Science.gov

Sample records for chemical kinetic modeling

  1. LLNL Chemical Kinetics Modeling Group

    SciTech Connect

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

    2008-09-24

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

  2. Chemical kinetics modeling

    SciTech Connect

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

    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.

  3. Chemical kinetics and combustion modeling

    SciTech Connect

    Miller, J.A.

    1993-12-01

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

  4. Chemical Kinetic Modeling of Advanced Transportation Fuels

    SciTech Connect

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

    2009-01-20

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

  5. Chemical Kinetic Modeling of Hydrogen Combustion Limits

    SciTech Connect

    Pitz, W J; Westbrook, C K

    2008-04-02

    A detailed chemical kinetic model is used to explore the flammability and detonability of hydrogen mixtures. In the case of flammability, a detailed chemical kinetic mechanism for hydrogen is coupled to the CHEMKIN Premix code to compute premixed, laminar flame speeds. The detailed chemical kinetic model reproduces flame speeds in the literature over a range of equivalence ratios, pressures and reactant temperatures. A series of calculation were performed to assess the key parameters determining the flammability of hydrogen mixtures. Increased reactant temperature was found to greatly increase the flame speed and the flammability of the mixture. The effect of added diluents was assessed. Addition of water and carbon dioxide were found to reduce the flame speed and thus the flammability of a hydrogen mixture approximately equally well and much more than the addition of nitrogen. The detailed chemical kinetic model was used to explore the detonability of hydrogen mixtures. A Zeldovich-von Neumann-Doring (ZND) detonation model coupled with detailed chemical kinetics was used to model the detonation. The effectiveness on different diluents was assessed in reducing the detonability of a hydrogen mixture. Carbon dioxide was found to be most effective in reducing the detonability followed by water and nitrogen. The chemical action of chemical inhibitors on reducing the flammability of hydrogen mixtures is discussed. Bromine and organophosphorus inhibitors act through catalytic cycles that recombine H and OH radicals in the flame. The reduction in H and OH radicals reduces chain branching in the flame through the H + O{sub 2} = OH + O chain branching reaction. The reduction in chain branching and radical production reduces the flame speed and thus the flammability of the hydrogen mixture.

  6. Chemical Kinetic Models for Advanced Engine Combustion

    SciTech Connect

    Pitz, William J.; Mehl, Marco; Westbrook, Charles K.

    2014-10-22

    The objectives for this project are as follows: Develop detailed chemical kinetic models for fuel components used in surrogate fuels for compression ignition (CI), homogeneous charge compression ignition (HCCI) and reactivity-controlled compression-ignition (RCCI) engines; and Combine component models into surrogate fuel models to represent real transportation fuels. Use them to model low-temperature combustion strategies in HCCI, RCCI, and CI engines that lead to low emissions and high efficiency.

  7. Chemical kinetics and modeling of planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Yung, Yuk L.

    1990-01-01

    A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols.

  8. A kinetic model for chemical neurotransmission

    NASA Astrophysics Data System (ADS)

    Ramirez-Santiago, Guillermo; Martinez-Valencia, Alejandro; Fernandez de Miguel, Francisco

    Recent experimental observations in presynaptic terminals at the neuromuscular junction indicate that there are stereotyped patterns of cooperativeness in the fusion of adjacent vesicles. That is, a vesicle in hemifusion process appears on the side of a fused vesicle and which is followed by another vesicle in a priming state while the next one is in a docking state. In this talk we present a kinetic model for this morphological pattern in which each vesicle state previous to the exocytosis is represented by a kinetic state. This chain states kinetic model can be analyzed by means of a Master equation whose solution is simulated with the stochastic Gillespie algorithm. With this approach we have reproduced the responses to the basal release in the absence of stimulation evoked by the electrical activity and the phenomena of facilitation and depression of neuromuscular synapses. This model offers new perspectives to understand the underlying phenomena in chemical neurotransmission based on molecular interactions that result in the cooperativity between vesicles during neurotransmitter release. DGAPA Grants IN118410 and IN200914 and Conacyt Grant 130031.

  9. Chemical Kinetic Modeling of Biofuel Combustion

    NASA Astrophysics Data System (ADS)

    Sarathy, Subram Maniam

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

  10. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    SciTech Connect

    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.

  11. Detailed chemical kinetic modeling of cyclohexane oxidation.

    PubMed

    Silke, Emma J; Pitz, William J; Westbrook, Charles K; Ribaucour, Marc

    2007-05-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Rules for reaction rate constants are developed for the low-temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Because 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 with O2 through five-, six-, and seven-membered-ring transition states. The direct elimination of cyclohexene and HO2 from RO2 is included in the treatment using a modified rate constant of Cavallotti et al. (Proc. Combust. Inst. 2007, 31, 201). 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 cannot be simulated according to the current understanding of low-temperature chemistry. Possible "alternative" H-atom isomerizations leading to different products from the parent O2QOOH radical were included in the low-temperature chemical kinetic mechanism and were found to play a significant role.

  12. Application of Detailed Chemical Kinetics to Combustion Instability Modeling

    DTIC Science & Technology

    2016-01-04

    Briefing Charts 3. DATES COVERED (From - To) Nov 2015 – Jan 2016 4. TITLE AND SUBTITLE Application of Detailed Chemical Kinetics to Combustion Instability...Chemical Kinetics to Combustion Instability Modeling Matt Harvazinski, Doug Talley, Venke Sankaran Air Force Research Laboratory Edwards AFB, CA...Distribution A: approved for public release; distribution unlimited. 2 Challenges of Combustion Instability Damaged engine injector faceplate

  13. Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

    NASA Technical Reports Server (NTRS)

    Meagher, Nancy E.; Bates, Kami R.

    2000-01-01

    The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

  14. A Detailed Chemical Kinetic Model for TNT

    SciTech Connect

    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.

  15. Chemical Kinetic Models for HCCI and Diesel Combustion

    SciTech Connect

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

    2010-11-15

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

  16. Model reduction for chemical kinetics: An optimization approach

    SciTech Connect

    Petzold, L.; Zhu, W.

    1999-04-01

    The kinetics of a detailed chemically reacting system can potentially be very complex. Although the chemist may be interested in only a few species, the reaction model almost always involves a much larger number of species. Some of those species are radicals, which are very reactive species and can be important intermediaries in the reaction scheme. A large number of elementary reactions can occur among the species; some of these reactions are fast and some are slow. The aim of simplified kinetics modeling is to derive the simplest reaction system which retains the essential features of the full system. An optimization-based method for reduction of the number of species and reactions in chemical kinetics model is described. Numerical results for several reaction mechanisms illustrate the potential of this approach.

  17. Computer-Aided Construction of Chemical Kinetic Models

    SciTech Connect

    Green, William H.

    2014-12-31

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

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

    SciTech Connect

    Marinov, N.M.; Westbrook, C.K.; Cloutman, L.D.

    1995-09-01

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

  19. Chemical Kinetic Modeling of Combustion of Automotive Fuels

    SciTech Connect

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

    2006-11-10

    The objectives of this report are to: (1) Develop detailed chemical kinetic reaction models for components of fuels, including olefins and cycloalkanes used in diesel, spark-ignition and HCCI engines; (2) Develop surrogate mixtures of hydrocarbon components to represent real fuels and lead to efficient reduced combustion models; and (3) Characterize the role of fuel composition on production of emissions from practical automotive engines.

  20. Numerical Simulation of SNCR Technology with Simplified Chemical Kinetics Model

    NASA Astrophysics Data System (ADS)

    Blejchař, T.; Dolníčková, D.

    2013-04-01

    The paper deals with numerical simulation of SNCR method. For numerical modelling was used CFD code Ansys/CFX. SNCR method was described by dominant chemical reaction, which were look up NIST Chemical database. The reactions including reduction of NOx and concentration change of pollutants, like N2O and CO in flue gas too. Proposed chemical kinetics and CFD model was applied to two boilers. Both simulations were compared with experimental measurements. First simulation was used to validation of chemical mechanism. Second simulation was based on first simulation and it was used to verification of compiled SNCR chemical mechanism. Next the new variant of the reagent penetration lance was proposed and compared with the original variants.

  1. Chemical Kinetic Models for HCCI and Diesel Combustion

    SciTech Connect

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

    2008-10-30

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

  2. Progress in Chemical Kinetic Modeling for Surrogate Fuels

    SciTech Connect

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

    2008-06-06

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

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

    PubMed Central

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

    2013-01-01

    In the context of limiting the environmental impact of transportation, this paper reviews 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. PMID:21597604

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

    PubMed

    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

  5. Modeling of chemical inhibition from amyloid protein aggregation kinetics

    PubMed Central

    2014-01-01

    Backgrounds The process of amyloid proteins aggregation causes several human neuropathologies. In some cases, e.g. fibrillar deposits of insulin, the problems are generated in the processes of production and purification of protein and in the pump devices or injectable preparations for diabetics. Experimental kinetics and adequate modelling of chemical inhibition from amyloid aggregation are of practical importance in order to study the viable processing, formulation and storage as well as to predict and optimize the best conditions to reduce the effect of protein nucleation. Results In this manuscript, experimental data of insulin, Aβ42 amyloid protein and apomyoglobin fibrillation from recent bibliography were selected to evaluate the capability of a bivariate sigmoid equation to model them. The mathematical functions (logistic combined with Weibull equation) were used in reparameterized form and the effect of inhibitor concentrations on kinetic parameters from logistic equation were perfectly defined and explained. The surfaces of data were accurately described by proposed model and the presented analysis characterized the inhibitory influence on the protein aggregation by several chemicals. Discrimination between true and apparent inhibitors was also confirmed by the bivariate equation. EGCG for insulin (working at pH = 7.4/T = 37°C) and taiwaniaflavone for Aβ42 were the compounds studied that shown the greatest inhibition capacity. Conclusions An accurate, simple and effective model to investigate the inhibition of chemicals on amyloid protein aggregation has been developed. The equation could be useful for the clear quantification of inhibitor potential of chemicals and rigorous comparison among them. PMID:24572069

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

    SciTech Connect

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

    2011-03-01

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

  7. Gompertz kinetics model of fast chemical neurotransmission currents.

    PubMed

    Easton, Dexter M

    2005-10-01

    At a chemical synapse, transmitter molecules ejected from presynaptic terminal(s) bind reversibly with postsynaptic receptors and trigger an increase in channel conductance to specific ions. This paper describes a simple but accurate predictive model for the time course of the synaptic conductance transient, based on Gompertz kinetics. In the model, two simple exponential decay terms set the rates of development and decline of transmitter action. The first, r, triggering conductance activation, is surrogate for the decelerated rate of growth of conductance, G. The second, r', responsible for Y, deactivation of the conductance, is surrogate for the decelerated rate of decline of transmitter action. Therefore, the differential equation for the net conductance change, g, triggered by the transmitter is dg/dt=g(r-r'). The solution of that equation yields the product of G(t), representing activation, and Y(t), which defines the proportional decline (deactivation) of the current. The model fits, over their full-time course, published records of macroscopic ionic current associated with fast chemical transmission. The Gompertz model is a convenient and accurate method for routine analysis and comparison of records of synaptic current and putative transmitter time course. A Gompertz fit requiring only three independent rate constants plus initial current appears indistinguishable from a Markov fit using seven rate constants.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  9. Integration Strategies for Efficient Multizone Chemical Kinetics Models

    SciTech Connect

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

    2009-10-15

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

  10. Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

    PubMed

    Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

    2017-07-19

    Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

  11. Ab initio quantum chemical and kinetic modeling study of the pyrolysis kinetics of pyrrole

    SciTech Connect

    Martoprawiro, M.; Bacskay, G.B.; Mackie, J.C.

    1999-05-20

    The five-membered heterocyclic pyrrole moiety is an important structure in coals and derived tars, and the thermal decomposition reactions of pyrrole are important for production of precursors of the oxides of nitrogen, NO{sub x}, in the combustion of coals. The kinetics of pyrolysis of pyrrole have been investigated theoretically by ab initio quantum chemical techniques and by detailed chemical kinetic modeling of previously reported experimental results. The overall kinetics can be successfully modeled by a 117 step kinetic model that gives good agreement with temperature profiles of major products and also provides an acceptable fit for minor products. The thermochemistry and rate parameters of a number of key reactions have been obtained by ab initio calculations carried out at CASSCF, CASPT2, and G2(MP2) levels of theory. Several reaction pathways were investigated. The major product, HCN, arises principally from a hydrogen migration in pyrrole to form a cyclic carbene with the NH bond intact. Ring scission of this carbene leads to an allenic imine precursor of HCN and propyne. This is the decomposition pathway of lowest energy. Pyrolysis is preceded by the facile tautomerization of pyrrole to 2H-pyrrolenine. The latter can undergo CN fission to form an open chain biradical species, which is the precursor of the butenenitrile isomeric products, cis- and trans-crotononitrile and allyl cyanide. The biradical can also undergo facile H-fission to form cyanoallyl radical, which is an important precursor of acetylene, acetonitrile, and acrylonitrile, H{sub 2} also arises principally from H-fission of the biradical.

  12. Chemical Kinetic Modeling of HMX and TATB Laser Ignition Tests

    SciTech Connect

    Tarver, C M

    2004-03-02

    Recent laser ignition experiments on octahydro-1,3,5,7-tetranitro-1,3,5,7-terrazocine (HMX) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) subjected to laser fluxes ranging from 10 to 800 W/cm{sup 2} produced ignition times from seconds to milliseconds. Global chemical kinetic thermal decomposition models for HMX and TATB have been developed to calculate times to thermal explosion for experiments in the seconds to days time frame. These models are applied to the laser ignition experimental data in this paper. Excellent agreement was obtained for TATB, while the calculated ignition times were longer than experiment for HMX at lower laser fluxes. At the temperatures produced in the laser experiments, HMX melts. Melting generally increases condensed phase reaction rates so faster rates were used for three of the HMX reaction rates. This improved agreement with experiments at the lower laser fluxes but yielded very fast ignition at high fluxes. The calculated times to ignition are in reasonable agreement with the laser ignition experiments, and this justifies the use of these models for estimating reaction times at impact and shock ''hot spot'' temperatures.

  13. Detailed chemical kinetic modeling of diesel combustion with oxygenated fuels

    SciTech Connect

    Pitz, W J; Curran, H J; Fisher, E; Glaude, P A; Marinov, N M; Westbrook, C K

    1999-10-28

    The influence of oxygenated hydrocarbons as additives to diesel fuels on ignition, NOx emissions and soot production has been examined using a detailed chemical kinetic reaction mechanism. N-heptane was used as a representative diesel fuel, and methanol, ethanol, dimethyl ether and dimethoxymethane were used as oxygenated fuel additives. It was found that addition of oxygenated hydrocarbons reduced NOx levels and reduced the production of soot precursors. When the overall oxygen content in the fuel reached approximately 25% by mass, production of soot precursors fell effectively to zero, in agreement with experimental studies. The kinetic factors responsible for these observations are discussed.

  14. Identifiability of steady-state chemical kinetic models

    SciTech Connect

    Shvetsova-Shilovskaya, T.N.; Gorskii, V.G.

    1995-01-01

    The methodology for the local and global identifiability analysis of steady-state kinetic models of catalytic reactions is discussed. This methodology is based on the prior transformation of the model into the linear form so that the coefficients of the linear form are uniquely identifiable combinations of constants (observed parameters). Identifiability analysis is applied to several particular models.

  15. Application of Detailed Chemical Kinetics to Combustion Instability Modeling

    DTIC Science & Technology

    2016-01-04

    the stability characteristics. 15. SUBJECT TERMS N /A 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a...include area code) N /A Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std. 239.18 Application of Detailed Chemical Kinetics to Combustion...Frenklach, M., Moriarty, N ., Eiteneer, B., Goldenberg, M., Bowman, C., Hanson, R., Song, S., W. Gardiner, J., Lissianski, V., and Qin, Z., “GRI-Mech 3.0

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

    SciTech Connect

    Westbrook, C.K.; Marinov, N.; Pitz, W.J.; Curran, H.

    1996-10-01

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

  17. Parameter Estimates in Differential Equation Models for Chemical Kinetics

    ERIC Educational Resources Information Center

    Winkel, Brian

    2011-01-01

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

  18. Parameter Estimates in Differential Equation Models for Chemical Kinetics

    ERIC Educational Resources Information Center

    Winkel, Brian

    2011-01-01

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

  19. A chemical kinetic model for chemical vapor deposition of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Raji, K.; Thomas, Shijo; Sobhan, C. B.

    2011-10-01

    Carbon nanotubes (CNTs) are classified among the most promising novel materials due to their exceptional physical properties. Still, optimal fabrication of carbon nanotubes involves a number of challenges. Whatever be the fabrication method, a process optimization can be evolved only on the basis of a good theoretical model to predict the parametric influences on the final product. The work reported here investigates the dependence of the deposition parameters on the controllable parameters for carbon nanotube growth during Chemical vapor deposition (CVD), through a chemical kinetic model. The theoretical model consisted of the design equations and the energy balance equations, based on the reaction kinetics, for the plug flow and the batch reactor, which simulate the CVD system. The numerical simulation code was developed in-house in a g++ environment. The results predicted the growth conditions for CNT: the deposition temperature, pressure and number of atoms, which were found to be influenced substantially by the initial controllable parameters namely the temperature, volumetric flow rate of the carbon precursor, and the reaction time. An experimental study was also conducted on a CVD system developed in the laboratory, to benchmark the computational results. The experimental results were found to agree well with the theoretical predictions obtained from the model.

  20. Recent Advances in Detailed Chemical Kinetic Models for Large Hydrocarbon and Biodiesel Transportation Fuels

    SciTech Connect

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

    2009-03-30

    n-Hexadecane and 2,2,4,4,6,8,8-heptamethylnonane represent the primary reference fuels for diesel that are used to determine cetane number, a measure of the ignition property of diesel fuel. With the development of chemical kinetics models for these two primary reference fuels for diesel, a new capability is now available to model diesel fuel ignition. Also, we have developed chemical kinetic models for a whole series of large n-alkanes and a large iso-alkane to represent these chemical classes in fuel surrogates for conventional and future fuels. Methyl decanoate and methyl stearate are large methyl esters that are closely related to biodiesel fuels, and kinetic models for these molecules have also been developed. These chemical kinetic models are used to predict the effect of the fuel molecule size and structure on ignition characteristics under conditions found in internal combustion engines.

  1. Chemical kinetic modeling of component mixtures relevant to gasoline

    SciTech Connect

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

    2009-02-13

    Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. It is generally agreed that their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. In this work, a recently revised version of the kinetic model by the authors is used to analyze the combustion behavior of several components relevant to gasoline surrogate formulation. Particular attention is devoted to linear and branched saturated hydrocarbons (PRF mixtures), olefins (1-hexene) and aromatics (toluene). Model predictions for pure components, binary mixtures and multi-component gasoline surrogates are compared with recent experimental information collected in rapid compression machine, shock tube and jet stirred reactors covering a wide range of conditions pertinent to internal combustion engines. Simulation results are discussed focusing attention on the mixing effects of the fuel components.

  2. Chemical kinetic modeling of component mixtures relevant to gasoline

    SciTech Connect

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

    2008-05-29

    Detailed kinetic models of pyrolysis and combustion of hydrocarbon fuels are nowadays widely used in the design of internal combustion engines and these models are effectively applied to help meet the increasingly stringent environmental and energetic standards. In previous studies by the combustion community, such models not only contributed to the understanding of pure component combustion, but also provided a deeper insight into the combustion behavior of complex mixtures. One of the major challenges in this field is now the definition and the development of appropriate surrogate models able to mimic the actual features of real fuels. Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. Their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. Aside the most commonly used surrogates containing iso-octane and n-heptane only, the so called Primary Reference Fuels (PRF), new mixtures have recently been suggested to extend the reference components in surrogate mixtures to also include alkenes and aromatics. It is generally agreed that, including representative species for all the main classes of hydrocarbons which can be found in real fuels, it is possible to reproduce very effectively in a wide range of operating conditions not just the auto-ignition propensity of gasoline or Diesel fuels, but also their physical properties and their combustion residuals [1]. In this work, the combustion behavior of several components relevant to gasoline surrogate formulation is computationally examined. The attention is focused on the autoignition of iso-octane, hexene and their mixtures. Some important issues relevant to the experimental and modeling investigation of such fuels are discussed with the help of rapid compression machine data and calculations. Following the model validation, the behavior of mixtures is discussed on the

  3. Chemical and Biological Kinetics

    NASA Astrophysics Data System (ADS)

    Emanuel', N. M.

