pad generally produced a more mechanically controlled removal mechanism than the D100 pad.

  3. Cure kinetics, morphologies, and mechanical properties of thermoplastic/MWCNT modified multifunctional glassy epoxies prepared via continuous reaction methods

    Science.gov (United States)

    Cheng, Xiaole

    The primary goal of this dissertation is to develop a novel continuous reactor method to prepare partially cured epoxy prepolymers for aerospace prepreg applications with the aim of replacing traditional batch reactors. Compared to batch reactors, the continuous reactor is capable of solubilizing and dispersing a broad range of additives including thermoplastic tougheners, stabilizers, nanoparticles and curatives and advancing epoxy molecular weights and viscosities while reducing energy consumption. In order to prove this concept, polyethersulfone (PES) modified 4, 4'-diaminodiphenylsulfone (44DDS)/tetraglycidyl-4, 4'-diaminodiphenylmethane (TGDDM) epoxy prepolymers were firstly prepared using both continuous reactor and batch reactor methods. Kinetic studies confirmed the chain extension reaction in the continuous reactor is similar to the batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy (AFM) confirmed similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded mechanical properties of cured epoxy matrices produced from both reactors were equivalent. Effects of multifunctional epoxy compositions on thermoplastics phase-separated morphologies were systematically studied using a combination of AFM with nanomechanical mapping, spectroscopic and calorimetric techniques to provide new insights to tailor cured reaction induced phase separation (CRIPS) in multifunctional epoxy blend networks. Furthermore, how resultant crosslinked glassy polymer network and phase-separated morphologies correlated with mechanical properties are discussed in detail. Multiwall carbon nanotube (MWCNT)/TGDDM epoxy prepolymers were further prepared by combining the successful strategies for advancing epoxy chemistries and dispersing nanotubes using the continuous reactor

  4. Debromination of polybrominated diphenyl ethers by attapulgite-supported Fe/Ni bimetallic nanoparticles: Influencing factors, kinetics and mechanism.

    Science.gov (United States)

    Liu, Zongtang; Gu, Chenggang; Ye, Mao; Bian, Yongrong; Cheng, Yinwen; Wang, Fang; Yang, Xinglun; Song, Yang; Jiang, Xin

    2015-11-15

    To enhance the removal efficiency of 2,2',4,4'-tetrabromodiphenylether (BDE47) in aqueous solutions, novel attapulgite-supported Fe/Ni bimetallic nanoparticles (A-Fe/Ni), which were characterized by a core-shell nanoparticle structure and with an average diameter of 20-40 nm, were synthesized for use in BDE47 degradation. The presence of attapulgite in bimetallic systems could reduce Fe/Ni nanoparticle aggregation and enhance their reactivity. BDE47 was degraded with a significant improvement in removal efficiency of at least 96% by A-Fe/Ni that played a reductive role in the reaction. The degradation kinetics of BDE47 by A-Fe/Ni complied with pseudo-first-order characteristics. To better understand the removal mechanism, detailed analyses were performed for several influential parameters. The improved dosage of A-Fe/Ni was found to be beneficial, and higher values of initial concentration, pH, and methanol/water ratio hindered the degradation rate, which, for example, decreased significantly in mixtures with a methanol proportion higher than 50%. The identification of BDE47 degradation products revealed a stepwise debromination from n-bromo-DE to (n-1)-bromo-DE as a possible pathway, wherein the para-Br was more easily eliminated than ortho-Br. Our findings provide insight into the removal mechanism and evidence for polybrominated diphenyl ether debromination by clay-Fe/Ni bimetallic nanoparticles. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. A detailed kinetic study of the direct ring opening of cyclohexane and methylcyclohexane over monofunctional Ir/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Hui; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    The present study analyses a series of Al{sub 2}O{sub 3}-supported iridium catalysts with different pretreatments and addresses the kinetic features and structural requirements of direct ring opening of cyclohexane and methylcyclohexane catalyzed by Ir in absence of acid-catalyzed ring contraction. Mild reaction conditions and high H{sub 2}/hydrocarbon ratios (200-1000) were used to improve accuracy of kinetic measurements and to negate deactivation. Isomerization and dehydrogenation pathways were suppressed to low extents (1-5%) over the weakly acidic catalysts under the reaction conditions applied. Three main observations are shown: 1) initial selectivity to ring opening products (ROPs) increases with iridium dispersion; 2) optimal H{sub 2} pressures differ not only between primary and secondary products, but also among ROPs and fragments; 3) the air-calcination step before catalyst reduction imposes a significant impact on both activity and product distribution. (orig.)

  6. Biofilm Formation Mechanisms of Pseudomonas aeruginosa Predicted via Genome-Scale Kinetic Models of Bacterial Metabolism.

    Science.gov (United States)

    Vital-Lopez, Francisco G; Reifman, Jaques; Wallqvist, Anders

    2015-10-01

    A hallmark of Pseudomonas aeruginosa is its ability to establish biofilm-based infections that are difficult to eradicate. Biofilms are less susceptible to host inflammatory and immune responses and have higher antibiotic tolerance than free-living planktonic cells. Developing treatments against biofilms requires an understanding of bacterial biofilm-specific physiological traits. Research efforts have started to elucidate the intricate mechanisms underlying biofilm development. However, many aspects of these mechanisms are still poorly understood. Here, we addressed questions regarding biofilm metabolism using a genome-scale kinetic model of the P. aeruginosa metabolic network and gene expression profiles. Specifically, we computed metabolite concentration differences between known mutants with altered biofilm formation and the wild-type strain to predict drug targets against P. aeruginosa biofilms. We also simulated the altered metabolism driven by gene expression changes between biofilm and stationary growth-phase planktonic cultures. Our analysis suggests that the synthesis of important biofilm-related molecules, such as the quorum-sensing molecule Pseudomonas quinolone signal and the exopolysaccharide Psl, is regulated not only through the expression of genes in their own synthesis pathway, but also through the biofilm-specific expression of genes in pathways competing for precursors to these molecules. Finally, we investigated why mutants defective in anthranilate degradation have an impaired ability to form biofilms. Alternative to a previous hypothesis that this biofilm reduction is caused by a decrease in energy production, we proposed that the dysregulation of the synthesis of secondary metabolites derived from anthranilate and chorismate is what impaired the biofilms of these mutants. Notably, these insights generated through our kinetic model-based approach are not accessible from previous constraint-based model analyses of P. aeruginosa biofilm

  7. Kinetics and Mechanism of Oxidation of t-Butylbenzylamine by Diperiodatoargentate(III in Aqueous Alkali

    Directory of Open Access Journals (Sweden)

    Mahantesh A. Angadi

    2012-01-01

    Full Text Available t-Butylbenzylamine (t-BA is used as a free base in the synthesis of salbutamol drug. Its mechanism of oxidation was proposed from kinetic studies. The kinetics of oxidation of t-butylbenzylamine by diperiodatoargentate(III (DPA was studied spectrophotometrically by monitoring decrease in absorbance of DPA. The reaction was found to be first order each in [DPA] and [t-BA]. The effect of alkali concentration in a wide range on rate of reaction was studied. The rate of reaction was found to be increased with increase in [OH–] in the lower range of [OH–], decreasing effect in the middle range and at higher range again increasing effect on rate of reaction was observed. The added periodate retarded the rate of reaction. The polymerization test revealed that oxidation was occurred with the intervention free radical. A suitable mechanism was proposed for a middle range of [OH–]. The active species of silver(III periodate for all the three different stages of [OH–] are assayed. Rate law was derived and verified. The oxidative product of t-BA was characterized by LC-ESI-MS spectra.

  8. Extracting signal from noise: kinetic mechanisms from a Michaelis-Menten-like expression for enzymatic fluctuations.

    Science.gov (United States)

    Moffitt, Jeffrey R; Bustamante, Carlos

    2014-01-01

    Enzyme-catalyzed reactions are naturally stochastic, and precision measurements of these fluctuations, made possible by single-molecule methods, promise to provide fundamentally new constraints on the possible mechanisms underlying these reactions. We review some aspects of statistical kinetics: a new field with the goal of extracting mechanistic information from statistical measures of fluctuations in chemical reactions. We focus on a widespread and important statistical measure known as the randomness parameter. This parameter is remarkably simple in that it is the squared coefficient of variation of the cycle completion times, although it places significant limits on the minimal complexity of possible enzymatic mechanisms. Recently, a general expression has been introduced for the substrate dependence of the randomness parameter that is for rate fluctuations what the Michaelis-Menten expression is for the mean rate of product generation. We discuss the information provided by the new kinetic parameters introduced by this expression and demonstrate that this expression can simplify the vast majority of published models. © 2013 FEBS.

  9. Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

    Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

  10. Isotherm, thermodynamic, kinetics and adsorption mechanism studies of methyl orange by surfactant modified silkworm exuviae

    Energy Technology Data Exchange (ETDEWEB)

    Chen Hao, E-mail: chenhao2212@sohu.com [School of Pharmaceutical and Chemical Engineering, Taizhou University, Dongfang Road No. 605, Linhai 317000, Zhejiang (China); Zhao Jie; Wu Junyong; Dai Guoliang [School of Pharmaceutical and Chemical Engineering, Taizhou University, Dongfang Road No. 605, Linhai 317000, Zhejiang (China)

    2011-08-15

    This paper reports on the development of organo-modified silkworm exuviae (MSE) adsorbent prepared by using hexadecyltrimethylammonium bromide (HDTMAB) for removing methyl orange (MO), a model anionic dye, from aqueous solution. The natural and modified samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectroscopy (FT-IR). Batch adsorption experiments were carried out to remove MO from its aqueous solutions using SE and MSE. It was observed that the adsorption capacity of MSE is 5-6 times of SE. The different parameters effecting on the adsorption capacity such as pH of the solution, initial dye concentration, temperature and contact time have been investigated. Analysis of adsorption results obtained at different temperatures showed that the adsorption pattern on the MSE can be described perfectly with Langmuir isotherm model compared with Freundlich and Dubinin-Radushkevich (D-R) isotherm models, and the characteristic parameters for each adsorption isotherm were also determined. The adsorption process has been found exothermic in nature and thermodynamic parameters have been calculated. The adsorption kinetic followed the pseudo-second order kinetic model. The results of FT-IR, EDS and desorption studies all suggest that methyl orange adsorption onto the MSE should be mainly controlled by the hydrophobic interaction mechanism, along with a considerable contribution of the anionic exchange mechanism. The results indicate that HDTMAB-modified silkworm exuviae could be employed as low-cost material for the removal of methyl orange anionic dye from wastewater.

  11. Kinetics and Mechanism of the Aminolyses of Bis(2-oxo-3-oxazolidinyl) Phosphinic Chloride in Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Barai, Hasi Rani; Lee, Hai Whang [Inha Univ., Incheon (Korea, Republic of)

    2013-11-15

    The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and 35.0 .deg. C, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted S{sub N}2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects (k{sub H}/k{sub D}) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

  12. Cure kinetics and mechanical interfacial characteristics of zeolite/DGEBA composites

    Energy Technology Data Exchange (ETDEWEB)

    Park, Soo Jin; Kim, Young Mi [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Shin, Jae Sup [Chungbuk National Univ., Cheongju (Korea, Republic of)

    2003-10-15

    In this work, the zeolite/diglycidylether of bisphenol A(DGEBA) systems were investigated in terms of the cure kinetics and mechanical interfacial properties of the composites. The 4, 4-Diamino Diphenyl Methane(DDM) was used as a curing agent for epoxy. Two types of zeolite(PZ) were prepared with 15 and 35 wt% KOH treatments(15-BZ and 35-BZ, respectively) for 24 h, and their surface characteristics were studied by X-ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD). Cure kinetics of the composites were examined in the context of Differential Scanning Calorimetry(DSC), and mechanical interfacial properties were investigated in critical stress intensity factor(K{sub IC}) and critical strain energy release rate(G{sub IC}). In the results of XPS and XRD, sodium ion(Na) of zeolite was exchanged for potassium ion(K), resulting from the treatment of KOH. Also, Si{sub 2p}/A1{sub 2p} composition ratios of the treated zeolite were increased, which could be attributed to the weakening of A1-O bond in framework. Cure activation energy(E{sub a}) of 15-BZ composites was decreased, whereas K{sub IC} and G{sub IC} were increased, compared with those of the pure zeolite/DGEBA composites. It was probably accounted that the acidity of zeolite was increased by surface treatments and the cure reaction between zeolite and epoxy was influenced on the increased acidity of zeolite.

  13. Curing kinetics, mechanism and chemorheological behavior of methanol etherified amino/novolac epoxy systems

    Directory of Open Access Journals (Sweden)

    S. F. Zhao

    2014-02-01

    Full Text Available The curing kinetics and mechanism of epoxy novolac resin (DEN and modified epoxy novolac resin (MDEN with methanol etherified amino resin were studied by means of differential scanning calorimetry (DSC, Fourier transforminfrared (FT-IR spectroscopy and chemorheological analysis. Their kinetics parameters and models of the curing were examined utilizing isoconversional methods, Flynn-Wall-Ozawa and Friedman methods. For the DEN mixture, its average activation energy (Ea was 71.05 kJ/mol and the autocatalytic model was established to describe the curing reaction. The MDEN mixture exhibited three dominant curing processes, termed as reaction 1, reaction 2 and reaction 3; and their Ea were 70.05, 106.55 and 101.91 kJ/mol, respectively. Besides, Ea of reaction 1 was similar to that of DEN mixture, while Ea of reactions 2 and 3 corresponded to that of the etherification reaction between hydroxyl and epoxide group. Moreover, these three dominant reactions were nth order in nature. Furthermore, their curing mechanisms were proposed from the results of DSC and FTIR. The chemorheological behavior was also investigated to obtain better plastics products via optimizing the processing schedules.

  14. Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

    Institute of Scientific and Technical Information of China (English)

    刘润静; 陈建峰; 郭奋; 吉米; 沈志刚

    2003-01-01

    Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern''s equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃ lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151 kJ·mo1-1 while the literature value for normal calcite was approximately 200 kJ ·mol-1. The order of magnitude of Dre-exvonential factors was estimated to be 109 s-1.

  15. Isotherm, thermodynamic, kinetics and adsorption mechanism studies of methyl orange by surfactant modified silkworm exuviae.

    Science.gov (United States)

    Chen, Hao; Zhao, Jie; Wu, Junyong; Dai, Guoliang

    2011-08-15

    This paper reports on the development of organo-modified silkworm exuviae (MSE) adsorbent prepared by using hexadecyltrimethylammonium bromide (HDTMAB) for removing methyl orange (MO), a model anionic dye, from aqueous solution. The natural and modified samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectroscopy (FT-IR). Batch adsorption experiments were carried out to remove MO from its aqueous solutions using SE and MSE. It was observed that the adsorption capacity of MSE is 5-6 times of SE. The different parameters effecting on the adsorption capacity such as pH of the solution, initial dye concentration, temperature and contact time have been investigated. Analysis of adsorption results obtained at different temperatures showed that the adsorption pattern on the MSE can be described perfectly with Langmuir isotherm model compared with Freundlich and Dubinin-Radushkevich (D-R) isotherm models, and the characteristic parameters for each adsorption isotherm were also determined. The adsorption process has been found exothermic in nature and thermodynamic parameters have been calculated. The adsorption kinetic followed the pseudo-second order kinetic model. The results of FT-IR, EDS and desorption studies all suggest that methyl orange adsorption onto the MSE should be mainly controlled by the hydrophobic interaction mechanism, along with a considerable contribution of the anionic exchange mechanism. The results indicate that HDTMAB-modified silkworm exuviae could be employed as low-cost material for the removal of methyl orange anionic dye from wastewater.

  16. Lagging and Its Kinetic Mechanism of Hydrocarbon Re-generation from Organic Matters in Coals

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Based on the composite analysis of the coal sample series with natural and artificial maturation, the lagging and its kinetic mechanism of the hydrocarbon re-generation from the organic matters in coals were studied using the Rock-Eval gas chromatogram (Py-GC) method. The results show that the maturation at the hydrocarbon re-generation peak shifts regularly forward with increasing the starting maturation and the deadline of the hydrocarbon re-generation lies about at 4. 0% Ro. The difference value between the peak and starting maturation of the hydrocarbon regeneration develops in a parabola-like pattern with increasing the starting maturation, and the resolute and relative laggings evolve in stage, from which the lagging depth could be predicted. The peak half-width of the hydrocarbon re-generation curve develops as the starting maturation increases, which might indicate that the hydrocarbon-derived rocks with the starting maturation lied about at oil-generated peak might be relatively high in the hydrocarbon-regenerated amount. In the meantime, the mean reactivated energy of the coal samples with starting maturation develops in four stages that are highly consistent with those of the hydrocarbon-regenerated amount and lagging, which indicated that the hydrocarbon re-generation is strictly controlled by the geochemical mechanism of the reactive kinetics.

  17. Mechanism and kinetics for the reaction of O(3P) with DMSO: A theoretical study

    Science.gov (United States)

    Mandal, Debasish; Bagchi, Sabyasachi; Das, Abhijit K.

    2012-11-01

    Mechanism and kinetics for the reaction of DMSO with O(3P) have been investigated by M06-2X/MG3S, CBS-QB3 and G4MP2 methods. Four possible reaction pathways are identified. Among them, the O(3P) addition to S-atom followed by CH3 elimination is almost exclusive. Four pre-reactive complexes have been located. AIM theory is used to determine the nature of interactions in these complexes. Considering the formation of pre-reactive complex, the rate constant for major pathway is calculated using transition state theory applied to a two-step mechanism. Enthalpies of formation at 298.15 K (ΔfH°298.15) have been calculated using the composite CBS-QB3, G4MP2 and G3B3 methods.

  18. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)] anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25—40 ℃. The order of the redox reaction of lactic acid and DDA was found to be first-order. The rates increased with the increase in [OH-] and decreased with the increase in [tellurate]. No free radical was detected. In the view of this the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed, and the rate equation derived from the mechanism can be used to explain all the experimental results. The activation parameters(25 ℃) and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  19. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ)in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHANJin-huan; WANGLi; LIUBao-sheng; SHENShi-gang

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ)species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃)and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  20. An equivalent finite element method to kinetics analysis of complex mechanism

    Institute of Scientific and Technical Information of China (English)

    CHE Ren-wei; LU Nian-li

    2005-01-01

    The Finite Element Method was combined with the results from considerable analysis, producing a new kinetics analysis method of EFEM for a mechanism in truss, geared system, and assembled system. The equivalent principle and the motive differential equation of the system were derived by using an equivalent element, a virtual inertia matrix, and a systematic force matrix. The element' s mass matrix expression in the two dimensional and three dimensional mechanisms of the equivalent element was determined. The equivalent mass matrixes fashion of the Jacobin matrix, generalized coordinate matrix, and equivalent forces matrix were also determined. It was validated by two examples that the new method was normal, simple and direct, and had a higher efficiency than alternative methods; this is regardless of whether traditional methods are used with differential equations and calculated by using a computer.

  1. Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.

  2. Correlation of Impact Conditions, Interface Reactions, Microstructural Evolution, and Mechanical Properties in Kinetic Spraying of Metals: A Review

    Science.gov (United States)

    Kim, Jaeick; Lee, Changhee

    2016-09-01

    In the past, most studies into kinetic spraying technology focused on basic research, but a large portion of current research is devoted to industrial applications of the technology. To advance, however, studies about industrial applications of kinetic spraying require profound understanding of the scientific foundations of the kinetic spray process. Nevertheless, no one has yet provided a well-organized summary of the correlations among impact conditions, interface reactions, microstructural evolution, and mechanical properties across the whole field of kinetic spraying technology. This paper provides such an overview of these correlations for kinetic spraying of metals. For each correlation, the interactions between the given conditions and the material properties of the metal feedstock powder are the most influential. These interactions are so complicated that it is difficult to systematically classify all cases into certain types. Nonetheless, we try to explain and summarize the critical factors and their roles in each relationship.

  3. Correlation of Impact Conditions, Interface Reactions, Microstructural Evolution, and Mechanical Properties in Kinetic Spraying of Metals: A Review

    Science.gov (United States)

    Kim, Jaeick; Lee, Changhee

    2016-12-01

    In the past, most studies into kinetic spraying technology focused on basic research, but a large portion of current research is devoted to industrial applications of the technology. To advance, however, studies about industrial applications of kinetic spraying require profound understanding of the scientific foundations of the kinetic spray process. Nevertheless, no one has yet provided a well-organized summary of the correlations among impact conditions, interface reactions, microstructural evolution, and mechanical properties across the whole field of kinetic spraying technology. This paper provides such an overview of these correlations for kinetic spraying of metals. For each correlation, the interactions between the given conditions and the material properties of the metal feedstock powder are the most influential. These interactions are so complicated that it is difficult to systematically classify all cases into certain types. Nonetheless, we try to explain and summarize the critical factors and their roles in each relationship.

  4. Kinetics and mechanism of jack bean urease inhibition by Hg2+

    Directory of Open Access Journals (Sweden)

    Du Nana

    2012-12-01

    Full Text Available Abstract Background Jack bean urease (EC 3.5.1.5 is a metalloenzyme, which catalyzes the hydrolysis of urea to produce ammonia and carbon dioxide. The heavy metal ions are common inhibitors to control the rate of the enzymatic urea hydrolysis, which take the Hg2+ as the representative. Hg2+ affects the enzyme activity causing loss of the biological function of the enzyme, which threatens the survival of many microorganism and plants. However, inhibitory kinetics of urease by the low concentration Hg2+ has not been explored fully. In this study, the inhibitory effect of the low concentration Hg2+ on jack bean urease was investigated in order to elucidate the mechanism of Hg2+ inhibition. Results According to the kinetic parameters for the enzyme obtained from Lineweaver–Burk plot, it is shown that the Km is equal to 4.6±0.3 mM and Vm is equal to 29.8±1.7 μmol NH3/min mg. The results show that the inhibition of jack bean urease by Hg2+ at low concentration is a reversible reaction. Equilibrium constants have been determined for Hg2+ binding with the enzyme or the enzyme-substrate complexes (Ki =0.012 μM. The results show that the Hg2+ is a noncompetitive inhibitor. In addition, the kinetics of enzyme inhibition by the low concentration Hg2+ has been studied using the kinetic method of the substrate reaction. The results suggest that the enzyme first reversibly and quickly binds Hg2+ and then undergoes a slow reversible course to inactivation. Furthermore, the rate constant of the forward reactions (k+0 is much larger than the rate constant of the reverse reactions (k-0. By combining with the fact that the enzyme activity is almost completely lost at high concentration, the enzyme is completely inactivated when the Hg2+ concentration is high enough. Conclusions These results suggest that Hg2+ has great impacts on the urease activity and the established inhibition kinetics model is suitable.

  5. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  6. Influence of environmental conditions on the kinetics and mechanism of dehydration of carbamazepine dihydrate.

    Science.gov (United States)

    Han, J; Suryanarayanan, R

    1998-11-01

    The object of this project was to study the influence of temperature and water vapor pressure on the kinetics and mechanism of dehydration of carbamazepine dihydrate and to establish the relationship between the dehydration mechanism and the solid-state of the anhydrous phase formed. Three experimental techniques were utilized to study the kinetics of dehydration of carbamazepine dihydrate (C15H12N2O.2H2O)-thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and variable temperature powder X-ray diffractometry (VTXRD). These techniques respectively provide information about the changes in weight, heat flow and solid-state (phase) during the dehydration process. The instrumental setup was modified so that simultaneous control of both the temperature and the water vapor pressure was possible. The experiments were carried out at different temperatures, ranging from 26 to 64 degrees C. In the absence of water vapor, the dehydration followed the 2-dimensional phase boundary controlled model at all the temperatures studied. In the next stage, the water vapor pressure was altered while the studies were carried out at a single temperature of 44 degrees C. The dehydration was 2-dimensional phase boundary controlled at water vapor pressures or = 12.0 torr. In the former case, the anhydrous phase formed was X-ray amorphous while it was the crystalline anhydrous gamma-carbamazepine in the latter. Thus a relationship between the mechanism of dehydration and the solid-state of the product phase was evident. The dehydration conditions influence not only the mechanism but also the solid-state of the anhydrous phase formed. While the techniques of TGA and DSC have found extensive use in studying dehydration reactions, VTXRD proved to be an excellent complement in characterizing the solid-states of the reactant and product phases.

  7. Kinetics and reaction mechanism of phenol hydroxylation catalyzed by La-Cu4FeAlCO3

    Institute of Scientific and Technical Information of China (English)

    CHEN Chunxia; XU Chenghua; FENG Liangrong; SUO Jishuan; QIU Fali

    2005-01-01

    The present work synthesizes La-Cu4FeAlCO3 catalyst under microwave irradiation and characterizes its structure using XRD and IR techniques. The results show that the obtained La-Cu4FeAlCO3 has a hydrotalcite structure. In the phenol hydroxylation with H2O2 catalyzed by La-Cu4FeAlCO3, the effects of reaction time and phenol/H2O2 molar ratio on the phenol hydroxylation, and relationships between the initial hydroxylation rate with concentration of the catalyst, phenol, H2O2 and reaction temperature are also investigated in details. It is shown the phenol conversion can reach 50.09% (mol percent) in the phenol hydroxylation catalyzed by La-Cu4FeAlCO3, under the reaction conditions of the molar ratio of phenol/H2O2 1/2, the amount ratio of phenol/catalyst 20, reaction temperature 343 K, reaction time 120 min, 10 mL distilled water as solvent. Moreover, a kinetic equation of and the activation energy of Ea=58.37 kJ/mol are obtained according to the kinetic studies. Due to the fact that the HO-Cu+-OH species are detected in La-Cu4FeAlCO3/H2O2 system by XPS, the new mechanism about the generation of hydroxyl free radicals in the phenol hydroxylation is proposed, which is supposed that HO-Cu+-OH species are transition state in this reaction.

  8. Assessment of Reduced-Kinetics Mechanisms for Combustion of Jet Fuel in CFD Applications

    Science.gov (United States)

    Ajmani, Kumud; Kundu, Krihna P.; Yungster, Shaye J.

    2014-01-01

    A computational effort was undertaken to analyze the details of fluid flow in Lean-Direct Injection (LDI) combustors for next-generation LDI design. The National Combustor Code (NCC) was used to perform reacting flow computations on single-element LDI injector configurations. The feasibility of using a reduced chemical-kinetics approach, which optimizes the reaction rates and species to model the emissions characteristics typical of lean-burning gas-turbine combustors, was assessed. The assessments were performed with Reynolds- Averaged Navier-Stokes (RANS) and Time-Filtered Navier Stokes (TFNS) time-integration, with a Lagrangian spray model with the NCC code. The NCC predictions for EINOx and combustor exit temperature were compared with experimental data for two different single-element LDI injector configurations, with 60deg and 45deg axially swept swirler vanes. The effects of turbulence-chemistry interaction on the predicted flow in a typical LDI combustor were studied with detailed comparisons of NCC TFNS with experimental data.

  9. Kinetic studies of yeast polyA polymerase indicate an induced fit mechanism for nucleotide specificity.

    Science.gov (United States)

    Balbo, Paul B; Meinke, Gretchen; Bohm, Andrew

    2005-05-31

    Polyadenylate polymerase (PAP) catalyzes the synthesis of 3'-polyadenylate tails onto mRNA. A comprehensive steady-state kinetic analysis of PAP was conducted which included initial velocity studies of the forward and reverse reactions, inhibition studies, and the use of alternative substrates. The reaction (A(n) + ATP A(n+1) + PP(i)) is adequately described by a rapid equilibrium random mechanism. Several thermodynamic parameters for the reaction were determined or calculated, including the overall equilibrium constant (K(eq) = 84) and the apparent equilibrium constant of the internal step (K(int) = 4) which involves the rate-determining interconversion of central complexes. A large (100-fold) difference in Vmax accounts for nucleotide specificity (ATP vs CTP), despite an only 3-fold difference in Km. Comparison of the sulfur elemental effect on Vmax for ATP and CTP suggests that the chemical step is rate-determining for both reactions. Comparison of the sulfur elemental effect on Vmax/Km revealed differences in the mechanism by which either nucleotide is incorporated. Consistent with these data, an induced fit mechanism for nucleotide specificity is proposed whereby PAP couples a uniform binding mechanism, which selects for ATP, with a ground-state destabilization mechanism, which serves to accelerate the velocity for the correct substrate.

  10. Ground-state kinetics of bistable redox-active donor-acceptor mechanically interlocked molecules.

    Science.gov (United States)

    Fahrenbach, Albert C; Bruns, Carson J; Li, Hao; Trabolsi, Ali; Coskun, Ali; Stoddart, J Fraser

    2014-02-18

    The ability to design and confer control over the kinetics of theprocesses involved in the mechanisms of artificial molecular machines is at the heart of the challenge to create ones that can carry out useful work on their environment, just as Nature is wont to do. As one of the more promising forerunners of prototypical artificial molecular machines, chemists have developed bistable redox-active donor-acceptor mechanically interlocked molecules (MIMs) over the past couple of decades. These bistable MIMs generally come in the form of [2]rotaxanes, molecular compounds that constitute a ring mechanically interlocked around a dumbbell-shaped component, or [2]catenanes, which are composed of two mechanically interlocked rings. As a result of their interlocked nature, bistable MIMs possess the inherent propensity to express controllable intramolecular, large-amplitude, and reversible motions in response to redox stimuli. In this Account, we rationalize the kinetic behavior in the ground state for a large assortment of these types of bistable MIMs, including both rotaxanes and catenanes. These structures have proven useful in a variety of applications ranging from drug delivery to molecular electronic devices. These bistable donor-acceptor MIMs can switch between two different isomeric states. The favored isomer, known as the ground-state co-conformation (GSCC) is in equilibrium with the less favored metastable state co-conformation (MSCC). The forward (kf) and backward (kb) rate constants associated with this ground-state equilibrium are intimately connected to each other through the ground-state distribution constant, KGS. Knowing the rate constants that govern the kinetics and bring about the equilibration between the MSCC and GSCC, allows researchers to understand the operation of these bistable MIMs in a device setting and apply them toward the construction of artificial molecular machines. The three biggest influences on the ground-state rate constants arise from

  11. Parallel versus off-pathway Michaelis-Menten mechanism for single-enzyme kinetics of a fluctuating enzyme

    CERN Document Server

    Kumar, Ashutosh; Dua, Arti

    2015-01-01

    Recent fluorescence spectroscopy measurements of the turnover time distribution of single-enzyme turnover kinetics of $\\beta$-galactosidase provide evidence of Michaelis-Menten kinetics at low substrate concentration. However, at high substrate concentrations, the dimensionless variance of the turnover time distribution shows systematic deviations from the Michaelis-Menten prediction. This difference is attributed to conformational fluctuations in both the enzyme and the enzyme-substrate complex and to the possibility of both parallel and off-pathway kinetics. Here, we use the chemical master equation to model the kinetics of a single fluctuating enzyme that can yield a product through either parallel or off-pathway mechanisms. An exact expression is obtained for the turnover time distribution from which the mean turnover time and randomness parameters are calculated. The parallel and off-pathway mechanisms yield strikingly different dependences of the mean turnover time and the randomness parameter on the su...