    1981-10-01

    Examples of the application of the methods and ideas of chemical kinetics in various branches of chemistry and biology are considered and the results of studies on the kinetics and mechanisms of autoxidation and inhibited and catalysed oxidation of organic substances in the liquid phase are surveyed. Problems of the kinetics of the ageing of polymers and the principles of their stabilisation are discussed and certain trends in biological kinetics (kinetics of tumour growth, kinetic criteria of the effectiveness of chemotherapy, problems of gerontology, etc.) are considered. The bibliography includes 281 references.

  4. Chemical kinetic modeling study of the effects of oxygenated hydrocarbons on soot emissions from diesel engines.

    PubMed

    Westbrook, Charles K; Pitz, William J; Curran, Henry J

    2006-06-01

    A detailed chemical kinetic modeling approach is used to examine the phenomenon of suppression of sooting in diesel engines by the addition of oxygenated hydrocarbon species to the fuel. This suppression, which has been observed experimentally for a few years, is explained kinetically as a reduction in concentrations of soot precursors present in the hot products of a fuel-rich diesel ignition zone when oxygenates are included. The kinetic model is also used to show how different oxygenates, ester structures in particular, can have different soot-suppression efficiencies due to differences in the molecular structure of the oxygenated species.

  5. Chemical Kinetics Database

    National Institute of Standards and Technology Data Gateway

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  6. Chemical kinetic modeling of a methane opposed flow diffusion flame and comparison to experiments

    SciTech Connect

    Marinov, N.M., Pitz, W.J.; Westbrook, C.K.; Vincitore, A.M.; Senka, S.M.; Lutz, A.E.

    1998-01-01

    The chemical structure of an opposed flow, methane diffusion flame is studied using a chemical kinetic model and the results are compared to experimental measurements. The chemical kinetic paths leading to aromatics and polycyclic aromatics hydrocarbons (PAHs) in the diffusion flame are identified. These paths all involve resonantly stabilized radicals which include propargyl, allyl, cyclopentadienyl, and benzyl radicals. The modeling results show reasonable agreement with the experimental measurements for the large hydrocarbon aliphatic compounds, aromatics, and PAHs. the benzene was predicted to be formed primarily by the reaction sequence of Allyl plus Propargyl equals Fulvene plus H plus H followed by fulvene isomerization to benzene. Naphthalene was modeled using the reaction of benzyl with propargyl, while the combination of cyclopentadienyl radicals were shown to be a minor contributor in the diffusion flame. The agreement between the model and experiment for the four-ring PAHs was poor.

  7. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Margitan, J. J.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1985-01-01

    Rate constants and photochemical cross sections are presented. The primary application of the data is for modeling of the stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  8. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.

    1992-01-01

    As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory.

  9. Chemical kinetic and photochemical data for use in stratospheric modelling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Stief, L. J.; Kaufman, F.; Golden, D. M.; Hampton, R. F.; Kurylo, M. J.; Margitan, J. J.; Molina, M. J.; Watson, R. T.

    1979-01-01

    An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.

  10. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    SciTech Connect

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-05-20

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  11. Impact of chemical kinetic model reduction on premixed turbulent flame characteristics

    NASA Astrophysics Data System (ADS)

    Fillo, Aaron; Niemeyer, Kyle

    2016-11-01

    The use of detailed chemical kinetic models for direct numerical simulations (DNS) is prohibitively expensive. Current best practice for the development of reduced models is to match laminar burning parameters such as flame speed, thickness, and ignition delay time to predictions of the detailed chemical kinetic models. Prior studies using reduced models implicitly assumed that matching the homogeneous and laminar properties of the detailed model will result in similar behavior in a turbulent environment. However, this assumption has not been tested. Fillo et al. recently demonstrated experimentally that real jet fuels with similar chemistry and laminar burning parameters exhibit different turbulent flame speeds under the same flow conditions. This result raises questions about the validity of current best practices for the development of reduced chemical kinetic models for turbulent DNS. This study will investigate the validity of current best practices. Turbulent burning parameters, including flame speed, thickness, and stretch rate, will be compared for three skeletal mechanisms of the Princeton POSF 4658 mechanism, reduced using current best practice methods. DNS calculations of premixed, high-Karlovitz flames will be compared to determine if these methods are valid. This material is based upon work supported by the National Science Foundation under Grant No. 1314109-DGE.

  12. Chemical Looping Combustion Kinetics

    SciTech Connect

    Edward Eyring; Gabor Konya

    2009-03-31

    One of the most promising methods of capturing CO{sub 2} emitted by coal-fired power plants for subsequent sequestration is chemical looping combustion (CLC). A powdered metal oxide such as NiO transfers oxygen directly to a fuel in a fuel reactor at high temperatures with no air present. Heat, water, and CO{sub 2} are released, and after H{sub 2}O condensation the CO{sub 2} (undiluted by N{sub 2}) is ready for sequestration, whereas the nickel metal is ready for reoxidation in the air reactor. In principle, these processes can be repeated endlessly with the original nickel metal/nickel oxide participating in a loop that admits fuel and rejects ash, heat, and water. Our project accumulated kinetic rate data at high temperatures and elevated pressures for the metal oxide reduction step and for the metal reoxidation step. These data will be used in computational modeling of CLC on the laboratory scale and presumably later on the plant scale. The oxygen carrier on which the research at Utah is focused is CuO/Cu{sub 2}O rather than nickel oxide because the copper system lends itself to use with solid fuels in an alternative to CLC called 'chemical looping with oxygen uncoupling' (CLOU).

  13. History and Philosophy of Science through Models: The Case of Chemical Kinetics

    NASA Astrophysics Data System (ADS)

    Justi, Rosária; Gilbert, John K.

    The case for a greater role for the history and philosophy of science in science education is reviewed. It is argued that such a role can only be realised if it is based on both a credible analytical approach to the history and philosophy of science and if the evolution of a sufficient number of major themes in science is known in suitable detail. Adopting Lakatos' Theory of Scientific Research Programmes as the analytical approach, it is proposed that the development, use, and replacement, of specific models forms the core of such programmes.Chemical kinetics was selected as an exemplar major topic in chemistry. Eight models which have played a central role in the evolution of the study of chemical kinetics were identified by an analysis of the literature. The implications that these models have for the teaching and learning of chemistry today are discussed.

  14. Chemical Kinetics Laboratory Discussion Worksheet.

    PubMed

    Demoin, Dustin Wayne; Jurisson, Silvia S

    2013-09-10

    A laboratory discussion worksheet and its answer key provide instructors and students a discussion model to further the students' understanding of chemical kinetics. This discussion worksheet includes a section for students to augment their previous knowledge about chemical kinetics measurements, an initial check on students' understanding of basic concepts, a group participation model where students work on solving complex-conceptual problems, and a conclusion to help students connect this discussion to their laboratory or lecture class. Additionally, the worksheet has a detailed solution to a more advanced problem to help students understand how the concepts they have put together relate to problems they will encounter during later formal assessments.

  15. Chemical Kinetics Laboratory Discussion Worksheet

    PubMed Central

    Demoin, Dustin Wayne; Jurisson, Silvia S.

    2013-01-01

    A laboratory discussion worksheet and its answer key provide instructors and students a discussion model to further the students’ understanding of chemical kinetics. This discussion worksheet includes a section for students to augment their previous knowledge about chemical kinetics measurements, an initial check on students’ understanding of basic concepts, a group participation model where students work on solving complex-conceptual problems, and a conclusion to help students connect this discussion to their laboratory or lecture class. Additionally, the worksheet has a detailed solution to a more advanced problem to help students understand how the concepts they have put together relate to problems they will encounter during later formal assessments. PMID:24092948

  16. Modeling of scale-dependent bacterial growth by chemical kinetics approach.

    PubMed

    Martínez, Haydee; Sánchez, Joaquín; Cruz, José-Manuel; Ayala, Guadalupe; Rivera, Marco; Buhse, Thomas

    2014-01-01

    We applied the so-called chemical kinetics approach to complex bacterial growth patterns that were dependent on the liquid-surface-area-to-volume ratio (SA/V) of the bacterial cultures. The kinetic modeling was based on current experimental knowledge in terms of autocatalytic bacterial growth, its inhibition by the metabolite CO2, and the relief of inhibition through the physical escape of the inhibitor. The model quantitatively reproduces kinetic data of SA/V-dependent bacterial growth and can discriminate between differences in the growth dynamics of enteropathogenic E. coli, E. coli JM83, and Salmonella typhimurium on one hand and Vibrio cholerae on the other hand. Furthermore, the data fitting procedures allowed predictions about the velocities of the involved key processes and the potential behavior in an open-flow bacterial chemostat, revealing an oscillatory approach to the stationary states.

  17. Calibration of Chemical Kinetic Models Using Simulations of Small-Scale Cookoff Experiments

    SciTech Connect

    Wemhoff, A P; Becker, R C; Burnham, A K

    2008-02-26

    Establishing safe handling limits for explosives in elevated temperature environments is a difficult problem that often requires extensive simulation. The largest influence on predicting thermal cookoff safety lies in the chemical kinetic model used in these simulations, and these kinetic model reaction sequences often contain multiple steps. Several small-scale cookoff experiments, notably Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), One-Dimensional Time-to-Explosion (ODTX), and the Scaled Thermal Explosion (STEX) have been performed on various explosives to aid in cookoff behavior determination. Past work has used a single test from this group to create a cookoff model, which does not guarantee agreement with the other experiments. In this study, we update the kinetic parameters of an existing model for the common explosive 2,4,6-Trinitrotoluene (TNT) using DSC and ODTX experimental data at the same time by minimizing a global Figure of Merit based on hydrodynamic simulated data. We then show that the new kinetic model maintains STEX agreement, reduces DSC agreement, and improves ODTX and TGA agreement when compared to the original model. In addition, we describe a means to use implicit hydrodynamic simulations of DSC experiments to develop a reaction model for TNT melting.

  18. Computing minimal entropy production trajectories: an approach to model reduction in chemical kinetics.

    PubMed

    Lebiedz, D

    2004-04-15

    Advanced experimental techniques in chemistry and physics provide increasing access to detailed deterministic mass action models for chemical reaction kinetics. Especially in complex technical or biochemical systems the huge amount of species and reaction pathways involved in a detailed modeling approach call for efficient methods of model reduction. These should be automatic and based on a firm mathematical analysis of the ordinary differential equations underlying the chemical kinetics in deterministic models. A main purpose of model reduction is to enable accurate numerical simulations of even high dimensional and spatially extended reaction systems. The latter include physical transport mechanisms and are modeled by partial differential equations. Their numerical solution for hundreds or thousands of species within a reasonable time will exceed computer capacities available now and in a foreseeable future. The central idea of model reduction is to replace the high dimensional dynamics by a low dimensional approximation with an appropriate degree of accuracy. Here I present a global approach to model reduction based on the concept of minimal entropy production and its numerical implementation. For given values of a single species concentration in a chemical system all other species concentrations are computed under the assumption that the system is as close as possible to its attractor, the thermodynamic equilibrium, in the sense that all modes of thermodynamic forces are maximally relaxed except the one, which drives the remaining system dynamics. This relaxation is expressed in terms of minimal entropy production for single reaction steps along phase space trajectories. (c) 2004 American Institute of Physics.

  19. Computing minimal entropy production trajectories: An approach to model reduction in chemical kinetics

    NASA Astrophysics Data System (ADS)

    Lebiedz, D.

    2004-04-01

    Advanced experimental techniques in chemistry and physics provide increasing access to detailed deterministic mass action models for chemical reaction kinetics. Especially in complex technical or biochemical systems the huge amount of species and reaction pathways involved in a detailed modeling approach call for efficient methods of model reduction. These should be automatic and based on a firm mathematical analysis of the ordinary differential equations underlying the chemical kinetics in deterministic models. A main purpose of model reduction is to enable accurate numerical simulations of even high dimensional and spatially extended reaction systems. The latter include physical transport mechanisms and are modeled by partial differential equations. Their numerical solution for hundreds or thousands of species within a reasonable time will exceed computer capacities available now and in a foreseeable future. The central idea of model reduction is to replace the high dimensional dynamics by a low dimensional approximation with an appropriate degree of accuracy. Here I present a global approach to model reduction based on the concept of minimal entropy production and its numerical implementation. For given values of a single species concentration in a chemical system all other species concentrations are computed under the assumption that the system is as close as possible to its attractor, the thermodynamic equilibrium, in the sense that all modes of thermodynamic forces are maximally relaxed except the one, which drives the remaining system dynamics. This relaxation is expressed in terms of minimal entropy production for single reaction steps along phase space trajectories.

  20. ALCHEMIC: Advanced time-dependent chemical kinetics

    NASA Astrophysics Data System (ADS)

    Semenov, Dmitry A.

    2017-08-01

    ALCHEMIC solves chemical kinetics problems, including gas-grain interactions, surface reactions, deuterium fractionization, and transport phenomena and can model the time-dependent chemical evolution of molecular clouds, hot cores, corinos, and protoplanetary disks.

  1. A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

    DOE PAGES

    Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.; ...

    2017-02-05

    Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Furthermore, it is a key component used in surrogates to study the ignition and burning characteristics of gasoline fuels. This paper presents an updated chemical kinetic model for iso-octane combustion. Specifically, the thermodynamic data and reaction kinetics of iso-octane have been re-assessed based on new thermodynamic group values and recently evaluated rate coefficients from the literature. The adopted rate coefficients were either experimentally measured or determined by analogy to theoretically calculated values. New alternative isomerization pathways for peroxy-alkyl hydroperoxide (more » $$\\dot{O}$$OQOOH) radicals were added to the reaction mechanism. The updated kinetic model was compared against new ignition delay data measured in rapid compression machines (RCM) and a high-pressure shock tube. Our experiments were conducted at pressures of 20 and 40 atm, at equivalence ratios of 0.4 and 1.0, and at temperatures in the range of 632–1060 K. The updated model was further compared against shock tube ignition delay times, jet-stirred reactor oxidation speciation data, premixed laminar flame speeds, counterflow diffusion flame ignition, and shock tube pyrolysis speciation data available in the literature. Finally, the updated model was used to investigate the importance of alternative isomerization pathways in the low temperature oxidation of highly branched alkanes. When compared to available models in the literature, the present model represents the current state-of-the-art in fundamental thermochemistry and reaction kinetics of iso-octane; and thus provides the best prediction of wide ranging experimental data and fundamental insights into iso-octane combustion chemistry.« less

  2. Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher E.; Gokcen, Tahir; Meyyappan, M.

    2002-01-01

    A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

  3. Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher E.; Gokcen, Tahir; Meyyappan, M.

    2002-01-01

    A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

  4. Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

    PubMed

    Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

    2013-02-21

    A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

  5. Effect of chemical kinetics uncertainties on calculated constituents in a tropospheric photochemical model

    NASA Technical Reports Server (NTRS)

    Thompson, Anne M.; Stewart, Richard W.

    1991-01-01

    Random photochemical reaction rates are employed in a 1D photochemical model to examine uncertainties in tropospheric concentrations and thereby determine critical kinetic processes and significant correlations. Monte Carlo computations are used to simulate different chemical environments and their related imprecisions. The most critical processes are the primary photodissociation of O3 (which initiates ozone destruction) and NO2 (which initiates ozone formation), and the OH/methane reaction is significant. Several correlations and anticorrelations between species are discussed, and the ozone/transient OH correlation is examined in detail. One important result of the modeling is that estimates of global OH are generally about 25 percent uncertain, limiting the precision of photochemical models. Techniques for reducing the imprecision are discussed which emphasize the use of species and radical species measurements.

  6. Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer

    NASA Astrophysics Data System (ADS)

    Castonguay, Thomas C.; Wang, Feng

    2008-03-01

    In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

  7. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    PubMed

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Study of ethane hydrate formation kinetics using the chemical affinity model with and without presence of surfactants

    NASA Astrophysics Data System (ADS)

    Karimi, Reza; Varaminian, Farshad; Izadpanah, Amir A.

    2014-12-01

    In this article, we examine ethane hydrate formation kinetics with and without the presence of various surfactants. Firstly, the influences of stirring rate and initial pressure without the presence of surfactants are studied. The effects of four surfactants containing Sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), Polyoxyethylene (20) sorbitanmonopalmitate (Tween® 40), and TritonX-100 (TX-100) on ethane hydrate formation kinetics were experimentally investigated. Then the chemical affinity model is applied to model the ethane hydrate formation kinetics with and without surfactants. The kinetic parameters of the chemical affinity model were computed for the ethane hydrate formation with and without surfactants. We will see that the results of the modeling are in good agreement with the experimental data.

  9. Stretching-based diagnostics and reduction of chemical kinetic models with diffusion

    SciTech Connect

    Adrover, A. . E-mail: alex@giona.ing.uniroma1.it; Creta, F.; Giona, M.; Valorani, M.

    2007-08-10

    A new method for diagnostics and reduction of dynamical systems and chemical kinetic models is proposed. The method makes use of the local structure of the normal stretching rates by projecting the dynamics onto the local directions of maximal stretching. The approach is computationally very simple as it implies the spectral analysis of a symmetric matrix. Notwithstanding its simplicity, stretching-based analysis derives from a geometric basis grounded on the pointwise applications of concepts of normal hyperbolicity theory. As a byproduct, a simple reduction method is derived, equivalent to a 'local embedding algorithm', which is based on the local projection of the dynamics onto the 'most unstable and/or slow modes' compared to the time scale dictated by the local tangential dynamics. This method provides excellent results in the analysis and reduction of dynamical systems displaying relaxation towards an equilibrium point, limit cycles and chaotic attractors. Several numerical examples deriving from typical models of reaction/diffusion kinetics exhibiting complex dynamics are thoroughly addressed. The application to typical combustion models is also analyzed.

  10. The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study.

    PubMed

    Somers, Kieran P; Simmie, John M; Metcalfe, Wayne K; Curran, Henry J

    2014-03-21

    Due to the rapidly growing interest in the use of biomass derived furanic compounds as potential platform chemicals and fossil fuel replacements, there is a simultaneous need to understand the pyrolysis and combustion properties of such molecules. To this end, the potential energy surfaces for the pyrolysis relevant reactions of the biofuel candidate 2-methylfuran have been characterized using quantum chemical methods (CBS-QB3, CBS-APNO and G3). Canonical transition state theory is employed to determine the high-pressure limiting kinetics, k(T), of elementary reactions. Rice-Ramsperger-Kassel-Marcus theory with an energy grained master equation is used to compute pressure-dependent rate constants, k(T,p), and product branching fractions for the multiple-well, multiple-channel reaction pathways which typify the pyrolysis reactions of the title species. The unimolecular decomposition of 2-methylfuran is shown to proceed via hydrogen atom transfer reactions through singlet carbene intermediates which readily undergo ring opening to form collisionally stabilised acyclic C5H6O isomers before further decomposition to C1-C4 species. Rate constants for abstraction by the hydrogen atom and methyl radical are reported, with abstraction from the alkyl side chain calculated to dominate. The fate of the primary abstraction product, 2-furanylmethyl radical, is shown to be thermal decomposition to the n-butadienyl radical and carbon monoxide through a series of ring opening and hydrogen atom transfer reactions. The dominant bimolecular products of hydrogen atom addition reactions are found to be furan and methyl radical, 1-butene-1-yl radical and carbon monoxide and vinyl ketene and methyl radical. A kinetic mechanism is assembled with computer simulations in good agreement with shock tube speciation profiles taken from the literature. The kinetic mechanism developed herein can be used in future chemical kinetic modelling studies on the pyrolysis and oxidation of 2-methylfuran

  11. Chemical kinetic modeling of high pressure propane oxidation and comparison to experimental results

    SciTech Connect

    Koert, D.N.; Pitz, W.J.; Bozzelli, J.W.; Cernansky, N.P.