  12. Mechanical stress-induced switching kinetics of ferroelectric thin films at the nanoscale

    Science.gov (United States)

    Alsubaie, A.; Sharma, P.; Liu, G.; Nagarajan, V.; Seidel, J.

    2017-02-01

    We investigate ferroelectric domain structure and piezoelectric response under variable mechanical compressive stress in Pb(Zr0.2TiO0.8)O3 (PZT) thin films using high-resolution piezoresponse force microscopy (PFM) and an in situ sample bending stage. Measurements reveal a drastic change in the ferroelectric domain structure which is presented along with details of the mediating switching process involving domain wall motion, nucleation, and domain wall roughening under an applied external mechanical stimulus. Furthermore, local PFM hysteresis loops reveal significant changes in the observed coercive biases under applied stress. The PFM hysteresis loops become strongly imprinted under increasing applied compressive stress.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    Because of the complex composition of biomass, the chemical mechanism contains many different species and therefore a large number of reactions. Although biomass gas‐phase combustion is fairly well researched and understood, the proposed mechanisms are still complex and need very long computational...... time and powerful hardware resources. A reduction of the mechanism for biomass volatile oxidation has therefore been performed to avoid these difficulties. The selected detailed mechanism in this study contains 81 species and 703 elementary reactions. Necessity analysis is used to determine which......‐ and low‐temperature range with 26 and 52 species, respectively. The modeling conditions are selected in a way to mimic values in the range of temperature 700–1400°C, excess air ratio 0.8–3.3, and four different residence times: 1, 0.1, 0.01, and 0.001 s, since these variables are the main affecting...

  14. Kinetics and Mechanism of Oxidation of Leucine and Alanine by Ag(III Complex in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Changying Song

    2008-01-01

    Full Text Available Kinetics and mechanism of oxidation of leucine and alanine by Ag(III complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III complex and amino acids (leucine, alanine. The second-order rate constant, k−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.

  15. [Mechanism and kinetics of phenol degradation by TiO2 photocatalytic combined technologies].

    Science.gov (United States)

    Zhang, Yi; Huang, Ruo-Nan; Wang, Xiao-Min; Wang, Qi; Cong, Yan-Qing

    2013-02-01

    The combination H2O2, or electrical catalytic (EC) system with TiO2 photbcatalytic system for phenol degradation was investigated. The catalytic systems of TiO2/UV, H2O2/UV, TiO2/UV/H2O2 and TiO2/UV/EC were compared to investigate the phenol degradation mechanism and kinetic model. The degradation of phenol in TiO2/UV/H2O2 and TiO2/UV/EC system is more effective than that in TiO2/UV system. With the solution pH of 6, TiO, concentration of 0.2 g.L-1, UV illumination of 2 h, the photocatalysis removal efficiency of phenol reaches to 86%, if the current density of 12 mA.cm-2 is added, the removal efficiency of phenol could reach to 100%. The energy utilization in different catalytic systems was also compared. When phenol is degraded in 15 min, in TiO2/UV/EC system the energy utilization is the highest of 0.0306 g.(kW. h)-1 with the energy consumption of 0.0640 kW.h-1. It indicates that much more energy is used in TiO2/UV/EC system for phenol degradation. During the analysis of intermediate products in different catalysis systems, the first-order kinetic model of phenol degradation and intermediate products such as hydroquinone, catechol and benzoquinone formation were established. The kinetic model is validated the phenol degradation pathway in different catalysis systems, and also indicates the TiO2/UV/EC system could enhance phenol and intermediate products degradation.

  16. Kinetics and mechanism of reactions of the drug tiopronin with platinum(IV) complexes.

    Science.gov (United States)

    Huo, Shuying; Shi, Hongmei; Liu, Dongzhi; Shen, Shigang; Zhang, Jiong; Song, Changying; Shi, Tiesheng

    2013-08-01

    Tiopronin, a synthetic thiol-containing drug being used in treatments of cystinuria and certain types of rare arthritis, is also a hepatoprotective and a detoxifying agent. Many analytical methods have been developed based on its redox chemistry with metal ions/complexes, but the kinetic and mechanistic aspects are poorly understood. In this work, the oxidation of tiopronin by cisplatin prodrug and a model compound, cis-[Pt(NH3)2Cl4] and trans-[PtCl2(CN)4](2-), was investigated. The oxidation kinetics was followed by a stopped-flow spectrophotometer over a wide pH range under the pseudo first-order conditions of [Tiopronin]≫[Pt(IV)]. Time-resolved spectra were also recorded for both Pt(IV) complexes, enabling to establish an overall second-order rate law: -d[Pt(IV)]/dt=k'[Tiopronin][Pt(IV)], where k' pertains to observed second-order rate constants. Under the kinetic conditions, tiopronin was oxidized to form the tiopronin-disulfide exclusively as identified by mass spectrometry. A reaction mechanism was proposed, involving parallel reductions of the Pt(IV) complexes by the three protolytic tiopronin species as rate-determining steps. The rate constants for the rate-determining steps were derived. The fully deprotonated tiopronin is about 4×10(4) more reactive than its corresponding thiol form for both Pt(IV) complexes; the huge reactivity difference orchestrates closely with the fact that the nucleophilicity of thiolate is much higher than the corresponding thiol. Hence, the attack of the sulfur atom in thiol/thiolate of tiopronin on the axially-coordinated chloride in the Pt(IV) complexes is nucleophilic in nature in the rate-determining steps, resulting in a bridge formation and a subsequent bridged electron-transfer. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Kinetics and rate-limiting mechanisms of dolomitedissolution at various CO2 partial pressures

    Institute of Scientific and Technical Information of China (English)

    LIU; Zaihua

    2001-01-01

    [1]Lund, K., Fogler, H. S., McCune, C. C., Acidization I. The dissolution of dolomite in hydrochloric acid, Chem. Eng.Sci., 1973.28: 691-700.[2]Herman, J. S., The dissolution kinetics of calcite, dolomite and dolomite rocks in carbon dioxide water system, PH. D.Thes., Pennsylvania State Univ., 1982.[3]Busenberg, E., Plummer, L. N., The kinetics of dissolution of dolomite in CO2-H2O systems at 1.5 to 65℃ and 0 to 1atm Pco2, Amer. Jour. Sci., 1982, 282: 45-78.[4]Chou, L., Garrels, R. M., Wollast, R., Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals, Chem. Geol., 1989, 78: 269-282.[5]Liu, Z., Yuan, D., He, S. et al. Geochemical features of the geothermal CO2-water-carbonate rock system and analysis on its CO2 Sources, Science in China, Series D, 2000, 43(6): 569-576.[6]Shangguan, Z., Bai, C., Sun M., Mantle-derived magmatic gas releasing features at the Rehai area, Tengchong County,Yunnan Province, China, Science in China, Series D, 2000, 43(2): 132-140.[7]Dreybrodt, W., Lauckner, J., Liu, Z. et al., The kinetics of the reaction CO2+ H2O→H++ HCO3-as one of the rate limiting steps for the dissolution of calcite in the system H2O-CO2-CaCO3, Geochim. Cosmochim. Acta, 1996, 60:3375-3381.[8]Liu, Z., Dreybrodt, W., Dissolution kinetics of calcium carbonate minerals in H2O-CO2 solutions in turbulent flow: the roleof the diffusion boundary layer and the slow reaction H2O+CO2→H++HCO3-, Geochim. Cosmochim. Acta, 1997, 61:2879-2889.[9]Dreybrodt, W., Eisenlohr, L., Madry, B. et al., Precipitation kinetics of calcite in the system CaCO3-H2O-CO2: The conversion to CO2 by the slow process H++HCO3-~ CO2 + H2O as a rate limiting step, Geochim. Cosmochim. Acta, 1997,61: 3897-3904.[10]Dreybrodt, W., Buhmann, D., A mass transfer model for dissolution and precipitation of calcite from solutions in turbulent motion, Chem. Geol., 1991, 90: 107-122.[11]Dreybrodt, W., Processes in Karst Systems, Springer

  18. Detailed kinetics of EBV-specific CD4(+) and CD8(+) T cells during primary EBV infection in a kidney transplant patient

    NARCIS (Netherlands)

    E.R.W.A.N. Piriou; K. van Dort; J.F.L. Weel; F.J. Bemelman; L.E. Gamadia; M.H.J. van Oers; D. van Baarle

    2006-01-01

    The etiology of infectious mononucleosis is poorly understood and usually detected many weeks after infection. Here, we present a unique case of primary symptomatic EBV infection after kidney transplantation, in whom we analyzed both EBV-specific CD4(+) and CD8(+)T cells in detail from the moment of

  19. Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seok Woo; /Stanford U., Geballe Lab.; Lee, Hyun-Wook; /Stanford U., Materials Sci. Dept.; Ryu, Ill; /Brown U.; Nix, William D.; /Stanford U., Materials Sci. Dept.; Gao, Huajian; /Brown U.; Cui, Yi; /Stanford U., Materials Sci. Dept. /SLAC

    2015-06-01

    Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Herein, we demonstrate physical/mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Contract No. DE-AC02-76SF00515. SLAC-PUB-16300 2 lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high performance Li-ion batteries.

  20. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms.

    Science.gov (United States)

    Cui, You-Wei; Li, Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability.

  1. The kinetic mechanism of Human Thymidine Phosphorylase - a molecular target for cancer drug development.

    Science.gov (United States)

    Deves, Candida; Rostirolla, Diana Carolina; Martinelli, Leonardo Kras Borges; Bizarro, Cristiano Valim; Santos, Diogenes Santiago; Basso, Luiz Augusto

    2014-03-04

    Human Thymidine Phosphorylase (HTP), also known as the platelet-derived endothelial cell growth factor (PD-ECGF) or gliostatin, catalyzes the reversible phosphorolysis of thymidine (dThd) to thymine and 2-deoxy-α-d-ribose-1-phosphate (2dR1P). HTP is a key enzyme in the pyrimidine salvage pathway involved in dThd homeostasis in cells. HTP is a target for anticancer drug development as its enzymatic activity promotes angiogenesis. Here, we describe cloning, expression, and purification to homogeneity of recombinant TYMP-encoded HTP. Peptide fingerprinting and the molecular mass value of the homogenous protein confirmed its identity as HTP assessed by mass spectrometry. Size exclusion chromatography showed that HTP is a dimer in solution. Kinetic studies revealed that HTP displayed substrate inhibition for dThd. Initial velocity and isothermal titration calorimetry (ITC) studies suggest that HTP catalysis follows a rapid-equilibrium random bi-bi kinetic mechanism. ITC measurements also showed that dThd and Pi binding are favorable processes. The pH-rate profiles indicated that maximal enzyme activity was achieved at low pH values. Functional groups with apparent pK values of 5.2 and 9.0 are involved in dThd binding and groups with pK values of 6.1 and 7.8 are involved in phosphate binding.

  2. Kinetic Mechanism of OMP Synthase:  A Slow Physical Step Following

    DEFF Research Database (Denmark)

    Wang, G.P.; Lundegaard, Claus; Jensen, Kaj Frank

    1999-01-01

    quench experiments revealed burst kinetics for product formation in both the forward phosphoribosyltransferase and the reverse pyrophosphorolysis reactions. The steady-state rate in the forward reaction was preceded by a burst (nfwd = 1.5/dimer) of at least 300 s-1. In the pyrophosphorolysis reaction...... medium was increased with sucrose, the forward kcat decreased in proportion to ¿rel with a slope of 0.8. In the reverse reaction a more limited dependence of kcat (slope = 0.3) was observed. On the basis of the known structures of OPRTase, we propose that a highly conserved, catalytically important...... and equilibrium constants for the kinetic mechanism. PRPP bound to two sites per dimer with a KD of 33 µM. Binding of OMP and orotate also occurred to a single class of two sites per dimer, with KD values of 3 and 280 µM, respectively. Pyrophosphate binding to two sites was weak with a KD of 960 µ...

  3. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Asma, E-mail: asmadr@wol.net.pk [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan); Sharif, Mehwish [School of Biological Sciences, University of the Punjab, Lahore 54590 (Pakistan); Iqbal, Muhammad [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan)

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation {>=}0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g{sup -1}. The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  4. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms

    Science.gov (United States)

    Cui, You-Wei; Li, Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    2016-01-01

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability. PMID:27658113

  5. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Science.gov (United States)

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

  6. On the mechanisms and kinetics of evaporation of a compacted silt

    Directory of Open Access Journals (Sweden)

    Mpawenayo Régis

    2016-01-01

    Full Text Available In order to define a convective evaporation model able to reproduce the evaporation rates according to the atmospheric conditions, drying tests have been performed on cylindrical samples of a compacted silt in a closed chamber where the relative humidity of the air is controlled by means of saturated saline solutions. Calibrating such models using experimental results from small sample sizes can indeed be an interesting alternative to simplify the experimental procedures and to reduce the test duration in comparison with the standard in-situ tests (e.g. lysimeter. However the influence of the size of the samples on the kinetics of evaporation has to be investigated. Samples with different diameters and heights are therefore tested. The results show that the observed mechanisms of drying are similar to those at the scale of the geostructure if the dimensions of the sample are higher than a critical height and a critical diameter. We show then that the experimental critical height is consistent with the concept of critical length proposed by Lehman et al. (2008, who expresses analytically when the hydraulic connection between the sample surface and the drying front is upset. Finally the kinetics of evaporation recorded under different relative humidities highlight that the mass transfer coefficient defined in the convective evaporation model does not depend on the relative humidity.

  7. Desorption Kinetics and Mechanisms of CO2 on Amine-Based Mesoporous Silica Materials

    Directory of Open Access Journals (Sweden)

    Yang Teng

    2017-01-01

    Full Text Available Tetraethylenepentamine (TEPA-based mesoporous MCM-41 is used as the adsorbent to determine the CO2 desorption kinetics of amine-modified materials after adsorption. The experimental data of CO2 desorption as a function of time are derived by zero-length column at different temperatures (35, 50, and 70 °C and analyzed by Avrami’s fractional-order kinetic model. A new method is used to distinguish the physical desorption and chemical desorption performance of surface-modified mesoporous MCM-41. The activation energy Ea of CO2 physical desorption and chemical desorption calculated from Arrhenius equation are 15.86 kJ/mol and 57.15 kJ/mol, respectively. Furthermore, intraparticle diffusion and Boyd’s film models are selected to investigate the mechanism of CO2 desorption from MCM-41 and surface-modified MCM-41. For MCM-41, there are three rate-limiting steps during the desorption process. Film diffusion is more prominent for the CO2 desorption rates at low temperatures, and pore diffusion mainly governs the rate-limiting process under higher temperatures. Besides the surface reaction, the desorption process contains four rate-limiting steps on surface-modified MCM-41.

  8. CarD stabilizes mycobacterial open complexes via a two-tiered kinetic mechanism

    Science.gov (United States)

    Rammohan, Jayan; Ruiz Manzano, Ana; Garner, Ashley L.; Stallings, Christina L.; Galburt, Eric A.

    2015-01-01

    CarD is an essential and global transcriptional regulator in mycobacteria. While its biological role is unclear, CarD functions by interacting directly with RNA polymerase (RNAP) holoenzyme promoter complexes. Here, using a fluorescent reporter of open complex, we quantitate RPo formation in real time and show that Mycobacterium tuberculosis CarD has a dramatic effect on the energetics of RNAP bound complexes on the M. tuberculosis rrnAP3 ribosomal RNA promoter. The data reveal that Mycobacterium bovis RNAP exhibits an unstable RPo that is stabilized by CarD and suggest that CarD uses a two-tiered, concentration-dependent mechanism by associating with open and closed complexes with different affinities. Specifically, the kinetics of open-complex formation can be explained by a model where, at saturating concentrations of CarD, the rate of bubble collapse is slowed and the rate of opening is accelerated. The kinetics and open-complex stabilities of CarD mutants further clarify the roles played by the key residues W85, K90 and R25 previously shown to affect CarD-dependent gene regulation in vivo. In contrast to M. bovis RNAP, Escherichia coli RNAP efficiently forms RPo on rrnAP3, suggesting an important difference between the polymerases themselves and highlighting how transcriptional machinery can vary across bacterial genera. PMID:25697505

  9. Kinetics and mechanism of the reaction of sodium azide with hypochlorite in aqueous solution.

    Science.gov (United States)

    Betterton, Eric A; Lowry, Joe; Ingamells, Robin; Venner, Brad

    2010-10-15

    Production of toxic sodium azide (NaN(3)) surged worldwide over the past two decades to meet the demand for automobile air bag inflator propellant. Industrial activity and the return of millions of inflators to automobile recycling facilities are leading to increasing release of NaN(3) to the environment so there is considerable interest in learning more about its environmental fate. Water soluble NaN(3) could conceivably be found in drinking water supplies so here we describe the kinetics and mechanism of the reaction of azide with hypochlorite, which is often used in water treatment plants. The reaction stoichiometry is: HOCl + 2N(3)(-) = 3N(2) + Cl(-) + OH(-), and proceeds by a key intermediate chlorine azide, ClN(3), which subsequently decomposes by reaction with a second azide molecule in the rate determining step: ClN(3) + N(3)(-) --> 3N(2) + Cl(-) (k = 0.52+/-0.04 M(-1) s(-1), 25 degrees C, mu = 0.1 M). We estimate that the half-life of azide would be approximately 15 s at the point of chlorination in a water treatment plant and approximately 24 days at some point downstream where only residual chlorine remains. Hypochlorite is not recommended for treatment of concentrated azide waste due to formation of the toxic chlorine azide intermediate under acidic conditions and the slow kinetics under basic conditions.

  10. Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.

    Science.gov (United States)

    Selmeczi, Katalin; Michel, Carine; Milet, Anne; Gautier-Luneau, Isabelle; Philouze, Christian; Pierre, Jean-Louis; Schnieders, David; Rompel, Annette; Belle, Catherine

    2007-01-01

    Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements ((1)H, (31)P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.

  11. Correction: Reaction mechanisms in ionic liquids: the kinetics and mechanism of the reaction of O,O-diethyl (2,4-dinitrophenyl) phosphate triester with secondary alicyclic amines.

    Science.gov (United States)

    Pavez, Paulina; Millán, Daniela; Morales, Javiera; Rojas, Mabel; Céspedes, Daniel; Santos, José G

    2016-01-28

    Correction for 'Reaction mechanisms in ionic liquids: the kinetics and mechanism of the reaction of O,O-diethyl (2,4-dinitrophenyl) phosphate triester with secondary alicyclic amines' by Paulina Pavez et al., Org. Biomol. Chem., 2016, DOI: 10.1039/c5ob02128f.

  12. Detailed sedimentology and geomorphology elucidate mechanisms of formation of modern and historical sequences of minor moraines in the European Alps

    Science.gov (United States)

    Wyshnytzky, Cianna; Lukas, Sven

    2016-04-01

    Suites of closely-spaced minor moraines may help further understanding of glacier retreat and predict its geomorphological effects through the observations of moraine formation on short timescales. This research is common in lowland, maritime settings (Sharp, 1984; Boulton, 1986; Krüger, 1995; Reinardy et al., 2013), but remains sparse in high-mountain settings (Hewitt, 1967; Ono, 1985; Beedle et al., 2009; Lukas, 2012). This research presents detailed sedimentological and geomorphological research on minor moraines at two high-mountain settings in the Alps: Silvrettagletscher, Switzerland, as a modern setting and Schwarzensteinkees, Austria, as a historical setting. Geomorphological investigations included mapping and measurements through field observations and assessing aerial imagery. Additionally, terrestrial laser scanning and ground-penetrating radar data were collected in the Schwarzensteinkees foreland. Detailed sedimentological investigations followed excavation of seven moraines at Silvrettagletscher and five moraines at Schwarzensteinkees and include multiple scales of observation and measurements to support interpretations of sediment transport and deposition (e.g. Evans and Benn, 2004). The modern moraines at Silvrettagletscher, in the immediately proglacial foreland, have been forming since before 2003. Four mechanisms of formation show distinct sedimentological signatures: formerly ice-cored moraines (e.g. Kjær & Krüger, 2001; Lukas, 2012; Reinardy et al., 2013) , push moraine formation on a reverse bedrock slope (e.g. Lukas, 2012), push moraine formation incorporating sediments deposited in a former proglacial basin, and basal freeze-on (e.g. Andersen & Sollid, 1971; Krüger, 1995; Reinardy et al., 2013). Schwarzensteinkees still exists but is currently restricted to steeply-dipping bedrock slabs above the main valley. This study therefore investigates the moraines in the foreland that formed between approximately 1850 and 1930. The minor

  13. 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.

  14. 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.

  15. The kinetics and mechanism of dissociation of metal carbonyls in high infrared laser fields

    Science.gov (United States)

    Langsam, Y.; Ronn, A. M.

    1981-01-01

    The method of laser induced dielectric breakdown has been used to study the dissociation of three metal carbonyls. Following non-resonant excitation by a TEA CO 2 laser, amorphous micro-metallic particles are deposited. The identity of the various species within a laser induced plasma for a series of related reactant molecules, has been determined using infrared and visible real time fluorescence techniques. Based upon the energetics of dissociation and the relative magnitudes of the rates of activation and deactivation for various collision partners of the plasma fluorescence, an energy transfer map as well as probable mechanisms are proposed. The kinetics of a variety of chemical reactions under plasma conditions are discussed in terms of elementary collision theory. It is shown that the internal vibration manifold of the metal carbonyls is equilibrated prior to the dissociation in agreement with the majority of laser induced multiphoton dissociation experiments.

  16. 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.

  17. Study on the Kinetics of Aluminum Removal from Liquid Silicon to Slag with Mechanical Stirring

    Science.gov (United States)

    Lee, Jaewoo; White, Jesse F.; Hildal, Kjetil; Sichen, Du

    2016-12-01

    The kinetics of aluminum removal from silicon melt to CaO-SiO2-Al2O3 slag was studied. A recently designed experimental setup using mechanical stirring was employed to focus the study on the chemical reaction. The slag and metal were found to reach chemical equilibrium in 300 seconds. A simple model could reproduce the experimental data satisfactorily. Both the experimental results and the model prediction further confirmed that the process was controlled by the chemical reaction, since the reaction rate constant was found to be independent of the amount of slag and the initial slag composition. The experimental data at equilibrium were compared with the model calculations. The discrepancy between the model calculations and the experimental data strongly suggests the need for careful thermodynamic measurements.

  18. Mechanism and kinetics model of hydrolysis in anaerobic digestion of kitchen wastes

    Institute of Scientific and Technical Information of China (English)

    吴云; 张代钧; 杨钢

    2009-01-01

    The profile of hydrolysates during the anaerobic digestion of kitchen wastes was investigated. The experimental results show that the hysteresis of hydrolytic rate is mainly controlled by the diffusion effect. The hydrolytic mechanism of kitchen wastes is elaborated by taking the diffusion effect into consideration. A segment model of the hydrolysis for kitchen waste is formulated including the coefficient of diffusion resistance in the model. The coefficients of diffusion resistance for different particle sizes are 1.42,2.12 and 2.78 respectively based on the experimental data,in which the coefficients of diffusion resistance conform an exponential function. So,the partitioning kinetic model could be integrated as a unified experience model. The model is verified with experimental data,which shows that the model could predict the concentration of organic substances during the anaerobic digestion of kitchen wastes.

  19. Photocatalytic Degradation of Phenol Using a Nanocatalyst: The Mechanism and Kinetics

    Directory of Open Access Journals (Sweden)

    Y. Tao

    2013-01-01

    Full Text Available The study of photocatalytic degradation of phenol was exploited with nano-ZnO as immobilized photocatalysts in a laboratory scale photocatalytic reactor. The photocatalytic degradation mechanism and kinetics of phenol in water were studied using the solid-phase microextraction (SPME technique. Based on optimized headspace SPME conditions, phenol in water was first extracted by the fibre, which was subsequently inserted into an aqueous system with immobilized photocatalysts (nano-ZnO exposed to an irradiation source (i.e., ultraviolet A (UVA lamps. After different irradiation times (5–80 min, four main intermediates of photocatalytic degradation generated on the fibre were determined by GC-MS.

  20. Evaluation of kinetic parameters and redox mechanism of quinoxaline at glassy carbon electrode

    Directory of Open Access Journals (Sweden)

    Aleksić Mara M.

    2014-01-01

    Full Text Available The electrochemical behavior of a biologically important heterocyclic compound quinoxaline (QUI was investigated by cyclic voltammetry (CV in solutions of differing pH, using a glassy carbon electrode (GCE. The reduction of QUI occurs as a quasi-reversible reaction in acid medium, reaching reversibility in alkaline solutions. The kinetic parameters of the electrode process such as αnα, diffusion coefficient (D and heterogeneous rate constant (ks, were evaluated and discussed. Redox mechanism of QUI was proposed on the basis of experimental results. Reduction process involves a transfer of two electrons and two protons at the pyrazine ring of QUI forming a dihydro-derivative. In acid solutions, the product of QUI reduction undergoes irreversible oxidation in a one-electron process. The electrode processes was found to be diffusion controlled. [Projekat Ministarstva nauke Republike Srbije, br. 172033

  1. 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.

  2. Spectral methods in chemistry and physics applications to kinetic theory and quantum mechanics

    CERN Document Server

    Shizgal, Bernard

    2015-01-01

    This book is a pedagogical presentation of the application of spectral and pseudospectral methods to kinetic theory and quantum mechanics. There are additional applications to astrophysics, engineering, biology and many other fields. The main objective of this book is to provide the basic concepts to enable the use of spectral and pseudospectral methods to solve problems in diverse fields of interest and to a wide audience. While spectral methods are generally based on Fourier Series or Chebychev polynomials, non-classical polynomials and associated quadratures are used for many of the applications presented in the book. Fourier series methods are summarized with a discussion of the resolution of the Gibbs phenomenon. Classical and non-classical quadratures are used for the evaluation of integrals in reaction dynamics including nuclear fusion, radial integrals in density functional theory, in elastic scattering theory and other applications. The subject matter includes the calculation of transport coefficient...

  3. Enhanced boronizing kinetics of alloy steel assisted by surface mechanical attrition treatment

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Haopeng, E-mail: hpyang1993@163.com; Wu, Xiaochun, E-mail: xcwu@staff.shu.edu.cn; Yang, Zhe; Pu, Shengjun; Wang, Hongbin

    2014-03-25

    Highlights: • Nanostructured surface layer is fabricated on H13 steel assisted by SMAT. • The boronizing kinetics of SMAT sample can be enhanced remarkably. • Borided layer can delay fatigue cracks initiation and impede their propagation. -- Abstract: A nanostructured surface layer was fabricated on AISI H13 steel by means of surface mechanical attrition treatment (SMAT). Boronizing behaviors of the SMAT samples were systematically investigated in comparison with their coarse-grained counterparts. The boron diffusion depth of the SMAT sample with pack boriding treatment at 600 °C for 2 h was about 8 μm, which was much deeper than that of the coarse-grained sample. A much thicker borided layer on the SMAT sample can be synthesized by a duplex boronizing treatment at 600 °C followed by at a higher temperature. The borided layer was composed with monophase of Fe{sub 2}B and the growth of it exhibited a (0 0 2) preferred orientation. Moreover, the activation energy of boron diffusion for the SMAT sample is 140.3 kJ/mol, which is much lower than 209.4 kJ/mol for the coarse-grained counterpart. The results indicate that the boronizing kinetics can be significantly enhanced in the SMAT sample with a duplex boronizing treatment. Furthermore, the thermal fatigue tests show that the borided layer with excellent oxidation resistance and mechanical strength at elevated temperatures could effectively delay the thermal fatigue cracks initiation and impede their propagation. Therefore, the thermal fatigue property of H13 steel with a duplex boronizing treatment can be improved remarkably.

  4. Parallel versus Off-Pathway Michaelis-Menten Mechanism for Single-Enzyme Kinetics of a Fluctuating Enzyme.

    Science.gov (United States)

    Kumar, Ashutosh; Maity, Hiranmay; Dua, Arti

    2015-07-09

    Recent fluorescence spectroscopy measurements of the turnover time distribution of single-enzyme turnover kinetics of β-galactosidase provide evidence of Michaelis-Menten kinetics at low substrate concentration. However, at high substrate concentrations, the dimensionless variance of the turnover time distribution shows systematic deviations from the Michaelis-Menten prediction. This difference is attributed to conformational fluctuations in both the enzyme and the enzyme-substrate complex and to the possibility of both parallel- and off-pathway kinetics. Here, we use the chemical master equation to model the kinetics of a single fluctuating enzyme that can yield a product through either parallel- or off-pathway mechanisms. An exact expression is obtained for the turnover time distribution from which the mean turnover time and randomness parameters are calculated. The parallel- and off-pathway mechanisms yield strikingly different dependences of the mean turnover time and the randomness parameter on the substrate concentration. In the parallel mechanism, the distinct contributions of enzyme and enzyme-substrate fluctuations are clearly discerned from the variation of the randomness parameter with substrate concentration. From these general results, we conclude that an off-pathway mechanism, with substantial enzyme-substrate fluctuations, is needed to rationalize the experimental findings of single-enzyme turnover kinetics of β-galactosidase.

  5. The contribution of passive-elastic mechanisms to lower extremity joint kinetics during human walking.

    Science.gov (United States)

    Whittington, Ben; Silder, Amy; Heiderscheit, Bryan; Thelen, Darryl G

    2008-05-01

    The purpose of this study was to investigate the contribution of passive mechanisms to lower extremity joint kinetics in normal walking at slow, comfortable, and fast speeds. Twenty healthy young adults participated in a passive testing protocol in which the relaxed lower limb was manipulated through full sagittal hip, knee, and ankle ranges of motion while kinematics and applied forces were simultaneously measured. The relationship between passive joint moments and angles was modeled by a set of exponential functions that accounted for the stretch of uniarticular structures and biarticular muscles. Subject specific walking kinematics (80%, 100%, and 120% of preferred speed) were input into the passive models to estimate joint moments, power, and work attributable to passive mechanisms. Passive hip flexion moments were substantial from late stance through early swing, absorbing approximately 40% of the net negative work done during hip extension and producing over half of the net positive work done during the hip flexor power burst (H3). Passive ankle plantarflexor moments were also produced during pre-swing, but generated a smaller percentage ( approximately 10%) of the net ankle plantarflexor power burst (A2). The joint work attributed to passive structures increased significantly (pwalking speed. The biarticular rectus femoris and gastrocnemius allowed for net passive energy absorption at the knee and subsequent return at the hip and ankle (ppassive-elastic mechanisms can contribute substantially to normal human walking and that biarticular muscles play a role in passively transferring energy between joints.