    1995-11-08

    A pressure dependent kinetic mechanism for propane oxidation is developed and compared to experimental data from a high pressure flow reactor. The experiment conditions range from 10--15 atm, 650--800 K, and were performed at a residence time of 200 {micro}s for propane-air mixtures at an equivalence ratio of 0.4. The experimental results include data on negative temperature coefficient (NTC) behavior, where the chemistry describing this phenomena is considered critical in understanding automotive engine knock and cool flame oscillations. Results of the numerical model are compared to a spectrum of stable species profiles sampled from the flow reactor. Rate constants and product channels for the reaction of propyl radicals, hydroperoxy-propyl radicals and important isomers with O{sub 2} were estimated using thermodynamic properties, with multifrequency quantum Kassel Theory for k(E) coupled with modified strong collision analysis for fall-off. Results of the chemical kinetic model show an NTC region over nearly the same temperature regime as observed in the experiments. The model simulates properly the production of many of the major and minor species observed in the experiments. Numerical simulations show many of the key reactions involving propylperoxy radicals are in partial equilibrium at 10--15 atm. This indicates that their relative concentrations are controlled by a combination of thermochemistry and rate of minor reaction channels (bleed reactions) rather than primary reaction rates. This suggests that thermodynamic parameters of the oxygenated species, which govern equilibrium concentrations, are important. The modeling results show propyl radical and hydroperoxy-propyl radicals reaction with O{sub 2} proceeds, primarily, through thermalized adducts, not chemically activated channels.

  12. Modeling Multiphase Chemical Kinetics of OH Radical Reacting with Biomass Burning Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Arangio, Andrea; Slade, Jonathan H.; Berkemeier, Thomas; Knopf, Daniel A.; Shiraiwa, Manabu

    2014-05-01

    Levoglucosan, abietic acid and nitroguaiacol are commonly used as molecular tracers of biomass burning in source apportionment. Recent studies have demonstrated the decay of levoglucosan when the particles were exposed to atmospherically relevant concentration of OH radicals [1-3]. However, multiphase chemical kinetics of OH radical reacting with such compounds has not fully understood. Here we apply the kinetic multi-layer model for gas-particle interactions (KM-GAP) [4] to experimental data of OH exposure to levoglucosan, abietic acid and nitroguaiacol [1]. KM-GAP resolves the following mass transport and chemical reactions explicitly: gas-phase diffusion, reversible surface adsorption, surface reaction, surface-bulk transport, bulk diffusion and reaction. The particle shrink due to the evaporation of volatile reaction products is also considered. The time- and concentration-dependence of reactive uptake coefficient of OH radicals were simulated by KM-GAP. The measured OH uptake coefficients were fitted by a Monte Carlo (MC) filtering coupled with a genetic algorithm (GA) to derive physicochemical parameters such as bulk diffusion coefficient, Henry's law coefficient and desorption lifetime of OH radicals. We assessed the relative contribution of surface and bulk reactions to the overall uptake of OH radicals. Chemical half-life and the evaporation time scale of these compounds are estimated in different scenarios (dry, humid and cloud processing conditions) and at different OH concentrations. REFERENCES [1] J. H. Slade, D. A. Knopf, Phys. Chem. Chem. Phys., 2013, 15, 5898. [2] S. H. Kessler, J. D. Smith, D.L. Che, D.R. Worsnop, K. R. Wilson, J. H. Kroll, Environ. Sci. Technol., 2010, 44, 7005. [3] C. J. Hennigan, A. P. Sullivan, J. L. Collett Jr, A. L. Robinson, Geophys. Res. Lett., 2010, 37, L09806. [4] M. Shiraiwa, C. Pfrang, T. Koop, U. Pöschl, Atmos. Chem. Phys, 2012, 12, 2777.

  13. Autoignition of toluene reference fuels at high pressures modeled with detailed chemical kinetics

    SciTech Connect

    Andrae, J.C.G.; Bjoernbom, P.; Cracknell, R.F.; Kalghatgi, G.T.

    2007-04-15

    A detailed chemical kinetic model for the autoignition of toluene reference fuels (TRF) is presented. The toluene submechanism added to the Lawrence Livermore Primary Reference Fuel (PRF) mechanism was developed using recent shock tube autoignition delay time data under conditions relevant to HCCI combustion. For two-component fuels the model was validated against recent high-pressure shock tube autoignition delay time data for a mixture consisting of 35% n-heptane and 65% toluene by liquid volume. Important features of the autoignition of the mixture proved to be cross-acceleration effects, where hydroperoxy radicals produced during n-heptane oxidation dramatically increased the oxidation rate of toluene compared to the case when toluene alone was oxidized. Rate constants for the reaction of benzyl and hydroperoxyl radicals previously used in the modeling of the oxidation of toluene alone were untenably high for modeling of the mixture. To model both systems it was found necessary to use a lower rate and introduce an additional branching route in the reaction between benzyl radicals and O{sub 2}. Good agreement between experiments and predictions was found when the model was validated against shock tube autoignition delay data for gasoline surrogate fuels consisting of mixtures of 63-69% isooctane, 14-20% toluene, and 17% n-heptane by liquid volume. Cross reactions such as hydrogen abstractions between toluene and alkyl and alkylperoxy radicals and between the PRF were introduced for completion of chemical description. They were only of small importance for modeling autoignition delays from shock tube experiments, even at low temperatures. A single-zone engine model was used to evaluate how well the validated mechanism could capture autoignition behavior of toluene reference fuels in a homogeneous charge compression ignition (HCCI) engine. The model could qualitatively predict the experiments, except in the case with boosted intake pressure, where the initial

  14. Time-resolved simplified chemical kinetics modelling using computational singular perturbation

    NASA Technical Reports Server (NTRS)

    Lam, S. H.; Goussis, D. A.; Konopka, D.

    1989-01-01

    A CO-CH4-air reaction system is used to demonstrate the computational singular perturbation (CSP) method for deriving time-resolved simplified chemical kinetics models. CSP provides a programmable algorithm to group the given collection of elementary reactions into reaction groups which are ordered according to their speed. The concept of Importance Index k(m)exp s is introduced: k(m)exp s is defined to be a number between 0 and 1 which measures the importance of the m-th reaction group to the s-th reactant and can readily be computed from data generated by CSP. It is suggested that the robustness of the solutions of the reaction system can be qualitatively assessed by inspecting the Importance Index data.

  15. Chemical kinetics parameters and model validation for the gasification of PCEA nuclear graphite

    NASA Astrophysics Data System (ADS)

    El-Genk, Mohamed S.; Tournier, Jean-Michel P.; Contescu, Cristian I.

    2014-01-01

    A series of gasification experiments, using two right cylinder specimens (∼12.7 × 25.4 mm and 25.4 × 25.4 mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893-1015 K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%.

  16. Chemical kinetics parameters and model validation for the gasification of PCEA nuclear graphite

    SciTech Connect

    El-Genk, Mohamed S; Tournier, Jean-Michel; Contescu, Cristian I

    2014-01-01

    A series of gasification experiments, using two right cylinder specimens (~ 12.7 x 25.4 mm and 25.4 x 25.4 mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893-1015 K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%.

  17. An analytical kinetic model for chemical-vapor deposition of pureB layers from diborane

    NASA Astrophysics Data System (ADS)

    Mohammadi, V.; de Boer, W. B.; Nanver, L. K.

    2012-12-01

    In this paper, an analytical model is established to describe the deposition kinetics and the deposition chamber characteristics that determine the deposition rates of pure boron (PureB-) layers grown by chemical-vapor deposition (CVD) from diborane (B2H6) as gas source on a non-rotating silicon wafer. The model takes into consideration the diffusion mechanism of the diborane species through the stationary boundary layer over the wafer, the gas phase processes and the related surface reactions by applying the actual parabolic gas velocity and temperature gradient profiles in the reactor. These are calculated theoretically and also simulated with fluent software. The influence of an axial and lateral diffusion of diborane species and the validity of the model for laminar flow in experimental CVD processes are also treated. This model is based on a wide range of input parameters, such as initial diborane partial pressure, total gas flow, axial position on the wafer, deposition temperature, activation energy of PureB deposition from diborane, surface H-coverage, and reactor dimensions. By only adjusting these reactor/process parameters, the model was successfully transferred from the ASM Epsilon One to the Epsilon 2000 reactor which has totally different reactor conditions. The model's predictive capabilities have been verified by experiments performed at 700 °C in these two different ASM CVD reactors.

  18. Kinetic-fluid dynamics modeling of I2 dissociation in supersonic chemical oxygen-iodine lasers

    NASA Astrophysics Data System (ADS)

    Waichman, K.; Barmashenko, B. D.; Rosenwaks, S.

    2009-09-01

    The mechanism of I2 dissociation in supersonic chemical oxygen-iodine lasers (COILs) is studied applying kinetic-fluid dynamics modeling, where pathways involving the excited species I2(X Σ1g +,10≤v<25), I2(X Σ1g +,25≤v≤47), I2(A'Π32u), I2(AΠ31u), O2(X Σ3g -,v), O2(aΔ1g,v), O2(b Σ1g +,v), and I(P21/2) as intermediate reactants are included. The gist of the model is adding the first reactant and reducing the contribution of the second as compared to previous models. These changes, recently suggested by Azyazov, et al. [J. Chem. Phys. 130, 104306 (2009)], significantly improve the agreement with the measurements of the gain in a low pressure supersonic COIL for all I2 flow rates that have been tested in the experiments. In particular, the lack of agreement for high I2 flow rates, which was encountered in previous models, has been eliminated in the present model. It is suggested that future modeling of the COIL operation should take into account the proposed contribution of the above mentioned reactants.

  19. Chemical kinetics on extrasolar planets.

    PubMed

    Moses, Julianne I

    2014-04-28

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

  20. Dominant particles and reactions in a two-temperature chemical kinetic model of a decaying SF6 arc

    NASA Astrophysics Data System (ADS)

    Wang, Xiaohua; Gao, Qingqing; Fu, Yuwei; Yang, Aijun; Rong, Mingzhe; Wu, Yi; Niu, Chunping; Murphy, Anthony B.

    2016-03-01

    This paper is devoted to the computation of the non-equilibrium composition of an SF6 plasma, and determination of the dominant particles and reactions, at conditions relevant to high-voltage circuit breakers after current zero (temperatures from 12 000 K to 1000 K and a pressure of 4 atm). The non-equilibrium composition is characterized by departures from both thermal and chemical equilibrium. In thermal non-equilibrium process, the electron temperature (T e) is not equal to the heavy-particle temperature (T h), while for chemical non-equilibrium, a chemical kinetic model is adopted. In order to evaluate the reasonableness and reliability of the non-equilibrium composition, calculation methods for equilibrium composition based on Gibbs free energy minimization and kinetic composition in a one-temperature kinetic model are first considered. Based on the one-temperature kinetic model, a two-temperature kinetic model with the ratio T e/T h varying as a function of the logarithm of electron density ratio (n e/n\\text{e}\\max ) was established. In this model, T* is introduced to allow a smooth transition between T h and T e and to determine the temperatures for the rate constants. The initial composition in the kinetic models is obtained from the asymptotic composition as infinite time is approached at 12 000 K. The molar fractions of neutral particles and ions in the two-temperature kinetic model are consistent with the equilibrium composition and the composition obtained from the one-temperature kinetic model above 10 000 K, while significant differences appear below 10 000 K. Based on the dependence of the particle distributions on temperature in the two-temperature kinetic model, three temperature ranges, and the dominant particles and reactions in the respective ranges, are determined. The full model is then simplified into three models and the accuracy of the simplified models is assessed. The simplified models reduce the number of species and

  1. Acceleration of the KINETICS Integrated Dynamical/Chemical Computational Model Using MPI

    NASA Technical Reports Server (NTRS)

    Grossman, Max; Willacy, Karen; Allen, Mark

    2011-01-01

    Understanding the evolution of a planet's atmosphere not only provides a better theoretical understanding of planetary physics and the formation of planets, but also grants useful insight into Earth's own atmosphere. One of the tools used at JPL for the modeling of planetary atmospheres and protostellar disks is KINETICS. KINETICS can simulate years of complex dynamics and chemistry.

  2. Acceleration of the KINETICS Integrated Dynamical/Chemical Computational Model Using MPI

    NASA Technical Reports Server (NTRS)

    Grossman, Max; Willacy, Karen; Allen, Mark

    2011-01-01

    Understanding the evolution of a planet's atmosphere not only provides a better theoretical understanding of planetary physics and the formation of planets, but also grants useful insight into Earth's own atmosphere. One of the tools used at JPL for the modeling of planetary atmospheres and protostellar disks is KINETICS. KINETICS can simulate years of complex dynamics and chemistry.

  3. History and Philosophy of Science through Models: The Case of Chemical Kinetics.

    ERIC Educational Resources Information Center

    Justi, Rosaria; Gilbert, John K.

    1999-01-01

    A greater role for the history and philosophy of science in science education can only be realized if it is based on both a credible analytical approach--such as that of Lakatos--and if the evolution of a sufficient number of major themes in science is known in suitable detail. Considers chemical kinetics as an example topic. Contains 62…

  4. History and Philosophy of Science through Models: The Case of Chemical Kinetics.

    ERIC Educational Resources Information Center

    Justi, Rosaria; Gilbert, John K.

    1999-01-01

    A greater role for the history and philosophy of science in science education can only be realized if it is based on both a credible analytical approach--such as that of Lakatos--and if the evolution of a sufficient number of major themes in science is known in suitable detail. Considers chemical kinetics as an example topic. Contains 62…

  5. A new methodology to determine kinetic parameters for one- and two-step chemical models

    NASA Technical Reports Server (NTRS)

    Mantel, T.; Egolfopoulos, F. N.; Bowman, C. T.

    1996-01-01

    In this paper, a new methodology to determine kinetic parameters for simple chemical models and simple transport properties classically used in DNS of premixed combustion is presented. First, a one-dimensional code is utilized to performed steady unstrained laminar methane-air flame in order to verify intrinsic features of laminar flames such as burning velocity and temperature and concentration profiles. Second, the flame response to steady and unsteady strain in the opposed jet configuration is numerically investigated. It appears that for a well determined set of parameters, one- and two-step mechanisms reproduce the extinction limit of a laminar flame submitted to a steady strain. Computations with the GRI-mech mechanism (177 reactions, 39 species) and multicomponent transport properties are used to validate these simplified models. A sensitivity analysis of the preferential diffusion of heat and reactants when the Lewis number is close to unity indicates that the response of the flame to an oscillating strain is very sensitive to this number. As an application of this methodology, the interaction between a two-dimensional vortex pair and a premixed laminar flame is performed by Direct Numerical Simulation (DNS) using the one- and two-step mechanisms. Comparison with the experimental results of Samaniego et al. (1994) shows a significant improvement in the description of the interaction when the two-step model is used.

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

    PubMed

    Frank, Alex; Castaldi, Marco J

    2014-08-01

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

  7. Nitrogen Fixation by Gliding Arc Plasma: Better Insight by Chemical Kinetics Modelling.

    PubMed

    Wang, Weizong; Patil, Bhaskar; Heijkers, Stjin; Hessel, Volker; Bogaerts, Annemie

    2017-03-08

    The conversion of atmospheric nitrogen into valuable compounds, that is, so-called nitrogen fixation, is gaining increased interest, owing to the essential role in the nitrogen cycle of the biosphere. Plasma technology, and more specifically gliding arc plasma, has great potential in this area, but little is known about the underlying mechanisms. Therefore, we developed a detailed chemical kinetics model for a pulsed-power gliding-arc reactor operating at atmospheric pressure for nitrogen oxide synthesis. Experiments are performed to validate the model and reasonable agreement is reached between the calculated and measured NO and NO2 yields and the corresponding energy efficiency for NOx formation for different N2 /O2 ratios, indicating that the model can provide a realistic picture of the plasma chemistry. Therefore, we can use the model to investigate the reaction pathways for the formation and loss of NOx . The results indicate that vibrational excitation of N2 in the gliding arc contributes significantly to activating the N2 molecules, and leads to an energy efficient way of NOx production, compared to the thermal process. Based on the underlying chemistry, the model allows us to propose solutions on how to further improve the NOx formation by gliding arc technology. Although the energy efficiency of the gliding-arc-based nitrogen fixation process at the present stage is not comparable to the world-scale Haber-Bosch process, we believe our study helps us to come up with more realistic scenarios of entering a cutting-edge innovation in new business cases for the decentralised production of fertilisers for agriculture, in which low-temperature plasma technology might play an important role.

  8. A multiple shock tube and chemical kinetic modeling study of diethyl ether pyrolysis and oxidation.

    PubMed

    Yasunaga, K; Gillespie, F; Simmie, J M; Curran, H J; Kuraguchi, Y; Hoshikawa, H; Yamane, M; Hidaka, Y

    2010-09-02

    The pyrolysis and oxidation of diethyl ether (DEE) has been studied at pressures from 1 to 4 atm and temperatures of 900-1900 K behind reflected shock waves. A variety of spectroscopic diagnostics have been used, including time-resolved infrared absorption at 3.39 mum and time-resolved ultraviolet emission at 431 nm and absorption at 306.7 nm. In addition, a single-pulse shock tube was used to measure reactant, intermediate, and product species profiles by GC samplings at different reaction times varying from 1.2 to 1.8 ms. A detailed chemical kinetic model comprising 751 reactions involving 148 species was assembled and tested against the experiments with generally good agreement. In the early stages of reaction the unimolecular decomposition and hydrogen atom abstraction of DEE and the decomposition of the ethoxy radical have the largest influence. In separate experiments at 1.9 atm and 1340 K, it is shown that DEE inhibits the reactivity of an equimolar mixture of hydrogen and oxygen (1% of each).

  9. A reduced chemical kinetic model for IC engine combustion simulations with primary reference fuels

    SciTech Connect

    Ra, Youngchul; Reitz, Rolf D.

    2008-12-15

    A reduced chemical kinetic mechanism for the oxidation of primary reference fuel (PRF) has been developed and applied to model internal combustion engines. Starting from an existing reduced reaction mechanism for n-heptane oxidation, a new reduced n-heptane mechanism was generated by including an additional five species and their relevant reactions, by updating the reaction rate constants of several reactions pertaining to oxidation of carbon monoxide and hydrogen, and by optimizing reaction rate constants of selected reactions. Using a similar approach, a reduced mechanism for iso-octane oxidation was built and combined with the n-heptane mechanism to form a PRF mechanism. The final version of the PRF mechanism consists of 41 species and 130 reactions. Validation of the present PRF mechanism was performed with measurements from shock tube tests, and HCCI and direct injection engine experiments available in the literature. The results show that the present PRF mechanism gives reliable performance for combustion predictions, as well as computational efficiency improvements for multidimensional CFD simulations. (author)

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

    PubMed

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

    2007-06-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

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

  12. Premixed hydrocarbon stagnation flames : experiments and simulations to validate combustion chemical-kinetic models

    NASA Astrophysics Data System (ADS)

    Benezech, Laurent Jean-Michel

    A methodology based on the comparison of flame simulations relying on reacting flow models with experiment is applied to C1-C3 stagnation flames. The work reported targets the assessment and validation of the modeled reactions and reaction rates relevant to (C1-C3)-flame propagation in several detailed combustion kinetic models. A concensus does not, as yet, exist on the modeling of the reasonably well-understood oxidation of C1-C2 flames, and a better knowledge of C3 hydrocarbon combustion chemistry is required before attempting to bridge the gap between the oxidation of C1-C2 hydrocarbons and the more complex chemistry of heavier hydrocarbons in a single kinetic model. Simultaneous measurements of velocity and CH-radical profiles were performed in atmospheric propane(C3H8)- and propylene(C3H6)-air laminar premixed stagnation flames stabilized in a jet-wall configuration. These nearly-flat flames can be modeled by one-dimensional simulations, providing a means to validate kinetic models. Experimental data for these C3 flames and similar experimental data for atmospheric methane(CH4)-, ethane(C2H6)-, and ethylene(C2H4)-air flames are compared to numerical simulations performed with a one-dimensional hydrodynamic model, a multi-component transport formulation including thermal diffusion, and different detailed-chemistry models, in order to assess the adequacy of the models employed. A novel continuation technique between kinetic models was developed and applied successfully to obtain solutions with the less-robust models. The 2005/12 and 2005/10 releases of the San Diego mechanism are found to have the best overall performance in C3H8 and C3H6 flames, and in CH4, C2H6, and C2H4 flames, respectively. Flame position provides a good surrogate for flame speed in stagnation-flow stabilized flames. The logarithmic sensitivities of the simulated flame locations to variations in the kinetic rates are calculated via the "brute-force" method for fifteen representative flames

  13. A Chemical Kinetic Modeling Study of the Effects of Oxygenated Hydrocarbons on Soot Emissions from Diesel Engines

    SciTech Connect

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

    2005-11-14

    A detailed chemical kinetic modeling approach is used to examine the phenomenon of suppression of sooting in diesel engines by addition of oxygenated hydrocarbon species to the fuel. This suppression, which has been observed experimentally for a few years, is explained kinetically as a reduction in concentrations of soot precursors present in the hot products of a fuel-rich diesel ignition zone when oxygenates are included. Oxygenates decrease the overall equivalence ratio of the igniting mixture, producing higher ignition temperatures and more radical species to consume more soot precursor species, leading to lower soot production. The kinetic model is also used to show how different oxygenates, ester structures in particular, can have different soot-suppression efficiencies due to differences in molecular structure of the oxygenated species.