  6. Pre-steady-state Kinetic Analysis of a Family D DNA Polymerase from Thermococcus sp. 9°N Reveals Mechanisms for Archaeal Genomic Replication and Maintenance.

    Science.gov (United States)

    Schermerhorn, Kelly M; Gardner, Andrew F

    2015-09-04

    Family D DNA polymerases (polDs) have been implicated as the major replicative polymerase in archaea, excluding the Crenarchaeota branch, and bear little sequence homology to other DNA polymerase families. Here we report a detailed kinetic analysis of nucleotide incorporation and exonuclease activity for a Family D DNA polymerase from Thermococcus sp. 9°N. Pre-steady-state single-turnover nucleotide incorporation assays were performed to obtain the kinetic parameters, kpol and Kd, for correct nucleotide incorporation, incorrect nucleotide incorporation, and ribonucleotide incorporation by exonuclease-deficient polD. Correct nucleotide incorporation kinetics revealed a relatively slow maximal rate of polymerization (kpol ∼ 2.5 s(-1)) and especially tight nucleotide binding (Kd (dNTP) ∼ 1.7 μm), compared with DNA polymerases from Families A, B, C, X, and Y. Furthermore, pre-steady-state nucleotide incorporation assays revealed that polD prevents the incorporation of incorrect nucleotides and ribonucleotides primarily through reduced nucleotide binding affinity. Pre-steady-state single-turnover assays on wild-type 9°N polD were used to examine 3'-5' exonuclease hydrolysis activity in the presence of Mg(2+) and Mn(2+). Interestingly, substituting Mn(2+) for Mg(2+) accelerated hydrolysis rates > 40-fold (kexo ≥ 110 s(-1) versus ≥ 2.5 s(-1)). Preference for Mn(2+) over Mg(2+) in exonuclease hydrolysis activity is a property unique to the polD family. The kinetic assays performed in this work provide critical insight into the mechanisms that polD employs to accurately and efficiently replicate the archaeal genome. Furthermore, despite the unique properties of polD, this work suggests that a conserved polymerase kinetic pathway is present in all known DNA polymerase families. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  7. Pre-steady-state Kinetic Analysis of a Family D DNA Polymerase from Thermococcus sp. 9°N Reveals Mechanisms for Archaeal Genomic Replication and Maintenance*

    Science.gov (United States)

    Schermerhorn, Kelly M.; Gardner, Andrew F.

    2015-01-01

    Family D DNA polymerases (polDs) have been implicated as the major replicative polymerase in archaea, excluding the Crenarchaeota branch, and bear little sequence homology to other DNA polymerase families. Here we report a detailed kinetic analysis of nucleotide incorporation and exonuclease activity for a Family D DNA polymerase from Thermococcus sp. 9°N. Pre-steady-state single-turnover nucleotide incorporation assays were performed to obtain the kinetic parameters, kpol and Kd, for correct nucleotide incorporation, incorrect nucleotide incorporation, and ribonucleotide incorporation by exonuclease-deficient polD. Correct nucleotide incorporation kinetics revealed a relatively slow maximal rate of polymerization (kpol ∼2.5 s−1) and especially tight nucleotide binding (Kd(dNTP) ∼1.7 μm), compared with DNA polymerases from Families A, B, C, X, and Y. Furthermore, pre-steady-state nucleotide incorporation assays revealed that polD prevents the incorporation of incorrect nucleotides and ribonucleotides primarily through reduced nucleotide binding affinity. Pre-steady-state single-turnover assays on wild-type 9°N polD were used to examine 3′-5′ exonuclease hydrolysis activity in the presence of Mg2+ and Mn2+. Interestingly, substituting Mn2+ for Mg2+ accelerated hydrolysis rates >40-fold (kexo ≥110 s−1 versus ≥2.5 s−1). Preference for Mn2+ over Mg2+ in exonuclease hydrolysis activity is a property unique to the polD family. The kinetic assays performed in this work provide critical insight into the mechanisms that polD employs to accurately and efficiently replicate the archaeal genome. Furthermore, despite the unique properties of polD, this work suggests that a conserved polymerase kinetic pathway is present in all known DNA polymerase families. PMID:26160179

  8. Author Details

    African Journals Online (AJOL)

    Journal Home > Advanced Search > Author Details ... Intra‑Operative Airway Management in Patients with Maxillofacial Trauma having Reduction and ... Clinical Parameters and Challenges of Managing Cervicofacial Necrotizing Fasciitis in a ...

  9. Author Details

    African Journals Online (AJOL)

    Journal Home > Advanced Search > Author Details. Log in or ... Difficult airway management in a patient with giant malignant goitre scheduled for thyroidectomy - case report ... Airway Management Dilemma in a Patient with Maxillofacial Injury

  10. Author Details

    African Journals Online (AJOL)

    Journal Home > Advanced Search > Author Details ... Sequencing for Batch Production in a Group Flowline Machine Shop ... Sampling Plans for Monitoring Quality Control Process at a Plastic Manufacturing Firm in Nigeria: A Case Study

  11. PAH growth initiated by propargyl addition: Mechanism development and computational kinetics

    KAUST Repository

    Raj, Abhijeet Dhayal

    2014-04-24

    Polycyclic aromatic hydrocarbon (PAH) growth is known to be the principal pathway to soot formation during fuel combustion, as such, a physical understanding of the PAH growth mechanism is needed to effectively assess, predict, and control soot formation in flames. Although the hydrogen abstraction C2H2 addition (HACA) mechanism is believed to be the main contributor to PAH growth, it has been shown to under-predict some of the experimental data on PAHs and soot concentrations in flames. This article presents a submechanism of PAH growth that is initiated by propargyl (C 3H3) addition onto naphthalene (A2) and the naphthyl radical. C3H3 has been chosen since it is known to be a precursor of benzene in combustion and has appreciable concentrations in flames. This mechanism has been developed up to the formation of pyrene (A4), and the temperature-dependent kinetics of each elementary reaction has been determined using density functional theory (DFT) computations at the B3LYP/6-311++G(d,p) level of theory and transition state theory (TST). H-abstraction, H-addition, H-migration, β-scission, and intramolecular addition reactions have been taken into account. The energy barriers of the two main pathways (H-abstraction and H-addition) were found to be relatively small if not negative, whereas the energy barriers of the other pathways were in the range of (6-89 kcal·mol-1). The rates reported in this study may be extrapolated to larger PAH molecules that have a zigzag site similar to that in naphthalene, and the mechanism presented herein may be used as a complement to the HACA mechanism to improve prediction of PAH and soot formation. © 2014 American Chemical Society.

  12. Kinetics of germanium nanowire growth by the vapor-solid-solid mechanism with a Ni-based catalyst

    Directory of Open Access Journals (Sweden)

    Shruti V. Thombare

    2013-12-01

    Full Text Available The kinetics of vapor-solid-solid (VSS Ge nanowire growth using a Ni-based catalyst were investigated to probe the rate-limiting step for this complex nanoscale crystal growth process. The effects of key parameters such as temperature and precursor partial pressure on the nanowire growth rate were studied in order to gain detailed insights into the growth kinetics. Two different regimes were observed for VSS growth of Ge nanowires as function of temperature. At higher temperatures (345 °C–375 °C, kinetics data suggest that mass transport of germane precursor to the catalyst surface is rate limiting. At lower temperatures (<345 °C, either surface reaction of the GeH4 precursor on the catalyst or incorporation of Ge into the nanowire across the wire/catalyst interface is rate limiting.

  13. Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

    Science.gov (United States)

    Frenklach, M.; Clary, D. W.; Ramachandra, M. K.

    1985-01-01

    Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation.

  14. Removal of bentazone from micro-polluted water using MIEX resin: Kinetics, equilibrium, and mechanism

    Institute of Scientific and Technical Information of China (English)

    Zequn Liu; Xiaomin Yan; Mary Drikas; Danong Zhou; Dongsheng Wang; Min Yang; Jiuhui Qu

    2011-01-01

    The contamination of surface and ground water by bentazone has attracted increasing global concern in recent years.We conducted a detailed investigation using MIEX resin to eliminate bentazone from waters.Batch experiments were carried out to evaluate the effect of process parameters, such as retention time, resin amount, and initial pesticide concentration, on removal efficiency of bentazone.Results showed the sorption process was fast and bentazone could be efficiently removed in 30 minutes.The kinetic process of bentazone sorption on MIEX resin was well described by pseudo second-order model and intraparticle diffusion was the rate controlling step.The MIEX resin possessed the highest sorption capacity of 0.2656 mmol/mL for bentazone according to Langmuir fitting.Bentazone is a hydrophobic ionizable organic compound, and both ionic charge and hydrophobic aromatic structure governed the sorption characteristics on MIEX resin.The different removal efficiencies of ionic and non-ionic pesticides, combined with the charge balance equations of bentazone, SO42-, NO3- and Cl-, indicated that removal of bentazone using MIEX resin occurred primarily via ion exchange.

  15. Rule-based programming and strategies for automated generation of detailed kinetic models for gas phase combustion of polycyclic hydrocarbon molecules; Programmation par regles et strategies pour la generation automatique de mecanismes de combustion d'hydrocarbures polycycliques

    Energy Technology Data Exchange (ETDEWEB)

    Ibanescu, L.

    2004-06-15

    The primary objective of this thesis is to explore the approach of using rule-based systems and strategies, for a complex problem of chemical kinetic: the automated generation of reaction mechanisms. The chemical reactions are naturally expressed as conditional rewriting rules. The control of the chemical reactions chaining is easy to describe using a strategies language, such as the one of the ELAN system, developed in the Protheo team. The thesis presents the basic concepts of the chemical kinetics, the chemical and computational problems related to the conception and validation of a reaction mechanism, and gives a general structure for the generator of reaction mechanisms called GasEI. Our research focuses on the primary mechanism generator. We give solutions for encoding the chemical species, the reactions and their chaining, and we present the prototype developed in ELAN. The representation of the chemical species uses the notion of molecular graphs, encoded by a term structure called GasEI terms. The chemical reactions are expressed by rewriting rules on molecular graphs, encoded by a set of conditional rewriting rules on GasEI terms. The strategies language of the ELAN system is used to express the reactions chaining in the primary mechanism generator. This approach is illustrated by coding ten generic reactions of the oxidizing pyrolysis. Qualitative chemical validations of the prototype show that our approach gives, for acyclic molecules, the same results as the existing mechanism generators, and for polycyclic molecules produces original results.

  16. Kinetics and Mechanism of Dionaea muscipula Trap Closing1[C][OA

    Science.gov (United States)

    Volkov, Alexander G.; Adesina, Tejumade; Markin, Vladislav S.; Jovanov, Emil

    2008-01-01

    The Venus flytrap (Dionaea muscipula) possesses an active trapping mechanism to capture insects with one of the most rapid movements in the plant kingdom, as described by Darwin. This article presents a detailed experimental investigation of trap closure by mechanical and electrical stimuli and the mechanism of this process. Trap closure consists of three distinctive phases: a silent phase with no observable movement; an accelerated movement of the lobes; and the relaxation of the lobes in their closed state, resulting in a new equilibrium. Uncouplers and blockers of membrane channels were used to investigate the mechanisms of different phases of closing. Uncouplers increased trap closure delay and significantly decreased the speed of trap closure. Ion channel blockers and aquaporin inhibitors increased time of closing. Transmission of a single electrical charge between a lobe and the midrib causes closure of the trap and induces an electrical signal propagating between both lobes and midrib. The Venus flytrap can accumulate small subthreshold charges, and when the threshold value is reached, the trap closes. Repeated application of smaller charges demonstrates the summation of stimuli. The cumulative character of electrical stimuli points to the existence of electrical memory in the Venus flytrap. The observed fast movement can be explained by the hydroelastic curvature model without invoking buckling instability. The new hydroelastic curvature mechanism provides an accurate description of the authors' experimental data. PMID:18065564

  17. Facile synthesis of hydrotalcite and its thermal decomposition kinetics mechanism study with masterplots method

    Energy Technology Data Exchange (ETDEWEB)

    Long, Qiwei; Xia, Yao [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Liao, Sen, E-mail: liaosen@gxu.edu.cn [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Li, Yu; Wu, Wenwei [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Huang, Yingheng [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); School of Materials Science and Engineering, Guangxi University, Nanning, Guangxi 530004 (China)

    2014-03-01

    Graphical abstract: - Highlights: • The values of E{sub α} were determined with advanced isoconversional procedure. • Masterplots and nonlinear methods were used to study the mechanisms. • Mechanism equations obtained from the two methods are the same. • Nonlinear method is more efficient than Masterplots method. - Abstract: The hydrotalcite, Mg{sub 4}Al{sub 2}(OH){sub 12}CO{sub 3}·3H{sub 2}O, was synthesized via low-heating solid-state reaction at 80 °C. The thermal decomposition of Mg{sub 4}Al{sub 2}(OH){sub 12}CO{sub 3}·3H{sub 2}O experienced two stages. The apparent activation energy E{sub a} was estimated with Vyazovkin procedure. The average values of E{sub a} associated with the two stages were determined to be 110.9 ± 10.3, 140.3 ± 4.2 kJ mol{sup −1}, respectively, which the two stages are single-step kinetic processes. Masterplots and nonlinear methods were used to define the most probable reaction mechanisms of the two stages. The results show that the reaction mechanism functions of the two stages are as follows: (i) g(α) = (1 − α){sup −2} − 1, (ii) g(α) = (1 − α){sup −1/2} − 1, respectively. The values of pre-exponential factor A for the two stages were obtained on the basis of E{sub a} and g(α). Besides, some thermodynamic functions (ΔS{sup #}, ΔH{sup #} and ΔG{sup #}) of the transition state complexes for the two stages were also calculated.

  18. Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Vahteristo, K.

    2010-07-01

    -trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair. (orig.)

  19. Kinetics and mechanisms of degradation of chloroacetonitriles by the UV/H2O2 process.

    Science.gov (United States)

    Ling, Li; Sun, Jianliang; Fang, Jingyun; Shang, Chii

    2016-08-01

    Haloacetonitriles (HANs) are emerging disinfection by-products (DBPs) that are more toxic than the regulated DBPs and widely found in the chlorinated/chloraminated water. This paper studied kinetics and mechanisms of the degradation of chloroacetonitriles (CANs) by the UV/H2O2 process at pH 6 and 7.5 and H2O2 concentrations of 1 × 10(-3) M, 5 × 10(-3) M and 1 × 10(-2) M. The degradation followed pseudo first-order degradation kinetics. The degradation rate of monochloroacetonitrile (MCAN) remained similar, while those of dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN) increased with increasing pH and H2O2 concentrations. The different trends were attributed to the changing contributions of the two major mechanisms: the nucleophilic attack by hydroperoxide ions ( [Formula: see text] ) and the hydroxyl radical (•OH) oxidation. The second-order rate constants of [Formula: see text] towards MCAN, DCAN and TCAN were determined to be 11.8 (±0.62), 4.83 (±0.01) × 10(3), and 2.54 (±0.23) × 10(5) M(-1) s(-1), respectively, while that of •OH were 8.7 × 10(6), 4.4 × 10(6), and degradation of TCAN was mainly attributed to the [Formula: see text] nucleophilic attack, while that of MCAN was dominated by the •OH oxidation. DCAN was degraded by both mechanisms. The nucleophilic attack increased linearly with increasing [Formula: see text] concentration as a result of increasing H2O2 concentration and/or pH, while the •OH oxidation was less dependent on H2O2 concentrations and/or pH. The nucleophilic attack mainly transformed HANs to haloacetamides, while the •OH oxidation dechlorinated HANs. This paper firstly illustrated the importance of the [Formula: see text] nucleophilic attack, in addition to the •OH oxidation, on the CAN degradation in the UV/H2O2 process.

  20. Inhibition of myeloperoxidase-mediated protein nitration by tempol: Kinetics, mechanism, and implications.

    Science.gov (United States)

    Vaz, Sandra M; Augusto, Ohara

    2008-06-17

    Despite the therapeutic potential of tempol (4-hydroxy-2,2,6,6-tetra-methyl-1-piperidinyloxy) and related nitroxides as antioxidants, their effects on peroxidase-mediated protein tyrosine nitration remain unexplored. This posttranslational protein modification is a biomarker of nitric oxide-derived oxidants, and, relevantly, it parallels tissue injury in animal models of inflammation and is attenuated by tempol treatment. Here, we examine tempol effects on ribonuclease (RNase) nitration mediated by myeloperoxidase (MPO), a mammalian enzyme that plays a central role in various inflammatory processes. Some experiments were also performed with horseradish peroxidase (HRP). We show that tempol efficiently inhibits peroxidase-mediated RNase nitration. For instance, 10 muM tempol was able to inhibit by 90% the yield of 290 muM 3-nitrotyrosine produced from 370 muM RNase. The effect of tempol was not completely catalytic because part of it was consumed by recombination with RNase-tyrosyl radicals. The second-order rate constant of the reaction of tempol with MPO compound I and II were determined by stopped-flow kinetics as 3.3 x 10(6) and 2.6 x 10(4) M(-1) s(-1), respectively (pH 7.4, 25 degrees C); the corresponding HRP constants were orders of magnitude smaller. Time-dependent hydrogen peroxide and nitrite consumption and oxygen production in the incubations were quantified experimentally and modeled by kinetic simulations. The results indicate that tempol inhibits peroxidase-mediated RNase nitration mainly because of its reaction with nitrogen dioxide to produce the oxammonium cation, which, in turn, recycles back to tempol by reacting with hydrogen peroxide and superoxide radical to produce oxygen and regenerate nitrite. The implications for nitroxide antioxidant mechanisms are discussed.

  1. Dissolution kinetics and mechanisms at dolomite-water interfaces: effects of electrolyte specific ionic strength.

    Science.gov (United States)

    Xu, Man; Sullivan, Katie; Vanness, Garrett; Knauss, Kevin G; Higgins, Steven R

    2013-01-02

    Elucidating dissolution kinetics and mechanisms at carbonate mineral-water interfaces is essential to many environmental and geochemical processes, including geologic CO(2) sequestration in deep aquifers. In the present work, effects of background electrolytes on dolomite (CaMg(CO(3))(2)) reactivity were investigated by measuring step dissolution rates using in situ hydrothermal atomic force microscopy (HAFM) at 90 °C. Cleaved surfaces of dolomite were exposed to sodium chloride and tetramethylammonium chloride (TMACl) aqueous solutions with ionic strengths (I) ranging from 0 to 0.77 m at pH 4 and pH 9. HAFM results demonstrated that dolomite step retreat rates increased with increasing solution ionic strength and decreasing pH. Comparison of [481] and [441] steps revealed that the anisotropy of [481] and [441] step speeds became significant as solution ionic strength increased, with NaCl exerting more pronounced effects than TMACl for the same I. To interpret the different trends observed for NaCl and TMACl, a dissolution mechanism involving orientation-dependent ion adsorption and consequent edge free energy changes is proposed.

  2. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Science.gov (United States)

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

  3. Kinetic and Structural Insights into the Mechanism of AMPylation by VopS Fic Domain

    Energy Technology Data Exchange (ETDEWEB)

    Luong, Phi; Kinch, Lisa N.; Brautigam, Chad A.; Grishin, Nick V.; Tomchick, Diana R.; Orth, Kim (UTSMC)

    2010-07-19

    The bacterial pathogen Vibrio parahemeolyticus manipulates host signaling pathways during infections by injecting type III effectors into the cytoplasm of the target cell. One of these effectors, VopS, blocks actin assembly by AMPylation of a conserved threonine residue in the switch 1 region of Rho GTPases. The modified GTPases are no longer able to interact with downstream effectors due to steric hindrance by the covalently linked AMP moiety. Herein we analyze the structure of VopS and its evolutionarily conserved catalytic residues. Steady-state analysis of VopS mutants provides kinetic understanding on the functional role of each residue for AMPylation activity by the Fic domain. Further mechanistic analysis of VopS with its two substrates, ATP and Cdc42, demonstrates that VopS utilizes a sequential mechanism to AMPylate Rho GTPases. Discovery of a ternary reaction mechanism along with structural insight provides critical groundwork for future studies for the family of AMPylators that modify hydroxyl-containing residues with AMP.

  4. Biodegradation mechanisms and kinetics of azo dye 4BS by a microbial consortium.

    Science.gov (United States)

    He, Fang; Hu, Wenrong; Li, Yuezhong

    2004-10-01

    A microbial consortium consisting of a white-rot fungus 8-4* and a Pseudomonas 1-10 was isolated from wastewater treatment facilities of a local dyeing house by enrichment, using azo dye Direct Fast Scarlet 4BS as the sole source of carbon and energy, which had a high capacity for rapid decolorization of 4BS. To elucidate the decolorization mechanisms, decolorization of 4BS was compared between individual strains and the microbial consortium under different treatment processes. The microbial consortium showed a significant improvement on dye decolorization rates under either static or shaking culture, which might be attributed to the synergetic reaction of single strains. From the curve of COD values and the UV-visible spectra of 4BS solutions before and after decolorization cultivation with the microbial consortium, it was found that 4BS could be mineralized completely, and the results had been used for presuming the degrading pathway of 4BS. This study also examined the kinetics of 4BS decolorization by immobilized microbial consortium. The results demonstrated that the optimal decolorization activity was observed in pH range between four and 9, temperature range between 20 and 40 degrees C and the maximal specific decolorization rate occurred at 1,000 mg l(-1) of 4BS. The proliferation and distribution of microbial consortium were also microscopically observed, which further confirmed the decolorization mechanisms of 4BS.

  5. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  6. Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study

    Directory of Open Access Journals (Sweden)

    Biljana M. Šmit

    2015-10-01

    Full Text Available The mechanism and selectivity of a bicyclic hydantoin formation by selenium-induced cyclization are investigated. The proposed mechanism involves the intermediates formed by an electrophilic addition of the selenium reagent on a double bond of the starting 5-alkenylhydantoin prior the cyclization. These intermediates are readily converted into the more stable cyclic seleniranium cations. A key step of the mechanism is an intramolecular cyclization which is realized through an anti-attack of the internal nucleophile, the amidic nitrogen, to the seleniranium cation yielding the intermediate imidazolinium cations. Their deprotonation is followed by the formation of the fused bicyclic reaction products. Important intermediates and key transition states are studied by using density functional theory (DFT methods. The pathways of the reaction are investigated in detail. There are two regioselective pathways related to 5-exo and 6-endo products. Theoretical calculations and the monitoring of the cyclization reaction using 1H NMR spectroscopy are in a good agreement with the proposed mechanism and are consistent with our experimental results. The preferred pathway for formation of 5-exo products is confirmed.

  7. Dehydriding reaction kinetic mechanism of MgH2-Nb2O5 by Chou model

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Chou model was used to investigate the dehydriding reaction kinetic mechanism of MgH2-Nb2O5 hydrogen storage materials at 573 K.A new conception,"characteristic absorption/desorption time(yc)"was introduced to characterize the reaction rate.The fitting results show that for the hydrogen desorbing mechanism.the surface penetration iS the rate.controlling step.The mechanism remains the same even when the original particle size of Nb2O5 is before ball milling(BM)or when the BM time changes.And tc indicates that the desorption rate of MgH2-Nb2O5 will be faster than that of MgH2-Nb2O5 by BM.The dehydriding reaction rate of MgH2-Nb2O5(micro particle)BMed for 50 h is 4.76 times faster than that of the MgH2-Nb2O5(micro particle)BMed for 0.25 h,while the dehydriding reaction rate of MgH2-Nb2O5(nano particle)BMed for 50 h is only 1.1 8 times as that of the MgH2-Nb2O5 (nano particle)BMed for 0.25 h.The dehydriding reaction rate of the BMed MgH2-Nb2O5(nano particle)is 1-9 times faster than that of the BMed MgH2-Nb2O5(micro particle).

  8. Development of Kinetic Mechanisms for Next-Generation Fuels and CFD Simulation of Advanced Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); McNenly, Matt J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Whitesides, Russell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Killingsworth, Nick J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2015-12-17

    Predictive chemical kinetic models are needed to represent next-generation fuel components and their mixtures with conventional gasoline and diesel fuels. These kinetic models will allow the prediction of the effect of alternative fuel blends in CFD simulations of advanced spark-ignition and compression-ignition engines. Enabled by kinetic models, CFD simulations can be used to optimize fuel formulations for advanced combustion engines so that maximum engine efficiency, fossil fuel displacement goals, and low pollutant emission goals can be achieved.

  9. Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

    Science.gov (United States)

    Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic

  10. Kinetics and Mechanism of Calcium Hydroxide Conversion into Calcium Alkoxides: Implications in Heritage Conservation Using Nanolimes.

    Science.gov (United States)

    Rodriguez-Navarro, Carlos; Vettori, Irene; Ruiz-Agudo, Encarnacion

    2016-05-24

    Nanolimes are alcohol dispersions of Ca(OH)2 nanoparticles used in the conservation of cultural heritage. Although it was believed that Ca(OH)2 particles were inert when dispersed in short-chain alcohols, it has been recently shown that they can undergo transformation into calcium alkoxides. Little is known, however, about the mechanism and kinetics of such a phase transformation as well as its effect on the performance of nanolimes. Here we show that Ca(OH)2 particles formed after lime slaking react with ethanol and isopropanol and partially transform (fractional conversion, α up to 0.08) into calcium ethoxide and isopropoxide, respectively. The transformation shows Arrhenius behavior, with apparent activation energy Ea of 29 ± 4 and 37 ± 6 kJ mol(-1) for Ca-ethoxide and Ca-isopropoxide conversion, respectively. High resolution transmission electron microscopy analyses of reactant and product phases show that the alkoxides replace the crystalline structure of Ca(OH)2 along specific [hkl] directions, preserving the external hexagonal (platelike) morphology of the parent phase. Textural and kinetic results reveal that this pseudomorphic replacement involves a 3D diffusion-controlled deceleratory advancement of the reaction front. The results are consistent with an interface-coupled dissolution-precipitation replacement mechanism. Analysis of the carbonation of Ca(OH)2 particles with different degree of conversion into Ca-ethoxide (α up to 0.08) and Ca-isopropoxide (α up to 0.04) exposed to air (20 °C, 80% relative humidity) reveals that Ca-alkoxides significantly reduce the rate of transformation into cementing CaCO3 and induce the formation of metastable vaterite, as opposed to stable calcite which forms in untransformed Ca(OH)2 samples. Similar effects are obtained when a commercial nanolime partially transformed into Ca-ethoxide is subjected to carbonation. Such effects may hamper/delay the strengthening or consolidation effects of nanolimes, thus having

  11. Theory of the low frequency mechanical modes and Raman spectra of the M13 bacteriophage capsid with atomic detail.

    Science.gov (United States)

    Dykeman, Eric C; Sankey, Otto F

    2009-01-21

    We present a theoretical study of the low frequency vibrational modes of the M13 bacteriophage using a fully atomistic model. Using ideas from electronic structure theory, the few lowest vibrational modes of the M13 bacteriophage are determined using classical harmonic analysis. The relative Raman intensity is estimated for each of the mechanical modes using a bond polarizability model. Comparison of the atomic mechanical modes calculated here with modes derived from elastic continuum theory shows that a much richer spectrum emerges from an atomistic picture.

  12. Detailed Physiologic Characterization Reveals Diverse Mechanisms for Novel Genetic Loci Regulating Glucose and Insulin Metabolism in Humans

    Science.gov (United States)

    Ingelsson, Erik; Langenberg, Claudia; Hivert, Marie-France; Prokopenko, Inga; Lyssenko, Valeriya; Dupuis, Josée; Mägi, Reedik; Sharp, Stephen; Jackson, Anne U.; Assimes, Themistocles L.; Shrader, Peter; Knowles, Joshua W.; Zethelius, Björn; Abbasi, Fahim A.; Bergman, Richard N.; Bergmann, Antje; Berne, Christian; Boehnke, Michael; Bonnycastle, Lori L.; Bornstein, Stefan R.; Buchanan, Thomas A.; Bumpstead, Suzannah J.; Böttcher, Yvonne; Chines, Peter; Collins, Francis S.; Cooper, Cyrus C.; Dennison, Elaine M.; Erdos, Michael R.; Ferrannini, Ele; Fox, Caroline S.; Graessler, Jürgen; Hao, Ke; Isomaa, Bo; Jameson, Karen A.; Kovacs, Peter; Kuusisto, Johanna; Laakso, Markku; Ladenvall, Claes; Mohlke, Karen L.; Morken, Mario A.; Narisu, Narisu; Nathan, David M.; Pascoe, Laura; Payne, Felicity; Petrie, John R.; Sayer, Avan A.; Schwarz, Peter E. H.; Scott, Laura J.; Stringham, Heather M.; Stumvoll, Michael; Swift, Amy J.; Syvänen, Ann-Christine; Tuomi, Tiinamaija; Tuomilehto, Jaakko; Tönjes, Anke; Valle, Timo T.; Williams, Gordon H.; Lind, Lars; Barroso, Inês; Quertermous, Thomas; Walker, Mark; Wareham, Nicholas J.; Meigs, James B.; McCarthy, Mark I.; Groop, Leif; Watanabe, Richard M.; Florez, Jose C.

    2010-01-01

    OBJECTIVE Recent genome-wide association studies have revealed loci associated with glucose and insulin-related traits. We aimed to characterize 19 such loci using detailed measures of insulin processing, secretion, and sensitivity to help elucidate their role in regulation of glucose control, insulin secretion and/or action. RESEARCH DESIGN AND METHODS We investigated associations of loci identified by the Meta-Analyses of Glucose and Insulin-related traits Consortium (MAGIC) with circulating proinsulin, measures of insulin secretion and sensitivity from oral glucose tolerance tests (OGTTs), euglycemic clamps, insulin suppression tests, or frequently sampled intravenous glucose tolerance tests in nondiabetic humans (n = 29,084). RESULTS The glucose-raising allele in MADD was associated with abnormal insulin processing (a dramatic effect on higher proinsulin levels, but no association with insulinogenic index) at extremely persuasive levels of statistical significance (P = 2.1 × 10−71). Defects in insulin processing and insulin secretion were seen in glucose-raising allele carriers at TCF7L2, SCL30A8, GIPR, and C2CD4B. Abnormalities in early insulin secretion were suggested in glucose-raising allele carriers at MTNR1B, GCK, FADS1, DGKB, and PROX1 (lower insulinogenic index; no association with proinsulin or insulin sensitivity). Two loci previously associated with fasting insulin (GCKR and IGF1) were associated with OGTT-derived insulin sensitivity indices in a consistent direction. CONCLUSIONS Genetic loci identified through their effect on hyperglycemia and/or hyperinsulinemia demonstrate considerable heterogeneity in associations with measures of insulin processing, secretion, and sensitivity. Our findings emphasize the importance of detailed physiological characterization of such loci for improved understanding of pathways associated with alterations in glucose homeostasis and eventually type 2 diabetes. PMID:20185807

  13. Electrochemical mechanism and kinetics studies of haloperidol and its assay in commercial formulations

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Francisco W.P. [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil); Soares, Janete E.S. [Departamento de Farmacia, Faculdade de Farmacia, Odontologia e Enfermagem, Universidade Federal do Ceara, Rua Capitao Francisco Pedro, 1210 Rodolfo Teofilo 60430-370, Fortaleza, CE (Brazil); Becker, Helena; De Souza, Djenaine; Lima-Neto, Pedro de [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil); Correia, Adriana N., E-mail: adriana@ufc.b [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil)

    2011-02-01

    The kinetics and mechanism for electrochemical reduction of haloperidol, a psychotherapeutic drug used in the treatment of schizophrenia, were studied using square wave and cyclic voltammetries allied to a hanging mercury drop electrode. The experimental and voltammetric parameters were optimized at 0.04 mol L{sup -1} Brinton-Robinson buffer (pH 10), with a pulse potential frequency of 100 s{sup -1}, a pulse amplitude of 30 mV and scan increment of 2 mV. Two well-defined peaks were observed, which exhibited properties of fast electron transfer with a strong adsorption process of reactants and products on the electrode surface. The first peak was related to a fast and reversible anion-radical formation originating from the reduction of the carbonyl group, and the second was related to the irreversible reduction of the anion-radical previously formed. Analytical parameters such as: linearity range, equation of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday were compared to similar results obtained by use of the UV-vis spectrophotometry technique, and the analytical results obtained in commercial formulations show that the voltammetric procedure using a hanging mercury drop electrode is suitable for analyzing haloperidol in complex commercial formulation samples.