  14. Beyond mean-field approximations for accurate and computationally efficient models of on-lattice chemical kinetics.

    PubMed

    Pineda, M; Stamatakis, M

    2017-07-14

    Modeling the kinetics of surface catalyzed reactions is essential for the design of reactors and chemical processes. The majority of microkinetic models employ mean-field approximations, which lead to an approximate description of catalytic kinetics by assuming spatially uncorrelated adsorbates. On the other hand, kinetic Monte Carlo (KMC) methods provide a discrete-space continuous-time stochastic formulation that enables an accurate treatment of spatial correlations in the adlayer, but at a significant computation cost. In this work, we use the so-called cluster mean-field approach to develop higher order approximations that systematically increase the accuracy of kinetic models by treating spatial correlations at a progressively higher level of detail. We further demonstrate our approach on a reduced model for NO oxidation incorporating first nearest-neighbor lateral interactions and construct a sequence of approximations of increasingly higher accuracy, which we compare with KMC and mean-field. The latter is found to perform rather poorly, overestimating the turnover frequency by several orders of magnitude for this system. On the other hand, our approximations, while more computationally intense than the traditional mean-field treatment, still achieve tremendous computational savings compared to KMC simulations, thereby opening the way for employing them in multiscale modeling frameworks.

  15. Beyond mean-field approximations for accurate and computationally efficient models of on-lattice chemical kinetics

    NASA Astrophysics Data System (ADS)

    Pineda, M.; Stamatakis, M.

    2017-07-01

    Modeling the kinetics of surface catalyzed reactions is essential for the design of reactors and chemical processes. The majority of microkinetic models employ mean-field approximations, which lead to an approximate description of catalytic kinetics by assuming spatially uncorrelated adsorbates. On the other hand, kinetic Monte Carlo (KMC) methods provide a discrete-space continuous-time stochastic formulation that enables an accurate treatment of spatial correlations in the adlayer, but at a significant computation cost. In this work, we use the so-called cluster mean-field approach to develop higher order approximations that systematically increase the accuracy of kinetic models by treating spatial correlations at a progressively higher level of detail. We further demonstrate our approach on a reduced model for NO oxidation incorporating first nearest-neighbor lateral interactions and construct a sequence of approximations of increasingly higher accuracy, which we compare with KMC and mean-field. The latter is found to perform rather poorly, overestimating the turnover frequency by several orders of magnitude for this system. On the other hand, our approximations, while more computationally intense than the traditional mean-field treatment, still achieve tremendous computational savings compared to KMC simulations, thereby opening the way for employing them in multiscale modeling frameworks.

  16. Thermochemical analysis and kinetics aspects for a chemical model for camphene ozonolysis.

    PubMed

    Oliveira, R C de M; Bauerfeldt, G F

    2012-10-07

    In this work, a chemical model for the camphene ozonolysis, leading to carbonyl final products, is proposed and discussed on the basis of the thermochemical properties and kinetic data obtained at density functional theory levels of calculation. The mechanism is initiated by the electrophilic attack of ozone to the double bond in camphene leading to a 1,2,3-trioxolane intermediate, which decomposes to peroxy radicals and carbonyl compounds in a total of 10 elementary reactions. The thermodynamic properties (enthalpy and entropies differences) are calculated at 298 K. For the thermochemical evaluation, theoretical calculations are performed with the B3LYP, MPW1PW91, and mPW1K density functionals and the basis sets 6-31G(d), 6-31G(2d,2p), 6-31+G(d,p), and 6-31+G(2d,2p). Eventually, single point calculations adopting the 6-311++G(2d,2p) basis set are performed in order to improve the electronic energies. The enthalpy profiles suggest highly exothermic reactions for the individual steps, with a global enthalpy difference of -179.18 kcal mol(-1), determined at the B3LYP∕6-31+G(2d,2p) level. The Gibbs free energy differences for each step, at 298 K, calculated at the B3LYP∕6-311++G(2d,2p)∕∕B3LYP∕6-31+G(2d,2p) level, are used to estimate the composition of a final product mixture under equilibrium conditions as 58% of camphenilone and 42% of 6,6-dimethyl-ɛ-caprolactone-2,5-methylene. For the reaction kinetics, the bimolecular O(3) + camphene step is assumed to be rate determining in the global mechanism. A saddle point for the ozone addition to the double bond is located and rate constants are determined on the basis of the transition state theory. This saddle point is well represented by a loosely bound structure and corrections for the basis set superposition error (BSSE) are calculated, either by considering the effect over the geometry optimization procedure (here referred as CP1 procedure), or the effect of the BSSE over the electronic energy of a

  17. Thermochemical analysis and kinetics aspects for a chemical model for camphene ozonolysis

    NASA Astrophysics Data System (ADS)

    Oliveira, R. C. de M.; Bauerfeldt, G. F.

    2012-10-01

    In this work, a chemical model for the camphene ozonolysis, leading to carbonyl final products, is proposed and discussed on the basis of the thermochemical properties and kinetic data obtained at density functional theory levels of calculation. The mechanism is initiated by the electrophilic attack of ozone to the double bond in camphene leading to a 1,2,3-trioxolane intermediate, which decomposes to peroxy radicals and carbonyl compounds in a total of 10 elementary reactions. The thermodynamic properties (enthalpy and entropies differences) are calculated at 298 K. For the thermochemical evaluation, theoretical calculations are performed with the B3LYP, MPW1PW91, and mPW1K density functionals and the basis sets 6-31G(d), 6-31G(2d,2p), 6-31+G(d,p), and 6-31+G(2d,2p). Eventually, single point calculations adopting the 6-311++G(2d,2p) basis set are performed in order to improve the electronic energies. The enthalpy profiles suggest highly exothermic reactions for the individual steps, with a global enthalpy difference of -179.18 kcal mol-1, determined at the B3LYP/6-31+G(2d,2p) level. The Gibbs free energy differences for each step, at 298 K, calculated at the B3LYP/6-311++G(2d,2p)//B3LYP/6-31+G(2d,2p) level, are used to estimate the composition of a final product mixture under equilibrium conditions as 58% of camphenilone and 42% of 6,6-dimethyl-ɛ-caprolactone-2,5-methylene. For the reaction kinetics, the bimolecular O3 + camphene step is assumed to be rate determining in the global mechanism. A saddle point for the ozone addition to the double bond is located and rate constants are determined on the basis of the transition state theory. This saddle point is well represented by a loosely bound structure and corrections for the basis set superposition error (BSSE) are calculated, either by considering the effect over the geometry optimization procedure (here referred as CP1 procedure), or the effect of the BSSE over the electronic energy of a previously optimized

  18. A Sensitivity Test of the Ozone Solar Cycle Response with Respect to Chemical Kinetics and Model Parameters

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Li, K.; Li, C.; Liang, M.; Yung, Y. L.

    2012-12-01

    Previous studies have shown that the observed O3 solar cycle (SC) responses in upper and middle stratosphere are very different from those predicted by models. It is argued whether the differences are within the uncertainties of measurements and chemical kinetic rates. To answer this question, a simple one-dimensional (1-D) Caltech/JPL photochemical model is employed to study the discrepancies between observed and model O3 solar cycle responses. A simplified list of reactions is developed including Chapman, HOx, NOx and ClOx chemistry. We perform sensitivity tests on a significant portion of the kinetic rates to investigate whether the observed O3 SC response can be modeled using standard chemistry. Other model parameters such as eddy diffusivity are included in the tests. Finally, the optimal estimation method (OEM) is employed to derive a set of kinetic rate coefficients and model parameters that would minimize the difference between the observed and the model SC responses in O3. The outcome of retrieval represents the best-fit O3 response under the constraints of standard chemistry and measurement uncertainties.

  19. Quantum-chemical model evaluations of thermodynamics and kinetics of oxygen atom additions to narrow nanotubes.

    PubMed

    Slanina, Zdenĕk; Stobinski, Leszek; Tomasik, Piotr; Lin, Hong-Ming; Adamowicz, Ludwik

    2003-01-01

    This paper reports a computational study of oxygen additions to narrow nanotubes, a problem frequently studied with fullerenes. In fact, fullerene oxides were the first observed fullerene derivatives, and they have naturally attracted the attention of both experiment and theory. C60O had represented a long-standing case of experiment-theory disagreement, and there has been a similar problem with C60O2. The disagreement has been explained by kinetic rather than thermodynamic control. In this paper a similar computational approach is applied to narrow nanotubes. Recently, very narrow nanotubes have been observed with a diameter of 5 A and even with a diameter of 4 A. It has been supposed that the narrow nanotubes are closed by fragments of small fullerenes like C36 or C20. In this report we perform calculations for oxygen additions to such model nanotubes capped by fragments of D2d C36, D4d C32, and Ih C20 fullerenic cages (though the computational models have to be rather short). The three models have the following carbon contents: C84, C80, and C80. Both thermodynamic enthalpy changes and kinetic activation barriers for oxygen addition to six selected bonds are computed and analyzed. The lowest isomer (thermodynamically the most stable) is never of the 6/6 type, that is, the enthalpically favored structures are produced by oxygen additions to the nanotube tips. Interestingly enough, the lowest energy isomer has, for the D2d C36 and D4d C32 cases, the lowest kinetic activation barrier as well.

  20. HCCI experiments with toluene reference fuels modeled by a semidetailed chemical kinetic model

    SciTech Connect

    Andrae, J.C.G.; Brinck, T.; Kalghatgi, G.T.

    2008-12-15

    A semidetailed mechanism (137 species and 633 reactions) and new experiments in a homogeneous charge compression ignition (HCCI) engine on the autoignition of toluene reference fuels are presented. Skeletal mechanisms for isooctane and n-heptane were added to a detailed toluene submechanism. The model shows generally good agreement with ignition delay times measured in a shock tube and a rapid compression machine and is sensitive to changes in temperature, pressure, and mixture strength. The addition of reactions involving the formation and destruction of benzylperoxide radical was crucial to modeling toluene shock tube data. Laminar burning velocities for benzene and toluene were well predicted by the model after some revision of the high-temperature chemistry. Moreover, laminar burning velocities of a real gasoline at 353 and 500 K could be predicted by the model using a toluene reference fuel as a surrogate. The model also captures the experimentally observed differences in combustion phasing of toluene/n-heptane mixtures, compared to a primary reference fuel of the same research octane number, in HCCI engines as the intake pressure and temperature are changed. For high intake pressures and low intake temperatures, a sensitivity analysis at the moment of maximum heat release rate shows that the consumption of phenoxy radicals is rate-limiting when a toluene/n-heptane fuel is used, which makes this fuel more resistant to autoignition than the primary reference fuel. Typical CPU times encountered in zero-dimensional calculations were on the order of seconds and minutes in laminar flame speed calculations. Cross reactions between benzylperoxy radicals and n-heptane improved the model predictions of shock tube experiments for {phi}=1.0 and temperatures lower than 800 K for an n-heptane/toluene fuel mixture, but cross reactions had no influence on HCCI simulations. (author)

  1. A dynamic multi-timescale method for combustion modeling with detailed and reduced chemical kinetic mechanisms

    SciTech Connect

    Gou, Xiaolong; Sun, Wenting; Ju, Yiguang; Chen, Zheng

    2010-06-15

    A new on-grid dynamic multi-timescale (MTS) method is presented to increase significantly the computation efficiency involving multi-physical and chemical processes using detailed and reduced kinetic mechanisms. The methodology of the MTS method using the instantaneous timescales of different species is introduced. The definition of the characteristic time for species is examined and compared with that of the computational singular perturbation (CSP) and frozen reaction rate methods by using a simple reaction system. A hybrid multi-timescale (HMTS) algorithm is constructed by integrating the MTS method with an implicit Euler scheme, respectively, for species with and without the requirement of accurate time histories at sub-base timescales. The efficiency and the robustness of the MTS and HMTS methods are demonstrated by comparing with the Euler and VODE solvers for homogenous ignition and unsteady flame propagation of hydrogen, methane, and n-decane-air mixtures. The results show that both MTS and HMTS reproduce well the species and temperature histories and are able to decrease computation time by about one-order with the same kinetic mechanism. Compared to MTS, HMTS has slightly better computation efficiency but scarifies the stability at large base time steps. The results also show that with the increase of mechanism size and the decrease of time step, the computation efficiency of multi-timescale method increases compared to the VODE solver. In addition, it is shown that the integration of the multi-timescale method with the path flux analysis based mechanism reduction approach can further increase the computation efficiency. Unsteady simulations of outwardly propagating spherical n-decane-air premixed flames demonstrate that the multi-timescale method is rigorous for direct numerical simulations with both detailed and reduced chemistry and can dramatically improve the computation efficiency. (author)

  2. Modelling transport and degradation of de-icing chemicals in soil, assuming Monod kinetics with multiple electron-acceptors

    NASA Astrophysics Data System (ADS)

    Schotanus, D.; Meeussen, J. C. L.; van der Ploeg, M. J.; van der Zee, S. E. A. T. M.

    2012-04-01

    De-icing chemicals that contain propylene glycol are used at Oslo airport during winter time. A fraction of these chemicals is spilled on the runway and can be transported rapidly in the sandy soil in spring during snowmelt. Better insight into the chemical and physical processes that govern the fate of these chemicals in soil will help to estimate potential effects on the large unconfined aquifer in this area, and makes it possible to evaluate potential remedial actions. Micro-organisms in the soil can degrade propylene glycol, for which they need electron-acceptors. Under aerobic conditions, oxygen will be used as an electron-acceptor. From experiments, it is known that also anaerobic degradation occurs in this soil. During snowmelt, high infiltration rates can lead to locally saturated soil. In these parts, oxygen diffusion is limited and thus anaerobic conditions will occur. In these anaerobic regions, other electron-acceptors, such as manganese-oxides that are present in this soil, are used. However, frequent propylene glycol application may lead to a depletion of manganese-oxides and so to increased persistence and migration of propylene glycol in soil. To prevent this depletion and to enhance biodegradation, other electron-acceptors can be applied at the soil surface. Examples are the application of nitrate to the soil surface, and air injection. Model calculations could help to estimate required concentrations. The objectives of this study are 1) to create the reactive model, 2) to use this model to evaluate which parameters are determining leaching fluxes of propylene glycol from the soil, and 3) to evaluate the effectiveness of the different remediation strategies. Therefore, transient water flow, kinetic degradation, and redox chemistry were combined in one model. Degradation is modelled with Monod kinetics using multiple electron-acceptors. Oxygen diffusion in the gas phase, biomass growth, and oxidation and reduction of the important electron

  3. The mathematical properties of the quasi-chemical model for microorganism growth-death kinetics in foods.

    PubMed

    Ross, E W; Taub, I A; Doona, C J; Feeherry, F E; Kustin, K

    2005-03-15

    Knowledge of the mathematical properties of the quasi-chemical model [Taub, Feeherry, Ross, Kustin, Doona, 2003. A quasi-chemical kinetics model for the growth and death of Staphylococcus aureus in intermediate moisture bread. J. Food Sci. 68 (8), 2530-2537], which is used to characterize and predict microbial growth-death kinetics in foods, is important for its applications in predictive microbiology. The model consists of a system of four ordinary differential equations (ODEs), which govern the temporal dependence of the bacterial life cycle (the lag, exponential growth, stationary, and death phases, respectively). The ODE system derives from a hypothetical four-step reaction scheme that postulates the activity of a critical intermediate as an antagonist to growth (perhaps through a quorum sensing biomechanism). The general behavior of the solutions to the ODEs is illustrated by several examples. In instances when explicit mathematical solutions to these ODEs are not obtainable, mathematical approximations are used to find solutions that are helpful in evaluating growth in the early stages and again near the end of the process. Useful solutions for the ODE system are also obtained in the case where the rate of antagonist formation is small. The examples and the approximate solutions provide guidance in the parameter estimation that must be done when fitting the model to data. The general behavior of the solutions is illustrated by examples, and the MATLAB programs with worked examples are included in the appendices for use by predictive microbiologists for data collected independently.

  4. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

    PubMed

    Kozuch, Sebastian; Shaik, Sason

    2008-07-03

    A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

  5. Temperature rule for the speed of sound in water: a chemical kinetics model

    PubMed

    Okazaki

    2000-09-15

    Water forms three-dimensional polymeric structures due to the influence of hydrogen bonds and is fundamentally different from other substances. One of the simplest ways to analyze the structure of water in any system, such as hydration, is to measure the degree of compressibility, which can be determined from the speed of sound, by making use of the physical laws established by Newton and later perfected by Laplace. Although the speed of sound is strongly dependent on the temperature of a liquid, Laplace's equation does not refer to temperature in any of its terms. It is necessary, therefore, to determine the degree of temperature dependency. However, only approximate expressions of a fifth-order polynomial have been reported so far in the literature. In this paper, a universal method for describing the speed of sound from the perspective of physicochemical reaction kinetics is presented. It is shown that the speed of sound U [ms(-1)] changes with temperature T [K] according to a thermodynamically-derived formula given as U= exp(-A/T-BlnT+C) and that the motion and propagation phenomena of sound energy can also be regarded as chemical reactions.

  6. Mathematical description of complex chemical kinetics and application to CFD modeling codes

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1993-01-01

    A major effort in combustion research at the present time is devoted to the theoretical modeling of practical combustion systems. These include turbojet and ramjet air-breathing engines as well as ground-based gas-turbine power generating systems. The ability to use computational modeling extensively in designing these products not only saves time and money, but also helps designers meet the quite rigorous environmental standards that have been imposed on all combustion devices. The goal is to combine the very complex solution of the Navier-Stokes flow equations with realistic turbulence and heat-release models into a single computer code. Such a computational fluid-dynamic (CFD) code simulates the coupling of fluid mechanics with the chemistry of combustion to describe the practical devices. This paper will focus on the task of developing a simplified chemical model which can predict realistic heat-release rates as well as species composition profiles, and is also computationally rapid. We first discuss the mathematical techniques used to describe a complex, multistep fuel oxidation chemical reaction and develop a detailed mechanism for the process. We then show how this mechanism may be reduced and simplified to give an approximate model which adequately predicts heat release rates and a limited number of species composition profiles, but is computationally much faster than the original one. Only such a model can be incorporated into a CFD code without adding significantly to long computation times. Finally, we present some of the recent advances in the development of these simplified chemical mechanisms.