  14. Mechanism and kinetics of the reaction NO3 + C2H4.

    Science.gov (United States)

    Nguyen, Thanh Lam; Park, Jaehee; Lee, Kyungjun; Song, Kihyung; Barker, John R

    2011-05-19

    The reaction of NO(3) radical with C(2)H(4) was characterized using the B3LYP, MP2, B97-1, CCSD(T), and CBS-QB3 methods in combination with various basis sets, followed by statistical kinetic analyses and direct dynamics trajectory calculations to predict product distributions and thermal rate constants. The results show that the first step of the reaction is electrophilic addition of an O atom from NO(3) to an olefinic C atom from C(2)H(4) to form an open-chain adduct. A concerted addition reaction mechanism forming a five-membered ring intermediate was investigated, but is not supported by the highly accurate CCSD(T) level of theory. Master-equation calculations for tropospheric conditions predict that the collisionally stabilized NO(3)-C(2)H(4) free-radical adduct constitutes 80-90% of the reaction yield and the remaining products consist mostly of NO(2) and oxirane; the other products are produced in very minor yields. By empirically reducing the barrier height for the initial addition step by 1 kcal mol(-1) from that predicted at the CBS-QB3 level of theory and treating the torsional modes explicitly as one-dimensional hindered internal rotations (instead of harmonic oscillators), the computed thermal rate constants (including quantum tunneling) can be brought into very good agreement with the experimental data for the overall reaction rate constant.

  15. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides.

    Science.gov (United States)

    Björkbacka, Åsa; Yang, Miao; Gasparrini, Claudia; Leygraf, Christofer; Jonsson, Mats

    2015-09-28

    One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO˙). Both H2O2 and HO˙ are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO˙ are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

  16. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    Science.gov (United States)

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively.

  17. The fate of sotalol in aqueous chlorination: Kinetics, mechanisms and ecotoxicity assessment.

    Science.gov (United States)

    Khalit, Wan Nor Adira Wan; Tay, Kheng Soo

    2017-11-01

    Unmetabolized pharmaceuticals often enter the water treatment plants and exposed to various treatment processes. Among these water treatment processes, disinfection is a process which involves the application of chemical oxidation to remove pathogen. Untreated pharmaceuticals from primary and secondary treatment have the potential to be exposed to the chemical oxidation process during disinfection. This study investigated the kinetics and mechanism of the degradation of sotalol during chlorination process. Chlorination with hypochlorous acid (HOCl) as main reactive oxidant has been known as one of the most commonly used disinfection methods. The second order rate constant for the reaction between sotalol and free available chlorine (FAC) was found to decrease from 60.1 to 39.1M(-1)min(-1) when the pH was increased from 6 to 8. This result was mainly attributed by the decreased of HOCl concentration with increasing pH. In the real water samples, the presence of the higher amount of organic content was found to reduce the efficiency of chlorination in the removal of sotalol. This result showed that sotalol competes with natural organic matter to react with HOCl during chlorination. After 24h of FAC exposure, sotalol was found to produce three stable transformation by-products. These by-products are mainly chlorinated compounds. According to the acute and chronic toxicity calculated using ECOSAR computer program, the transformation by-products are more harmful than sotalol. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. [Removal Kinetics and Mechanism of Aniline by Manganese-oxide-modified Diatomite].

    Science.gov (United States)

    Xiao, Shao-dan; Liu, Lu; Jiang, Li-ying; Chen, Jian-meng

    2015-06-01

    A novel rapid green one-step method was developed for the preparation of manganese modified diatomite (Mn-D) by treating roasted diatomite with an acidic permanganate solution. The effects of calcination temperature and mass ratio of KMnO4 and diatomite (p) on aniline removal efficiency of Mn-D were investigated. The removal kinetics and mechanism of aniline by Mn-D were also discussed. The results showed that when the optimal calcination temperature was 450 degrees C, p was 1.6, and the loading amounts of δ-MnO2 was 0.82 g x g(-1), Mn-D had a great performance for aniline removal, and more than 80% of aniline was adsorbed within 10 minutes, accompanied with the release of Mn2+. In acidic conditions, the adsorption process on Mn-D followed pseudo-second-order and was mainly controlled by intra-particle diffusion. The best fitting of the experimental adsorption data was given by the Freundlich equation. Gas chromatograph-mass spectrometer was applied to identify the reaction intermediates at different times, and azobenzene was found to be the main reaction intermediate in the degradation system. Based on the above observations, the possible degradation pathway of aniline by Mn-D was proposed.

  19. KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

    Institute of Scientific and Technical Information of China (English)

    WANG Xiuzhi; LI Miaozhen; CHANG Zhiying; WANG Erjian

    1993-01-01

    α,α- dimethoxy- α-phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator.Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyl benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and κp/κt1/2 value were found to be 0.5 and 0.066 mol-1/2l1/2 s-1/2 , respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.

  20. Electro-oxidation of diclofenac at boron doped diamond: Kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Xu; Hou Yining; Liu Huijuan; Qiang Zhimin [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China); Qu Jiuhui [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China)], E-Mail: jhqu@mail.rcees.ac.cn

    2009-07-01

    Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at boron doped diamond electrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

  1. Vitamin B2-sensitised photooxidation of the ophthalmic drugs Timolol and Pindolol: kinetics and mechanism.

    Science.gov (United States)

    Criado, Susana; García, Norman A

    2004-01-01

    The kinetics and mechanistic aspects of the riboflavin-photosensitised oxidation of the topically administrable ophthalmic drugs Timolol (Tim) and Pindolol (Pin) were investigated in water-MeOH (9:1, v/v) solution employing light of wavelength > 400 nm. riboflavin, belonging to the vitamin B(2) complex, is a known human endogenous photosensitiser. The irradiation of riboflavin in the presence of ophthalmic drugs triggers a complex picture of competitive reactions which produces the photodegradation of both the drugs and the pigment itself. The mechanism was elucidated employing stationary photolysis, polarographic detection of dissolved oxygen, stationary and time-resolved fluorescence spectroscopy, and laser flash photolysis. Ophthalmic drugs quench riboflavin-excited singlet and triplet states. From the quenching of excited triplet riboflavin, the semireduced form of the pigment is generated, through an electron transfer process from the drug, with the subsequent production of superoxide anion radical (O(2)(*-)) by reaction with dissolved molecular oxygen. Through the interaction of dissolved oxygen with excited triplet riboflavin, the species singlet oxygen (O(2)((1)Delta(g))) is also generated to a lesser extent. Both O(2)(*-) and O(2)((1)Delta(g)) induce photodegradation of ophthalmic drugs, Tim being approximately 3-fold more easily photooxidisable than Pin, as estimated by oxygen consumption experiments.

  2. Kinetic mechanism of phenylalanine hydroxylase: intrinsic binding and rate constants from single-turnover experiments.

    Science.gov (United States)

    Roberts, Kenneth M; Pavon, Jorge Alex; Fitzpatrick, Paul F

    2013-02-12

    Phenylalanine hydroxylase (PheH) catalyzes the key step in the catabolism of dietary phenylalanine, its hydroxylation to tyrosine using tetrahydrobiopterin (BH(4)) and O(2). A complete kinetic mechanism for PheH was determined by global analysis of single-turnover data in the reaction of PheHΔ117, a truncated form of the enzyme lacking the N-terminal regulatory domain. Formation of the productive PheHΔ117-BH(4)-phenylalanine complex begins with the rapid binding of BH(4) (K(d) = 65 μM). Subsequent addition of phenylalanine to the binary complex to form the productive ternary complex (K(d) = 130 μM) is approximately 10-fold slower. Both substrates can also bind to the free enzyme to form inhibitory binary complexes. O(2) rapidly binds to the productive ternary complex; this is followed by formation of an unidentified intermediate, which can be detected as a decrease in absorbance at 340 nm, with a rate constant of 140 s(-1). Formation of the 4a-hydroxypterin and Fe(IV)O intermediates is 10-fold slower and is followed by the rapid hydroxylation of the amino acid. Product release is the rate-determining step and largely determines k(cat). Similar reactions using 6-methyltetrahydropterin indicate a preference for the physiological pterin during hydroxylation.

  3. Ozonation of parabens in aqueous solution: kinetics and mechanism of degradation.

    Science.gov (United States)

    Tay, Kheng Soo; Rahman, Noorsaadah Abd; Abas, Mhd Radzi Bin

    2010-12-01

    This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.

  4. Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography–mass spectrometry

    Directory of Open Access Journals (Sweden)

    JUN WANG

    2010-01-01

    Full Text Available As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3--dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography–mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems.

  5. Exact and user-friendly kinetic analysis of the two-step rapid equilibrium Michaelis-Menten mechanism.

    Science.gov (United States)

    Garneau-Tsodikova, Sylvie; Shkel, Irina A; Tsodikov, Oleg V

    2009-04-15

    Most enzyme kinetic experiments are carried out under pseudo-first-order conditions, that is, when one of the reactant species (the enzyme or the substrate) is in a large excess of the other species. More accurate kinetic information about the system can be gained without the restrictions of the pseudo-first-order conditions. We present a practical and general method of analysis of the common two-step rapid equilibrium Michaelis-Menten mechanism. The formalism is exact in that it does not involve any other approximations such as the steady-state, limitations on the reactant concentrations or on reaction times. We apply this method to the global analysis of kinetic progress curves for bovine alkaline phosphatase assays carried out under both pseudo-first-order and pseudo-second-order conditions.

  6. SENSITIVITY ANALYSIS OF KINETIC CONSTANTS AS A TOOL FOR ELUCIDATING THE POLYMERIZATION MECHANISM OF ACRYL-FURANIC COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Jurgen Lange

    2013-12-01

    Full Text Available By means of the sensitivity analysis of kinetics constants in a proposed mechanism for radical polymerization of acrylfuranic compounds [Furfuryl Acrylate (FA and Methacrylate (FM],it is elucidated which elementary steps are relevant in the phenomenology. In this analysis, the application of Come's methodology allows to classify the elementary steps of a mechanism in three categories: Non-sensible, Non-determinant, Sensible. The results obtained with this tool in modeling of experimental data in free radical polymerization of FA and FM suggest that kinetic mechanism consists mainly on five elementary steps: 1 Primary initiation, 2 propagation, 3 degradative transfers (which include intermolecular and primary, 4 re-initiation and 5 cross-termination. Thus, taking into account these elementary steps in mathematical modeling, the polymerization of FA and FM in different experimental conditions was successfully simulated.

  7. Mechanism of Cph1 phytochrome assembly from stopped-flow kinetics and circular dichroism.

    Science.gov (United States)

    Borucki, Berthold; Otto, Harald; Rottwinkel, Gregor; Hughes, Jonathan; Heyn, Maarten P; Lamparter, Tilman

    2003-11-25

    The kinetics and mechanism of the autocatalytic assembly of holo-Cph1 phytochrome (from Synechocystis) from the apoprotein and the bilin chromophores phycocyanobilin (PCB) and phycoerythrobilin (PEB) were investigated by stopped flow and circular dichroism. At 1:1 stoichiometry, pH 7.9, and 10 degrees C, SVD analysis of the kinetic data for PCB revealed three spectral components involving three transitions with time constants tau(1) approximately 150 ms, tau(2) approximately 2.5 s, and tau(3) approximately 50 s. Tau(1) was associated with a major red shift and transfer of oscillator strength from the Soret region to the 680 nm region. When the sulfhydryl group of cysteine 259 was blocked with iodoacetamide, preventing the formation of a covalent adduct, a noncovalent red-shifted complex (680 nm) was formed with a time constant of 200 ms. Tau(1) could thus be assigned to the formation of a noncovalent complex. The absorption changes during tau(1) are due to the formation of the extended conformation of the linear tetrapyrrole and to its protonation in the binding pocket. From the concentration and pH dependence of the kinetics we obtained a value of 1.5 microM for the K(D) of this noncovalent complex and a value of 8.4 for the pK(a) of the proton donor. The tau(2) component was associated with a blue shift of about 25 nm and was attributed to the formation of the covalent bond (P(r)), accompanied with the loss of the 3-3' double bond to ring A. Tau(3) was due to photoconversion to P(fr). For PEB, which is not photochromic, the formation of the noncovalent complex is faster (tau(1) = 70 ms), but the covalent bond formation is about 80 times slower (tau(2) = 200 s) than with the natural chromophore PCB. The CD spectra of the PCB adduct in the 250-800 nm range show that the chromophore geometries in P(r) and P(fr) are similar to those in plant phytochrome. The opposite rotational strengths of P(r) and P(fr) in the longest wavelength band suggest that the

  8. Shape, Thermodynamics, Kinetics and Growth Mechanisms of Metal and Bimetallic Nanoparticles

    Science.gov (United States)

    Peng, Lingxuan

    Metal and bimetallic nanoparticles are of interest and are widely used in various applications because of their unique optical, electronic, and catalytic properties, which differ from those of their bulk counterparts. Better understanding of the thermodynamic and kinetic properties of nanoparticles and their underlying growth mechanisms can serve as a basis for improving reproducibility and rational design of nanoparticle syntheses. The primary objective of this dissertation was to study the structural-related thermodynamic and kinetic properties of nanoparticles via the combination of experimental and theoretical techniques and to further unravel their underlying growth mechanisms. In this dissertation, the structure and elemental distribution of colloidally-synthesized bimetallic nanoparticles were characterized via scanning/transmission electron microscopy (S/TEM) and energy dispersive X-ray spectroscopy (EDX). In colloidally-synthesized bimetallic Pt/Pd nanoparticles, smooth composition gradients from the particle centers to their surfaces and corner enrichment of Pt were observed experimentally. A growth model was developed to demonstrate that the smooth composition gradients within the particles were the result of the difference in the deposition rate constants of Pd and Pt, causing Pd to deposit faster than Pt. The deposition rate constant ratio between Pd and Pt increased with total Pd and Pt precursor concentration. The corner Pt enrichment was a result of local thermodynamic control at the corners. At the nanoparticle corner, a Lyapunov stable solution could be achieved when the chemical potential at the corner equals the external chemical potential in the solution. This stable solution leads to size-independent corner rounding in colloidal synthesized nanoparticles. Strain-induced segregation in bimetallic multiply twinned particles, namely decahedral (Dh) and icosahedral (Ic) particles, was analyzed by an analytic first-order expansion within a

  9. Author Details

    African Journals Online (AJOL)

    Effect of cream formulation of fenugreek seed extract on some mechanical parameters of ... Little marvel) exposed to climate change in Riyadh city, KSA ... The status of rabies in Ethiopia: A retrospective record review ... Magnitude and variation of traffic air pollution as measured by CO in the City of Addis Ababa, Ethiopia

  10. A Single Mutation in a Tunnel to the Active Site Changes the Mechanism and Kinetics of Product Release in Haloalkane Dehalogenase LinB*

    Science.gov (United States)

    Biedermannová, Lada; Prokop, Zbyněk; Gora, Artur; Chovancová, Eva; Kovács, Mihály; Damborský, Jiří; Wade, Rebecca C.

    2012-01-01

    Many enzymes have buried active sites. The properties of the tunnels connecting the active site with bulk solvent affect ligand binding and unbinding and also the catalytic properties. Here, we investigate ligand passage in the haloalkane dehalogenase enzyme LinB and the effect of replacing leucine by a bulky tryptophan at a tunnel-lining position. Transient kinetic experiments show that the mutation significantly slows down the rate of product release. Moreover, the mechanism of bromide ion release is changed from a one-step process in the wild type enzyme to a two-step process in the mutant. The rate constant of bromide ion release corresponds to the overall steady-state turnover rate constant, suggesting that product release became the rate-limiting step of catalysis in the mutant. We explain the experimental findings by investigating the molecular details of the process computationally. Analysis of trajectories from molecular dynamics simulations with a tunnel detection software reveals differences in the tunnels available for ligand egress. Corresponding differences are seen in simulations of product egress using a specialized enhanced sampling technique. The differences in the free energy barriers for egress of a bromide ion obtained using potential of mean force calculations are in good agreement with the differences in rates obtained from the transient kinetic experiments. Interactions of the bromide ion with the introduced tryptophan are shown to affect the free energy barrier for its passage. The study demonstrates how the mechanism of an enzymatic catalytic cycle and reaction kinetics can be engineered by modification of protein tunnels. PMID:22745119

  11. A theoretical model for attachment lifetimes of kinetochore-microtubules: Mechano-kinetic "catch-bond" mechanism for error-correction

    CERN Document Server

    Shtylla, Blerta

    2013-01-01

    Before cell division, two identical copies of chromosomes are pulled apart by microtubule (MT) filaments that approach the chromosomes from the opposite poles a mitotic spindle. Connection between the MTs and the chromosomes are mediated by a molecular complex called kinetochore. An externally applied tension can lead to detachment of the MTs from the kinetochore; the mean lifetime of such an attachment is essentially a mean first-passage time. In their in-vitro pioneering single-kinetochore experiments, Akiyoshi et al. (Nature 468, 576 (2010)), observed that the mean lifetimes of reconstituted MT-kinetochore attachments vary non-monotonically with increasing tension. The counter-intuitive stabilization of the attachments by small load forces was interpreted in terms of a catch-bond-like mechanism based on a phenomenological 2-state kinetic model. Here we develop the first detailed microscopic model for studying the dependence of the lifetime of the MT-kinetochore attachment on (a) the structure, (b) energeti...

  12. Detailed Microstructural Characterization and Restoration Mechanisms of Duplex and Superduplex Stainless Steel Friction-Stir-Welded Joints

    Science.gov (United States)

    Santos, T. F. A.; Torres, E. A.; Lippold, J. C.; Ramirez, A. J.

    2016-12-01

    Duplex stainless steels are successfully used in a wide variety of applications in areas such as the food industry, petrochemical installations, and sea water desalination plants, where high corrosion resistance and high mechanical strength are required. However, during fusion welding operations, there can be changes to the favorable microstructure of these materials that compromise their performance. Friction stir welding with a non-consumable pin enables welded joints to be obtained in the solid state, which avoids typical problems associated with solidification of the molten pool, such as segregation of alloying elements and the formation of solidification and liquefaction cracks. In the case of superduplex stainless steels, use of the technique can avoid unbalanced proportions of ferrite and austenite, formation of deleterious second phases, or growth of ferritic grains in the heat-affected zone. Consolidated joints with full penetration were obtained for 6-mm-thick plates of UNS S32101 and S32205 duplex stainless steels, and S32750 and S32760 superduplex steels. The welding heat cycles employed avoided the conditions required for formation of deleterious phases, except in the case of the welded joint of the S32760 steel, where SEM images indicated the formation of secondary phases, as corroborated by decreased mechanical performance. Analysis using EBSD and transmission electron microscopy revealed continuous dynamic recrystallization by the formation of cellular arrays of dislocations in the ferrite and discontinuous dynamic recrystallization in the austenite. Microtexture evaluation indicated the presence of fibers typical of shear in the thermomechanically affected zone. These fibers were not obviously present in the stir zone, probably due to the intensity of microstructural reformulation to which this region was subjected.

  13. Kinetics and mechanism of the chain reaction between N-phenyl-1,4-benzoquinone monoimine and thiophenol

    Science.gov (United States)

    Varlamov, V. T.; Gadomsky, S. Ya.

    2017-05-01

    The kinetics of the reaction between N-phenyl-1,4-benzoquinone monoimine (quinone monoimine) and thiophenol is studied in chlorobenzene at 343 K. The reaction has the same mechanism proposed earlier for a similar reaction involving N,N'-diphenyl-1,4-benzoquinone diimine (quinone diimine). This mechanism has two paths: chain and nonchain. An important difference between the kinetics of the two reactions is the apparent reversible nature of the chain reaction in the quinone monoimine + thiophenol system. This nature reveals itself when the concentrations of thiophenol are comparable to or slightly higher than the concentrations of quinone imine. In light of this, kinetic research is conducted under conditions where the concentrations of thiophenol are significantly higher than those of quinone monoimine, allowing us to simplify the kinetic features and obtain interpretable data. The rate constants of the reaction's elementary steps are estimated and found to be three to five times lower for the reaction involving quinone monoamine than for the one involving quinone diimine. Both reactions have relatively short chains whose lengths do not exceed several tens of units.

  14. Recombinant Escherichia coli GMP reductase: kinetic, catalytic and chemical mechanisms, and thermodynamics of enzyme-ligand binary complex formation.

    Science.gov (United States)

    Martinelli, Leonardo Krás Borges; Ducati, Rodrigo Gay; Rosado, Leonardo Astolfi; Breda, Ardala; Selbach, Bruna Pelegrim; Santos, Diógenes Santiago; Basso, Luiz Augusto

    2011-04-01

    Guanosine monophosphate (GMP) reductase catalyzes the reductive deamination of GMP to inosine monophosphate (IMP). GMP reductase plays an important role in the conversion of nucleoside and nucleotide derivatives of guanine to adenine nucleotides. In addition, as a member of the purine salvage pathway, it also participates in the reutilization of free intracellular bases. Here we present cloning, expression and purification of Escherichia coli guaC-encoded GMP reductase to determine its kinetic mechanism, as well as chemical and thermodynamic features of this reaction. Initial velocity studies and isothermal titration calorimetry demonstrated that GMP reductase follows an ordered bi-bi kinetic mechanism, in which GMP binds first to the enzyme followed by NADPH binding, and NADP(+) dissociates first followed by IMP release. The isothermal titration calorimetry also showed that GMP and IMP binding are thermodynamically favorable processes. The pH-rate profiles showed groups with apparent pK values of 6.6 and 9.6 involved in catalysis, and pK values of 7.1 and 8.6 important to GMP binding, and a pK value of 6.2 important for NADPH binding. Primary deuterium kinetic isotope effects demonstrated that hydride transfer contributes to the rate-limiting step, whereas solvent kinetic isotope effects arise from a single protonic site that plays a modest role in catalysis. Multiple isotope effects suggest that protonation and hydride transfer steps take place in the same transition state, lending support to a concerted mechanism. Pre-steady-state kinetic data suggest that product release does not contribute to the rate-limiting step of the reaction catalyzed by E. coli GMP reductase.

  15. Kinetic analysis and molecular modeling of the inhibition mechanism of roneparstat (SST0001) on human heparanase

    Science.gov (United States)

    Pala, Daniele; Rivara, Silvia; Mor, Marco; Milazzo, Ferdinando Maria; Roscilli, Giuseppe; Pavoni, Emiliano; Giannini, Giuseppe

    2016-01-01

    Heparanase is a β-d-glucuronidase which cleaves heparan sulfate chains in the extracellular matrix and on cellular membranes. A dysregulated heparanase activity is intimately associated with cell invasion, tumor metastasis and angiogenesis, making heparanase an attractive target for the development of anticancer therapies. SST0001 (roneparstat; Sigma-Tau Research Switzerland S.A.) is a non-anticoagulant 100% N-acetylated and glycol-split heparin acting as a potent heparanase inhibitor, currently in phase I in advanced multiple myeloma. Herein, the kinetics of heparanase inhibition by roneparstat is reported. The analysis of dose-inhibition curves confirmed the high potency of roneparstat (IC50 ≈ 3 nM) and showed, at higher concentrations, a Hill coefficient consistent with the engagement of two molecules of inhibitor. A homology model of human heparanase GS3 construct was built and used for docking experiments with inhibitor fragments. The model has high structural similarity with the recently reported crystal structure of human heparanase. Different interaction schemes are proposed, which support the hypothesis of a complex binding mechanism involving the recruitment of one or multiple roneparstat chains, depending on its concentration. In particular, docking solutions were obtained in which (i) a single roneparstat molecule interacts with both heparin-binding domains (HBDs) of heparanase or (ii) two fragments of roneparstat interact with either HBD-1 or HBD-2, consistent with the possibility of different inhibitor:enzyme binding stoichiometries. This study provides unique insights into the mode of action of roneparstat as well as clues of its interaction with heparanase at a molecular level, which could be exploited to design novel potential inhibitor molecules. PMID:26762172

  16. Iminothiazoline-Sulfonamide Hybrids as Jack Bean Urease Inhibitors; Synthesis, Kinetic Mechanism and Computational Molecular Modeling.

    Science.gov (United States)

    Saeed, Aamer; Mahmood, Shams-Ul; Rafiq, Muhammad; Ashraf, Zaman; Jabeen, Farukh; Seo, Sung-Yum

    2016-03-01

    The present work reports the synthesis of several 2-iminothiazoline derivatives of sulfanilamide (3a-j) as inhibitors of jack bean ureases. The title compounds were synthesized by the heterocyclization of sulfanilamide thioureas with propragyl bromide in dry ethanol in the presence of 1,8-Diazabicyclo[5.4.0]undec-7-ene as a base. All of the compounds showed higher urease inhibitory activity than the standard thiourea. The compounds (3h) and (3i) exhibited excellent enzyme inhibitory activity with IC50 0.064 and 0.058 μm, respectively, while IC50 of thiourea is 20.9 μm. The kinetic mechanism analyzed by Dixon plot showed that compound (3h) is a mixed-type inhibitor while (3i) is a competitive one. Docking studies suggested that Asp633, Ala636, His492, Ala440, Lue523, Asp494 and Arg439 are the major interacting residues in the binding site of the protein and may have an instrumental role in the inhibition of enzyme's function. 2-iminothiazoline analogues (3a-j) showed good docking score (-10.6466 to -8.7215 Kcal/mol) and binding energy (London dG ranging from -14.4825 to -10.4087 Kcal/mol) which is far better than the standard thiourea (binding score in S field -4.5790 Kcal/mol London dG -4.7726 Kcal/mol). Our results inferred compound (3i) may serve as a structural model for the design of most potent urease inhibitors.

  17. Kinetics and Mechanism Study of Competitive Inhibition of Jack-Bean Urease by Baicalin

    Directory of Open Access Journals (Sweden)

    Lirong Tan

    2013-01-01

    Full Text Available Baicalin (BA is the principal component of Radix Scutellariae responsible for its pharmacological activity. In this study, kinetics and mechanism of inhibition by BA against jack-bean urease were investigated for its therapeutic potential. It was revealed that the IC50 of BA against jack-bean urease was 2.74 ± 0.51 mM, which was proved to be a competitive and concentration-dependent inhibition with slow-binding progress curves. The rapid formation of initial BA-urease complex with an inhibition constant of Ki=3.89 × 10−3 mM was followed by a slow isomerization into the final complex with an overall inhibition constant of Ki*=1.47×10-4 mM. High effectiveness of thiol protectors against BA inhibition indicated that the strategic role of the active-site sulfhydryl group of the urease was involved in the blocking process. Moreover, the inhibition of BA was proved to be reversible due to the fact that urease could be reactivated by dithiothreitol but not reactant dilution. Molecular docking assay suggested that BA made contacts with the important activating sulfhydryl group Cys-592 residues and restricted the mobility of the active-site flap. Taken together, it could be deduced that BA was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for treatments on urease-related diseases.

  18. Ozonation of benzotriazole and methylindole: Kinetic modeling, identification of intermediates and reaction mechanisms.

    Science.gov (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldán, Gloria; Rodríguez, Elena

    2015-01-23

    The ozonation of 1H-benzotriazole (BZ) and 3-methylindole (ML), two emerging contaminants that are frequently present in aquatic environments, was investigated. The experiments were performed with the contaminants (1μM) dissolved in ultrapure water. The kinetic study led to the determination of the apparent rate constants for the ozonation reactions. In the case of 1H-benzotriazole, these rate constants varied from 20.1 ± 0.4M(-1)s(-1) at pH=3 to 2143 ± 23 M(-1)s(-1) at pH=10. Due to its acidic nature (pKa=8.2), the degree of dissociation of this pollutant was determined at every pH of work, and the specific rate constants of the un-dissociated and dissociated species were evaluated, being the values of these rate constants 20.1 ± 2.0 and 2.0 ± 0.3 × 10(3)M(-1)s(-1), respectively. On the contrary, 3-methylindole does not present acidic nature, and therefore, it can be proposed an average value for its rate constant of 4.90 ± 0.7 × 10(5)M(-1)s(-1) in the whole pH range 3-10. Further experiments were performed to identify the main degradation byproducts (10 mg L(-1) of contaminants, 0.023 gh(-1) of ozone). Up to 8 intermediates formed in the ozonation of 3-methylindole were identified by LC-TOFMS, while 6 intermediates were identified in the ozonation of 1H-benzotriazole. By considering these intermediate compounds, the reaction mechanisms were proposed and discussed. Finally, evaluated rate constants allowed to predict and modeling the oxidation of these micropollutants in general aquatic systems.

  19. The role of background electrolytes on the kinetics and mechanism of calcite dissolution

    Science.gov (United States)

    Ruiz-Agudo, E.; Kowacz, M.; Putnis, C. V.; Putnis, A.

    2010-02-01

    The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl - salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F - and Li + are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F -, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.

  20. 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}.

  1. Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic.

    Science.gov (United States)

    Suksabye, Parinda; Nakajima, Akira; Thiravetyan, Paitip; Baba, Yoshinari; Nakbanpote, Woranan

    2009-01-30

    The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, alpha-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in alpha-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while alpha-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of alpha-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively.

  2. Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic

    Energy Technology Data Exchange (ETDEWEB)

    Suksabye, Parinda [Joint Graduate School of Energy and Environment, King Mongkut' s University of Technology Thonburi, 91 Pracha-Utit Road, Bangmod, Thungkru, Bangkok 10140 (Thailand); Nakajima, Akira [Division of Chemistry, Department of Medical Science, Faculty of Medicine, University of Miyazaki, Kiyotake, Miyazaki 889 1692 (Japan); Thiravetyan, Paitip [Division of Biotechnology, School of Bioresources and Technology, King Mongkut' s University of Technology Thonburi, 83 Moo.8 Thakham, Bangkhuntien, Bangkok 10150 (Thailand)], E-mail: paitip.thi@kmutt.ac.th; Baba, Yoshinari [Department of applied Chemistry, Faculty of Technology, University of Miyazaki, Gakuen-Kibabadai, Miyazaki 889 2192 (Japan); Nakbanpote, Woranan [Pilot Plant Development and Training Institute, King Mongkut' s University of Technology Thonburi, 83 Moo.8 Thakham, Bangkhuntien, Bangkok 10150 (Thailand)

    2009-01-30

    The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, {alpha}-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in {alpha}-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while {alpha}-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of {alpha}-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively.

  3. Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron.

    Science.gov (United States)

    Liang, Liping; Yang, Wenjun; Guan, Xiaohong; Li, Jialing; Xu, Zijian; Wu, Jiang; Huang, Yuying; Zhang, Xiangzi

    2013-10-01

    The kinetics of Se(IV) removal by zero valent iron (ZVI) open to the air as a function of pH and the involved mechanisms were investigated in this study. The specific rate constants of Se(IV) removal by ZVI decreased from 92.87 to 6.87 L h(-1) m(-2) as pH increased from 4.0 to 7.0. The positive correlation between the removal rate of Se(IV) and the generation rate of Fe(II) and the depression of Se(IV) removal in the presence of 1,10-phenanthroline indicated that both ZVI and adsorbed Fe(II) on ZVI surface contributed to the reductive removal of Se(IV). The soft X-ray STXM measurement confirmed the adsorption of Fe(II) on the surface of ZVI and freshly formed ferric (hydr)oxides. Se(IV) was removed by adsorption followed by reduction to Se(0) on ZVI surface at pH 4.0-7.0, as revealed by XANES spectra. A core-shell structure was observed when ZVI reacted with Se(IV)-containing solution for 3 h at pH 6.0. Se(IV) was reduced to Se(0) and co-precipitated with the freshly formed Fe(III), forming the shell surrounding the iron core. After reaction for 24 h, the generated Se(0) was surrounded by multiple layers of Fe(III) oxides/hydroxides. SEM images and XRD patterns revealed that the corrosion products of ZVI at pH 6.0 transformed from amorphous iron hydroxides to lepidocrocite (γ-FeOOH) as reaction proceeded. The final corrosion products of ZVI contained both lepidocrocite and goethite at pH 5.0 while they were X-ray amorphous at pH 4.0 and 7.0.

  4. Kinetics and mechanism study of competitive inhibition of jack-bean urease by baicalin.

    Science.gov (United States)

    Tan, Lirong; Su, Jiyan; Wu, Dianwei; Yu, Xiaodan; Su, Zuqing; He, Jingjin; Wu, Xiaoli; Kong, Songzhi; Lai, Xiaoping; Lin, Ji; Su, Ziren

    2013-01-01

    Baicalin (BA) is the principal component of Radix Scutellariae responsible for its pharmacological activity. In this study, kinetics and mechanism of inhibition by BA against jack-bean urease were investigated for its therapeutic potential. It was revealed that the IC₅₀ of BA against jack-bean urease was 2.74 ± 0.51 mM, which was proved to be a competitive and concentration-dependent inhibition with slow-binding progress curves. The rapid formation of initial BA-urease complex with an inhibition constant of K(i) = 3.89 × 10⁻³ mM was followed by a slow isomerization into the final complex with an overall inhibition constant of K(i)* = 1.47 × 10⁻⁴ mM. High effectiveness of thiol protectors against BA inhibition indicated that the strategic role of the active-site sulfhydryl group of the urease was involved in the blocking process. Moreover, the inhibition of BA was proved to be reversible due to the fact that urease could be reactivated by dithiothreitol but not reactant dilution. Molecular docking assay suggested that BA made contacts with the important activating sulfhydryl group Cys-592 residues and restricted the mobility of the active-site flap. Taken together, it could be deduced that BA was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for treatments on urease-related diseases.

  5. Mechanism of thrombocytopenia in liver cirrhosis: Kinetics of indium-111 tropolone labelled platelets

    Energy Technology Data Exchange (ETDEWEB)

    Aoki, Yoshinori; Hirai, Kenji; Tanikawa, Kyuichi (Kurume Univ., Fukuoka (Japan). 2. Dept. of Medicine)

    1993-02-01

    Using indium-111 tropolone-labelled platelets, a study of platelet kinetics was performed on the basis of the relationship between platelet count, platelet survival time, platelet dynamics, platelet-associated immunoglobulin G (PA-IgG) and splenic volume in 31 patients with liver cirrhosis and a platelet count of less than 100 x 10[sup 9]/1: The mean platelet count was 46.6 [+-] 25.3 x 10[sup 9]/1, and the mean platelet survival time was 6.50 [+-] 1.33 days. The mean uptake into the spleen was 43.2% [+-] 14.8% on the 1st day, and 53.7% [+-] 14.3% on the 7th day. The mean PA-IgG level was 107.6 [+-] 66.0 ng/10[sup 7] platelets in five patients with chronic active hepatitis who were studied as controls the mean platelet count was 197 [+-] 30 x 10[sup 9]/1, the mean platelet survival time 9.33 [+-] 0.78 days, and the mean PA-IgG 21.2 [+-] 2.9 ng/10[sup 7] platelets. The former two parameters were significantly higher, and the latter significantly lower. In liver cirrhosis, the platelet count showed a positive correlation with the platelet survival time and a negative correlation with PA-IgG and the splenic volume. These results suggest that the increases in both the splenic platelet pool and platelet destruction in the spleen through immunological mechanisms may influence thrombocytopenia in liver cirrhosis. (orig.).

  6. Polycaprolactone/maltodextrin nanocarrier for intracellular drug delivery: formulation, uptake mechanism, internalization kinetics, and subcellular localization.

    Science.gov (United States)

    Korang-Yeboah, Maxwell; Gorantla, Yamini; Paulos, Simon A; Sharma, Pankaj; Chaudhary, Jaideep; Palaniappan, Ravi

    2015-01-01

    Prostate cancer (PCa) disease progression is associated with significant changes in intracellular and extracellular proteins, intracellular signaling mechanism, and cancer cell phenotype. These changes may have direct impact on the cellular interactions with nanocarriers; hence, there is the need for a much-detailed understanding, as nanocarrier cellular internalization and intracellular sorting mechanism correlate directly with bioavailability and clinical efficacy. In this study, we report the differences in the rate and mechanism of cellular internalization of a biocompatible polycaprolactone (PCL)/maltodextrin (MD) nanocarrier system for intracellular drug delivery in LNCaP, PC3, and DU145 PCa cell lines. PCL/MD nanocarriers were designed and characterized. PCL/MD nanocarriers significantly increased the intracellular concentration of coumarin-6 and fluorescein isothiocyanate-labeled bovine serum albumin, a model hydrophobic and large molecule, respectively. Fluorescence microscopy and flow cytometry analysis revealed rapid internalization of the nanocarrier. The extent of nanocarrier cellular internalization correlated directly with cell line aggressiveness. PCL/MD internalization was highest in PC3 followed by DU145 and LNCaP, respectively. Uptake in all PCa cell lines was metabolically dependent. Extraction of endogenous cholesterol by methyl-β-cyclodextrin reduced uptake by 75%±4.53% in PC3, 64%±6.01% in LNCaP, and 50%±4.50% in DU145, indicating the involvement of endogenous cholesterol in cellular internalization. Internalization of the nanocarrier in LNCaP was mediated mainly by macropinocytosis and clathrin-independent pathways, while internalization in PC3 and DU145 involved clathrin-mediated endocytosis, clathrin-independent pathways, and macropinocytosis. Fluorescence microscopy showed a very diffused and non-compartmentalized subcellular localization of the PCL/MD nanocarriers with possible intranuclear localization and minor colocalization in

  7. Electroanalysis of cardioselective beta-adrenoreceptor blocking agent acebutolol by disposable graphite pencil electrodes with detailed redox mechanism

    Directory of Open Access Journals (Sweden)

    Atmanand M. Bagoji

    2016-12-01

    Full Text Available A simple economic graphite pencil electrode (GPE was used for analysis of cardioselective, hydrophilic-adrenoreceptor blocking agent, acebutolol (ACBT using the cyclic voltammetric, linear sweep voltammetric, differential pulse voltammetric (DPV, and square-wave voltammetric (SWV techniques. The dependence of the current on pH, concentration, and scan rate was investigated to optimize the experimental condition for determination of ACBT. The electrochemical behavior of the ACBT at GPE was a diffusion-controlled process. A probable electro-redox mechanism was proposed. Under the optimal conditions, the anodic peak current was linearly proportional to the concentration of ACBT in the range from 1.00 to 15.0 μM with a limit of detection 1.26 × 10−8 M for DPV and 1.28 × 10−8 M for the SWV. This method was applied for quantitative determination of the ACBT levels in urine as real samples. The obtained recovery ranges for ACBT in urine were from 95.4 to101% as found by the standard addition technique. Further interference study was also carried with some common interfering substances.

  8. Theoretical investigation on the detailed mechanism of the OH-initiated atmospheric photooxidation of o-xylene

    Science.gov (United States)

    Huang, Mingqiang; Zhang, Weijun; Wang, Zhenya; Hao, Liqing; Zhao, Wenwu; Liu, Xianyun; Long, Bo; Fang, Li

    The reaction mechanism for o-xylene with OH radical and O2 was studied by density functional theory (DFT) method. The geometries of the reactants, intermediates, transition states, and products were optimized at B3LYP/6-31G(d,p) level. The corresponding vibration frequencies were calculated at the same level. The single-point calculations for all the stationary points were carried out at the B3LYP/6-311++G(2df,2pd) level using the B3LYP/6-31G(d,p) optimized geometries. Reaction energies for the formation of the aromatic intermediate radicals have been obtained to determine their relative stability and reversibility, and their activation barriers have been analyzed to assess the energetically favorable pathways to propagate the o-xylene oxidation. The results of the theoretical study indicate that OH addition to o-xylene forms ipso, meta, and para isomers of o-xylene-OH adducts, and the ipso o-xylene adduct is the most stable among these isomers. Oxygen is expected to add to the o-xylene-OH adducts forming o-xylene peroxy radicals. And subsequent ring closure of the peroxyl radicals to form bicyclic radicals. With relatively low barriers, isomerization of the o-xylene bicyclic radicals to more stable epoxide radicals likely occurs, competing with O2 addition to form bicyclic peroxy radicals. The study provides thermochemical data for assessment of the photochemical production potential of ozone and formation of toxic products and secondary organic aerosol from o-xylene photooxidation.0

  9. Kinetics of cellular transformation and competing precipitation mechanisms during sub-eutectoid annealing of U10Mo alloys

    Energy Technology Data Exchange (ETDEWEB)

    Jana, S.; Devaraj, A.; Kovarik, L.; Arey, B.; Sweet, L.; Varga, T.; Lavender, C.; Joshi, V.

    2017-11-01

    Transformation kinetics of metastable body-centered cubic γ-UMo phase in U-10 wt.percent Mo alloy during annealing at sub-eutectoid temperatures of 500C and 400C has been determined as a function of time using detailed microstructural characterization by scanning electron microscopy, X-ray diffraction analysis, scanning transmission electron microscopy, and atom probe tomography. Based on the results, we found that the phase transformation is initiated by cellular transformation at both the temperatures, which results in formation of a lamellar microstructure along prior γ-UMo grain boundaries.

  10. Kinetics and Mechanism of the Thermal Decomposition Reaction of 3,3-Bis(azidomethyl)oxetane/Tetrahydrofuran Copolymer

    Institute of Scientific and Technical Information of China (English)

    LUO, Yang(罗阳); CHEN, Pei(陈沛); ZHAO, Feng-Qi(赵凤起); HU, Rong-Zu(胡劳祖); LI, Shang-Wen(李上文); GAO, Yin(高茵)

    2004-01-01

    The thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) copolymer in a temperature-programmed mode have been investigated by means of DSC, TG-DTG, fast and lower thermolysis/FTIR and TG-MS. The reaction mechanism was proposed. The apparent activation energy and pre-exponential constant of exothermic decomposition reaction of the compound at 0.1 MPa are 167.04 kJ·mol-1 and 1014.41 s-1, respectively. The corresponding critical temperatures of thermal explosion obtained from the onset temperature Te and the peak temperature Tp are 223.20 and 245.78 ℃, respectively. The kinetic equation of the exothermic decomposition process of BAMO/THF at 0.1 MPa could be expressed as:dα/dT= 1015.19 [-ln(1-α)]2/3e-2.009×104/T

  11. Kinetics and Mechanism of Oxidation of Phenyl Acetic Acid and Dl-Mandelic Acid by Permanganate in Acid Medium

    Directory of Open Access Journals (Sweden)

    B.Syama Sundar

    2014-06-01

    Full Text Available 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 with Mn (VII in case of DL-Mandelic acid. The following order of reactivity is observed: DL-Mandelic acid > Phenyl acetic acid. The high reactivity of DL-Mandelic acid over phenyl acetic acid may be due to different mechanisms operating with the two substrates and benzaldehyde is the final product in both the cases.

  12. Predictions of NO{sub x} formation in an NH{sub 3}-doped syngas flame using CFD combined with a detailed reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brink, A.; Norstroem, T.; Kilpinen, P.; Hupa, M. [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

    1997-12-31

    The formation of NO{sub x} in a CO/H{sub 2}/CH{sub 4}/NH{sub 3} jet in a co-flowing air stream was modeled by use of CFD combined with a comprehensive detailed reaction mechanism. The comprehensive mechanism involved 340 reversible elementary reactions between 55 species. Three different approaches to include the detailed reaction mechanism were tested. In approach I, all chemistry was described with the comprehensive mechanism. In approaches IIa and IIb the comprehensive mechanism was used in post-processing calculations of the nitrogen chemistry. In approach IIa, the temperatures of the reacting structures obtained in the main calculations were used, whereas in approach IIb, the inlet temperatures to the reacting structures were taken from the main calculation. In approach IIIa and IIIb, empirical reaction mechanisms describing the nitrogen chemistry were tested. The turbulence-chemistry interaction was accounted for with a new model, which combines the Eddy-Dissipation Concept with a model based on the `Exchange by Interaction with the Mean`. There was a clear difference between the computed results and the measured ones. The use of approach I resulted in an obvious overprediction of the lift-off height. The predicted molar NO{sub x} yield with the approaches IIa and IIb were 89 % and 85 %, respectively, whereas a yield of 23 % had been measured. With the empirical mechanisms used in approach IIIa, a similar NO{sub x} yield was predicted as with approaches IIa and IIb. With IIIb the predicted NO{sub x} yield was 40 %. However, in this case 67 % of the NH{sub 3} remained unreacted. The reason for the large difference between the calculated NO{sub x} yield and the measured one reported in the literature is a poor modeling of the initial part of the fuel jet. A possible reason for this is the coarse grid. (author) 15 refs.

  13. Detailed characterization of the cooperative mechanism of Ca(2+) binding and catalytic activation in the Ca(2+) transport (SERCA) ATPase.

    Science.gov (United States)

    Zhang, Z; Lewis, D; Strock, C; Inesi, G; Nakasako, M; Nomura, H; Toyoshima, C

    2000-08-01

    Expression of heterologous SERCA1a ATPase in Cos-1 cells was optimized to yield levels that account for 10-15% of the microsomal protein, as revealed by protein staining on electrophoretic gels. This high level of expression significantly improved our characterization of mutants, including direct measurements of Ca(2+) binding by the ATPase in the absence of ATP, and measurements of various enzyme functions in the presence of ATP or P(i). Mutational analysis distinguished two groups of amino acids within the transmembrane domain: The first group includes Glu771 (M5), Thr799 (M6), Asp800 (M6), and Glu908 (M8), whose individual mutations totally inhibit binding of the two Ca(2+) required for activation of one ATPase molecule. The second group includes Glu309 (M4) and Asn796 (M6), whose individual or combined mutations inhibit binding of only one and the same Ca(2+). The effects of mutations of these amino acids were interpreted in the light of recent information on the ATPase high-resolution structure, explaining the mechanism of Ca(2+) binding and catalytic activation in terms of two cooperative sites. The Glu771, Thr799, and Asp800 side chains contribute prominently to site 1, together with less prominent contributions by Asn768 and Glu908. The Glu309, Asn796, and Asp800 side chains, as well as the Ala305 (and possibly Val304 and Ile307) carbonyl oxygen, contribute to site 2. Sequential binding begins with Ca(2+) occupancy of site 1, followed by transition to a conformation (E') sensitive to Ca(2+) inhibition of enzyme phosphorylation by P(i), but still unable to utilize ATP. The E' conformation accepts the second Ca(2+) on site 2, producing then a conformation (E' ') which is able to utilize ATP. Mutations of residues (Asp813 and Asp818) in the M6/M7 loop reduce Ca(2+) affinity and catalytic turnover, suggesting a strong influence of this loop on the correct positioning of the M6 helix. Mutation of Asp351 (at the catalytic site within the cytosolic domain

  14. Kinetics and mechanisms of oxidation of 2D woven C/SiC composites; 1: Experimental approach

    Energy Technology Data Exchange (ETDEWEB)

    Lamouroux, F.; Camus, G. (UMR 47, Pessac (France). Lab. des Composites Thermostructuraux); Thebault, J. (Societe Europeenne de Propulsion, Saint Medard-en-Jalles (France))

    1994-08-01

    The oxidation behavior of a 2D woven C/SiC composite partly protected with a SiC seal coating and heat-treated (stabilized) at 1,600 C in inert gas has been investigated through an experimental approach based on thermogravimetric analyses and optical/electron microscopy. Results of the tests, performed under flowing oxygen, have shown that the oxidation behavior of the composite material in terms of oxidation kinetics and morphological evolutions is related to the presence of thermal microcracks in the seal coating as well as in the matrix. Three different temperature domains exist. At low temperatures (< 800 C), the mechanisms of reaction between carbon and oxygen control the oxidation kinetics and are associated with a uniform degradation of the carbon reinforcement. At intermediate temperatures, (between 800 and 1,100 C), the oxidation kinetics are controlled by the gas-phase diffusion through a network of microcracks in the SiC coatings, resulting in a nonuniform degradation of the carbon phases. At high temperatures (> 1,100 C), such diffusion mechanisms are limited by sealing of the microcracks by silica; therefore, the degradation of the composite remains superficial. The study of the oxidation behavior of (i) the heat-treated composite in a lower oxygen content environment (dry air) and (ii) the as-processed (unstabilized) composite in dry oxygen confirms the different mechanisms proposed to explain the oxidation behavior of the composite material.

  15. Kinetic study on aminolysis of 4-pyridyl benzoate and o-4-pyridyl thionobenzoate in acetonitrile: Factors influencing reactivity and reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Um, Ik Hwan; Kim, Min Young [Dept. of Chemistry, and Nano Science, Ewha Womans University, Seoul (Korea, Republic of); Lee, Jae In [Dept. of Chemistry, and Plant Resources Research Institute, Duksung Women' s University, Seoul (Korea, Republic of)

    2016-10-15

    A kinetic study on nucleophilic substitution reactions of 4-pyridyl benzoate (2a) and O-4-pyridyl thionobenzoate (2b) with a series of cyclic secondary amines in acetonitrile at 25.0°C is reported. Plots of pseudo-first-order rate constant (k{sub obsd}) vs. [amine] are linear and pass through the origin for the reactions of 2a but curve upward for those of 2b. The upward curvature observed for the reactions of 2b is typical for reactions that proceed through a stepwise mechanism with a zwitterionic intermediate T{sup ±}, which decomposes to the products via uncatalyzed and catalyzed routes competitively. The reaction of 2a has been suggested to proceed through a stepwise mechanism with T±, in which expulsion of the leaving group occurs in the rate-determining step on the basis of a linear Broensted-type plot with β{sub nuc} = 0.77. The catalyzed reaction of 2b from T{sup ±} has been proposed to proceed through a concerted mechanism with a six-membered cyclic transition state rather than via a stepwise pathway with an anionic intermediate T{sup −}. Factors influencing reactivity and reaction mechanism are discussed in detail.

  16. Multiple inhibition of glutathione S-transferase A from rat liver by glutathione derivatives: kinetic analysis supporting a steady-state random sequential mechanism.

    Science.gov (United States)

    Jakobson, I; Warholm, M; Mannervik, B

    1979-01-01

    Glutathione derivatives inhibit glutathione S-transferase A [cf. Biochem. J. (1975) 147, 513--522]. The steady-state kinetics of this inhibition have been investigated in detail by using S-octyglutathione, glutathione disulphide and S-(2-chloro-4-nitrophenyl)glutathione: the last compound is a product of the enzyme-catalused reaction. Interpreted in terms of generalized denotations of inhibition patterns, the compounds were found to be competitive with the substrate glutathione. Double-inhibition experiments involving simultaneous use of two inhibitors indicated exclusive binding of the inhibitors to the enzyme. The discrimination between alternative rate equations has been based on the results of weighted non-linear regression analysis. The experimental error was determined by replicate measurements and was found to increase with velocity. The established error structure was used as a basis for weighting in the regression and to construct confidence levels for the judgement of goodness-of-fit of rate equations fitted to experimental data. The results obtained support a steady-state random model for the mechanism of action of glutathione S-transferase A and exclude a number of simple kinetic models. PMID:444209

  17. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir–Hinshelwood–Hougen–Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir–Hinshelwood–Hougen–Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  18. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism.

    Science.gov (United States)

    Azarhoosh, Mohammad Javad; Halladj, Rouein; Askari, Sima

    2017-10-25

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  19. Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

    Institute of Scientific and Technical Information of China (English)

    WANG Dunjia; FANG Zhengdong; HAN Deyan

    2005-01-01

    The polyoxometalate complex (CPFX·HCl)4H5BW12O40·12H2O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a our-step process consisting of the simultaneous collapse of Keggin anion. The intermediate and residue of the decomposition were identified by mean of TG-DTG, IR, and XRD technique. The non-isothermal kinetic data were analyzed by the Achar method and Coats-Redfern method. The apparent activation energy (E) and the pre-exponential factor (ln A) of each decomposition were obtained. The most probable thermal decomposition reaction mechanisms were proposed by comparison of the kinetic parameters. The kinetic equation for both the second stage and the third stage can be expressed as dα/dt = Ae-EIRT·(1 - α)2, and the fourth stage dα/dt = Ae-EIRT·( 1 - α). And their athematic expressions of the kinetic compensation effects of thermal decomposition reaction were also determined.

  20. 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.

  1. Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex in perchloric acid medium

    Indian Academy of Sciences (India)

    T V N Partha Sarathi; A Kalyan Kumar; K Krishna Kishore; P Vani

    2005-07-01

    Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H+] decreases the rate. Hence it can be inferred that the reactive species of the substrate is the zwitterionic form and that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law as elucidated.

  2. Interaction mechanisms and kinetics of ferrous ion and hexagonal birnessite in aqueous systems.

    Science.gov (United States)

    Gao, Tianyu; Shen, Yougang; Jia, Zhaoheng; Qiu, Guohong; Liu, Fan; Zhang, Yashan; Feng, Xionghan; Cai, Chongfa

    2015-12-01

    In soils and sediments, manganese oxides and oxygen usually participate in the oxidation of ferrous ions. There is limited information concerning the interaction process and mechanisms of ferrous ions and manganese oxides. The influence of air (oxygen) on reaction process and kinetics has been seldom studied. Because redox reactions usually occur in open systems, the participation of air needs to be further investigated. To simulate this process, hexagonal birnessite was prepared and used to oxidize ferrous ions in anoxic and aerobic aqueous systems. The influence of pH, concentration, temperature, and presence of air (oxygen) on the redox rate was studied. The redox reaction of birnessite and ferrous ions was accompanied by the release of Mn(2+) and K(+) ions, a significant decrease in Fe(2+) concentration, and the formation of mixed lepidocrocite and goethite during the initial stage. Lepidocrocite did not completely transform into goethite under anoxic condition with pH about 5.5 within 30 days. Fe(2+) exhibited much higher catalytic activity than Mn(2+) during the transformation from amorphous Fe(III)-hydroxide to lepidocrocite and goethite under anoxic conditions. The release rates of Mn(2+) were compared to estimate the redox rates of birnessite and Fe(2+) under different conditions. Redox rate was found to be controlled by chemical reaction, and increased with increasing Fe(2+) concentration, pH, and temperature. The formation of ferric (hydr)oxides precipitate inhibited the further reduction of birnessite. The presence of air accelerated the oxidation of Fe(2+) to ferric oxides and facilitated the chemical stability of birnessite, which was not completely reduced and dissolved after 18 days. As for the oxidation of aqueous ferrous ions by oxygen in air, low and high pHs facilitated the formation of goethite and lepidocrocite, respectively. The experimental results illustrated the single and combined effects of manganese oxide and air on the transformation

  3. Development of a Surface Plasmon Resonance Assay for the Characterization of Small-Molecule Binding Kinetics and Mechanism of Binding to Kynurenine 3-Monooxygenase.

    Science.gov (United States)

    Poda, Suresh B; Kobayashi, Masakazu; Nachane, Ruta; Menon, Veena; Gandhi, Adarsh S; Budac, David P; Li, Guiying; Campbell, Brian M; Tagmose, Lena

    2015-10-01

    Kynurenine 3-monooxygenase (KMO), a pivotal enzyme in the kynurenine pathway, was identified as a potential therapeutic target for treating neurodegenerative and psychiatric disorders. In this article, we describe a surface plasmon resonance (SPR) assay that delivers both kinetics and the mechanism of binding (MoB) data, enabling a detailed characterization of KMO inhibitors for the enzyme in real time. SPR assay development included optimization of the protein construct and the buffer conditions. The stability and inhibitor binding activity of the immobilized KMO were significantly improved when the experiments were performed at 10°C using a buffer containing 0.05% n-dodecyl-β-d-maltoside (DDM) as the detergent. The KD values of the known KMO inhibitors (UPF648 and RO61-8048) from the SPR assay were in good accordance with the biochemical LC/MS/MS assay. Also, the SPR assay was able to differentiate the binding kinetics (k(a) and k(d)) of the selected unknown KMO inhibitors. For example, the inhibitors that showed comparable IC50 values in the LC/MS/MS assay displayed differences in their residence time (τ = 1/k(d)) in the SPR assay. To better define the MoB of the inhibitors to KMO, an SPR-based competition assay was developed, which demonstrated that both UPF648 and RO61-8048 bound to the substrate-binding site. These results demonstrate the potential of the SPR assay for characterizing the affinity, the kinetics, and the MoB profiles of the KMO inhibitors.

  4. Growth kinetics and mechanism of Pd{sub 2}Zn{sub 9} at the interface of Pd substrate with molten Sn–9wt.%Zn solder

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chao-Hong, E-mail: chmchw@ccu.edu.tw; Li, Kuan-Ting

    2015-08-15

    A uniform Pd{sub 2}Zn{sub 9} layer was formed at the interface between liquid-state Sn–9wt.%Zn and Pd substrate. Detailed observation revealed a unique cruciform pattern formation of the Pd{sub 2}Zn{sub 9} phase. The Pd{sub 2}Zn{sub 9} layer ruptured at the edges, where no reaction phase was formed. The growth kinetics of Pd{sub 2}Zn{sub 9} was systematically investigated at temperatures of 220–260 °C. In particular, a linear reaction-limited growth was found in the initial reaction stage. While growing to approximately 5 μm thick, the growth rate gradually decreased over the subsequent reaction and obeyed a parabolic relationship. The growth kinetics parameters and the corresponding activation energies were determined. Additionally, the microstructure in the Pd{sub 2}Zn{sub 9} layer was characterized using focused ion beam microscopy. The Pd{sub 2}Zn{sub 9} layer consisted of four distinct sublayers with different grain structures. The growth behavior of Pd{sub 2}Zn{sub 9} was further discussed through a series of observations on microstructural evolutions at different reaction durations. - Highlights: • Linear growth of Pd{sub 2}Zn{sub 9} was found in the liquid-state Sn–9wt.%Zn/Pd reaction. • After growing to ~5 μm thick, the parabolic growth became dominant. • Unique cruciform pattern formation was observed in the Pd{sub 2}Zn{sub 9} phase. • FIB characterization revealed that the Pd{sub 2}Zn{sub 9} consisted of four sublayers. • The growth kinetics and mechanism of Pd{sub 2}Zn{sub 9} were discussed.

  5. A statistical mechanical theory of proton transport kinetics in hydrogen-bonded networks based on population correlation functions with applications to acids and bases.

    Science.gov (United States)

    Tuckerman, Mark E; Chandra, Amalendu; Marx, Dominik

    2010-09-28

    Extraction of relaxation times, lifetimes, and rates associated with the transport of topological charge defects in hydrogen-bonded networks from molecular dynamics simulations is a challenge because proton transfer reactions continually change the identity of the defect core. In this paper, we present a statistical mechanical theory that allows these quantities to be computed in an unbiased manner. The theory employs a set of suitably defined indicator or population functions for locating a defect structure and their associated correlation functions. These functions are then used to develop a chemical master equation framework from which the rates and lifetimes can be determined. Furthermore, we develop an integral equation formalism for connecting various types of population correlation functions and derive an iterative solution to the equation, which is given a graphical interpretation. The chemical master equation framework is applied to the problems of both hydronium and hydroxide transport in bulk water. For each case it is shown that the theory establishes direct links between the defect's dominant solvation structures, the kinetics of charge transfer, and the mechanism of structural diffusion. A detailed analysis is presented for aqueous hydroxide, examining both reorientational time scales and relaxation of the rotational anisotropy, which is correlated with recent experimental results for these quantities. Finally, for OH(-)(aq) it is demonstrated that the "dynamical hypercoordination mechanism" is consistent with available experimental data while other mechanistic proposals are shown to fail. As a means of going beyond the linear rate theory valid from short up to intermediate time scales, a fractional kinetic model is introduced in the Appendix in order to describe the nonexponential long-time behavior of time-correlation functions. Within the mathematical framework of fractional calculus the power law decay ∼t(-σ), where σ is a parameter of the

  6. 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.

  7. Kinetics and mechanisms of pyrolysis of polyborosilazanes to thermally stable amorphous and crystalline states by a novel synthesis route

    Science.gov (United States)

    Lee, Jongsang

    the preceramic polymers, the mechanisms and kinetics of the structural and compositional changes associated with thermal decomposition were determined. Hydrothermal stability of the pyrolyzed or partially pyrolyzed products was evaluated by exposing material to 350°C and 3000 psi in water. After hydrothermal exposures, the boron content of the effluent from a dissolved polyborosilazane preceramic polymer in water was determined to be below 200 ppm. Results show that the low-cost polyborosilazane preceramic polymer remains hydrothermally stable, under both severe hydrothermal conditions and elevated temperature heat treatments.