  7. Mathematical Description of Complex Chemical Kinetics and Application to CFD Modeling Codes

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1993-01-01

    A major effort in combustion research at the present time is devoted to the theoretical modeling of practical combustion systems. These include turbojet and ramjet air-breathing engines as well as ground-based gas-turbine power generating systems. The ability to use computational modeling extensively in designing these products not only saves time and money, but also helps designers meet the quite rigorous environmental standards that have been imposed on all combustion devices. The goal is to combine the very complex solution of the Navier-Stokes flow equations with realistic turbulence and heat-release models into a single computer code. Such a computational fluid-dynamic (CFD) code simulates the coupling of fluid mechanics with the chemistry of combustion to describe the practical devices. This paper will focus on the task of developing a simplified chemical model which can predict realistic heat-release rates as well as species composition profiles, and is also computationally rapid. We first discuss the mathematical techniques used to describe a complex, multistep fuel oxidation chemical reaction and develop a detailed mechanism for the process. We then show how this mechanism may be reduced and simplified to give an approximate model which adequately predicts heat release rates and a limited number of species composition profiles, but is computationally much faster than the original one. Only such a model can be incorporated into a CFD code without adding significantly to long computation times. Finally, we present some of the recent advances in the development of these simplified chemical mechanisms.

  8. Mathematical description of complex chemical kinetics and application to CFD modeling codes

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1993-01-01

    A major effort in combustion research at the present time is devoted to the theoretical modeling of practical combustion systems. These include turbojet and ramjet air-breathing engines as well as ground-based gas-turbine power generating systems. The ability to use computational modeling extensively in designing these products not only saves time and money, but also helps designers meet the quite rigorous environmental standards that have been imposed on all combustion devices. The goal is to combine the very complex solution of the Navier-Stokes flow equations with realistic turbulence and heat-release models into a single computer code. Such a computational fluid-dynamic (CFD) code simulates the coupling of fluid mechanics with the chemistry of combustion to describe the practical devices. This paper will focus on the task of developing a simplified chemical model which can predict realistic heat-release rates as well as species composition profiles, and is also computationally rapid. We first discuss the mathematical techniques used to describe a complex, multistep fuel oxidation chemical reaction and develop a detailed mechanism for the process. We then show how this mechanism may be reduced and simplified to give an approximate model which adequately predicts heat release rates and a limited number of species composition profiles, but is computationally much faster than the original one. Only such a model can be incorporated into a CFD code without adding significantly to long computation times. Finally, we present some of the recent advances in the development of these simplified chemical mechanisms.

  9. Kinetics of microbial degradation of deicing chemicals in percolated porous media - the modeling perspective

    NASA Astrophysics Data System (ADS)

    Wehrer, Markus; Lissner, Heidi; Totsche, Kai

    2013-04-01

    A quantitative knowledge of the fate of deicing chemicals in the subsurface can be provided by analysis of laboratory and field experiments with numerical simulation models. In the present study, experimental data of microbial degradation of the deicing chemical propylene glycol (PG) under flow conditions in soil columns and field lysimeters were simulated to analyze the process conditions of degradation and to obtain the according parameters. Results from the column experiment were evaluated applying different scenarios of an advection-dispersion model using HYDRUS-1D. To reconstruct the data, different competing degradation models were included, i.e., zero order, first order and inclusion of a growing and decaying biomass. The general breakthrough behavior of propylene glycol in soil columns can be simulated well using a coupled model of solute transport and degradation with growth and decay of biomass. The susceptibility of the model to non-unique solutions was investigated using systematical forward and inverse simulations. We found that the model tends to equifinal solutions under certain conditions. Complex experimental boundary conditions can help to avoid this. Under field conditions, the situation is far more complex than in the laboratory. Studying the fate of PG with undisturbed lysimeters we found that aerobic and anaerobic degradation occurs simultaneously. We attribute this to the physical structure and the aggregated nature of the undisturbed soil material . This results in the presence of spatially disjoint oxidative and reductive regions of microbial activity and requires, but is not fully reflected by a dual porosity model. Currently, the numerical simulation of this system is in progress, considering several flow and transport models. A stochastic global search algorithm (DREAM-ZS) is used in conjuction with HYDRUS-1D to avoid local minima in the inverse simulations. The study shows the current limitations and potentials of modeling degradation

  10. Kinetics Study of Solid Ammonia Borane Hydrogen Release – Modeling and Experimental Validation for Chemical Hydrogen Storage

    SciTech Connect

    Choi, Yong-Joon; Ronnebro, Ewa; Rassat, Scot D.; Karkamkar, Abhijeet J.; Maupin, Gary D.; Holladay, Jamelyn D.; Simmons, Kevin L.; Brooks, Kriston P.

    2014-02-24

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which 16.2 wt% hydrogen can be utilized below 200°C. We have investigated the kinetics of hydrogen release from AB and from an AB-methyl cellulose (AB/MC) composite at temperatures of 160-300°C using both experiments and modeling. The purpose of our study was to show safe hydrogen release without thermal runaway effects and to validate system model kinetics. AB/MC released hydrogen at ~20°C lower than neat AB and at a rate that is two times faster. Based on the experimental results, the kinetics equations were revised to better represent the growth and nucleation process during decomposition of AB. We explored two different reactor concepts; Auger and fixed bed. The current Auger reactor concept turned out to not be appropriate, however, we demonstrated safe self-propagation of the hydrogen release reaction of solid AB/MC in a fixed bed reactor.

  11. A novel kinetic model for chemical energy accommodation on silica surface

    NASA Astrophysics Data System (ADS)

    Di Benedetto, S.; Bruno, C.

    2013-06-01

    A new phenomenological catalysis model for silica surface has been developed, the main feature of which is the capability of accounting for chemical energy accommodation (CEA), i. e., the effective transfer of chemical energy to the catalyst surface by catalytically formed molecules. In this new model the interaction time between a just-formed molecule and the surface is compared with the time of other processes, and the efficiency of the interaction depends on the coupling between the molecules interaction time before desorption and the phonon frequency distribution (a characteristic period of surface vibration). These two quantities have been evaluated for the case of oxygen atoms impacting a silica surface. To this aim, a new three dimensional model of the interaction potential between the surface atoms and the impacting atom has been built and utilized inside the bulk structure of crystalline silica. Finally, the model has been validated using data collected during a test campaign in the CIRA SCIROCCO Plasma Wind Tunnel (PWT) on a full-scale aerodynamic spacecraft component.

  12. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

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

    2009-03-09

    n-Hexadecane and 2,2,4,4,6,8,8-heptamethylnonane represent the primary reference fuels for diesel that are used to determine cetane number, a measure of the ignition property of diesel fuel. With the development of chemical kinetics models for both primary reference fuels, a new capability is now available to model diesel fuel ignition. Additionally, we have developed chemical kinetic models for a whole series of large n-alkanes and a large iso-alkane to represent these chemical classes in fuel surrogates for conventional and future fuels. These chemical kinetic models are used to predict the effect of the aforementioned fuel components on ignition characteristics under conditions found in internal combustion engines.

  13. Lattice-Gas Model Description of Kinetic Roughening and Fluctuations in Chemical Wave Propagation

    NASA Astrophysics Data System (ADS)

    Tammaro, Michael; Evans, Jim

    1996-03-01

    The ZGB model [1] for CO-oxidation on surfaces displays a discontinuous transition from a reactive to a CO-poisoned state, with increasing CO partial pressure. We consider the evolution of the interface between these two states in the vicinity of the poisoning transition [2]. We observe large ``intrinsic fluctuations" at the interface of the order of 10-20 lattice spacings, together with the gradual development of long-wavelength fluctuations. The latter are described by the KPZ-theory for noise-induced kinetic roughening of driven interfaces, for CO partial pressures strictly below the poisoning transition. Distinct behavior is observed and characterized right at the transition. We also show that the influence of introducing surface diffusion of adsorbed reactants into the model is to dramatically quench the intrinsic fluctuations. [1] R.M. Ziff, E. Gulari, and Y. Barshad, Phys. Rev. Lett. 56, p.2553 (1986). [2] J.W. Evans and T.R. Ray, Phys. Rev. E 50, p.4302 (1994).

  14. Fast Prediction of HCCI and PCCI Combustion with an Artificial Neural Network-Based Chemical Kinetic Model

    SciTech Connect

    Piggott, W T; Aceves, S M; Flowers, D L; Chen, J Y

    2007-09-26

    We have added the capability to look at in-cylinder fuel distributions using a previously developed ignition model within a fluid mechanics code (KIVA3V) that uses an artificial neural network (ANN) to predict ignition (The combined code: KIVA3V-ANN). KIVA3V-ANN was originally developed and validated for analysis of Homogeneous Charge Compression Ignition (HCCI) combustion, but it is also applicable to the more difficult problem of Premixed Charge Compression Ignition (PCCI) combustion. PCCI combustion refers to cases where combustion occurs as a nonmixing controlled, chemical kinetics dominated, autoignition process, where the fuel, air, and residual gas mixtures are not necessarily as homogeneous as in HCCI combustion. This paper analyzes the effects of introducing charge non-uniformity into a KIVA3V-ANN simulation. The results are compared to experimental results, as well as simulation results using a more physically representative and computationally intensive code (KIVA3V-MPI-MZ), which links a fluid mechanics code to a multi-zone detailed chemical kinetics solver. The results indicate that KIVA3V-ANN produces reasonable approximations to the more accurate KIVA3V-MPI-MZ at a much reduced computational cost.

  15. An approach for modeling surface reaction kinetics in chemical vapor deposition processes

    SciTech Connect

    Wang, Y.F.; Pollard, R.

    1995-05-01

    A methodology is presented for determining the rate constants of elementary surface reactions that can take place in chemical vapor deposition (CVD) processes. The calculations consider well-defined surfaces that can have one or more dangling bonds at a given site and adsorbates that can take up one or more different bonding configurations. Rate constants for each reaction are obtained independently of any process data using statistical mechanics, transition state theory, and bond dissociation energies. Specifically, the reactions are divided in transition state structures and determine preexponential factors, and the requirement of thermodynamic consistency is used to estimate activation energies. The level of sophistication of the calculations is suitable for treating the large number of plausible steps that could take place in a practical CVD system. Incorporation of the calculated rate constants into a reactor model that includes the effects of fluid flow, transport phenomena, and reactions in the gas and at the growing surface enables dominant reaction pathways and rate-limiting steps to be identified. Moreover, the dependence of growth rate and species compositions on operating conditions can be predicted without fitting any parameters. The utility of the approach is illustrated by modeling low pressure deposition of tungsten from tungsten hexafluoride and silane. This model treats 35 reactions in the gas and 213 reactions at the growing surface. Results are compared with available experimental data and sensitivity studies are used to assess the limitations of the approach.

  16. Microscopic Models for Chemical Thermodynamics

    NASA Astrophysics Data System (ADS)

    Malyshev, V. A.

    2005-06-01

    We introduce an infinite particle system dynamics, which includes stochastic chemical kinetics models, the classical Kac model and free space movement. We study energy redistribution between two energy types (kinetic and chemical) in different time scales, similar to energy redistribution in the living cell. One example is considered in great detail, where the model provides main formulas of chemical thermodynamics.

  17. First-Principles Chemical Kinetic Modeling of Methyl trans-3-Hexenoate Epoxidation by HO2.

    PubMed

    Cagnina, S; Nicolle, A; de Bruin, T; Georgievskii, Y; Klippenstein, S J

    2017-03-09

    The design of innovative combustion processes relies on a comprehensive understanding of biodiesel oxidation kinetics. The present study aims at unraveling the reaction mechanism involved in the epoxidation of a realistic biodiesel surrogate, methyl trans-3-hexenoate, by hydroperoxy radicals using a bottom-up theoretical kinetics methodology. The obtained rate constants are in good agreement with experimental data for alkene epoxidation by HO2. The impact of temperature and pressure on epoxidation pathways involving H-bonded and non-H-bonded conformers was assessed. The obtained rate constant was finally implemented into a state-of-the-art detailed combustion mechanism, resulting in fairly good agreement with engine experiments.

  18. First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2

    DOE PAGES

    Cagnina, S.; Nicolle, Andre; de Bruin, T.; ...

    2017-02-16

    The design of innovative combustion processes relies on a comprehensive understanding of biodiesel oxidation kinetics. The present study aims at unraveling the reaction mechanism involved in the epoxidation of a realistic biodiesel surrogate, methyl trans-3-hexenoate, by hydroperoxy radicals using a bottom-up theoretical kinetics methodology. The obtained rate constants are in good agreement with experimental data for alkene epoxidation by HO2. The impact of temperature and pressure on epoxidation pathways involving H-bonded and non-H-bonded conformers was assessed. As a result, the obtained rate constant was finally implemented into a state-of-the-art detailed combustion mechanism, resulting in fairly good agreement with engine experiments.

  19. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

    DOE PAGES

    Keromnes, Alan; Metcalfe, Wayne K.; Heufer, Karl A.; ...

    2013-03-12

    The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrationsmore » lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2 showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values

  20. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

    SciTech Connect

    Keromnes, Alan; Metcalfe, Wayne K.; Heufer, Karl A.; Donohoe, Nicola; Das, Apurba K.; Sung, Chih -Jen; Herzler, Jurgen; Naumann, Clemens; Griebel, Peter; Mathieu, Olivier; Krejci, Michael C.; Petersen, Eric L.; Pitz, William J.; Curran, Henry J.

    2013-03-12

    The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2

  1. Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants.

    PubMed

    Gu, Qing; Bravo-Díaz, Carlos; Romsted, Laurence S

    2013-06-15

    Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

  2. Enhancing Thai Students' Learning of Chemical Kinetics

    ERIC Educational Resources Information Center

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

    2009-01-01

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

  3. Enhancing Thai Students' Learning of Chemical Kinetics

    ERIC Educational Resources Information Center

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

    2009-01-01

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

  4. Updated Chemical Kinetics and Sensitivity Analysis Code

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, Krishnan

    2005-01-01

    An updated version of the General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code has become available. A prior version of LSENS was described in "Program Helps to Determine Chemical-Reaction Mechanisms" (LEW-15758), NASA Tech Briefs, Vol. 19, No. 5 (May 1995), page 66. To recapitulate: LSENS solves complex, homogeneous, gas-phase, chemical-kinetics problems (e.g., combustion of fuels) that are represented by sets of many coupled, nonlinear, first-order ordinary differential equations. LSENS has been designed for flexibility, convenience, and computational efficiency. The present version of LSENS incorporates mathematical models for (1) a static system; (2) steady, one-dimensional inviscid flow; (3) reaction behind an incident shock wave, including boundary layer correction; (4) a perfectly stirred reactor; and (5) a perfectly stirred reactor followed by a plug-flow reactor. In addition, LSENS can compute equilibrium properties for the following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static and one-dimensional-flow problems, including those behind an incident shock wave and following a perfectly stirred reactor calculation, LSENS can compute sensitivity coefficients of dependent variables and their derivatives, with respect to the initial values of dependent variables and/or the rate-coefficient parameters of the chemical reactions.

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

    SciTech Connect

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

    2011-03-16

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

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

    PubMed Central

    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.

    2013-01-01

    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

  7. Adequacy of kinetic models

    SciTech Connect

    Kiperman, S.L.

    1995-01-01

    The problems associated with the accuracy of kinetic models in heterogeneous catalysis and their adequacy to experimental data and reaction mechanisms are considered. The prospects for the further improvement and use of these models is also explored.

  8. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

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

    2008-12-15

    Detailed chemical kinetic models are needed to simulate the combustion of current and future transportation fuels. These models should represent the various chemical classes in these fuels. Conventional diesel fuels are composed of n-alkanes, iso-alkanes, cycloalkanes and aromatics (Farrell et al. 2007). For future fuels, there is a renewed interest in Fischer-Tropsch (F-T) processes which can be used to synthesize diesel and other transportation fuels from biomass, coal and natural gas. F-T diesel fuels are expected to be similar to F-T jet fuels which are commonly comprised of iso-alkanes with some n-alkanes (Smith and Bruno, 2008). Thus, n-alkanes and iso-alkanes are common chemical classes in these conventional and future fuels. This paper reports on the development of chemical kinetic models of large n-alkanes and iso-alkanes to represent these chemical classes in conventional and future fuels. Two large iso-alkanes are 2,2,4,4,6,8,8-heptamethylnonane, which is a primary reference fuel for diesel, and isooctane, a primary reference fuel for gasoline. Other iso-alkanes are branched alkanes with a single methyl side chain, typical of most F-T fuels. The chemical kinetic models are then used to predict the effect of these fuel components on ignition characteristics under conditions found in internal combustion engines.

  9. Kinetic-fluid dynamics modeling of I{sub 2} dissociation in supersonic chemical oxygen-iodine lasers

    SciTech Connect

    Waichman, K.; Barmashenko, B. D.; Rosenwaks, S.

    2009-09-15

    The mechanism of I{sub 2} dissociation in supersonic chemical oxygen-iodine lasers (COILs) is studied applying kinetic-fluid dynamics modeling, where pathways involving the excited species I{sub 2}(X {sup 1}SIGMA{sub g}{sup +},10<=v<25), I{sub 2}(X {sup 1}SIGMA{sub g}{sup +},25<=v<=47), I{sub 2}(A{sup '} {sup 3}PI{sub 2u}), I{sub 2}(A {sup 3}PI{sub 1u}), O{sub 2}(X {sup 3}SIGMA{sub g}{sup -},v), O{sub 2}(a {sup 1}DELTA{sub g},v), O{sub 2}(b {sup 1}SIGMA{sub g}{sup +},v), and I({sup 2}P{sub 1/2}) as intermediate reactants are included. The gist of the model is adding the first reactant and reducing the contribution of the second as compared to previous models. These changes, recently suggested by Azyazov, et al. [J. Chem. Phys. 130, 104306 (2009)], significantly improve the agreement with the measurements of the gain in a low pressure supersonic COIL for all I{sub 2} flow rates that have been tested in the experiments. In particular, the lack of agreement for high I{sub 2} flow rates, which was encountered in previous models, has been eliminated in the present model. It is suggested that future modeling of the COIL operation should take into account the proposed contribution of the above mentioned reactants.

  10. Diesel Surrogate Fuels for Engine Testing and Chemical-Kinetic Modeling: Compositions and Properties

    PubMed Central

    Mueller, Charles J.; Cannella, William J.; Bays, J. Timothy; Bruno, Thomas J.; DeFabio, Kathy; Dettman, Heather D.; Gieleciak, Rafal M.; Huber, Marcia L.; Kweon, Chol-Bum; McConnell, Steven S.; Pitz, William J.; Ratcliff, Matthew A.

    2016-01-01

    The primary objectives of this work were to formulate, blend, and characterize a set of four ultralow-sulfur diesel surrogate fuels in quantities sufficient to enable their study in single-cylinder-engine and combustion-vessel experiments. The surrogate fuels feature increasing levels of compositional accuracy (i.e., increasing exactness in matching hydrocarbon structural characteristics) relative to the single target diesel fuel upon which the surrogate fuels are based. This approach was taken to assist in determining the minimum level of surrogate-fuel compositional accuracy that is required to adequately emulate the performance characteristics of the target fuel under different combustion modes. For each of the four surrogate fuels, an approximately 30 L batch was blended, and a number of the physical and chemical properties were measured. This work documents the surrogate-fuel creation process and the results of the property measurements. PMID:27330248

  11. Diesel Surrogate Fuels for Engine Testing and Chemical-Kinetic Modeling: Compositions and Properties.

    PubMed

    Mueller, Charles J; Cannella, William J; Bays, J Timothy; Bruno, Thomas J; DeFabio, Kathy; Dettman, Heather D; Gieleciak, Rafal M; Huber, Marcia L; Kweon, Chol-Bum; McConnell, Steven S; Pitz, William J; Ratcliff, Matthew A

    2016-02-18

    The primary objectives of this work were to formulate, blend, and characterize a set of four ultralow-sulfur diesel surrogate fuels in quantities sufficient to enable their study in single-cylinder-engine and combustion-vessel experiments. The surrogate fuels feature increasing levels of compositional accuracy (i.e., increasing exactness in matching hydrocarbon structural characteristics) relative to the single target diesel fuel upon which the surrogate fuels are based. This approach was taken to assist in determining the minimum level of surrogate-fuel compositional accuracy that is required to adequately emulate the performance characteristics of the target fuel under different combustion modes. For each of the four surrogate fuels, an approximately 30 L batch was blended, and a number of the physical and chemical properties were measured. This work documents the surrogate-fuel creation process and the results of the property measurements.