  8. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  9. Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

    KAUST Repository

    Kuti, Olawole

    2014-04-01

    Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68 species and 283 reactions) were implemented in the CONVERGE CFD to simulate the spray and combustion processes of the two fuels. Tetradecane (C14H30) and n- heptane (C7H 16) were used as surrogates for diesel. For the palm biodiesel, the mixture of methyl decanoate (C11H20O2), methyl-9-decenoate (C11H19O2) and n-heptane was used as surrogate. The palm biodiesel surrogates were combined in proportions based on the previous GC-MS results for the five major biodiesel components namely methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate. The Favre-Averaged Navier Stokes based simulation using the renormalization group (RNG) k-ε turbulent model was implemented in the numerical calculations of the spray formation processes while the SAGE chemical kinetic solver is used for the detailed kinetic modeling. The SAGE chemical kinetic solver is directly coupled with the gas phase calculations by renormalization group (RNG) k-ε turbulent model using a well-stirred reactor model. Validations of the spray liquid length, ignition delay and flame lift-off length data were performed against previous experimental results. The simulated liquid length, ignition delay and flame lift-off length were validated at an ambient density of 15kg/m3, and injection pressure conditions of 100, 200 and 300 MPa were utilized. The predicted liquid length, ignition delay and flame lift-off length agree with the trends obtained in the experimental data at all injection conditions. Copyright © 2014 SAE International.

  10. Pre-steady-state Kinetic Analysis of a Family D DNA Polymerase from Thermococcus sp. 9°N Reveals Mechanisms for Archaeal Genomic Replication and Maintenance*

    OpenAIRE

    Schermerhorn, Kelly M.; Gardner, Andrew F.

    2015-01-01

    Family D DNA polymerases (polDs) have been implicated as the major replicative polymerase in archaea, excluding the Crenarchaeota branch, and bear little sequence homology to other DNA polymerase families. Here we report a detailed kinetic analysis of nucleotide incorporation and exonuclease activity for a Family D DNA polymerase from Thermococcus sp. 9°N. Pre-steady-state single-turnover nucleotide incorporation assays were performed to obtain the kinetic parameters, k pol and Kd , for corre...

  11. A biofriendly silica gel for in situ protein entrapment: biopolymer-assisted formation and its kinetic mechanism.

    Science.gov (United States)

    Wang, Guan-Hai; Zhang, Li-Ming

    2009-03-05

    In an attempt to develop a biofriendly sol-gel route for the rapid formation of biofunctional silica gels, a biopolymer with good biocompatibility was used to assist the gelation of glycol-modified tetraethoxysilane (GMT) in aqueous system without the addition of any organic solvents. It was found that the biopolymer used could act as an effective accelerator for the sol-gel transition of GMT and an increase of its amount could shorten greatly the gelation time. For such a gelation reaction, its apparent activation energy was determined to be 64.9 kJ/mol according to the Arrhenius equation. In particular, the kinetic mechanism for the formation of the silica gel was investigated by using dynamic theological data and a scaling fractal model. It was revealed that the biopolymer used could change the sol-gel transition mechanism from reaction-limited kinetics to diffusion-limited kinetics. Circular dichroism analyses confirmed the suitability of using the resultant silica gel for the in situ protein encapsulation.

  12. The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Harvey F. Fisher

    2013-07-01

    Full Text Available Much of our understanding of the mechanisms of enzyme-catalyzed reactions is based on steady-state kinetic studies. Experimentally, this approach depends solely on the measurement of rates of free product appearance (d[P]/dt, a mechanistically and mathematically complex entity. Despite the ambiguity of this observed parameter, the method’s success is due in part to the elaborate rigorously derived algebraic theory on which it is based. Transient-state kinetics, on the other hand, despite its ability to observe the formation of intermediate steps in real time, has contributed relatively little to the subject due in, some measure, to the lack of such a solid mathematical basis. Here we discuss the current state of existing transient-state theory and the difficulties in its realistic application to experimental data. We describe a basic analytic theory of transient-state kinetic isotope effects in the form of three novel fundamental rules. These rules are adequate to define an extended mechanism, locating the isotope-sensitive step and identifying missing steps from experimental data. We demonstrate the application of these rules to resolved component time courses of the phenylalanine dehydrogenase reaction, extending the previously known reaction by one new prehydride transfer step and two new post hydride transfer steps. We conclude with an assessment of future directions in this area.

  13. Kinetics and mechanism of the oxidation of some vicinal and non-vicinal diols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Jaya Gosain; Pradeep K Sharma

    2003-04-01

    Kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers, by tetrabutylammonium tribromide (TBATB) has been studied. The vicinal diols yield products arising out of glycol-bond fission, while the non-vicinal diols produce the hydroxycarbonyl compounds. The reaction is first-order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to diols. The reaction fails to induce the polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The oxidation of [1,1,2,2-2H4] ethanediol shows the absence of any primary kinetic isotope effect. Values of solvent isotope effect, (H2O)/(D2O), at 288 K for the oxidation of ethanediol, propane-1,3-diol and 3-methoxybutan-1-ol are 3.41, 0.98 and 1.02 respectively. A mechanism involving a glycol-bond fission has been proposed for the oxidation of vicinal diols. Non-vicinal diols are oxidised by a hydride-transfer mechanism, as they are monohydric alcohols.

  14. The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

    Science.gov (United States)

    Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

    2016-08-07

    The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

  15. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil [Propellants Branch, Rocket Propulsion Division, Aerospace Systems Directorate, Air Force Research Laboratory, AFRL/RQRP, 10 E. Saturn Blvd., Edwards AFB, California 93524 (United States)

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which

  16. Kinetic Mechanism of Uracil Phosphoribosyltransferase from Escherichia coli and Catalytic Importance of the Conserved Proline in the PRPP Binding Site

    DEFF Research Database (Denmark)

    Lundegaard, Claus; Jensen, Kaj Frank

    1999-01-01

    catalytic properties with the properties of the wild-type protein. We found that UPRTase of E. coli obeyed the kinetics of a sequential mechanism with the binding of PRPP preceding the binding of uracil. The basic kinetic constants were derived from initial velocity measurements, product inhibition......, and ligand binding assays. The change of Pro 131 to Asp caused a 50-60-fold reduction of the catalytic rate (kcat) in both directions of the reaction and approximately a 100-fold increase in the KM for uracil. The KM for PRPP was strongly diminished by the mutation, but kcat/KM,PRPP and the dissociation...... constant (KD,PRPP) were nearly unaffected. We conclude that the proline in the PRPP binding site of UPRTase is of only little importance for binding of PRPP to the free enzyme, but is critical for binding of uracil to the enzyme-PRPP complex and for the catalytic rate....

  17. Evaluation of reaction mechanisms and the kinetic parameters for the transesterification of castor oil by liquid enzymes

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy

    2017-01-01

    The use of liquid enzymes for the production of biodiesel as an alternative to chemical catalysts requires significant investigation due to the lack of experimental data for the various feedstock and catalyst combinations. In this paper, reaction rates and kinetic modeling...... of the transesterification of castor oil with methanol using the enzyme Eversa® Transform as catalyst were investigated. Reactions were carried out for 8 hours at 35 °C with: an alcohol-to-oil molar ratio equal to 6:1, a 5 wt% of liquid enzyme solution and addition of 5 wt% of water by weight of castor oil. From...... methanolysis rates of glycerides obtained, indicated that transesterification dominates over hydrolysis. The mechanism among the four models proposed that gave the best fit could be simplified, eliminating the kinetic parameters with negligible effects on the reaction rates. This model was able to fit...

  18. Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

    Science.gov (United States)

    Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

    2017-06-01

    Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. New Patterns in Steady-State Chemical Kinetics: Intersections, Coincidences, Map of Events (Two-Step Mechanism

    Directory of Open Access Journals (Sweden)

    Daniel Branco Pinto

    2015-10-01

    Full Text Available New patterns of steady-state chemical kinetics for continuously stirred-tank reactors (CSTR have been found, i.e., intersections, maxima and coincidences, for two-step mechanism A↔B→C. There were found elegant analytical relationships for characteristics of these patterns (space times, values of concentrations and rates allowing kinetic parameters to be easily determined. It was demonstrated that for the pair of species involved into the irreversible reaction (B and C, the space time of their corresponding concentration dependence intersection is invariant and does not depend on the initial conditions of the system. Maps of patterns are presented for visualization of their combinations and ranking in space time, and values of concentration and rates.

  20. Reaction mechanisms in ionic liquids: the kinetics and mechanism of the reaction of O,O-diethyl (2,4-dinitrophenyl) phosphate triester with secondary alicyclic amines.

    Science.gov (United States)

    Pavez, Paulina; Millán, Daniela; Morales, Javiera; Rojas, Mabel; Céspedes, Daniel; Santos, José G

    2016-01-28

    The reactions of O,O-diethyl 2,4-dinitrophenyl phosphate triester (1) with secondary alicyclic (SA) amines in the ionic liquids [Bmim]BF4 and [Bmim]DCA were subjected to a kinetic study. Eyring plots were obtained for the title reactions in the above ionic liquids (ILs) and also in aqueous ethanol (44 wt% ethanol). Two different reaction pathways were observed in [Bmim]BF4: nucleophilic attack at the phosphoryl center, SN2(P), and at the C-1 aromatic carbon, SN(Ar), where the product distribution remained constant and independent of the amine nature. In contrast, in [Bmim]DCA only the SN2(P) pathway was found. From the kinetic analysis of the SN2(P) pathway in both ILs, curved upwards plots of kobsdvs. 1-formylpiperazine concentration were obtained. Based on the kinetic behavior, a change in the mechanism of the SN2(P) pathway is proposed for the aminolysis of 1, from a concerted process in aqueous ethanol to a stepwise mechanism, through a zwitterionic pentacoordinate intermediate, when [Bmim]BF4 and [Bmim]DCA are used as the solvents of the reaction.

  1. Kinetics and Mechanism of Deoxygenation Reactions over Proton-Form and Molybdenum-Modified Zeolite Catalysts

    Science.gov (United States)

    Bedard, Jeremy William

    The depletion of fossil fuel resources and the environmental consequences of their use have dictated the development of new sources of energy that are both sustainable and economical. Biomass has emerged as a renewable carbon feedstock that can be used to produce chemicals and fuels traditionally obtained from petroleum. The oxygen content of biomass prohibits its use without modification because oxygenated hydrocarbons are non-volatile and have lower energy content. Chemical processes that eliminate oxygen and keep the carbon backbone intact are required for the development of biomass as a viable chemical feedstock. This dissertation reports on the kinetic and mechanistic studies conducted on high and low temperature catalytic processes for deoxygenation of biomass precursors to produce high-value chemicals and fuels. Low temperature, steady state reaction studies of acetic acid and ethanol were used to identify co-adsorbed acetic acid/ethanol dimers as surface intermediates within specific elementary steps involved in the esterification of acetic acid with ethanol on zeolites. A reaction mechanism involving two dominating surface species, an inactive ethanol dimeric species adsorbed on Bronsted sites inhibiting ester formation and a co-adsorbed complex of acetic acid and ethanol on the active site reacting to produce ethyl acetate, is shown to describe the reaction rate as a function of temperature (323 -- 383 K), acetic acid (0.5 -- 6.0 kPa), and ethanol (5.0 -- 13.0 kPa) partial pressure on proton-form BEA, FER, MFI, and MOR zeolites. Measured differences in rates as a function of zeolite structure and the rigorous interpretation of these differences in terms of esterification rate and equilibrium constants is presented to show that the intrinsic rate constant for the activation of the co-adsorbed complex increases in the order FER carbon dioxide with methane (CH3COOH/CH4 = 0.04-0.10, HCOOH/CH 4 = 0.01-0.03, CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 formulations at

  2. Kinetics, thermodynamics, and mechanism of the formation of benzaldehyde-S(IV) adducts

    Energy Technology Data Exchange (ETDEWEB)

    Olson, T.M.; Boyce, S.D.; Hoffmann, M.R.

    1986-05-22

    The kinetics and mechanism of the formation of ..cap alpha..-hydroxyphenylmethanesulfonate (HPMS) by the addition of bisulfite to benzaldehyde were studied at low pH. A three-term rate law was observed as d(HPMS)/dt - (k/sub 1/..cap alpha../sub 2/ + (k/sub 2/ + k/sub 3/K/sub H-/(H/sup +/))..cap alpha../sub 1/)(S(IV))/sub t/(C/sub 6/H/sub 5/CHO) where ..cap alpha../sub 1/ = (HSO/sub 2//sup -/)/(S(IV)), ..cap alpha../sub 3/ = (SO/sub 2//sup 2 -/)/(S(IV)), and K/sub H/ is the proton association constant of benzaldehyde. The rate-limiting steps of each term appeared to be the nucleophilic attack of SO/sub 3//sup 2 -/ on the carbonyl carbon of benzaldehyde, the attack of HSO/sub 3//sup -/ on the carbonyl carbon, and the attack by HSO/sub 3//sup -/ on the protonated carbon of the carbocation, C/sub 6/H/sub 5/C/sup +/H(OH), respectively. Over the pH range of most natural systems, only the k/sub 1/ and k/sub 2/ steps contribute to adduct formation while the k/sub 3/ term becomes important for pH < 1. At 25/sup 0/C and ..mu.. = 1.0 M, the intrinsic rate constants were determined to be k/sub 1/ = (2.15 +- 0.09) x 10/sup 4/ M/sup -1/ s/sup -1/, k/sub 2/ = (0.71 +- 0.03) M/sup -1/ s/sup -1/, k/sub 3/ approx. 2.5 x 10/sup 7/ M/sup -1/ s/sup -1/. Para-substitution on the benzaldehyde ring resulted in a slight increase in reactivity for p-NO/sub 2/- and p-Cl-, and a decrease for p-OH-, p-OCH/sub 3/-, and p-CH/sub 3/-C/sub 6/H/sub 5/CHO. The equilibrium association constant, K = (C/sub 6/H/sub 5/CH(OH)SO/sub 3//sup -/)/(HSO/sub 3//sup -/)(C/sub 6/H/sub 5/CHO), at 25/sup 0/C was determined to be 4.8 (+-0.8) x 10/sup 3/ at ..mu.. = 0.1 M and 0.98 (+- 0.11) x 10/sup 3/ M/sup -1/ at ..mu.. = 1.0 M. ..delta..H/sup 0/ and ..delta..S/sup 0/ was determined to be -64.6 kJ mol/sup -1/ and -146 J mol/sup -1/ deg/sup -1/, respectively.

  3. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn Charles [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  4. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn C.

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  5. The kinetics and mechanism of induced thermal decomposition of peroxomonosulphate by phase transfer catalysts

    Indian Academy of Sciences (India)

    T Balakrishnan; S Damodar Kumar

    2000-08-01

    The kinetics of induced decomposition of potassium peroxomonosulphate (PMS) by the phase transfer catalysts (PTC), viz. tetrabutylammonium chloride [TBAC] and tetrabutylphosphonium chloride [TBPC] have been investigated. The effect of [PMS], [PTC], ionic strength of the medium and temperature on the rate of decomposition of PMS was studied. The rate of decomposition of PMS was monitored under pseudo-first-order condition at a constant temperature (50 ± 0 1°C). The rate of decomposition was first order with respect to PMS for TBAC and half order for TBPC. The order with respect of PTC was found to be unity for TBAC and half order for TBPC. A suitable kinetic scheme has been proposed to account for the experimental data and its significance is discussed.

  6. Degradation kinetics and mechanisms of phenol in photo-Fenton process

    Institute of Scientific and Technical Information of China (English)

    何锋; 雷乐成

    2004-01-01

    Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD; while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.

  7. Revisiting the Kinetics and Mechanism of the Tetrathionate-Hypochlorous Acid Reaction in Nearly Neutral Medium

    Science.gov (United States)

    Varga, Dénes; Horváth, Attila K.

    2009-11-01

    The tetrathionate-hypochlorous acid reaction has been investigated in nearly neutral medium at I = 0.5 M ionic strength and T = 25.0 ± 0.1 °C in dihydrogen-phosphate-hydrogen-phosphate buffer by UV-vis spectrophotometry. In excess of hypochlorous acid, the stoichiometry was found to be S4O62- + 7HOCl + 3H2O → 4SO42- + 7Cl- + 13H+, but in excess of tetrathionate colloidal sulfur precipitates. On the basis of the simultaneous evaluation of the kinetic curves, a nine-step kinetic model with four fitted and five fixed rate coefficients is proposed. Analogous oxidation reactions of tetrathionate are also compared and discussed.

  8. Assessment and treatment planning of lateral intracranial dural arteriovenous fistulas in 3 T MRI and DSA: A detailed analysis under consideration of time-resolved imaging of contrast kinetics (TRICKS) and ce-MRA sequences

    Energy Technology Data Exchange (ETDEWEB)

    Ertl, L.; Brueckmann, H.; Patzig, M.; Brem, C.; Forbrig, R.; Fesl, G. [Ludwig-Maximilians-University, Grosshadern Campus, Department of Neuroradiology, Institute of Clinical Radiology, Munich (Germany); Kunz, M. [Ludwig-Maximilians-University, Grosshadern Campus, Department of Neurosurgery, Munich (Germany)

    2016-12-15

    The current gold standard in the assessment of lateral intracranial dural arteriovenous fistulas (LDAVF) is digital subtraction angiography (DSA). However, magnetic resonance imaging (MRI) is a non-invasive emerging tool for the evaluation of such lesions. The aim of our study was to compare the DSA to our 3 T MR-imaging protocol including a highly spatial resolved (ce-MRA) and a temporal resolved (''time-resolved imaging of contrast kinetics'', TRICKS) contrast-enhanced MR angiography to evaluate if solely DSA can remain the gold-standard imaging modality for the treatment planning of LDAVF. We retrospectively reviewed matched pairs of DSA and 3 T MRI examinations of 24 patients with LDAVF (03/2008-04/2014) by the same list of relevant criteria for an endovascular LDAVF treatment planning. In particular, we determined intermodality agreement for the Cognard classification, the identifeication of arterial feeders, and the detailed assessment of each venous drainage pattern. Intermodality agreement for the Cognard classification was excellent (k = 1.0). Whereas MRI failed in identifying small arterial feeders, it was superior to the DSA in the assessment of the sinus and the venous drainage pattern. The combination of MRI and DSA is the new gold standard in LDAVF treatment planning. (orig.)

  9. Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

    Science.gov (United States)

    2017-01-01

    A critical step toward the rational design of new catalysts that achieve selective and efficient reduction of CO2 to specific hydrocarbons and oxygenates is to determine the detailed reaction mechanism including kinetics and product selectivity as a function of pH and applied potential for known systems. To accomplish this, we apply ab initio molecular metadynamics simulations (AIMμD) for the water/Cu(100) system with five layers of the explicit solvent under a potential of −0.59 V [reversible hydrogen electrode (RHE)] at pH 7 and compare with experiment. From these free-energy calculations, we determined the kinetics and pathways for major products (ethylene and methane) and minor products (ethanol, glyoxal, glycolaldehyde, ethylene glycol, acetaldehyde, ethane, and methanol). For an applied potential (U) greater than −0.6 V (RHE) ethylene, the major product, is produced via the Eley–Rideal (ER) mechanism using H2O + e–. The rate-determining step (RDS) is C–C coupling of two CO, with ΔG‡ = 0.69 eV. For an applied potential less than −0.60 V (RHE), the rate of ethylene formation decreases, mainly due to the loss of CO surface sites, which are replaced by H*. The reappearance of C2H4 along with CH4 at U less than −0.85 V arises from *CHO formation produced via an ER process of H* with nonadsorbed CO (a unique result). This *CHO is the common intermediate for the formation of both CH4 and C2H4. These results suggest that, to obtain hydrocarbon products selectively and efficiency at pH 7, we need to increase the CO concentration by changing the solvent or alloying the surface. PMID:28167767

  10. Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments.

    Science.gov (United States)

    Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

    2015-01-01

    In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0-2.2 M) than the formation of the native state (0-1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7-2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin.

  11. Kinetic Model of Mitochondrial Krebs Cycle: Unraveling the Mechanism of Salicylate Hepatotoxic Effects

    OpenAIRE

    Mogilevskaya, Ekaterina; Demin, Oleg; Goryanin, Igor

    2006-01-01

    This paper studies the effect of salicylate on the energy metabolism of mitochondria using in silico simulations. A kinetic model of the mitochondrial Krebs cycle is constructed using information on the individual enzymes. Model parameters for the rate equations are estimated using in vitro experimental data from the literature. Enzyme concentrations are determined from data on respiration in mitochondrial suspensions containing glutamate and malate. It is shown that inhibition in succinate d...

  12. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    Science.gov (United States)

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  13. Kinetic Model of Mitochondrial Krebs Cycle: Unraveling the Mechanism of Salicylate Hepatotoxic Effects

    OpenAIRE

    Mogilevskaya, Ekaterina; Demin, Oleg; Goryanin, Igor

    2006-01-01

    This paper studies the effect of salicylate on the energy metabolism of mitochondria using in silico simulations. A kinetic model of the mitochondrial Krebs cycle is constructed using information on the individual enzymes. Model parameters for the rate equations are estimated using in vitro experimental data from the literature. Enzyme concentrations are determined from data on respiration in mitochondrial suspensions containing glutamate and malate. It is shown that inhibition in succinate d...

  14. 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.

  15. Mechanism of Cooperativity and Nonlinear Release Kinetics in Multivalent Dendrimer-Atropine Complexes.

    Science.gov (United States)

    Mukherjee, Jhindan; Wong, Pamela T; Tang, Shengzhuang; Gam, Kristina; Coulter, Alexa; Baker, James R; Choi, Seok Ki

    2015-12-01

    Despite extensive studies on drug delivery using multivalent complexation systems, the biophysical basis for release kinetics remains poorly defined. The present study addresses this aspect involved in the complexation of a fifth generation poly(amidoamine) (PAMAM) dendrimer with atropine, an essential antidote used for treating organophosphate poisoning. First, we designed (1)H NMR titration studies for determining the molecular basis of the drug complexation with a glutarate-modified anionic dendrimer. These provide evidence pointing to a combination of electrostatic and hydrophobic interactions as the driving forces for dendrimer complexation with the alkaloid drug molecule. Second, using LC-MS/MS spectrometry, we determined the dissociation constants (KD) at steady state and also measured the drug release kinetics of atropine complexes with four negatively charged dendrimer types. Each of these dendrimers has a high payload capacity for up to ∼ 100 atropine molecules. However, the affinity of the atropine to the carrier was highly dependent on the drug to dendrimer ratio. Thus, a complex made at a lower loading ratio (≤ 0.1) displayed greater atropine affinity (KD ≈ μM) than other complexes prepared at higher ratios (>10), which showed only mM affinity. This negative cooperative variation in affinity is tightly associated with the nonlinear release kinetics observed for each complex in which drug release occurs more slowly at the later time phase at a lower loading ratio. In summary, the present study provides novel insights on the cooperativity as the mechanistic basis for nonlinear release kinetics observed in multivalent carrier systems.

  16. Kinetics of Vapor-Solid Phase Transitions: Structure, Growth, and Mechanism

    Science.gov (United States)

    Midya, Jiarul; Das, Subir K.

    2017-04-01

    The kinetics of the separation between low and high density phases in a single component Lennard-Jones model is studied via molecular dynamics simulations, at very low temperatures, in the space dimension d =2 . For densities close to the vapor branch of the coexistence curve, disconnected nanoscale clusters of the high density phase exhibit essentially ballistic motion. Starting from nearly circular shapes, at the time of nucleation, these clusters grow via sticky collisions, gaining filamentlike nonequilibrium structure at a later time, with a very low fractal dimensionality. The origin of the latter is shown to lie in the low mobility of the constituent particles, in the corresponding cluster reference frame, due to the (quasi-long-range) crystalline order. Standard self-similarity in the domain pattern, typically observed in the kinetics of phase transitions, is found to be absent. This invalidates the common method, that provides a growth law comparable to that in solid mixtures, of quantifying growth. An appropriate alternative approach, involving the fractality, quantifies the growth of the characteristic "length" to be a power law with time, the exponent being strongly temperature dependent. The observed growth law is in agreement with the outcome of a nonequilibrium kinetic theory.

  17. Early Events, Kinetic Intermediates and the Mechanism of Protein Folding in Cytochrome c

    Directory of Open Access Journals (Sweden)

    David S. Kliger

    2009-04-01

    Full Text Available Kinetic studies of the early events in cytochrome c folding are reviewed with a focus on the evidence for folding intermediates on the submillisecond timescale. Evidence from time-resolved absorption, circular dichroism, magnetic circular dichroism, fluorescence energy and electron transfer, small-angle X-ray scattering and amide hydrogen exchange studies on the t £ 1 ms timescale reveals a picture of cytochrome c folding that starts with the ~ 1-ms conformational diffusion dynamics of the unfolded chains. A fractional population of the unfolded chains collapses on the 1 – 100 ms timescale to a compact intermediate IC containing some native-like secondary structure. Although the existence and nature of IC as a discrete folding intermediate remains controversial, there is extensive high time-resolution kinetic evidence for the rapid formation of IC as a true intermediate, i.e., a metastable state separated from the unfolded state by a discrete free energy barrier. Final folding to the native state takes place on millisecond and longer timescales, depending on the presence of kinetic traps such as heme misligation and proline mis-isomerization. The high folding rates observed in equilibrium molten globule models suggest that IC may be a productive folding intermediate. Whether it is an obligatory step on the pathway to the high free energy barrier associated with millisecond timescale folding to the native state, however, remains to be determined.

  18. Kinetics and Mechanism for Oxidation of L-Proline by Bis(hydrogen periodato) argentate (Ⅲ) Complex Anion

    Institute of Scientific and Technical Information of China (English)

    SUN Han-Wen; SHI Hong-Mei; SHEN Shi-Gang; FANG Wei-Jun; GUO Zhi-Feng

    2008-01-01

    Oxidation of L-proline by bis(hydrogen periodato)argentate(Ⅲ) complex anion, [Ag(HIO6)2]5-, has been studied in aqueous alkaline medium in the temperature range of 25-40 ℃ by use of conventional spectrophotometry.Under the conditions for kinetic measurements, the oxidation results in decarboxylation of proline, giving rise to γ-aminobutyrate as identified by mass spectrometry. The oxidation kinetics is first order with respect to the silver(Ⅲ)and proline concentrations; the second-order rate constants, decreasing with increasing [periodate], are essentially independent of [OH-]. The kinetic results were interpreted in terms of a reaction mechanism which involves a pre-equilibrium between [Ag(HIO6)2]5- and [Ag(HIO6)(H2O)(OH)]2-, a mono-periodate coordinated silver(Ⅲ)complex. Both Ag(Ⅲ) complexes are reduced parallelly by the fully deprotonated form of proline in reductant and shows a lower reactivity than [Ag(HIO6)(OH)(H2O)]2-.

  19. Theoretical Study of CH3CH=CH2+O(1D) Reaction:Mechanism and Kinetics

    Institute of Scientific and Technical Information of China (English)

    WU Nai-nan; LIU Hong-xia; DUAN Xue-mei; LIU Jing-yao

    2012-01-01

    The mechanism and kinetics for the reaction of propene(CH3CH=CH2) molecule with O(1D) atom were investigated theoretically.The electronic structure information of the potential energy surface(PES) was obtained at the B3LYP/6-31 l+G(d,p) level,and the single-point energies were refined by the multi-level MCG3-MPWB method.The calculated results show that O(1D) atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C(OH)CH2(IM1),CH3CHCHOH(IM2),CH2OHCHCH2(IM3)and cycloCH2OCHCH3(IM4),respectively,on the singlet PES.The branching ratios as well as the pressure- and temperaturedependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus(RRKM) theories.The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2+O(1D) reaction.

  20. Kinetic evidence for different mechanisms of interaction of black mamba toxins MT alpha and MT beta with muscarinic receptors.

    Science.gov (United States)

    Jolkkonen, M; Oras, A; Toomela, T; Karlsson, E; Järv, J; Akerman, K E

    2001-01-01

    By studying the influence of two toxins from the black mamba Dendroaspis polylepis on the kinetics of [3H]-N-methylscopolamine binding to muscarinic acetylcholine receptors from rat cerebral cortex, it was revealed that these toxins, MT alpha and MT beta, interact with the receptors via kinetically distinct mechanisms. MT beta bound to receptors in a one-step, readily reversible process with the dissociation constant K(d)=5.3 microM. The binding mechanism of MTalpha was more complex, involving at least two consecutive steps. A fast receptor-toxin complex formation (K(T)=3.8 microM) was followed by a slow process of isomerisation of this complex (k(i)=1.8 x 10(-2) s(-1), half-time 39 s). A similar two-step interaction mechanism has been established for a related toxin, MT2 from the green mamba D. angusticeps (K(T)=1.4 microM, k(i)=8.3 x 10(-4) s(-1), half-time 840 s). The slow isomerisation process delays the effect of MT alpha and MT2, but increases their apparent potency compared to toxins unable to induce the isomerisation process.

  1. Kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts

    Directory of Open Access Journals (Sweden)

    A. Z. Moshfegh

    2004-06-01

    Full Text Available   In this investigation kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts have been studied. In this context, adsorption kinetics of both N2/Fe (100 and H2/Fe (100systems is initially investigated. By using statistical mechanic approach, we have determined the adsorption coefficient for N2 and H2 molecules as well as transition probability of different states of adsorption and dissociation of the reactants molecules. The effect of surface catalyst temperature on the reaction rate (TOF is studied under different reactant partial pressures. The mechanism of NH3 synthesis is suggested based on LH surface reactions model. According to the obtained results, activation energy for the reaction over Fe (100 and K/Fe(100 (for θk=0.1ML was determined 19.6 and 11.1 kcal/mole, respectively. The order of reaction on both catalysts with respect to PN2 and PH2 was unity and negative, respectively. Based on our data analysis, the NH3 synthesis obeys Temkin isotherm.

  2. The effect of antimony presence in anodic copper on kinetics and mechanism of anodic dissolution and cathodic deposition of copper

    Directory of Open Access Journals (Sweden)

    Stanković Z.D.

    2008-01-01

    Full Text Available The influence of the presence of Sb atoms, as foreign metal atoms in anode copper, on kinetics, and, on the mechanism of anodic dissolution and cathodic deposition of copper in acidic sulfate solution has been investigated. The galvanostatic single-pulse method has been used. Results indicate that presence of Sb atoms in anode copper increase the exchange current density as determined from the Tafel analysis of the electrode reaction. It is attributed to the increase of the crystal lattice parameter determined from XRD analysis of the electrode material.

  3. Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non...