  12. Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 5

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1982-01-01

    Sets of rate constants and photochemical cross sections compiled which were evaluated. The primary application of the data is in the modeling of stratospheric processes on the ozone layer and its possible perturbation by anthropogenic and natural phenomena are emphasized.

  13. Chemical kinetics and photochemical data for use in stratospheric modeling. Evaluation number 6

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1983-01-01

    Evaluated sets of rate constants and photochemical cross sections are presented. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  14. Chemical kinetics of geminal recombination

    SciTech Connect

    Levin, P.P.; Khudyakov, I.V.; Brin, E.F.; Kuz'min, V.A.

    1988-09-01

    The kinetics of geminal recombination of triplet radical pairs formed in photoreduction of benzophenone by p-cresol in glycerin solution was studied by pulsed laser photolysis. The experiments were conducted at several temperatures and in a constant magnetic field of H = 0.34 T. The parameters in six kinetic equations describing geminal recombination were determined with a computer. The values of the sums of the squares of the residual deviations of the approximation were obtained. It was found that the kinetics are best described by the functions proposed by Noyes and Shushin. It was shown that it is necessary to use the mutual diffusion coefficient of the radicals, which is significantly smaller than the sum of the estimations of the experimental values of the radical diffusion coefficients, for describing the kinetics due to the correlations of the molecular motions of the radicals in the cage.

  15. Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

    NASA Technical Reports Server (NTRS)

    Balasubramaniam, R; Gokoglu, S.; Hegde, U.

    2009-01-01

    We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

  16. Chemical kinetics and oil shale process design

    SciTech Connect

    Burnham, A.K.

    1993-07-01

    Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.

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

    SciTech Connect

    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.

  18. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling. Evaluation No. 12

    NASA Technical Reports Server (NTRS)

    DeMore, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.

    1997-01-01

    This is the twelfth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  19. Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.; Wilson, C. H.

    1980-01-01

    The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

  20. Detailed Chemical Kinetic Modeling of Iso-octane SI-HCCI Transition

    SciTech Connect

    Havstad, Mark A; Aceves, Salvador M; McNenly, Matthew J; Piggott, William T; Edwards, Kevin Dean; Wagner, Robert M; Daw, C Stuart; FINNEY, Charles E A

    2010-01-01

    We 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 (SI) combustion to homogenous 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 we 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 scenario is consistent with that implemented in previously reported experimental measurements on an experimental engine equipped with variable valve actuation. We find that the model captures many of the important experimental trends, including stable SI combustion at low EGR (-0.10), a transition to highly unstable combustion at intermediate EGR, and finally stable HCCI combustion at very high EGR (-0.75). Remaining differences between the predicted and experimental instability patterns indicate that there is further room for model improvement.

  1. Particle-based modeling of heterogeneous chemical kinetics including mass transfer

    NASA Astrophysics Data System (ADS)

    Sengar, A.; Kuipers, J. A. M.; van Santen, Rutger A.; Padding, J. T.

    2017-08-01

    Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

  2. Chemical kinetics and photochemical data for use in stratospheric modeling evaluation Number 8

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Molina, M. J.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1987-01-01

    This is the eighth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109.

  3. Nonlinear response theory in chemical kinetics.

    PubMed

    Kryvohuz, Maksym; Mukamel, Shaul

    2014-01-21

    A theory of nonlinear response of chemical kinetics, in which multiple perturbations are used to probe the time evolution of nonlinear chemical systems, is developed. Expressions for nonlinear chemical response functions and susceptibilities, which can serve as multidimensional measures of the kinetic pathways and rates, are derived. A new class of multidimensional measures that combine multiple perturbations and measurements is also introduced. Nonlinear fluctuation-dissipation relations for steady-state chemical systems, which replace operations of concentration measurement and perturbations, are proposed. Several applications to the analysis of complex reaction mechanisms are provided.

  4. Nonlinear response theory in chemical kinetics

    PubMed Central

    Kryvohuz, Maksym; Mukamel, Shaul

    2014-01-01

    A theory of nonlinear response of chemical kinetics, in which multiple perturbations are used to probe the time evolution of nonlinear chemical systems, is developed. Expressions for nonlinear chemical response functions and susceptibilities, which can serve as multidimensional measures of the kinetic pathways and rates, are derived. A new class of multidimensional measures that combine multiple perturbations and measurements is also introduced. Nonlinear fluctuation-dissipation relations for steady-state chemical systems, which replace operations of concentration measurement and perturbations, are proposed. Several applications to the analysis of complex reaction mechanisms are provided. PMID:25669367

  5. Chemical kinetic mechanistic models to investigate cancer biology and impact cancer medicine

    NASA Astrophysics Data System (ADS)

    Stites, Edward C.

    2013-04-01

    Traditional experimental biology has provided a mechanistic understanding of cancer in which the malignancy develops through the acquisition of mutations that disrupt cellular processes. Several drugs developed to target such mutations have now demonstrated clinical value. These advances are unequivocal testaments to the value of traditional cellular and molecular biology. However, several features of cancer may limit the pace of progress that can be made with established experimental approaches alone. The mutated genes (and resultant mutant proteins) function within large biochemical networks. Biochemical networks typically have a large number of component molecules and are characterized by a large number of quantitative properties. Responses to a stimulus or perturbation are typically nonlinear and can display qualitative changes that depend upon the specific values of variable system properties. Features such as these can complicate the interpretation of experimental data and the formulation of logical hypotheses that drive further research. Mathematical models based upon the molecular reactions that define these networks combined with computational studies have the potential to deal with these obstacles and to enable currently available information to be more completely utilized. Many of the pressing problems in cancer biology and cancer medicine may benefit from a mathematical treatment. As work in this area advances, one can envision a future where such models may meaningfully contribute to the clinical management of cancer patients.

  6. Modeling the chemical kinetics of atmospheric plasma for cell treatment in a liquid solution

    SciTech Connect

    Kim, H. Y.; Kang, S. K.; Lee, H. Wk.; Lee, H. W.; Kim, G. C.; Lee, J. K.

    2012-07-15

    Low temperature atmospheric pressure plasmas have been known to be effective for living cell inactivation in a liquid solution but it is not clear yet which species are key factors for the cell treatment. Using a global model, we elucidate the processes through which pH level in the solution is changed from neutral to acidic after plasma exposure and key components with pH and air variation. First, pH level in a liquid solution is changed by He{sup +} and He(2{sup 1}S) radicals. Second, O{sub 3} density decreases as pH level in the solution decreases and air concentration decreases. It can be a method of removing O{sub 3} that causes chest pain and damages lung tissue when the density is very high. H{sub 2}O{sub 2}, HO{sub 2}, and NO radicals are found to be key factors for cell inactivation in the solution with pH and air variation.

  7. Mass Conservation and Chemical Kinetics.

    ERIC Educational Resources Information Center

    Barbara, Thomas M.; Corio, P. L.

    1980-01-01

    Presents a method for obtaining all mass conservation conditions implied by a given mechanism in which the conditions are used to simplify integration of the rate equations and to derive stoichiometric relations. Discusses possibilities of faulty inference of kinetic information from a given stoichiometry. (CS)

  8. Mass Conservation and Chemical Kinetics.

    ERIC Educational Resources Information Center

    Barbara, Thomas M.; Corio, P. L.

    1980-01-01

    Presents a method for obtaining all mass conservation conditions implied by a given mechanism in which the conditions are used to simplify integration of the rate equations and to derive stoichiometric relations. Discusses possibilities of faulty inference of kinetic information from a given stoichiometry. (CS)

  9. Kinetic and transport modeling of the metallorganic chemical vapor deposition of InP from trimethylindium and phosphine and comparison with experiments

    SciTech Connect

    Theodoropoulos, C.; Ingle, N.K.; Montziaris, T.J.; Chen, Z.Y.; Liu, P.L.; Kioseoglou, G.; Petrou, A.

    1995-06-01

    Gas phase and surface kinetic models describing the growth of InP by metallorganic chemical vapor deposition (MOCVD) using trimethylindium and phosphine diluted in hydrogen have been developed. A realistic model of the process was obtained by incorporating the kinetics into a two-dimensional transport model of the flow, heat, and mass transfer in horizontal MOCVD reactors. The unknown rate parameters of two surface growth reactions were estimated by comparing predicted growth rates of InP with the ones obtained from an atmospheric-pressure horizontal MOCVD reactor during heteroepitaxy of InP on GaAs. Sensitivity analysis of the reactions led to a reduced kinetic scheme, which can be used for predicting film growth rates with the same accuracy as a more detailed kinetic model, but with smaller computational requirements. The reduced kinetic model was subsequently tested against three sets of InP growth data reported in the literature and it successfully predicted observed growth rates and trends. Finally, parametric studies were performed on the computer to investigate the effects of changing the inlet velocity of the carrier gas, the operating pressure, and the inlet mole fraction of trimethylindium on the growth rate of the films. The proposed model may become a useful tool for reactor design, optimization, and scale-up of InP MOCVD.

  10. Chemical kinetics of Estane aging in PBX

    SciTech Connect

    Pack, R.T.; Hanson, D.E.; Redondo, A.

    1997-12-01

    The Plastic-Bonded Explosive PBX 9501 is about 95% HMX, 2.5% Estane 5703, 2.5% nitroplasticizer (NP), and 0.1% stabilizer by weight. The NP, BDNPA/F, is a eutectic mixture of bis(2,2-dinitropropyl) acetal and bis(2,2-dinitropropyl)formal. The stabilizer is diphenylamine (DPA) or Irganox 1010. The Estane, a polyester-polyurethane, slowly degrades with time. Knowledge of the effect of the Estane aging on the mechanical properties of the PBX 9501 is required to predict with confidence the useful lifetime of the explosive with respect to safety and reliability. A detailed master equation model of the chemical mechanisms and kinetics of the aging of Estane 5703 in PBX 9501 is being developed. Its output will be used as input into other models being developed to calculate the changes in the mechanical properties of the PBX.

  11. Application of a Genetic Algorithm to the Optimization of Rate Constants in Chemical Kinetic Models for Combustion Simulation of HCCI Engines

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Kyu; Ito, Kazuma; Yoshihara, Daisuke; Wakisaka, Tomoyuki

    For numerically predicting the combustion processes in homogeneous charge compression ignition (HCCI) engines, practical chemical kinetic models have been explored. A genetic algorithm (GA) has been applied to the optimization of the rate constants in detailed chemical kinetic models, and a detailed kinetic model (592 reactions) for gasoline reference fuels with arbitrary octane number between 60 and 100 has been obtained from the detailed reaction schemes for iso-octane and n-heptane proposed by Golovitchev. The ignition timing in a gasoline HCCI engine has been predicted reasonably well by zero-dimensional simulation using the CHEMKIN code with this detailed kinetic model. An original reduced reaction scheme (45 reactions) for dimethyl ether (DME) has been derived from Curran’s detailed scheme, and the combustion process in a DME HCCI engine has been predicted reasonably well in a practical computation time by three-dimensional simulation using the authors’ GTT code, which has been linked to the CHEMKIN subroutines with the proposed reaction scheme and also has adopted a modified eddy dissipation combustion model.

  12. S3 and S4 abundances and improved chemical kinetic model for the lower atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2013-07-01

    Mixing ratios of S3 and S4 are obtained from reanalysis of the spectra of true absorption in the visible range retrieved by Maiorov et al. (Maiorov, B.S. et al. [2005]. Solar Syst. Res. 39, 267-282) from the Venera 11 observations. These mixing ratios are fS3 = 11 ± 3 ppt at 3-10 km and 18 ± 3 ppt at 10-19 km, fS4 = 4 ± 4 ppt at 3-10 km and 6 ± 2 ppt at 10-19 km, and show a steep decrease in both S3 and S4 above 19 km. Photolysis rates of S3 and S4 at various altitudes are calculated using the Venera 11 spectra and constant photolysis yields as free parameters. The chemical kinetic model for the Venus lower atmosphere (Krasnopolsky, V.A. [2007]. Icarus 191, 25-37) has been improved by inclusion of the S4 cycle from Yung et al. (Yung, Y.L. et al. [2009]. J. Geophys. Res. 114, E00B34), reduction of the H2SO4 and CO fluxes at the upper boundary of 47 km by a factor of 4 in accord with the recent photochemical models for the middle atmosphere, by using a closed lower boundary for OCS instead of a free parameter for this species at the surface, and some minor updates. Our model with the S4 cycle but without the SO3 + 2 OCS reaction suggested by Krasnopolsky and Pollack (Krasnopolsky, V.A., Pollack, J.B. [1994]. Icarus 109, 58-78) disagrees with the observations of OCS, CO, S3, and S4. However, inclusion of the S4 cycle improves the model fit to all observational constraints. The best-fit activation energy of 7800 K for thermolysis of S4 supports the S4 enthalpy from Mills (Mills, K.C. [1974]. Thermodynamic Data for Inorganic Sulfides, Selenides and Tellurides. Butterworths, London). Chemistry of the Venus lower atmosphere is initiated by disequilibrium products H2SO4 and CO from the middle atmosphere, photolysis of S3 and S4, and thermochemistry in the lowest scale height. The chemistry is mostly driven by sulfur that is formed in a slow reaction SO + SO, produces OCS, and results in dramatic changes in abundances of OCS, CO, and free sulfur allotropes. The SX + OCS

  13. Establishment of a finite element model for extracting chemical reaction kinetics in a micro-flow injection system with high throughput sampling.

    PubMed

    Wu, Zeng-Qiang; Du, Wen-Bin; Li, Jin-Yi; Xia, Xing-Hua; Fang, Qun

    2015-08-01

    Numerical simulation can provide valuable insights for complex microfluidic phenomena coupling mixing and diffusion processes. Herein, a novel finite element model (FEM) has been established to extract chemical reaction kinetics in a microfluidic flow injection analysis (micro-FIA) system using high throughput sample introduction. To reduce the computation burden, the finite element mesh generation is performed with different scales based on the different geometric sizes of micro-FIA. In order to study the contribution of chemical reaction kinetics under non-equilibrium condition, a pseudo-first-order chemical kinetics equation is adopted in the numerical simulations. The effect of reactants diffusion on reaction products is evaluated, and the results demonstrate that the Taylor dispersion plays a determining role in the micro-FIA system. In addition, the effects of flow velocity and injection volume on the reaction product are also simulated. The simulated results agree well with the ones from experiments. Although gravity driven flow is used to the numerical model in the present study, the FEM model also can be applied into the systems with other driving forces such as pressure. Therefore, the established FEM model will facilitate the understanding of reaction mechanism in micro-FIA systems and help us to optimize the manifold of micro-FIA systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Modelling of the physico-chemical behaviour of clay minerals with a thermo-kinetic model taking into account particles morphology in compacted material.

    NASA Astrophysics Data System (ADS)

    Sali, D.; Fritz, B.; Clément, C.; Michau, N.

    2003-04-01

    Modelling of fluid-mineral interactions is largely used in Earth Sciences studies to better understand the involved physicochemical processes and their long-term effect on the materials behaviour. Numerical models simplify the processes but try to preserve their main characteristics. Therefore the modelling results strongly depend on the data quality describing initial physicochemical conditions for rock materials, fluids and gases, and on the realistic way of processes representations. The current geo-chemical models do not well take into account rock porosity and permeability and the particle morphology of clay minerals. In compacted materials like those considered as barriers in waste repositories, low permeability rocks like mudstones or compacted powders will be used : they contain mainly fine particles and the geochemical models used for predicting their interactions with fluids tend to misjudge their surface areas, which are fundamental parameters in kinetic modelling. The purpose of this study was to improve how to take into account the particles morphology in the thermo-kinetic code KINDIS and the reactive transport code KIRMAT. A new function was integrated in these codes, considering the reaction surface area as a volume depending parameter and the calculated evolution of the mass balance in the system was coupled with the evolution of reactive surface areas. We made application exercises for numerical validation of these new versions of the codes and the results were compared with those of the pre-existing thermo-kinetic code KINDIS. Several points are highlighted. Taking into account reactive surface area evolution during simulation modifies the predicted mass transfers related to fluid-minerals interactions. Different secondary mineral phases are also observed during modelling. The evolution of the reactive surface parameter helps to solve the competition effects between different phases present in the system which are all able to fix the chemical

  15. Boron combustion model development with kinetic sensitivity analysis and measurement of key chemical-rate parameters. Final report, 1 Jan 88-31 Dec 90

    SciTech Connect

    Brown, R.C.; Kolb, C.E.; Cho, S.Y.; Yetter, R.A.; Rabitz, H.R.

    1991-01-01

    This report presents kinetics models for the chemically facilitated gasification of the ubiguitous boron oxide coating that inhibits particulate boron ignition and the second stage high temperature boron surface burning that occurs once the oxide coating has been removed. These models include a homogeneous gas phase oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multicomponent gas phase diffusion and heterogeneous reactions between gas phase oxidation products and the boron oxide/boron surface. Kinetic mechanisms are formulated to describe the heterogeneous surface reactions for both B2O3(1) and B(s) surfaces in terms of simple adsorption and desorption reaction steps. Thermochemical parameters for these reaction steps are estimated from the current heats of formation and gas phase bond energies for the major reactants. Reaction rate parameters are estimated from available experimental data or using elementary transition state theory arguments.

  16. Chemical kinetic modeling of the oxidation of large alkane fuels: n-octane and iso-octane

    SciTech Connect

    Axelsson, E.I.; Brezinsky, K.; Dryer, F.L.; Pitz, W.J.; Westbrook, C.K.

    1986-01-13

    The development of detailed chemical kinetic reaction mechanisms for oxidation of n-octane and iso-octane is described, with emphasis on the factors which are specific to many large hydrocarbon fuel molecules. Elements which are of particular importance are found to include site-specific abstraction of H atoms, radical isomerization of alkyl radicals by internal H atom abstraction, and rapid ..beta..-scission of the alkyl radicals. These features, combined with distinctions in the types of intermediate olefin species produced, are used to explain the significant differences in the rate of oxidation between n-octane and iso-octane. 24 refs., 3 figs., 1 tab.

  17. Kinetic Monte Carlo simulations of anisotropic Si(100) etching: Modeling the chemical origins of characteristic etch morphologies.

    PubMed

    Gupta, Ankush; Aldinger, Brandon S; Faggin, Marc F; Hines, Melissa A

    2010-07-28

    An atomistic, chemically realistic, kinetic Monte Carlo simulator of anisotropic Si(100) etching was developed. Surface silicon atoms were classified on the basis of their local structure, and all atoms of each class were etched with the same rate. A wide variety of morphologies, including rough, striped, and hillocked, was observed. General reactivity trends were correlated with specific morphological features. The production of long rows of unstrained dihydride species, recently observed in NH(4)F (aq) etching of Si(100), could only be explained by the rapid etching of dihydrides that are adjacent to (strained) monohydrides-so-called "alpha-dihydrides." Some etch kinetics promoted the formation of {111}-microfaceted pyramidal hillocks, similar in structure to those observed experimentally during Si(100) etching. Pyramid formation was intrinsic to the etch kinetics. In contrast with previously postulated mechanisms of pyramid formation, no masking agent (e.g., impurity, gas bubble) was required. Pyramid formation was explained in terms of the slow etch rate of the {111} sides, {110} edges, and the dihydride species that terminated the apex of the pyramid. As a result, slow etching of Si(111) surfaces was a necessary, but insufficient, criterion for microfacet formation on Si(100) surfaces.

  18. Oxidative desulfurization: kinetic modelling.

    PubMed

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

    2009-01-30

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

  19. Inflation Rates, Car Devaluation, and Chemical Kinetics

    NASA Astrophysics Data System (ADS)

    Pogliani, Lionello; Berberan-Santos, Màrio N.