  4. Regional differences of energetics, mechanics, and kinetics of myosin cross-bridge in human ureter smooth muscle.

    Science.gov (United States)

    Vargiu, Romina; Perinu, Anna; Tintrup, Frank; Broccia, Francesca; Lisa, Antonello De

    2015-01-01

    This study provides information about baseline mechanical properties of the entire muscle and the molecular contractile mechanism in human ureter smooth muscle and proposed to investigate if changes in mechanical motor performance in different regions of isolated human ureter are attributable to differences in myosin crossbridge interactions. Classic mechanical, contraction and energetic parameters derived from the tension-velocity relationship were studied in ureteral smooth muscle strips oriented longitudinally and circularly from abdominal and pelvic human ureter parts. By applying of Huxley's mathematical model we calculated the total working crossbridge number per mm(2) (Ψ), elementary force per single crossbridge (Π0), duration of maximum rate constant of crossbridge attachment 1/f1 and detachment 1/g2 and peak mechanical efficiency (Eff.max). Abdominal longitudinal smooth muscle strips exhibited significantly higher maximum isometric tension and faster maximum unloaded shortening velocity compared to pelvic ones. Contractile differences were associated with significantly higher crossbridge number per mm(2). Abdominal longitudinal muscle strips showed a lower duration of maximum rate constant of crossbridge attachment and detachment and higher peak mechanical efficiency than pelvic ones. Such data suggest that the abdominal human ureter showed better mechanical motor performance mainly related to a higher crossbridge number and crossbridge kinetics differences. Such results were more evident in the longitudinal rather than in the circular layer.

  5. Investigating the chemical mechanisms of the functionalization and fragmentation of hydrocarbons in the heterogeneous oxidation by OH using a stochastic kinetics model

    Science.gov (United States)

    Wiegel, A. A.; Wilson, K. R.; Hinsberg, B.; Houle, F. A.

    2014-12-01

    While the heterogeneous oxidation of atmospheric organic aerosols influences their effects on climate, air quality, and visibility, a more detailed understanding of the chemical mechanisms in heterogeneous oxidation is crucial for improving models of their chemical evolution in the atmosphere. Previous experimental work in our lab has shown two general reaction pathways for organic aerosol upon oxidation: functionalization, which adds additional oxygen functional groups to the carbon skeleton, and fragmentation, which leads to C-C bond scission and lower molecular weight oxidized products. Furthermore, these pathways were also found to be dependent on molecular structure, with more branched or oxidized hydrocarbons undergoing more fragmentation than less branched or oxidized hydrocarbons. However, while the mechanisms of hydrocarbon oxidation have been studied extensively in the gas phase, to what extent the gas phase mechanisms of hydrocarbon oxidation can be reliably applied to heterogeneous or bulk oxidation in aerosol remains unclear. To investigate the role of the condensed phase and molecular structure in the mechanism of heterogeneous organic aerosol oxidation, stochastic kinetics models are developed and compared to measurements of the products in the oxidation of hydrocarbons. Within the aerosol bulk, condensed phase rate coefficients and product branching ratios for peroxy reactions lead to different product distributions than those expected from gas phase peroxy reactions due to the presence of the liquid radical cage at the reaction site. As a result, tertiary alcohols and ketones were found to be the predominate products in the oxidation of squalane as observed in experiments. As the aerosol becomes further oxidized, β-scission of alkoxy radicals with neighboring functional groups is the primary fragmentation pathway leading to lower volatility products. In conjunction with this fragmentation mechanism, elimination of CO2 from acyloxy radicals was

  6. A new kinetic model based on the remote control mechanism to fit experimental data in the selective oxidation of propene into acrolein on biphasic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Abdeldayem, H.M.; Ruiz, P.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Thyrion, F.C. [Unite des Procedes Faculte des Sciences Appliquees, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium)

    1998-12-31

    A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with {alpha}-Sb{sub 2}O{sub 4} (donor) in different proportions. The presence of {alpha}-Sb{sub 2}O{sub 4} changes the reaction order, the activation energy of the reaction and the number of active sites of MoO{sub 3} produced by oxygen spillover. These changes are consistent with a modification in the degree of irrigation of the surface by oxygen spillover. The fitting of the model to experimental results shows that the number of sites created by O{sub SO} increases with the amount of {alpha}-Sb{sub 2}O{sub 4}. (orig.)

  7. Final Report: Mechanisms of sputter ripple formation: coupling among energetic ions, surface kinetics, stress and composition

    Energy Technology Data Exchange (ETDEWEB)

    Chason, Eric; Shenoy, Vivek

    2013-01-22

    Self-organized pattern formation enables the creation of nanoscale surface structures over large areas based on fundamental physical processes rather than an applied template. Low energy ion bombardment is one such method that induces the spontaneous formation of a wide variety of interesting morphological features (e.g., sputter ripples and/or quantum dots). This program focused on the processes controlling sputter ripple formation and the kinetics controlling the evolution of surfaces and nanostructures in high flux environments. This was done by using systematic, quantitative experiments to measure ripple formation under a variety of processing conditions coupled with modeling to interpret the results.

  8. Mechanism and kinetics of spontaneous nanotube growth driven by screw dislocations.

    Science.gov (United States)

    Morin, Stephen A; Bierman, Matthew J; Tong, Jonathan; Jin, Song

    2010-04-23

    Single-crystal nanotubes are commonly observed, but their formation is often not understood. We show that nanotube growth can be driven by axial screw dislocations: Self-perpetuating growth spirals enable anisotropic growth, and the dislocation strain energy overcomes the surface energy required for creating a new inner surface forming hollow tubes spontaneously. This was demonstrated through solution-grown zinc oxide nanotubes and nanowires by controlling supersaturation using a flow reactor and confirmed using microstructural characterization. The agreement between experimental growth kinetics and those predicted from fundamental crystal growth theories confirms that the growth of these nanotubes is driven by dislocations.

  9. Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

    Indian Academy of Sciences (India)

    A K Srivastava; Ajey Kumar Chaurasia

    2004-01-01

    Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C ± 0·1°C. The system follows non-ideal radical kinetics ( ∝ [M]1.4 [I]0.44) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value of $k_{p}^{2}/k_{t}$ were 64 kJ mol-1 and 0.173 × 10-3 l mol-1 s-1 respectively.

  10. Kinetics and Mechanism of Oxidation of Glutamic Acid by N-Bromophthalimide in Aqueous Acidic Medium

    OpenAIRE

    2011-01-01

    The kinetics of oxidation of glutamic acid (Glu) with N-bromophthalimide (NBP) was studied in perchloric acid medium at 30 °C by potentiometric method. The reaction is first order each in NBP and glutamic acid and is negative fractional order in [H+]. Addition of KBr or the reaction product, phthalimide had no effect on the rate. Similarly variation of ionic strength of the medium did not affect the rate of the reaction. Also the rate increased with decrease in dielectric constant of the reac...

  11. 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 N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), 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 N(2) 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 H(2)-air, CH(4)-air and C(2)H(4)-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 C(3)H(8)-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 C(3)H(8)-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 H(2)-air, CH(4)-air and C(2)H(4)-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

  12. Methanol and 2-methyl-1-propanol (isobutanol) coupling to ethers and dehydration over Nafion H: Selectivity, kinetics, and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Nunan, J.G.; Klier, K.; Herman, R.G. (Lehigh Univ., Bethlehem, PA (United States))

    1993-02-01

    The dehydration of a mixture of methanol and isobutanol has been studied over the sulfonic acid Nafion H catalyst. Dehydration products consisted of dimethyl ether (DME), di-isobutyl ether (DIBE), methyl-isobutyl ether (MIBE), butenes, octenes, and traces of methyl-tertiarybutyl ether (MTBE). At low temperatures and high alcohol pressures (P [ge] 150 kPa), the dehydration product slate was dominated by ether formation with selectivity within the ethers significantly in favor of the mixed ether, MIBE. The rates of ether and butene formation as a function of alcohol pressure could be described by Langmuir-Hinshelwood kinetics in which competitive adsorption of the two alcohols on the surface -SO[sub 3]H sites was the dominant feature. The kinetics of isobutanol dehydration to isobutene were consistent with a dual-site mechanism involving the cooperative action of a free surface -SO[sub 3]H site and an adjacent adsorbed alcohol molecule. Dehydration to ethers was consistent with the reaction of two adsorbed alcohols, also by a dual-site mechanism. As a consequence, dehydration to symmetric ethers showed saturation-type kinetics as a function of alcohol pressure, while the rate of isobutene formation went through a distinct maximum. Due to the competitive adsorption of methanol and isobutanol, the mixed ether MIBE was formed at a maximum rate with an optimum ratio of partial pressures of the two alcohols. The high selectivity to MIBE was explained by stronger adsorption of isobutanol on the catalyst surface as compared to methanol. The absence of MTBE and the predominance of products such as MIBE and 2,5-dimethylhexene suggests that dehydration to give free carbenium ions that subsequently rearrange to the more stable tertiary intermediate was not occurring. It was proposed that the alcohols react with the -SO[sub 3]H groups to give oxonium ions or esters. These intermediates couple to give the product ethers or octenes. 24 refs., 13 figs., 1 tab.

  13. Ozonolysis of alpha-pinene and beta-pinene: kinetics and mechanism.

    Science.gov (United States)

    Zhang, Dan; Zhang, Renyi

    2005-03-15

    A combined quantum-chemical and RRKM/ME (ME--master equation) approach is employed to investigate the structures, energetics, and kinetics of intermediate and stable species, and the yields of stabilized carbonyl oxides and OH radicals from the alpha-pinene and beta-pinene ozonolysis reactions. The cycloaddition of O(3) is highly exothermic, with the reaction energies of 55.1 and 51.1 kcal mol(-1) for alpha- and beta-pinenes, respectively. Cleavage of primary ozonides yields carbonyl oxides with the barrier height of 12.2-17.5 kcal mol(-1). For the prompt reactions of carbonyl oxides from alpha- and beta-pinene ozonolysis, H migration to hydroperoxides represents the dominant pathway over ring closure to dioxiranes. The kinetic calculations indicate a significant portion of stabilization for alpha- and beta-carbonyl oxides. The yields of stabilized carbonyl oxides are estimated to be 0.34 for alpha-pinene and 0.22 for beta-pinene. The applicability of theoretical methods for investigation of oxidation reactions of large hydrocarbon molecules is demonstrated.

  14. Kinetics and mechanism of arsenate removal by nanosized iron oxide-coated perlite.

    Science.gov (United States)

    Mostafa, M G; Chen, Yen-Hua; Jean, Jiin-Shuh; Liu, Chia-Chuan; Lee, Yao-Chang

    2011-03-15

    This study discussed the adsorption kinetics of As(V) onto nanosized iron oxide-coated perlite. The effects of pH, initial concentration of As(V) and common anions on the adsorption efficiency were also investigated. It was observed that a 100% As(V) adsorption was achieved at pH value of 4-8 from the initial concentration containing 1.0 mg-As(V)L(-1) and the adsorption percentage depended on the initial concentration; the phosphate and silicate ions would not interfere with the adsorption efficiency. Furthermore, nanosized iron oxide-coated perlite (IOCP) has been shown to be an effective adsorbent for the removal of arsenate from water. The adsorption kinetics were studied using pseudo-first- and pseudo-second-order models, and the experimental data fitted well with the pseudo-second-order model. Moreover, it suggests that the Langmuir isotherm is more adequate than the Freundlich isotherm in simulating the adsorption isotherm of As(V). The adsorption rate constant is 44.84 L mg(-1) and the maximum adsorption capacity is 0.39 mg g(-1). These findings indicate that the adsorption property of IOCP gives the compound a great potential for applications in environmental remediation.

  15. Kinetics and mechanism of the reaction of gold(III chloride complexes with formic acid

    Directory of Open Access Journals (Sweden)

    Pacławski K.

    2015-01-01

    Full Text Available In this work, the results of kinetic studies of the redox reaction of gold(III chloride complexes ([AuCl4]- with formic acid, are presented. Obtained data suggest the complex character of the reaction which leads to the [AuCl2]- and [AuCl3(COOH]- ions formation as intermediates. In the pH range over 2.5, the final product of the reaction is metallic gold. From the analysis of kinetic data, the rate limiting step is found to be the gold metallic phase formation. The stage of Au(III reduction is relatively fast with the second-order rate constant equal to 61.8 M-1s-1 at temperature 50ºC. The rate of the studied reaction depends on the temperature, reactants concentration and chloride ions concentration. As a result of the data analysis, the scheme of the reaction path has been suggested. Also, the values of enthalpy and entropy of activation for the reaction have been determined.

  16. Adsorption/desorption of Direct Yellow 28 on apatitic phosphate: Mechanism, kinetic and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    H. El Boujaady

    2014-10-01

    Full Text Available In this study, the adsorption potential of apatitic tricalcium phosphate for the removal of Direct Yellow 28 (DY28 from aqueous solution has been investigated by using batch mode experiments. The effects of different parameters such as pH, adsorbent dosage, initial dye concentration, contact time, addition of ions and temperature have been studied to understand the adsorption behavior of the adsorbent under various conditions. The adsorbent has been characterized by pHzpc measurement, chemical analyses, FTIR, XRD and TEM. The Langmuir and Freundlich models are found to be the best to describe the equilibrium isotherm data, with a maximum monolayer adsorption capacity of 67.02 mg g−1. Thermodynamic parameters including the Gibbs free energy ΔG, enthalpy ΔH, and entropy ΔS have revealed that the adsorption of DY28 on the apatitic tricalcium phosphate is feasible, spontaneous and endothermic. Among the kinetic models tested for apatitic tricalcium phosphate, the pseudo-second-order model fits the kinetic data well. The introduction of orthophosphate ions in the medium causes a decrease of adsorption. The addition of Ca2+ ions favors the adsorption. The results of this study have demonstrated the effectiveness and feasibility of the apatitic tricalcium phosphate for the removal of DY28 from aqueous solution.

  17. Kinetics and mechanism of the cutinase-catalyzed transesterification of oils in AOT reversed micellar system.

    Science.gov (United States)

    Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

    2011-11-01

    The kinetics of the enzymatic transesterification between a mixture of triglycerides (oils) and methanol for biodiesel production in a bis(2-ethylhexyl) sodium sulfosuccinate (AOT)/isooctane reversed micellar system, using recombinant cutinase from Fusarium solani pisi as a catalyst, was investigated. In order to describe the results that were obtained, a mechanistic scheme was proposed, based on the literature and on the experimental data. This scheme includes the following reaction steps: the formation of the active enzyme-substrate complex, the addition of an alcohol molecule to the complex followed by the separation of a molecule of the fatty acid alkyl ester and a glycerol moiety, and release of the active enzyme. Enzyme inhibition and deactivation effects due to methanol and glycerol were incorporated in the model. This kinetic model was fitted to the concentration profiles of the fatty acid methyl esters (the components of biodiesel), tri-, di- and monoglycerides, obtained for a 24 h transesterification reaction performed in a stirred batch reactor under different reaction conditions of enzyme and initial substrates concentration.

  18. Synthesis, kinetic mechanism and docking studies of vanillin derivatives as inhibitors of mushroom tyrosinase.

    Science.gov (United States)

    Ashraf, Zaman; Rafiq, Muhammad; Seo, Sung-Yum; Babar, Mustafeez Mujtaba; Zaidi, Najam-us-Sahar Sadaf

    2015-09-01

    The purpose of the present study was to discover the extent of contribution to antityrosinase activity by adding hydroxy substituted benzoic acid, cinnamic acid and piperazine residues to vanillin. The study showed the transformation of vanillin into esters as shown in (4a-4d), (6a-6b), and (8a-8b). In addition, the relationship between structures of these esters and their mushroom tyrosinase inhibitory activity was explored. The kinetics of inhibition on mushroom tyrosinase by these esters was also investigated. It was found that hydroxyl substituted benzoic acid derivatives were weak inhibitors; however hydroxy or chloro substituted cinnamic acid and piperazine substituted derivatives were able to induce significant tyrosinase inhibition. The mushroom tyrosinase (PDBID 2ZWE) was docked with synthesized vanillin derivatives and their calculated binding energies were compared with experimental IC50 values which provided positive correlation. The most potent derivative 2-(4-formyl-2-methoxyphenoxy)-2-oxoethyl (2E)-3-(4-hydroxyphenyl)prop-2-enoate (6a) possesses hydroxy substituted cinnamic acid scaffold having IC50 value 16.13 μM with binding energy of -7.2 kcal/mol. The tyrosinase inhibitory activity of (6a) is comparable with standard kojic acid. Kinetic analysis indicated that compound 6a was mixed-type tyrosinase inhibitor with inhibition constant values Ki (13 μM) and Ki' (53 μM) and formed reversible enzyme inhibitor complex. The active vanillin analog (6a) was devoid of toxic effects as shown in cytotoxic studies.

  19. Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling.

    Science.gov (United States)

    Wu, Lei; Liu, Lin; Gao, Bin; Muñoz-Carpena, Rafael; Zhang, Ming; Chen, Hao; Zhou, Zuhao; Wang, Hao

    2013-12-10

    Although graphene oxide (GO) has been used in many applications to improve human life quality, its environmental fate and behavior are still largely unknown. In this work, a novel approach that combines experimental measurements and theoretical calculations was used to determine the aggregation kinetics of GO sheets in aqueous solutions under different chemistry conditions (e.g., cation valence and pH). Experimental data showed that both cation valence and pH showed significant effect on the aggregation of GO sheets. The measured critical coagulation concentrations were in good agreement with the predictions of the extended Schulze-Hardy rule. Ca(2+) and Mg(2+) were more effective than Na(+) in aggregating the GO sheets, which could be attributed to the cross-linking between GO sheets by the divalent cations through "bridging" the functional groups at the edges of the GO sheets. When solution pH increases, deprotonation of carboxylic groups was found to play a key role in increasing GO sheet stability and surface charge development. These results suggested that edge-to-edge and face-to-face interactions were the dominant modes of GO aggregation in the presence of divalent metal ions and H(+), respectively. A modified attachment efficiency (α) model was developed on the basis of the Maxwell approach with considerations of both primary and secondary minima. The model predictions matched the experimental measurements of the aggregation kinetics of GO sheets in aqueous solutions under all of the tested experimental conditions well.

  20. Kinetics and mechanism of the oxidation of bromide by periodate in aqueous acidic solution.

    Science.gov (United States)

    Szél, Viktor; Csekő, György; Horváth, Attila K

    2014-11-13

    The periodate–bromide reaction has been studied spectrophotometrically mainly in excess of bromide ion, monitoring the formation of the total amount of bromine at 450 nm at acidic buffered conditions and at a constant ionic strength in the presence of a phosphoric acid/dihydrogen phosphate buffer. The stoichiometry of the reaction was established to be strictly IO4(–) + 2Br(–) + 2H(+) → Br2 + IO3(–) + H2O. The formal kinetic order of the reactants was found to be perfectly one and two in the cases of periodate and bromide, respectively, but that of the hydrogen ion lies between one and two. We have also provided experimental evidence that dihydrogen phosphate accelerates the formation of bromine, suggesting the appearance of strong buffer assistance. On the basis of the experiments, a simple two-step kinetic model is proposed involving BrIO3 as a key intermediate that perfectly explains all of the experimental findings. Furthermore, we have also shown that in huge excess of bromide, the apparent rate coefficient obtained from the individual curve fitting method of the absorbance–time series is necessarily independent of the initial periodate concentration that may falsely be interpreted as the rate of bromine formation is also independent of the concentration of periodate.

  1. Kinetic mechanism for HIV-1 neutralization by antibody 2G12 entails reversible glycan binding that slows cell entry.

    Science.gov (United States)

    Platt, Emily J; Gomes, Michelle M; Kabat, David

    2012-05-15

    Despite structural knowledge of broadly neutralizing monoclonal antibodies (NMAbs) complexed to HIV-1 gp120 and gp41 envelope glycoproteins, virus inactivation mechanisms have been difficult to prove, in part because neutralization assays are complex and were previously not understood. Concordant with recent evidence that HIV-1 titers are determined by a race between entry of cell-attached virions and competing inactivation processes, we show that NMAb 2G12, which binds to gp120 N-glycans with α (1, 2)-linked mannose termini and inhibits replication after passive transfer into patients, neutralizes by slowing entry of adsorbed virions. Accordingly, apparent neutralization is attenuated when a kinetically competing virus inactivation pathway is blocked. Moreover, removing 2G12 from media causes its dissociation from virions coupled to accelerated entry and restored infectivity, demonstrating the reversibility of neutralization. A difference between 2G12 dissociation and infectivity recovery rates implies that the inhibited complexes at virus-cell junctions contain several 2G12's that must dissociate before entry commences. Quantitative microscopy of 2G12 binding and dissociation from single virions and studies using a split CCR5 coreceptor suggest that 2G12 competitively inhibits interactions between gp120's V3 loop and the tyrosine sulfate-containing CCR5 amino terminus, thereby reducing assembly of complexes that catalyze entry. These results reveal a unique reversible kinetic mechanism for neutralization by an antibody that binds near a critical V3 region in the glycan shield of gp120.

  2. Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

    Institute of Scientific and Technical Information of China (English)

    ZHAI Yong-qing; LIU Hong-mei; YANG Lin; YANG Guo-zhong; SONG Wen-yu; LIU Yu-kai

    2007-01-01

    In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298-313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN](》)[Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H+] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.

  3. Mechanism of Inhibition of Novel Tryptophan Hydroxylase Inhibitors Revealed by Co-crystal Structures and Kinetic Analysis.

    Science.gov (United States)

    Cianchetta, Giovanni; Stouch, Terry; Yu, Wangsheng; Shi, Zhi-Cai; Tari, Leslie W; Swanson, Ronald V; Hunter, Michael J; Hoffman, Isaac D; Liu, Qingyun

    2010-04-14

    Trytophan Hydroxylase Type I (TPH1), most abundantly expressed in the gastrointestinal tract, initiates the synthesis of serotonin by catalyzing hydroxylation of tryptophan in the presence of biopterin and oxygen. We have previously described three series of novel, periphery-specific TPH1 inhibitors that selectively deplete serotonin in the gastrointestinal tract. We have now determined co-crystal structures of TPH1 with three of these inhibitors at high resolution. Analysis of the structural data showed that each of the three inhibitors fills the tryptophan binding pocket of TPH1 without reaching into the binding site of the cofactor pterin, and induces major conformational changes of the enzyme. The enzyme-inhibitor complexes assume a compact conformation that is similar to the one in tryptophan complex. Kinetic analysis showed that all three inhibitors are competitive versus the substrate tryptophan, consistent with the structural data that the compounds occupy the tryptophan binding site. On the other hand, all three inhibitors appear to be uncompetitive versus the cofactor 6-methyltetrahydropterin, which is not only consistent with the structural data but also indicate that the hydroxylation reaction follows an ordered binding mechanism in which a productive complex is formed only if tryptophan binds only after pterin, similar to the kinetic mechanisms of tyrosine and phenylalanine hydroxylase.

  4. Pressure and surface tension of an active simple liquid: a comparison between kinetic, mechanical and free-energy based approaches.

    Science.gov (United States)

    Marini Bettolo Marconi, Umberto; Maggi, Claudio; Melchionna, Simone

    2016-06-29

    We discuss different definitions of pressure for a system of active spherical particles driven by a non-thermal coloured noise. We show that mechanical, kinetic and free-energy based approaches lead to the same result up to first order in the non-equilibrium expansion parameter. The first prescription is based on a generalisation of the kinetic mesoscopic virial equation and expresses the pressure exerted on the walls in terms of the average of the virial of the inter-particle forces. In the second approach, the pressure and the surface tension are identified with the volume and area derivatives, respectively, of the partition function associated with the known stationary non-equilibrium distribution of the model. The third method is a mechanical approach and is related to the work necessary to deform the system. The pressure is obtained by comparing the expression of the work in terms of local stress and strain with the corresponding expression in terms of microscopic distribution. This is determined from the force balance encoded in the Born-Green-Yvon equation. Such a method has the advantage of giving a formula for the local pressure tensor and the surface tension even in inhomogeneous situations. By direct inspection, we show that the three procedures lead to the same values of the pressure, and give support to the idea that the partition function, obtained via the unified coloured noise approximation, is more than a formal property of the system, but determines the stationary non-equilibrium thermodynamics of the model.

  5. Kinetics and Mechanism of Micellar Catalyzed Oxidation of Dextrose by N-Bromosuccinimide in H2SO4 Medium

    Directory of Open Access Journals (Sweden)

    Minu Singh

    2014-01-01

    Full Text Available Kinetics and mechanism of micellar catalyzed N-bromosuccinimide oxidation of dextrose in H2SO4 medium was investigated under pseudo-first-order condition temperature of 40°C. The results of the reactions studied over a wide range of experimental conditions show that NBS shows a first order dependence, fractional order, on dextrose and negative fractional order dependence on sulfuric acid. The determined stoichiometric ratio was 1 : 1 (dextrose : N-bromosuccinimide. The variation of Hg(OAC2 and succinimide (reaction product has insignificant effect on reaction rate. Effects of surfactants, added acrylonitrile, added salts, and solvent composition variation have been studied. The Arrhenius activation energy and other thermodynamic activation parameters are evaluated. The rate law has been derived on the basis of obtained data. A plausible mechanism has been proposed from the results of kinetic studies, reaction stoichiometry, and product analysis. The role of anionic and nonionic micelle was best explained by the Berezin’s model.

  6. Investigation of feedback on neutron kinetics and thermal hydraulics from detailed online fuel behavior modeling during a boron dilution transient in a PWR with the two-way coupled code system DYN3D-TRANSURANUS

    Energy Technology Data Exchange (ETDEWEB)

    Holt, L., E-mail: lars.holt@tuev-sued.de [TÜV SÜD Energietechnik GmbH Baden-Württemberg, Gottlieb-Daimler-Str. 7, 70794 Filderstadt (Germany); Technical University München, Department of Nuclear Engineering, Boltzmannstr. 15, D-85748 Garching bei München (Germany); Rohde, U.; Kliem, S.; Baier, S. [Helmholtz-Zentrum Dresden—Rossendorf, Reactor Safety Division, PO Box 510119, D-01314 Dresden (Germany); Seidl, M. [E.ON Kernkraft GmbH, Tresckowstr. 5, D-30457 Hannover (Germany); Van Uffelen, P. [European Commission, Joint Research Centre, Institute for Transuranium Elements, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Macián-Juan, R. [Technical University München, Department of Nuclear Engineering, Boltzmannstr. 15, D-85748 Garching bei München (Germany)

    2016-02-15

    Highlights: • General coupling interface was developed for the fuel performance code TRANSURANUS. • With this new tool simplified fuel behavior models in codes can be replaced. • The reactor dynamics code DYN3D was coupled to TRANSURANUS at assembly level. • The feedback from detailed online fuel behavior modeling is analyzed for reactivity initiated accident (RIA). • The thermal hydraulics can be affected strongly even in fresh fuel assemblies. - Abstract: Recently the reactor dynamics code DYN3D (including an internal fuel behavior model) was coupled to the fuel performance code TRANSURANUS at assembly level. The coupled code system applies the new general TRANSURANUS coupling interface, hence it can be used for one-way or two-way coupling. In the coupling, DYN3D provides process time, time-dependent rod power and thermal hydraulics conditions to TRANSURANUS, which in case of the two-way coupling approach replaces completely the internal DYN3D fuel behavior model and transfers parameters like radial fuel temperature distribution and cladding temperature back to DYN3D. For the first time results of the coupled code system are presented for a post-critical-heat-flux heat transfer. The corresponding heat transfer regime is mostly film boiling, where the cladding temperature can rise several hundreds of degrees. The simulated boron dilution transient assumed an injection of a 36 m{sup 3} slug of under-borated coolant into a German pressurized water reactor (PWR) core initiated from a sub-critical reactor state (extreme reactivity initiated accident (RIA) conditions). The feedback from detailed fuel behavior modeling was found negligible on the neutron kinetics and thermal hydraulics during the first power rise. In a later phase of the transient, the node injected energy can differ 25 J/g, even still around 20 J/g for nodes without film boiling. Furthermore, the thermal hydraulics can be affected strongly even in fresh fuel assemblies, where film boiling

  7. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  8. Mechanism of oxidation of L-methionine by iron(III)-1,10-phenanthroline complex - A kinetic study

    Indian Academy of Sciences (India)

    P Vani; K Krishna Kishore; R Rambabu; L S A Dikshitulu

    2001-08-01

    Kinetics and mechanism of oxidation of L-methionine by iron(III)-1, 10-phenanthroline complex have been studied in perchloric acid medium. The reaction is first order each in iron(III) and methionine. Increase in [phenanthroline] increases the rate while increase in [HClO4] decreases it. While the reactive species of the substrate is the zwitterionic form, that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law $$\\dfrac{d[Fe(phen)^{2+}_3]}{dt} = \\dfrac{k_2 K_4 K_3 K^2_2 [Fe^{III}] [\\text{phen}^2] [\\text{Met}]}{(1+K_1 [H^+]) ([H^+]^2 + K_4 K_3 K^2_2[\\text{phen}]^2)}.$$

  9. Mechanism and Kinetics Analysis of NO/SO2/N2/O2 Dissociation Reactions in Non-Thermal Plasma

    Institute of Scientific and Technical Information of China (English)

    WANG Xinliang; LI Tingting; WEI Dongxiang; WEI Yanli; GU Fan

    2008-01-01

    The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons' impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

  10. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    Science.gov (United States)

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-06

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Ejecta cloud from the AIDA space project kinetic impact on the secondary of a binary asteroid: I. mechanical environment and dynamical model

    Science.gov (United States)

    Yu, Yang; Michel, Patrick; Schwartz, Stephen R.; Naidu, Shantanu P.; Benner, Lance A. M.

    2017-01-01

    An understanding of the post-impact dynamics of ejecta clouds are crucial to the planning of a kinetic impact mission to an asteroid, and also has great implications for the history of planetary formation. The purpose of this article is to track the evolution of ejecta produced by AIDA mission, which targets for kinetic impact the secondary of near-Earth binary asteroid (65803) Didymos on 2022, and to feedback essential informations to AIDA's ongoing phase-A study. We present a detailed dynamic model for the simulation of an ejecta cloud from a binary asteroid that synthesizes all relevant forces based on a previous analysis of the mechanical environment. We apply our method to gain insight into the expected response of Didymos to the AIDA impact, including the subsequent evolution of debris and dust. The crater scaling relations from laboratory experiments are employed to approximate the distributions of ejecta mass and launching speed. The size distribution of fragments is modeled with a power law fitted from observations of real asteroid surface. A full-scale demonstration is simulated using parameters specified by the mission. We report the results of the simulation, which include the computed spread of the ejecta cloud and the recorded history of ejecta accretion and escape. The violent period of the ejecta evolution is found to be short, and is followed by a stage where the remaining ejecta is gradually cleared. Solar radiation pressure proves to be efficient in cleaning dust-size ejecta, and the simulation results after two weeks shows that large debris on polar orbits (perpendicular to the binary orbital plane) has a survival advantage over smaller ejecta and ejecta that keeps to low latitudes.

  12. Evaluation of reduced chemical kinetic mechanisms used for modeling mild combustion for natural gas

    Directory of Open Access Journals (Sweden)

    Hamdi Mohamed

    2009-01-01

    Full Text Available A numerical and parametric study was performed to evaluate the potential of reduced chemistry mechanisms to model natural gas chemistry including NOx chemistry under mild combustion mode. Two reduced mechanisms, 5-step and 9-step, were tested against the GRI-Mech3.0 by comparing key species, such as NOx, CO2 and CO, and gas temperature predictions in idealized reactors codes under mild combustion conditions. It is thus concluded that the 9-step mechanism appears to be a promising reduced mechanism that can be used in multi-dimensional codes for modeling mild combustion of natural gas.

  13. Kinetics and rate-limiting mechanisms of dolomitedissolution at various CO2 partial pressures

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolo-mite dissolution in flowing CO2-H2O system. Experiments run in the solutions equilibrated withvarious CO2 partial pressures (PCO2) from 30 to 100000 Pa. It shows that dissolution rates ofdolomite are related with rotating speeds at conditions far from equilibrium. This was explained bymodified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after ad-dition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO2 conversion. However,great differences occur among various CO2 partial pressures. The experimental observations givea conclusion that the modified DBL model enables one to predict dissolution rates and their be-haviour at various PCO2 with satisfactory precision at least far from equilibrium.

  14. Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal.

    Science.gov (United States)

    Mayakaduwa, S S; Kumarathilaka, Prasanna; Herath, Indika; Ahmad, Mahtab; Al-Wabel, Mohammed; Ok, Yong Sik; Usman, Adel; Abduljabbar, Adel; Vithanage, Meththika

    2016-02-01

    We investigated the removal of aqueous glyphosate using woody (dendro) biochar obtained as a waste by product from bioenergy industry. Equilibrium isotherms and kinetics data were obtained by adsorption experiments. Glyphosate adsorption was strongly pH dependent occurring maximum in the pH range of 5-6. The protonated amino moiety of the glyphosate molecule at this pH may interact with π electron rich biochar surface via π-π electron donor-acceptor interactions. Isotherm data were best fitted to the Freundlich and Temkin models indicating multilayer sorption of glyphosate. The maximum adsorption capacity of dendro biochar for glyphosate was determined by the isotherm modeling to be as 44 mg/g. Adsorption seemed to be quite fast, reaching the equilibrium glyphosate removal.

  15. Kinetic model of mitochondrial Krebs cycle: unraveling the mechanism of salicylate hepatotoxic effects.

    Science.gov (United States)

    Mogilevskaya, Ekaterina; Demin, Oleg; Goryanin, Igor

    2006-10-01

    This paper studies the effect of salicylate on the energy metabolism of mitochondria using in silico simulations. A kinetic model of the mitochondrial Krebs cycle is constructed using information on the individual enzymes. Model parameters for the rate equations are estimated using in vitro experimental data from the literature. Enzyme concentrations are determined from data on respiration in mitochondrial suspensions containing glutamate and malate. It is shown that inhibition in succinate dehydrogenase and alpha-ketoglutarate dehydrogenase by salicylate contributes substantially to the cumulative inhibition of the Krebs cycle by salicylates. Uncoupling of oxidative phosphorylation has little effect and coenzyme A consumption in salicylates transformation processes has an insignificant effect on the rate of substrate oxidation in the Krebs cycle. It is found that the salicylate-inhibited Krebs cycle flux can be increased by flux redirection through addition of external glutamate and malate, and depletion in external alpha-ketoglutarate and glycine concentrations.

  16. Factors influencing adsorption and desorption of trimethoprim on marine sediments: mechanisms and kinetics.

    Science.gov (United States)

    Li, Jia; Zhang, Hua

    2017-08-05

    Adsorption-desorption behavior of ionic antibiotics in natural aquatic environment is complex, especially in coastal or estuary area where influencing factors such as pH and salinity usually varied in a wide range. In this study, batch-type and stirred flow chamber (SFC) experiments were carried out to simulate the sorption-desorption behavior of trimethoprim (TMP) in seawater-sediment system. Equilibrium and kinetic modeling were carried out to determine the rate and extent of TMP sorption on two marine sediments with different properties. Sediment BHB (K d , 6.40 L kg(-1)) has a greater sorption capacity compared with sediment LZB (K d , 3.40 L kg(-1)), which is related to the higher content of organic carbon and clay of sediment BHB. Adsorption of TMP varied in the pH range of 6.9 to 8.1 with maximum adsorption at pH 7.4. Increasing salinity and presence of phosphate and nitrate led to decreased TMP sorption. Attenuated total reflection Fourier transform infrared (ATR-FTIR) analysis demonstrated the formation of hydrogen bond between TMP and marine sediments. Adsorption of TMP on marine sediments was a non-equilibrium process that can be described with second-order kinetic model. Our analysis suggested that chemical non-equilibrium was the rate controlling process and intraparticle diffusion was also involved in TMP adsorption. A moderate desorption percentage (16.4-22.8% for LZB and 32.5-42.0%for BHB) was observed. Overall, the results showed that environmental factors and time-dependent processes need to be considered in modeling the fate and transport of TMP in coastal/estuarine waters.

  17. Research Article. Kinetics and Mechanism of Drug Release from Loratadine Orodispersible Tablets Developed without Lactose

    Directory of Open Access Journals (Sweden)

    Ciurba Adriana

    2017-03-01

    Full Text Available Objective: The aim of this study is to develop lactose-free orodispersible tablets with loratadine for patients with lactose intolerance. Materials and methods: Seven compositions (F1-F7 of 10 mg loratadine were prepared in form of orally disintegrating tablets, by direct compression, using croscarmellose sodium and pre-gelatinized starch in various concentrations as superdisintegrants, diluted with microcrystalline cellulose and combined with mannitol and maltodextrin as binder agents. The tablets had been studied in terms of their pharmacotechnical characteristics, by determining: the weight uniformity of the tablets, their friability, breaking strength and disintegration time, drug content and the dissolution profile of loratadine. The statistical analyses were performed with GraphPad Prism Software Inc. As dependent variables, both the hardness of the tablets and their disintegration ability differ between batches due to their compositional differences (as independent variables. DDSolver were used for modeling the kinetic of the dissolution processes by fitting the dissolution profiles with time-dependent equations (Zero-order, First-order, Higuchi, Korsmeyer-Peppas, Peppas-Sahlin. Results: All proposed formulas shows rapid disintegration, in less than 15 seconds, and the dissolution loratadine spans a period of about 10 minutes. Akaike index as well as R2 adjusted parameter have demonstrated that the studied dissolution profiles are the best fitted by Zero-order kinetic. Conclusion: In conclusion, association of croscarmellose sodium (7.5% with pre-gelatinized starch (6% as superdisintegrants and mannitol as the binder agent (35%, positively influences the dissolution properties of loratadine from orally fast dispersible tablets.

  18. Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development

    NARCIS (Netherlands)

    Davis, S.E.; Benavidez, A.; Gosselink, R.W.; Bitter, J.H.; Jong, de K.P.; Datye, A.K.; Davis, R.J.

    2014-01-01

    The reaction mechanism of 5-hydroxymethylfurfural (HMF) oxidation in neutral aqueous solution with O2 to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA) was evaluated over a 3 wt% Pt/activated carbon catalyst in a semibatch reactor and confirmed that the mechanism

  19. Modelling time-dependent mechanical behaviour of softwood using deformation kinetics

    DEFF Research Database (Denmark)

    Engelund, Emil Tang; Svensson, Staffan

    2010-01-01

    The time-dependent mechanical behaviour (TDMB) of softwood is relevant, e.g., when wood is used as building material where the mechanical properties must be predicted for decades ahead. The established mathematical models should be able to predict the time-dependent behaviour. However, these models...

  20. Nucleation and growth mechanisms of nano magnesium hydride from the hydrogen sorption kinetics.

    Science.gov (United States)

    Mooij, Lennard; Dam, Bernard

    2013-07-21

    We use a combination of hydrogenography and Johnson-Mehl-Avrami-Kolmogorov (JMAK) analyses to identify (1) the driving force dependence of the nucleation and growth mechanism of MgH2 in thin film multilayers of Mg (10 nm) and (2) the nucleation and growth mechanism of Mg in the earlier formed MgH2, i.e. the hydrogen desorption process. We conclude that JMAK may be successfully applied to obtain the nucleation and growth mechanism of hydrogen absorption. The desorption mechanism, however, is not simply the reverse of the absorption mechanism. We find evidence that the barrier for nucleation of Mg is small. The dehydrogenation probably involves the formation of voids, which is energetically more favorable than elastic and plastic deformation of the multilayer.

  1. Mechanical and morphological investigation of virgin polyethylene and silver nanoparticle-loaded nanocomposites film: comprehensive analysis of kinetic models for non-isothermal crystallization

    Indian Academy of Sciences (India)

    RAJESH KUMAR SAHOO; BISHNU PRASAD PANDA; SANJAY KUMAR NAYAK; SMITA MOHANTY

    2017-04-01

    This research was accomplished to examine the mechanical, morphological and crystallization kinetics study of polyethylene/silver nanoparticles (Ag-NPs) nanocomposite films. In this research, low-density polyethylene (LDPE) nanocomposite films were prepared containing Ag-NPs using maleic-anhydride-grafted low-density polyethylene (LDPE-g-MAH) as a compatibilizer by the melt mixing process. From mechanical property evaluation, it is revealed that the LDPE/LDPE-g-MAH/Ag-NPs nanocomposite films showed decreased tensile strength as compared with virgin LDPE matrix. Thermal characteristics of the prepared virgin LDPE and its nanocomposite films were studied by differential scanning calorimetry (DSC). Comprehensive analysis of different kinetic modelssuch as the Avrami and Mo model on non-isothermal crystallization kinetics was performed in order to correlate the rate of crystallization and its various kinetic parameters. Further, the macrokinetic equation as proposed by Malkinhas been applied to describe the kinetics of crystallization in the light of the Avrami equation. Concerning virgin LDPE and Ag-NP-reinforced LDPE, the former shows primary crystallization, whereas the later exhibits both primaryand secondary crystallization with varying Avrami exponents. Kinetic parameters are recognized, and confirm the influence of Ag-NPs on crystallization kinetics. X-ray diffraction spectroscopy and transmission electron microscopicanalysis of the nanocomposite films were conducted to verify the dispersion of inorganic filler particles in the resulting hybrids.

  2. Kinetic analysis of acid orange 7 degradation by pulsed discharge plasma combined with activated carbon and the synergistic mechanism exploration.

    Science.gov (United States)

    Guo, He; Wang, Huijuan; Wu, Qiangshun; Zhou, Guangshun; Yi, Chengwu

    2016-09-01

    The synergistic technique of pulsed discharge plasma (PDP) and activated carbon (AC) was built to investigate the kinetics of acid orange 7 (AO7) degradation under different conditions of AC addition, electrode gap, initial pH value of solution, gas variety and gas flow rate. Emission spectra of OH and O, UV-vis absorption spectra of the AO7 solution and TOC removal were measured to illustrate the synergistic mechanism of the PDP and the AC. The obtained results indicated that the kinetic constant of AO7 degradation increased from 0.00947 min(-1) to 0.01419 min(-1) when 4 g AC was added into the PDP system; AO7 degradation was higher in the case of alkaline solution when oxygen was used as the flow gas in the PDP/AC system, 2 L/min oxygen flow was more favorable for the degradation. Results of the relative emission intensities of OH and O indicated the catalytic effect of the AC on the active species formation as well as the important role of the two radicals for the AO7 degradation. There was no new peaks appeared by the UV-vis analysis of the AO7 solution after 60 min treatment. The highest TOC removal in the PDP/AC system was 30.3%, which was achieved under the condition of 4 L/min air flow rate and 3 initial pH value.

  3. Probing kinetic drug binding mechanism in voltage-gated sodium ion channel: open state versus inactive state blockers.

    Science.gov (United States)

    Pal, Krishnendu; Gangopadhyay, Gautam

    2015-01-01

    The kinetics and nonequilibrium thermodynamics of open state and inactive state drug binding mechanisms have been studied here using different voltage protocols in sodium ion channel. We have found that for constant voltage protocol, open state block is more efficient in blocking ionic current than inactive state block. Kinetic effect comes through peak current for mexiletine as an open state blocker and in the tail part for lidocaine as an inactive state blocker. Although the inactivation of sodium channel is a free energy driven process, however, the two different kinds of drug affect the inactivation process in a different way as seen from thermodynamic analysis. In presence of open state drug block, the process initially for a long time remains entropy driven and then becomes free energy driven. However in presence of inactive state block, the process remains entirely entropy driven until the equilibrium is attained. For oscillating voltage protocol, the inactive state blocking is more efficient in damping the oscillation of ionic current. From the pulse train analysis it is found that inactive state blocking is less effective in restoring normal repolarisation and blocks peak ionic current. Pulse train protocol also shows that all the inactive states behave differently as one inactive state responds instantly to the test pulse in an opposite manner from the other two states.

  4. Enhanced removal of nitrate from water using nZVI@MWCNTs composite: synthesis, kinetics and mechanism of reduction.

    Science.gov (United States)

    Babaei, Ali Akbar; Azari, Ali; Kalantary, Roshanak Rezaei; Kakavandi, Babak

    2015-01-01

    Herein, multi-wall carbon nanotubes (MWCNTs) were used as the carrier of nano-zero valent iron (nZVI) particles to fabricate a composite known as nZVI@MWCNTs. The composite was then characterized and applied in the nitrate removal process in a batch system under anoxic conditions. The influential parameters such as pH, various concentrations of nitrate and composite were investigated within 240 min of the reaction. The mechanism, kinetics and end-products of nitrate reduction were also evaluated. Results revealed that the removal nitrate percentage for nZVI@MWCNTs composite was higher than that of nZVI and MWCNTs alone. Experimental data from nitrate reduction were fitted to the Langmuir-Hinshelwood kinetic model. The values of observed rate constant (kobs) decreased with increasing the initial concentration of nitrate. Our experiments proved that the nitrate removal efficiency was favorable once both high amounts of nZVI@MWCNTs and low concentrations of nitrate were applied. The predominant end-products of the nitrate reduction were ammonium (84%) and nitrogen gas (15%). Our findings also revealed that ZVI@MWCNTs is potentially a good composite for removal/reduction of nitrate from aqueous solutions.

  5. Insight on RDX degradation mechanism by Rhodococcus strains using 13C and 15N kinetic isotope effects.

    Science.gov (United States)

    Bernstein, Anat; Ronen, Zeev; Gelman, Faina

    2013-01-02

    The explosive Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is known to be degraded aerobically by various isolates of the Rhodococcus species, with denitration being the key step, mediated by Cytochrome P450. Our study aimed at gaining insight into the RDX degradation mechanism by Rhodococcus species and comparing isotope effects associated with RDX degradation by distinct Rhodococcus strains. For these purposes, enrichment in (13)C and (15)N isotopes throughout RDX denitration was studied for three distinct Rhodococcus strains, isolated from soil and groundwater in an RDX-contaminated site. The observable (15)N enrichment throughout the reaction, together with minor (13)C enrichment, suggests that N-N bond cleavage is likely to be the key rate-limiting step in the reaction. The similarity in the kinetic (15)N isotope effect between the three tested strains suggests that either isotope-masking effects are negligible, or are of a similar extent for all tested strains. The lack of variability in the kinetic (15)N isotope effect allows the interpretation of environmental studies with greater confidence.

  6. Kinetics and Mechanisms of the Acid-base Reaction Between NH3 and HCOOH in Interstellar Ice Analogs

    Science.gov (United States)

    Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh; Fayolle, Edith C.

    2016-10-01

    Interstellar complex organic molecules are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no-energy barriers. Here we present a study of the kinetics and mechanisms of a potential ion-generating, acid-base reaction between NH3 and HCOOH to form the salt NH{}4+HCOO-. We observe salt growth at temperatures as low as 15 K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow “pre-reaction” step followed by a fast reaction step. The reaction energy barrier is determined to be 70 ± 30 K with a pre-exponential factor 1.4 ± 0.4 × 10-3 s-1. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and orientation of reactant molecules. For a diffusion-limited case, the pre-reaction barrier is 770 ± 110 K with a pre-exponential factor of ˜7.6 × 10-3 s-1. Acid-base chemistry of common ice constituents is thus a potential cold pathway to generating ions in interstellar ices.

  7. Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

    Science.gov (United States)

    Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

    2017-09-11

    Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log Kow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log Kow), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

  8. Kinetics and mechanisms of the acid-base reaction between NH$_3$ and HCOOH in interstellar ice analogs

    CERN Document Server

    Bergner, Jennifer B; Rajappan, Mahesh; Fayolle, Edith C

    2016-01-01

    Interstellar complex organic molecules (COMs) are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no energy barriers. Here we present a study of a the kinetics and mechanisms of a potential ion-generating acid-base reaction between NH$_{3}$ and HCOOH to form the salt NH$_{4}^{+}$HCOO$^{-}$. We observe salt growth at temperatures as low as 15K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow "pre-reaction" step followed by a fast reaction step. The reaction energy barrier is determined to be 70 $\\pm$ 30K with a pre-exponential factor 1.4 $\\pm$ 0.4 x 10$^{-3}$ s$^{-1}$. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and or...

  9. Epoxide hydrolase-catalyzed enantioselective conversion of trans-stilbene oxide: Insights into the reaction mechanism from steady-state and pre-steady-state enzyme kinetics.

    Science.gov (United States)

    Archelas, Alain; Zhao, Wei; Faure, Bruno; Iacazio, Gilles; Kotik, Michael

    2016-02-01

    A detailed kinetic study based on steady-state and pre-steady-state measurements is described for the highly enantioselective epoxide hydrolase Kau2. The enzyme, which is a member of the α/β-hydrolase fold family, preferentially reacts with the (S,S)-enantiomer of trans-stilbene oxide (TSO) with an E value of ∼200. The enzyme follows a classical two-step catalytic mechanism with formation of an alkyl-enzyme intermediate in the first step and hydrolysis of this intermediate in a rate-limiting second step. Tryptophan fluorescence quenching during TSO conversion appears to correlate with alkylation of the enzyme. The steady-state data are consistent with (S,S) and (R,R)-TSO being two competing substrates with marked differences in k(cat) and K(M) values. The high enantiopreference of the epoxide hydrolase is best explained by pronounced differences in the second-order alkylation rate constant (k2/K(S)) and the alkyl-enzyme hydrolysis rate k3 between the (S,S) and (R,R)-enantiomers of TSO. Our data suggest that during conversion of (S,S)-TSO the two active site tyrosines, Tyr(157) and Tyr(259), serve mainly as electrophilic catalysts in the alkylation half-reaction, polarizing the oxirane oxygen of the bound epoxide through hydrogen bond formation, however, without fully donating their hydrogens to the forming alkyl-enzyme intermediate.

  10. Mechanisms and kinetics study on the trihalomethanes formation with carbon nanoparticle precursors.

    Science.gov (United States)

    Du, Tingting; Wang, Yingying; Yang, Xin; Wang, Wei; Guo, Haonan; Xiong, Xinyu; Gao, Rui; Wuli, Xiati; Adeleye, Adeyemi S; Li, Yao

    2016-07-01

    With lots of carbon nanoparticles (CNPs) applied in the industry, the possibilities of their environmental release have received much attention. As the CNPs may enter drinking water systems, and persist in water and wastewater treatment systems, their possible reaction with disinfectants should be studied. In this study, the formation of trihalomethanes (THMs) with 5 types of carbon nanotubes (CNTs), graphene oxide (GO) and reduced graphene oxide (rGO) was investigated. All CNPs could act as precursors of THMs in aqueous phase. Total concentrations of THMs formed with CNPs varied from 0.24 to 0.95 μM, much lower than that formed from chlorinated Suwannee River Natural Organic Matter (SRNOM) (approximately 9 μM). The kinetics of THMs formation with GO was 0.0814 M(-1) s(-1), which is higher than most of the chlorinated humic acid obtained from different natural waters. The study indicates that during chlorination, C-Cl bond could be formed on the surface of CNPs. However, carbon atoms at the middle of two meta-positioned OH groups on the benzene ring are more active and may prefer to form THMs with chlorine oxidation. The influences of pH and reactant doses on the formation of THMs were also discussed.

  11. Rapid kinetic methods to dissect steroidogenic cytochrome P450 reaction mechanisms.

    Science.gov (United States)

    Yoshimoto, Francis K; Auchus, Richard J

    2016-07-01

    All cytochrome P450 enzyme reactions involve a catalytic cycle with several discreet physical or chemical steps. This cycle ends with the formation of the reactive heme iron-oxygen complex, which oxygenates substrate. While the steps might be very similar for each P450 enzyme, the rates of each step varies tremendously for each enzyme and sometimes even for different reactions catalyzed by the same enzyme. For example, the rate-limiting step for most bacterial P450 enzymes, with turnover numbers over 1000s(-1), is the second electron transfer. In contrast, steroidogenic P450s from eukaryotes catalyze much slower reactions, with turnover numbers of ∼5-250min(-1); therefore, assumptions about kinetic properties for the mammalian P450 enzymes based on the bacterial enzymes are tenuous. In order to dissect the rates for individual steps, special techniques that isolate individual steps and/or single turnovers are required. This article will review the theoretical principles and practical considerations for several of these techniques, with illustrative published examples. The reader should gain an appreciation for the appropriate methods used to interrogate particular steps in the P450 reaction cycle.

  12. Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China.

    Science.gov (United States)

    Liu, Peiya; Li, Yujiao; Wen, Qinliang; Dong, Changxun; Pan, Genxing

    2015-08-01

    Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu(2+)) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu(2+) sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu(2+) sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu(2+) sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu(2+) (R(2)>0.97), and it was still good under different pH values (R(2)>0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu(2+) sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu(2+) sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu(2+) sorption. It indicated that aluminum dissolution is associated with non-specific sorption.

  13. Molecular mechanisms, thermodynamics, and dissociation kinetics of knob-hole interactions in fibrin

    CERN Document Server

    Kononova, Olga; Zhmurov, Artem; Alekseenko, Andrey; Cheng, Chai-Ho; Agarwal, Silvi; Marx, Kenneth A; Weisel, John W; Barsegov, Valeri

    2015-01-01

    Polymerization of fibrin, the primary structural protein of blood clots and thrombi, occurs through binding of knobs 'A' and 'B' in the central nodule of fibrin monomer to complementary holes 'a' and 'b' in the beta- and gamma-nodules, respectively, of another monomer. We characterized the A:a and B:b knob-hole interactions under varying solution conditions using Molecular Dynamics simulations of the structural models of fibrin(ogen) fragment D complexed with synthetic peptides GPRP (knob 'A' mimetic) and GHRP (knob 'B' mimetic). The strength of A:a and B:b knob-hole complexes was roughly equal, decreasing with pulling force; yet, the dissociation kinetics were sensitive to variations in acidity (pH=5-7) and temperature (T=25-37 C). There were similar structural changes in holes 'a' and 'b' during forced dissociation of the knob-hole complexes: elongation of loop I, stretching of interior region, and translocation of the moveable flap. The disruption of the knob-hole interactions was not an "all-or-none" tran...

  14. Laser flash-photolysis and gas discharge in N2O-containing mixture: kinetic mechanism

    Science.gov (United States)

    Kosarev, Ilya; Popov, Nikolay; Starikovskaia, Svetlana; Starikovskiy, Andrey; mipt Team

    2011-10-01

    The paper is devoted to further experimental and theoretical analysis of ignition by ArF laser flash-photolysis and nanosecond discharge in N2O-containing mixture has been done. Additional experiments have been made to assure that laser emission is distributed uniformly throughout the cross-section. The series of experiments was proposed and carried out to check validity of O(1D) determination in experiments on plasma assisted ignition initiated by flash-photolysis. In these experiments, ozone density in the given mixture (mixture composition and kinetics has been preliminary analyzed) was measured using UV light absorption in Hartley band. Good coincidence between experimental data and results of calculations have been obtained Temporal behavior of energy input, electric field and electric current has been measured and analyzed. These data are considered as initial conditions for numerical modeling of the discharge in O2:N2O:H2:Ar = 0.3:1:3:5 mixture. Ion-molecular reactions and reactions of active species production in Ar:H2:O2:N2O mixture were analyzed. The set of reactions to describe chemical transformation in the system due to the discharge action has been selected.

  15. Nanoporous anodic titanium dioxide layers as potential drug delivery systems: Drug release kinetics and mechanism.

    Science.gov (United States)

    Jarosz, Magdalena; Pawlik, Anna; Szuwarzyński, Michał; Jaskuła, Marian; Sulka, Grzegorz D

    2016-07-01

    Nanoporous anodic titanium dioxide (ATO) layers on Ti foil were prepared via a three step anodization process in an electrolyte based on an ethylene glycol solution with fluoride ions. Some of the ATO samples were heat-treated in order to achieve two different crystallographic structures - anatase (400°C) and a mixture of anatase and rutile (600°C). The structural and morphological characterizations of ATO layers were performed using a field emission scanning electron microscope (SEM). The hydrophilicity of ATO layers was determined with contact angle measurements using distilled water. Ibuprofen and gentamicin were loaded effectively inside the ATO nanopores. Afterwards, an in vitro drug release was conducted for 24h under a static and dynamic flow conditions in a phosphate buffer solution at 37°C. The drug concentrations were determined using UV-Vis spectrophotometry. The absorbance of ibuprofen was measured directly at 222nm, whether gentamicin was determined as a complex with silver nanoparticles (Ag NPs) at 394nm. Both compounds exhibited long term release profiles, despite the ATO structure. A new release model, based on the desorption of the drug from the ATO top surface followed by the desorption and diffusion of the drug from the nanopores, was derived. The proposed release model was fitted to the experimental drug release profiles, and kinetic parameters were calculated.

  16. Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on superoxide radicals

    Institute of Scientific and Technical Information of China (English)

    Yang Li; Junfeng Niu; Lifeng Yin; Wenlong Wang; Yueping Bao; Jing Chen; Yanpei Duan

    2011-01-01

    The micron grade multi-metal oxide bismuth silicate (Bi12SiO20,BSO) was prepared by the chemical solution decomposition technique.Photocatalytic degradation of pentachlorophenol (PCP) was investigated in the presence of BSO under xenon lamp irradiation.The reaction kinetics followed pseudo first-order and the degradation ratio achieved 99.1% after 120 min at an initial PCP concentration of 2.0 mg/L.The pH decreased from 6.2 to 4.6 and the dechlorination ratio was 68.4% after 120 min at an initial PCP concentration of 8.0 mg/L.The results of electron spin resonance showed that superoxide radical (O2-) was largely responsible for the photocatalytic degradation of PCP.Interestingly,this result was different from that of previous photocatalytic reactions where valence band holes or hydroxyl radicals played the role of major oxidants.Some aromatic compounds and aliphatic carboxylic acids were determined by GC/MS as the reaction intermediates,which indicated that O2- can attack the bond between the carbon and chlorine atoms to form less chlorinated aromatic compounds.The aromatic compounds were further oxidized by O2- to generate aliphatic carboxylic acids which can be finally mineralized to CO2 and H2O.

  17. The Kinetics and Mechanism of Spontaneous Dispersion of Ionic Compounds Onto Surfaces of Supports

    Institute of Scientific and Technical Information of China (English)

    汪传宝; 谢有畅; 唐有祺

    1994-01-01

    The dispersion kinetics of ionic compounds on the surfaces of supports is studied by using atemperature-programmed X-ray diffractometer.It is observed that for a given ionic compound/support mix-ture,there exists a critical dispersion temperature T_c,at which the ionic compound starts to disperse ontothe surface of the support at an appreciable rate.The dispersion process has 2 steps:the ions first leave thesurface of the ionic compound for the external surface of the support,and then the ions diffuse to the wholesurface of the support.For the dispersion of ionic compounds with high melting points,the first step is rate-determining.Their critical dispersion temperatures and dispersion activation energies depend on the ioniccompounds themselves and increase with their melting points,but are independent of supports.For the dis-persion of ionic compounds with low melting points,the second step is rate-determining.Their critical dis-persion temperatures and dispersion activation energies depend on both the ionic compounds and the sup-ports.

  18. Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation

    Institute of Scientific and Technical Information of China (English)

    Xiaofang Xie; Yongqing Zhang; Weilin Huang; Shaobing Huang

    2012-01-01

    Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature,persulfate concentration and pH conditions were examined in batch experiments.The results showed that,the aniline degradation followed pseudo first-order reaction model.Aniline degradation rate increased with increasing temperature or persulfate concentration.In the pH range of 3 to 11,a low aniline degradation rate was obtained at strong acid system (pH 3),while a high degradation rate was achieved at strong alkalinity (pH 11).Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5,7 and 9).Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology.And nitrobenzene,4-4'-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation meehanism of aniline was also tentatively proposed.

  19. The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines.

    Science.gov (United States)

    Stirling, Matthew J; Sweeney, Gemma; MacRory, Kerry; Blacker, A John; Page, Michael I

    2016-04-14

    The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction. The decrease in ee is not due to racemisation of the product amine, but because the rate of formation of the (R)-enantiomer follows first-order kinetics whereas that for the (S)-enantiomer is zero-order. This difference in reaction order explains the change in selectivity as the reaction proceeds - the rate formation of the (R)-enantiomer decreases exponentially with time while that for the (S)-enantiomer remains constant. A reaction scheme is proposed which requires rate-limiting hydride transfer from the iridium hydride to the iminium ion for the first-order rate of formation of the (R)-enantiomer amine and rate-limiting dissociation of the product for the zero-order rate of formation of the (S)-enantiomer.

  20. Mechanism and Kinetics for the Dissolution of Apatitic Materials in Acid Solutions

    Directory of Open Access Journals (Sweden)

    Calmanovici C.E.

    1997-01-01

    Full Text Available Abstract - This work concerns the study of the digestion step in the production process of phosphoric acid. Some qualitative experiments indicate that the difference between the pH at the surface of the phosphate and that in the bulk of the solution is negligible and that the dissolution is controlled by diffusion of products away from the phosphate particle. In further experiments, to isolate the dissolution phenomenon from the formation of calcium sulfate, the sulfuric acid normally used industrially is replaced by hydrochloric acid. The phosphate material used in our experiments is a model apatitic material: synthetic hydroxyapatite (HAP. The dissolution of calcium hydroxyapatite was studied with increasing amounts of calcium and phosphate at different temperatures. A simple method was developed for this observation based on the time required for complete dissolution of the HAP powder. The results confirm that the dissolution is controlled by a diffusional process through an interface of calcium and phosphate ions released from the solid surface. A kinetic model for the dissolution of apatitic materials is proposed which assumes a shrinking particle behaviour controlled by diffusion of calcium ions. The experimental results are fitted to this model to determine the mass transfer constant for HAP dissolution in acid solutions. The activation energy of the reaction is about 14kJ/mol. This study was carried on in conditions similar to the industrial ones for the production of phosphoric acid by the dihydrate-process