    1996-10-01

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

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

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Fegley, Bruce, Jr.

    1990-05-01

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

  2. Chemical Dosing and First-Order Kinetics

    ERIC Educational Resources Information Center

    Hladky, Paul W.

    2011-01-01

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

  3. Chemical Dosing and First-Order Kinetics

    ERIC Educational Resources Information Center

    Hladky, Paul W.

    2011-01-01

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

  4. Chemical Kinetic Characterization of Combustion Toluene

    SciTech Connect

    Pitz, W J; Seiser, R; Bozzelli, J W; Da Costa, I; Fournet, R; Billaud, F; Battin-Leclerc, F; Seshadri, K; Westbrook, C K

    2001-03-20

    A study is performed to elucidate the chemical kinetic mechanism of combustion of toluene. A detailed chemical kinetic mechanism for toluene was improved by adding a more accurate description of the phenyl + O{sub 2} reaction channels. Results of the chemical kinetic mechanism are compared with experimental data obtained from premixed and nonpremixed systems. Under premixed conditions, predicted ignition delay times are compared with new experimental data obtained in shock tube. Also, calculated species concentration histories are compared to experimental flow reactor data from the literature. Critical conditions of extinction and ignition were measured in strained laminar flows under nonpremixed conditions in the counterflow configuration. Numerical calculations are performed using the chemical kinetic mechanism at conditions corresponding to those in the experiments. Critical conditions of extinction and ignition are predicted and compared with the experimental data. For both premixed and nonpremixed systems, sensitivity analysis was used to identify the reaction rate constants that control the overall rate of oxidation in each of the systems considered.

  5. Kinetic Modeling of Biological Systems

    PubMed Central

    Petzold, Linda; Pettigrew, Michel F.

    2010-01-01

    The dynamics of how the constituent components of a natural system interact defines the spatio-temporal response of the system to stimuli. Modeling the kinetics of the processes that represent a biophysical system has long been pursued with the aim of improving our understanding of the studied system. Due to the unique properties of biological systems, in addition to the usual difficulties faced in modeling the dynamics of physical or chemical systems, biological simulations encounter difficulties that result from intrinsic multiscale and stochastic nature of the biological processes. This chapter discusses the implications for simulation of models involving interacting species with very low copy numbers, which often occur in biological systems and give rise to significant relative fluctuations. The conditions necessitating the use of stochastic kinetic simulation methods and the mathematical foundations of the stochastic simulation algorithms are presented. How the well-organized structural hierarchies often seen in biological systems can lead to multiscale problems, and possible ways to address the encountered computational difficulties are discussed. We present the details of the existing kinetic simulation methods, and discuss their strengths and shortcomings. A list of the publicly available kinetic simulation tools and our reflections for future prospects are also provided. PMID:19381542

  6. Kinetic Modeling of Biological Systems

    SciTech Connect

    Resat, Haluk; Petzold, Linda; Pettigrew, Michel F.

    2009-04-21

    The dynamics of how its constituent components interact define the spatio-temporal response of a natural system to stimuli. Modeling the kinetics of the processes that represent a biophysical system has long been pursued with the aim of improving our understanding of the studied system. Due to the unique properties of biological systems, in addition to the usual difficulties faced in modeling the dynamics of physical or chemical systems, biological simulations encounter difficulties that result from intrinsic multiscale and stochastic nature of the biological processes. This chapter discusses the implications for simulation of models involving interacting species with very low copy numbers, which often occur in biological systems and give rise to significant relative fluctuations. The conditions necessitating the use of stochastic kinetic simulation methods and the mathematical foundations of the stochastic simulation algorithms are presented. How the well-organized structural hierarchies often seen in biological systems can lead to multiscale problems, and possible ways to address the encountered computational difficulties are discussed. We present the details of the existing kinetic simulation methods, and discuss their strengths and shortcomings. A list of the publicly available kinetic simulation tools and our reflections for future prospects are also provided.

  7. Technical note: Monte Carlo genetic algorithm (MCGA) for model analysis of multiphase chemical kinetics to determine transport and reaction rate coefficients using multiple experimental data sets

    NASA Astrophysics Data System (ADS)

    Berkemeier, Thomas; Ammann, Markus; Krieger, Ulrich K.; Peter, Thomas; Spichtinger, Peter; Pöschl, Ulrich; Shiraiwa, Manabu; Huisman, Andrew J.

    2017-06-01

    We present a Monte Carlo genetic algorithm (MCGA) for efficient, automated, and unbiased global optimization of model input parameters by simultaneous fitting to multiple experimental data sets. The algorithm was developed to address the inverse modelling problems associated with fitting large sets of model input parameters encountered in state-of-the-art kinetic models for heterogeneous and multiphase atmospheric chemistry. The MCGA approach utilizes a sequence of optimization methods to find and characterize the solution of an optimization problem. It addresses an issue inherent to complex models whose extensive input parameter sets may not be uniquely determined from limited input data. Such ambiguity in the derived parameter values can be reliably detected using this new set of tools, allowing users to design experiments that should be particularly useful for constraining model parameters. We show that the MCGA has been used successfully to constrain parameters such as chemical reaction rate coefficients, diffusion coefficients, and Henry's law solubility coefficients in kinetic models of gas uptake and chemical transformation of aerosol particles as well as multiphase chemistry at the atmosphere-biosphere interface. While this study focuses on the processes outlined above, the MCGA approach should be portable to any numerical process model with similar computational expense and extent of the fitting parameter space.

  8. Kinetic studies of elementary chemical reactions

    SciTech Connect

    Durant, J.L. Jr.

    1993-12-01

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

  9. The H-theorem for the physico-chemical kinetic equations with discrete time and for their generalizations

    NASA Astrophysics Data System (ADS)

    Adzhiev, S. Z.; Melikhov, I. V.; Vedenyapin, V. V.

    2017-08-01

    In this paper the generalizations of the physico-chemical kinetics equations, including classical and quantum physico-chemical kinetics, coagulation-fragmentation equations, discrete velocity models of classical and quantum kinetic equation and, generally speaking, all discrete physico-chemical kinetics is considered. We make time discrete in these equations and prove the H-theorem.

  10. A high temperature and atmospheric pressure experimental and detailed chemical kinetic modelling study of 2-methyl furan oxidation

    PubMed Central

    Somers, Kieran P.; Simmie, John M.; Gillespie, Fiona; Burke, Ultan; Connolly, Jessica; Metcalfe, Wayne K.; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Curran, Henry J.

    2013-01-01

    An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.0 for mixtures of 1% fuel in argon in the temperature range 1200–1800 K at atmospheric pressure. Laminar burning velocities were determined using the heat-flux method for mixtures of 2MF in air at equivalence ratios of 0.55–1.65, initial temperatures of 298–398 K and atmospheric pressure. A detailed chemical kinetic mechanism consisting of 2059 reactions and 391 species has been constructed to describe the oxidation of 2MF and is used to simulate experiment. Accurate reproduction of the experimental data has been obtained over all conditions with the developed mechanism. Rate of production and sensitivity analyses have been carried out to identify important consumption pathways of the fuel and key kinetic parameters under these conditions. The reactions of hydrogen atom with the fuel are highlighted as important under all experimental conditions studied, with abstraction by the hydrogen atom promoting reactivity and hydrogen atom addition to the furan ring inhibiting reactivity. This work, to the authors knowledge, is the first to combine theoretical and experimental work to describe the oxidation of any of the alkylated furans. The mechanism developed herein to describe 2MF combustion should also function as a sub-mechanism to describe the oxidation of 2,5-dimethyl furan whilst also providing key insights into the oxidation of this similar biofuel candidate. PMID:23814505

  11. Mechanism of chemical degradation and determination of solubility by kinetic modeling of the highly unstable sesquiterpene lactone nobilin in different media.

    PubMed

    Thormann, Ursula; De Mieri, Maria; Neuburger, Markus; Verjee, Sheela; Altmann, Peter; Hamburger, Matthias; Imanidis, Georgios

    2014-10-01

    The objective of this work was first to investigate the chemical degradation of the sesquiterpene lactone nobilin and determine its solubility under conditions of concurrent degradation for partially amorphous starting material; second, to determine the effect of biorelevant media used in the in vitro measurement of intestinal absorption on degradation and solubility of nobilin. Purely aqueous medium (aq-TMCaco ), fasted and fed state simulated intestinal fluid (FaSSIF-TMCaco and FeSSIF-TMCaco ), and two liposomal formulations (LiposomesFaSSIF and LiposomesFeSSIF ) with the same lipid concentration as FaSSIF-TMCaco and FeSSIF-TMCaco were used. Degradation products were identified by nuclear magnetic resonance and X-ray crystallography and the order of reaction kinetics was determined. Solubility was deduced with a mathematical model encompassing dissolution, degradation, and reprecipitation kinetics that took into account particle size distribution of the solid material. Degradation mechanism of nobilin involved water-catalyzed opening of the lactone ring and transannular cyclization resulting in five degradation products. Degradation followed first-order kinetics in aq-TMCaco and FaSSIF-TMCaco , and higher-order kinetics in FeSSIF-TMCaco and the two liposomal formulations, whereas degradation in the latter media was diminished. Solubility of nobilin increased in the order: aq-TMCaco < FaSSIF-TMCaco , < LiposomesFaSSIF < FeSSIF-TMCaco < LiposomesFeSSIF . Improvement of stability and solubility was consistent with the incorporation of the nobilin molecule into colloidal lipid particles. The developed kinetic model is proposed to be a useful tool for deducing solubility under dynamic conditions. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  12. Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

    SciTech Connect

    Westbrook, C.K.

    2000-07-07

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

  13. pyJac: Analytical Jacobian generator for chemical kinetics

    NASA Astrophysics Data System (ADS)

    Niemeyer, Kyle E.; Curtis, Nicholas J.; Sung, Chih-Jen

    2017-06-01

    Accurate simulations of combustion phenomena require the use of detailed chemical kinetics in order to capture limit phenomena such as ignition and extinction as well as predict pollutant formation. However, the chemical kinetic models for hydrocarbon fuels of practical interest typically have large numbers of species and reactions and exhibit high levels of mathematical stiffness in the governing differential equations, particularly for larger fuel molecules. In order to integrate the stiff equations governing chemical kinetics, generally reactive-flow simulations rely on implicit algorithms that require frequent Jacobian matrix evaluations. Some in situ and a posteriori computational diagnostics methods also require accurate Jacobian matrices, including computational singular perturbation and chemical explosive mode analysis. Typically, finite differences numerically approximate these, but for larger chemical kinetic models this poses significant computational demands since the number of chemical source term evaluations scales with the square of species count. Furthermore, existing analytical Jacobian tools do not optimize evaluations or support emerging SIMD processors such as GPUs. Here we introduce pyJac, a Python-based open-source program that generates analytical Jacobian matrices for use in chemical kinetics modeling and analysis. In addition to producing the necessary customized source code for evaluating reaction rates (including all modern reaction rate formulations), the chemical source terms, and the Jacobian matrix, pyJac uses an optimized evaluation order to minimize computational and memory operations. As a demonstration, we first establish the correctness of the Jacobian matrices for kinetic models of hydrogen, methane, ethylene, and isopentanol oxidation (number of species ranging 13-360) by showing agreement within 0.001% of matrices obtained via automatic differentiation. We then demonstrate the performance achievable on CPUs and GPUs using py

  14. Secondary organic aerosol formation from aqueous chemistry of glyoxal, methylglyoxal, and glycolaldehyde in atmospheric waters: Chemical insights and kinetic model studies

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Altieri, K. E.; Perri, M. J.; Carlton, A. G.; Seitzinger, S.; Turpin, B. J.

    2010-12-01

    Aqueous chemistry in clouds, fog and aerosol water is now considered an important source of secondary organic aerosol (SOA). Modeling studies confirm that the underlying chemistry is kinetically favorable. Laboratory studies have begun to validate and refine the aqueous chemical mechanisms. Field observations, such as the atmospheric abundance of oxalate, ubiquitous presence of high molecular weight or humic-like substances (HULIS), high ambient O/C ratios, and correlations between SOA and aerosol liquid water content provide atmospheric evidence for SOA formation through aqueous chemistry. In the aqueous phase, small and volatile (C2-C3) but water soluble organic compounds undergo radical (photooxidation) and non-radical (acid/base catalysis) reactions, or reactions with inorganic constituents (sulfate, nitrate or ammonia) to form low volatility products including organic acids, organic-inorganic complexes and oligomers. These products are expected to remain at least in part in the particle phase after water evaporation, forming SOA. While not traditionally considered to be SOA precursors, atmospherically abundant and water soluble organic compounds like glyoxal (C2), methylglyoxal (C3) and glycolaldehyde (C2) have great potential to form SOA via aqueous chemistry. This paper presents a unified reaction mechanism and full kinetic model for the aqueous-phase reaction of glyoxal, methylglyoxal, glycolaldehyde, pyruvic acid and acetic acid with OH radical and validates this mechanism, in part, with laboratory experiments. At cloud relevant concentrations (~1E-6 M), the major product is oxalic acid and formation is well predicted by the previous cloud model (Lim et al., 2005). As concentrations increase radical-radical reactions become increasingly important and yield higher molecular weight products. The full kinetic model suggests that SOA formed in aerosol water (where organic concentrations are > 1 M) is comprised of high molecular weight multifunctional compounds

  15. Reduced chemical kinetics for propane combustion

    NASA Technical Reports Server (NTRS)

    Ying, Shuh-Jing; Nguyen, Hung Lee

    1990-01-01

    It is pointed out that a detailed chemical kinetics mechanism for the combustion of propane consists of 40 chemical species and 118 elementary chemical reactions. An attempt is made to reduce the number of chemical species and elementary chemical reactions so that the computer run times and storage requirements may be greatly reduced in three-dimensional gas turbine combustion flow calculations, while maintaining accurate predictions of the propane combustion and exhaust emissions. By way of a sensitivity analysis, the species of interest and chemical reactions are classified in descending order of importance. Nineteen species are chosen, and their pressure, temperature, and concentration profiles are presented for the reduced mechanisms, which are then compared with those from the full 118 reactions. It is found that 45 reactions involving 27 species have to be kept for comparable agreement. A comparison of the results obtained from the 45 reactions to that of the full 118 shows that the pressure and temperature profiles and concentrations of C3H8, O2, N2, H2O, CO, and CO2 are within 10 percent of maximum change.

  16. Simulating Chemical Kinetics Without Differential Equations: A Quantitative Theory Based on Chemical Pathways.

    PubMed

    Bai, Shirong; Skodje, Rex T

    2017-08-17

    A new approach is presented for simulating the time-evolution of chemically reactive systems. This method provides an alternative to conventional modeling of mass-action kinetics that involves solving differential equations for the species concentrations. The method presented here avoids the need to solve the rate equations by switching to a representation based on chemical pathways. In the Sum Over Histories Representation (or SOHR) method, any time-dependent kinetic observable, such as concentration, is written as a linear combination of probabilities for chemical pathways leading to a desired outcome. In this work, an iterative method is introduced that allows the time-dependent pathway probabilities to be generated from a knowledge of the elementary rate coefficients, thus avoiding the pitfalls involved in solving the differential equations of kinetics. The method is successfully applied to the model Lotka-Volterra system and to a realistic H2 combustion model.

  17. Simulating flame lift-off characteristics of diesel and biodiesel fuels using detailed chemical-kinetic mechanisms and LES turbulence model.

    SciTech Connect

    Som, S; Longman, D. E.; Luo, Z; Plomer, M; Lu, T; Senecal, P.K.; Pomraning, E

    2012-01-01

    Combustion in direct-injection diesel engines occurs in a lifted, turbulent diffusion flame mode. Numerous studies indicate that the combustion and emissions in such engines are strongly influenced by the lifted flame characteristics, which are in turn determined by fuel and air mixing in the upstream region of the lifted flame, and consequently by the liquid breakup and spray development processes. From a numerical standpoint, these spray combustion processes depend heavily on the choice of underlying spray, combustion, and turbulence models. The present numerical study investigates the influence of different chemical kinetic mechanisms for diesel and biodiesel fuels, as well as Reynolds-averaged Navier-Stokes (RANS) and large eddy simulation (LES) turbulence models on predicting flame lift-off lengths (LOLs) and ignition delays. Specifically, two chemical kinetic mechanisms for n-heptane (NHPT) and three for biodiesel surrogates are investigated. In addition, the RNG k-{epsilon} (RANS) model is compared to the Smagorinsky based LES turbulence model. Using adaptive grid resolution, minimum grid sizes of 250 {micro}m and 125 {micro}m were obtained for the RANS and LES cases respectively. Validations of these models were performed against experimental data from Sandia National Laboratories in a constant volume combustion chamber. Ignition delay and flame lift-off validations were performed at different ambient temperature conditions. The LES model predicts lower ignition delays and qualitatively better flame structures compared to the RNG k-{epsilon} model. The use of realistic chemistry and a ternary surrogate mixture, which consists of methyl decanoate, methyl 9-decenoate, and NHPT, results in better predicted LOLs and ignition delays. For diesel fuel though, only marginal improvements are observed by using larger size mechanisms. However, these improved predictions come at a significant increase in computational cost.

  18. Perspective: Stochastic algorithms for chemical kinetics

    PubMed Central

    Gillespie, Daniel T.; Hellander, Andreas; Petzold, Linda R.

    2013-01-01

    We outline our perspective on stochastic chemical kinetics, paying particular attention to numerical simulation algorithms. We first focus on dilute, well-mixed systems, whose description using ordinary differential equations has served as the basis for traditional chemical kinetics for the past 150 years. For such systems, we review the physical and mathematical rationale for a discrete-stochastic approach, and for the approximations that need to be made in order to regain the traditional continuous-deterministic description. We next take note of some of the more promising strategies for dealing stochastically with stiff systems, rare events, and sensitivity analysis. Finally, we review some recent efforts to adapt and extend the discrete-stochastic approach to systems that are not well-mixed. In that currently developing area, we focus mainly on the strategy of subdividing the system into well-mixed subvolumes, and then simulating diffusional transfers of reactant molecules between adjacent subvolumes together with chemical reactions inside the subvolumes. PMID:23656106

  19. Modelling Heart Rate Kinetics

    PubMed Central

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  20. Modelling heart rate kinetics.

    PubMed

    Zakynthinaki, Maria S

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).

  1. Mechanistic quantitative structure-activity relationship model for the photoinduced toxicity of polycyclic aromatic hydrocarbons. 1: Physical model based on chemical kinetics in a two-compartment system

    SciTech Connect

    Krylov, S.N.; Huang, X.D.; Zeiler, L.F.; Dixon, D.G.; Greenberg, B.M.

    1997-11-01

    A quantitative structure-activity relationship model for the photoinduced toxicity of 16 polycyclic aromatic hydrocarbons (PAHs) to duckweed (Lemna gibba) in simulated solar radiation (SSR) was developed. Lemna gibba was chosen for this study because toxicity could be considered in two compartments: water column and leaf tissue. Modeling of photoinduced toxicity was described by photochemical reactions between PAHs and a hypothetical group of endogenous biomolecules (G) required for normal growth, with damage to G by PAHs and/or photomodified PAHs in SSR resulting in impaired growth. The reaction scheme includes photomodification of PAHs, uptake of PAHs into leaves, triplet-state formation of intact PAHs, photosensitization reactions that damage G, and reactions between photomodified PAHs and G. The assumptions used were: the PAH photomodification rate is slower than uptake of chemicals into leaves, the PAH concentration in aqueous solution is nearly constant during a toxicity test, the fluence rate of actinic radiation is lower within leaves than in the aqueous phase, and the toxicity of intact PAHs in the dark is negligible. A series of differential equations describing the reaction kinetics of intact and photomodifed PAHs with G was derived. The resulting equation for PAH toxicity was a function of treatment period, initial PAH concentration, relative absorbance of SSR by each PAH, quantum yield for formation of triplet-state PAH, and rate of PAH photomodification. Data for growth in the presence of intact and photomodified PAHs were used to empirically solve for a photosensitization constant (PSC) and a photomodification constant (PMC) for each of the 16 PAHs tested. For 9 PAHs the PMC dominates and for 7 PAHs the PSC dominates.

  2. High Fidelity Modeling of Turbulent Mixing and Chemical Kinetics Interactions in a Post-Detonation Flow Field

    NASA Astrophysics Data System (ADS)

    Sinha, Neeraj; Zambon, Andrea; Ott, James; Demagistris, Michael

    2015-06-01

    Driven by the continuing rapid advances in high-performance computing, multi-dimensional high-fidelity modeling is an increasingly reliable predictive tool capable of providing valuable physical insight into complex post-detonation reacting flow fields. Utilizing a series of test cases featuring blast waves interacting with combustible dispersed clouds in a small-scale test setup under well-controlled conditions, the predictive capabilities of a state-of-the-art code are demonstrated and validated. Leveraging physics-based, first principle models and solving large system of equations on highly-resolved grids, the combined effects of finite-rate/multi-phase chemical processes (including thermal ignition), turbulent mixing and shock interactions are captured across the spectrum of relevant time-scales and length scales. Since many scales of motion are generated in a post-detonation environment, even if the initial ambient conditions are quiescent, turbulent mixing plays a major role in the fireball afterburning as well as in dispersion, mixing, ignition and burn-out of combustible clouds in its vicinity. Validating these capabilities at the small scale is critical to establish a reliable predictive tool applicable to more complex and large-scale geometries of practical interest.

  3. Three-stage autoignition of gasoline in an HCCI engine: An experimental and chemical kinetic modeling investigation

    SciTech Connect

    Machrafi, Hatim; Cavadias, Simeon

    2008-12-15

    The alternative HCCI combustion mode presents a possible means for decreasing the pollution with respect to conventional gasoline or diesel engines, while maintaining the efficiency of a diesel engine or even increasing it. This paper investigates the possibility of using gasoline in an HCCI engine and analyzes the autoignition of gasoline in such an engine. The compression ratio that has been used is 13.5, keeping the inlet temperature at 70 C, varying the equivalence ratio from 0.3 to 0.54, and the EGR (represented by N{sub 2}) ratio from 0 to 37 vol%. For comparison, a PRF95 and a surrogate containing 11 vol% n-heptane, 59 vol% iso-octane, and 30 vol% toluene are used. A previously validated kinetic surrogate mechanism is used to analyze the experiments and to yield possible explanations to kinetic phenomena. From this work, it seems quite possible to use the high octane-rated gasoline for autoignition purposes, even under lean inlet conditions. Furthermore, it appeared that gasoline and its surrogate, unlike PRF95, show a three-stage autoignition. Since the PRF95 does not contain toluene, it is suggested by the kinetic mechanism that the benzyl radical, issued from toluene, causes this so-defined ''obstructed preignition'' and delaying thereby the final ignition for gasoline and its surrogate. The results of the kinetic mechanism supporting this explanation are shown in this paper. (author)

  4. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by (3)O2; Implications for Combustion Modeling and Simulation.

    PubMed

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

    2017-03-09

    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

  5. Evaluating temperature and fuel stratification for heat-release rate control in a reactivity-controlled compression-ignition engine using optical diagnostics and chemical kinetics modeling

    SciTech Connect

    Musculus, Mark P. B.; Kokjohn, Sage L.; Reitz, Rolf D.

    2015-04-23

    We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injection strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still significant

  6. Chemical Weathering Kinetics of Basalt on Venus

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1997-01-01

    The purpose of this project was to experimentally measure the kinetics for chemical weathering reactions involving basalt on Venus. The thermochemical reactions being studied are important for the CO2 atmosphere-lithosphere cycle on Venus and for the atmosphere-surface reactions controlling the oxidation state of the surface of Venus. These reactions include the formation of carbonate and scapolite minerals, and the oxidation of Fe-bearing minerals. These experiments and calculations are important for interpreting results from the Pioneer Venus, Magellan, Galileo flyby, Venera, and Vega missions to Venus, for interpreting results from Earth-based telescopic observations, and for the design of new Discovery class (e.g., VESAT) and New Millennium missions to Venus such as geochemical landers making in situ elemental and mineralogical analyses, and orbiters, probes and balloons making spectroscopic observations of the sub-cloud atmosphere of Venus.

  7. Optimization of KINETICS Chemical Computation Code

    NASA Technical Reports Server (NTRS)

    Donastorg, Cristina

    2012-01-01

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

  8. Chemical Conversion Pathways and Kinetic Modeling for the OH-Initiated Reaction of Triclosan in Gas-Phase

    PubMed Central

    Zhang, Xue; Zhang, Chenxi; Sun, Xiaomin; Kang, Lingyan; Zhao, Yan

    2015-01-01

    As a widely used antimicrobial additive in daily consumption, attention has been paid to the degradation and conversion of triclosan for a long time. The quantum chemistry calculation and the canonical variational transition state theory are employed to investigate the mechanism and kinetic property. Besides addition and abstraction, oxidation pathways and further conversion pathways are also considered. The OH radicals could degrade triclosan to phenols, aldehydes, and other easily degradable substances. The conversion mechanisms of triclosan to the polychlorinated dibenzopdioxin and furan (PCDD/Fs) and polychlorinated biphenyls (PCBs) are clearly illustrated and the toxicity would be strengthened in such pathways. Single radical and diradical pathways are compared to study the conversion mechanism of dichlorodibenzo dioxin (DCDD). Furthermore, thermochemistry is discussed in detail. Kinetic property is calculated and the consequent ratio of kadd/ktotal and kabs/ktotal at 298.15 K are 0.955 and 0.045, respectively. Thus, the OH radical addition reactions are predominant, the substitute position of OH radical on triclosan is very important to generate PCDD and furan, and biradical is also a vital intermediate to produce dioxin. PMID:25867482

  9. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect

    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.

  10. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect

    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.

  11. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect

    Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K.

    2008-08-15

    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 and co-workers 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. (author)

  12. Solid-state stability of spray-dried insulin powder for inhalation: chemical kinetics and structural relaxation modeling of Exubera above and below the glass transition temperature.

    PubMed

    Sadrzadeh, Negar; Miller, Danforth P; Lechuga-Ballesteros, David; Harper, Nancy J; Stevenson, Cynthia L; Bennett, David B

    2010-09-01

    The effect of temperature on the chemical stability of an amorphous spray-dried insulin powder formulation (Exubera) was evaluated in the solid state at constant moisture content. The chemical stability of the powder was assessed using reversed-phase high-performance liquid chromatography (RP-HPLC) and high-performance-size exclusion chromatography (HP-SEC). The major degradants in spray-dried insulin produced during heat stressing were identified as A21-desamidoinsulin (A21) and high molecular weight protein (HMWP). As expected, the rates of formation of A21 and HMWP were observed to increase with temperature. A stretched-time kinetic model (degradation rate is proportional to the square root of time) was applied to the degradant profiles above and below the glass transition temperature (T(g)) and apparent reaction rate constants were determined. Below T(g), isothermal enthalpy of relaxation measurements were used to assess the effect of temperature on molecular mobility. The formation of A21 and HMWP was found to follow an Arrhenius temperature dependence above and below the T(g). Comparison of reaction rate constants to those estimated from structural relaxation experiments suggests that the reaction pathways to form A21 and HMWP below the T(g) may be coupled with the molecular motions involved in structural relaxation.

  13. Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels

    DOE Data Explorer

    The central feature of the Combustion Chemistry project at LLNL is the development, validation, and application of detailed chemical kinetic reaction mechanisms for the combustion of hydrocarbon and other types of chemical fuels. For the past 30 years, LLNL's Chemical Sciences Division has built hydrocarbon mechanisms for fuels from hydrogen and methane through much larger fuels including heptanes and octanes. Other classes of fuels for which models have been developed include flame suppressants such as halons and organophosphates, and air pollutants such as soot and oxides of nitrogen and sulfur. Reaction mechanisms have been tested and validated extensively through comparisons between computed results and measured data from laboratory experiments (e.g., shock tubes, laminar flames, rapid compression machines, flow reactors, stirred reactors) and from practical systems (e.g., diesel engines, spark-ignition engines, homogeneous charge, compression ignition (HCCI) engines). These kinetic models are used to examine a wide range of combustion systems.

  14. Degradation of di(2-ethyl hexyl) phthalate by Fusarium culmorum: Kinetics, enzymatic activities and biodegradation pathway based on quantum chemical modelingpathway based on quantum chemical modeling.

    PubMed

    Ahuactzin-Pérez, Miriam; Tlecuitl-Beristain, Saúl; García-Dávila, Jorge; González-Pérez, Manuel; Gutiérrez-Ruíz, María Concepción; Sánchez, Carmen

    2016-10-01

    Di(2-ethylhexyl) phthalate (DEHP) is a plasticizer widely used in the manufacture of plastics, and it is an environmental contaminant. The specific growth rate (μ), maximum biomass (Xmax), biodegradation constant of DEHP (k), half-life (t1/2) of DEHP biodegradation and removal efficiency of DEHP, esterase and laccase specific activities, and enzymatic yield parameters were evaluated for Fusarium culmorum grown on media containing glucose and different concentrations of DEHP (0, 500 and 1000mg/L). The greatest μ and the largest Xmax occurred in media supplemented with 1000mg of DEHP/L. F. culmorum degraded 95% of the highest amount of DEHP tested (1000mg/L) within 60h of growth. The k and t1/2 were 0.024h(-1) and 28h, respectively, for both DEHP concentrations. The removal efficiency of DEHP was 99.8% and 99.9% for 1000 and 500mg/L, respectively. Much higher specific esterase activity than specific laccase activity was observed in all media tested. The compounds of biodegradation of DEHP were identified by GC-MS. A DEHP biodegradation pathway by F. culmorum was proposed on the basis of the intermolecular flow of electrons of the identified intermediate compounds using quantum chemical modeling. DEHP was fully metabolized by F. culmorum with butanediol as the final product. This fungus offers great potential in bioremediation of environments polluted with DEHP. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Maximum probability reaction sequences in stochastic chemical kinetic systems.

    PubMed

    Salehi, Maryam; Perkins, Theodore J

    2010-01-01

    The detailed behavior of many molecular processes in the cell, such as protein folding, protein complex assembly, and gene regulation, transcription and translation, can often be accurately captured by stochastic chemical kinetic models. We investigate a novel computational problem involving these models - that of finding the most-probable sequence of reactions that connects two or more states of the system observed at different times. We describe an efficient method for computing the probability of a given reaction sequence, but argue that computing most-probable reaction sequences is EXPSPACE-hard. We develop exact (exhaustive) and approximate algorithms for finding most-probable reaction sequences. We evaluate these methods on test problems relating to a recently-proposed stochastic model of folding of the Trp-cage peptide. Our results provide new computational tools for analyzing stochastic chemical models, and demonstrate their utility in illuminating the behavior of real-world systems.

  16. Maximum Probability Reaction Sequences in Stochastic Chemical Kinetic Systems

    PubMed Central

    Salehi, Maryam; Perkins, Theodore J.

    2010-01-01

    The detailed behavior of many molecular processes in the cell, such as protein folding, protein complex assembly, and gene regulation, transcription and translation, can often be accurately captured by stochastic chemical kinetic models. We investigate a novel computational problem involving these models – that of finding the most-probable sequence of reactions that connects two or more states of the system observed at different times. We describe an efficient method for computing the probability of a given reaction sequence, but argue that computing most-probable reaction sequences is EXPSPACE-hard. We develop exact (exhaustive) and approximate algorithms for finding most-probable reaction sequences. We evaluate these methods on test problems relating to a recently-proposed stochastic model of folding of the Trp-cage peptide. Our results provide new computational tools for analyzing stochastic chemical models, and demonstrate their utility in illuminating the behavior of real-world systems. PMID:21629860

  17. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    PubMed

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

  18. Modeling the chemical kinetics of high-pressure glow discharges in mixtures of helium with real air

    NASA Astrophysics Data System (ADS)

    Stalder, K. R.; Vidmar, R. J.; Nersisyan, G.; Graham, W. G.

    2006-05-01

    Atmospheric and near-atmospheric pressure glow discharges generated in both pure helium and helium-air mixtures have been studied using a plasma chemistry code originally developed for simulations of electron-beam-produced air plasmas. Comparisons are made with experimental data obtained from high-pressure glow discharges in helium-air mixtures developed by applying sinusoidal voltage wave forms between two parallel planar metallic electrodes covered by glass plates, with frequencies ranging from 10 to 50 kHz and electric field strengths up to 5 kV/cm. The code simulates the plasma chemistry following periodic pulsations of ionization in prescribed E/N environments. Many of the rate constants depend on gas temperature, electron temperature, and E/N. In helium plasmas with small amounts (~850 ppm) of air added, rapid conversion of atomic helium ions to molecular helium ions dominate the positive ion kinetics and these species are strongly modulated while the radical species are not. The charged and neutral species concentrations at atmospheric pressure with air impurity levels up to 10 000 ppm are predicted. The negative ion densities are very small but increase as the air impurity level is raised, which indicates that in helium-based systems operated in open air the concentration of negative ions would be significant. If water vapor at typical humidity levels is present as one of the impurities, hydrated cluster ions eventually comprise a significant fraction of the charged species.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Detailed Chemical Kinetic Mechanisms for Combustion of Oxygenated Fuels

    SciTech Connect

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

    2000-01-11

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

  1. A kinetic model of precipitate evolution

    SciTech Connect

    Rohrer, C.L.; Hyland, R.W. Jr.; Asta, M.D.; Foiles, S.M.

    1996-12-31

    Chemical reaction rate theory is used to model the kinetics of precipitation reactions in Al alloys, including the effects of continuous cooling and thermally generated point defects. The computational method models the processes of nucleation, growth, and coarsening within a single framework. Calculated time and temperature dependent precipitate number densities and sizes during the homogeneous precipitation of the Al{sub 3}Sc phase in an Al-.11 at% Sc alloy are shown to compare favorably with experimental observations.

  2. LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1994-01-01

    which provides the relationships between the predictions of a kinetics model and the input parameters of the problem. LSENS provides for efficient and accurate chemical kinetics computations and includes sensitivity analysis for a variety of problems, including nonisothermal conditions. LSENS replaces the previous NASA general chemical kinetics codes GCKP and GCKP84. LSENS is designed for flexibility, convenience and computational efficiency. A variety of chemical reaction models can be considered. The models include static system, steady one-dimensional inviscid flow, reaction behind an incident shock wave including boundary layer correction, and the perfectly stirred (highly backmixed) reactor. In addition, computations of equilibrium properties can be performed for the following assigned states, enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static problems LSENS computes sensitivity coefficients with respect to the initial values of the dependent variables and/or the three rates coefficient parameters of each chemical reaction. To integrate the ODEs describing chemical kinetics problems, LSENS uses the packaged code LSODE, the Livermore Solver for Ordinary Differential Equations, because it has been shown to be the most efficient and accurate code for solving such problems. The sensitivity analysis computations use the decoupled direct method, as implemented by Dunker and modified by Radhakrishnan. This method has shown greater efficiency and stability with equal or better accuracy than other methods of sensitivity analysis. LSENS is written in FORTRAN 77 with the exception of the NAMELIST extensions used for input. While this makes the code fairly machine independent, execution times on IBM PC compatibles would be unacceptable to most users. LSENS has been successfully implemented on a Sun4 running SunOS and a DEC VAX running VMS. With minor modifications, it should also be easily implemented on other

  3. LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1994-01-01

    which provides the relationships between the predictions of a kinetics model and the input parameters of the problem. LSENS provides for efficient and accurate chemical kinetics computations and includes sensitivity analysis for a variety of problems, including nonisothermal conditions. LSENS replaces the previous NASA general chemical kinetics codes GCKP and GCKP84. LSENS is designed for flexibility, convenience and computational efficiency. A variety of chemical reaction models can be considered. The models include static system, steady one-dimensional inviscid flow, reaction behind an incident shock wave including boundary layer correction, and the perfectly stirred (highly backmixed) reactor. In addition, computations of equilibrium properties can be performed for the following assigned states, enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static problems LSENS computes sensitivity coefficients with respect to the initial values of the dependent variables and/or the three rates coefficient parameters of each chemical reaction. To integrate the ODEs describing chemical kinetics problems, LSENS uses the packaged code LSODE, the Livermore Solver for Ordinary Differential Equations, because it has been shown to be the most efficient and accurate code for solving such problems. The sensitivity analysis computations use the decoupled direct method, as implemented by Dunker and modified by Radhakrishnan. This method has shown greater efficiency and stability with equal or better accuracy than other methods of sensitivity analysis. LSENS is written in FORTRAN 77 with the exception of the NAMELIST extensions used for input. While this makes the code fairly machine independent, execution times on IBM PC compatibles would be unacceptable to most users. LSENS has been successfully implemented on a Sun4 running SunOS and a DEC VAX running VMS. With minor modifications, it should also be easily implemented on other

  4. Evaluating temperature and fuel stratification for heat-release rate control in a reactivity-controlled compression-ignition engine using optical diagnostics and chemical kinetics modeling

    DOE PAGES

    Musculus, Mark P. B.; Kokjohn, Sage L.; Reitz, Rolf D.

    2015-04-23

    We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injectionmore » strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still

  5. Investigating the chemical mechanisms of the functionalization and fragmentation of hydrocarbons in the heterogeneous oxidation by OH using a stochastic kinetics model

    NASA Astrophysics Data System (ADS)

    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. GPU-based flow simulation with detailed chemical kinetics

    NASA Astrophysics Data System (ADS)

    Le, Hai P.; Cambier, Jean-Luc; Cole, Lord K.

    2013-03-01

    The current paper reports on the implementation of a numerical solver on the Graphic Processing Units (GPUs) to model reactive gas mixtures with detailed chemical kinetics. The solver incorporates high-order finite volume methods for solving the fluid dynamical equations coupled with stiff source terms. The chemical kinetics are solved implicitly via an operator-splitting method. We explored different approaches in implementing a fast kinetics solver on the GPU. The detail of the implementation is discussed in the paper. The solver is tested with two high-order shock capturing schemes: MP5 (Suresh and Huynh, 1997) [9] and ADERWENO (Titarev and Toro, 2005) [10]. Considering only the fluid dynamics calculation, the speed-up factors obtained are 30 for the MP5 scheme and 55 for ADERWENO scheme. For the fully-coupled solver, the performance gain depended on the size of the reaction mechanism. Two different examples of chemistry were explored. The first mechanism consisted of 9 species and 38 reactions, resulting in a speed-up factor up to 35. The second, larger mechanism, consisted of 36 species and 308 reactions, resulting in a speed-up factor of up to 40.

  7. Analytical Derivation of Moment Equations in Stochastic Chemical Kinetics

    PubMed Central

    Sotiropoulos, Vassilios; Kaznessis, Yiannis N.

    2011-01-01

    The master probability equation captures the dynamic behavior of a variety of stochastic phenomena that can be modeled as Markov processes. Analytical solutions to the master equation are hard to come by though because they require the enumeration of all possible states and the determination of the transition probabilities between any two states. These two tasks quickly become intractable for all but the simplest of systems. Instead of determining how the probability distribution changes in time, we can express the master probability distribution as a function of its moments, and, we can then write transient equations for the probability distribution moments. In 1949, Moyal defined the derivative, or jump, moments of the master probability distribution. These are measures of the rate of change in the probability distribution moment values, i.e. what the impact is of any given transition between states on the moment values. In this paper we present a general scheme for deriving analytical moment equations for any N-dimensional Markov process as a function of the jump moments. Importantly, we propose a scheme to derive analytical expressions for the jump moments for any N-dimensional Markov process. To better illustrate the concepts, we focus on stochastic chemical kinetics models for which we derive analytical relations for jump moments of arbitrary order. Chemical kinetics models are widely used to capture the dynamic behavior of biological systems. The elements in the jump moment expressions are a function of the stoichiometric matrix and the reaction propensities, i.e the probabilistic reaction rates. We use two toy examples, a linear and a non-linear set of reactions, to demonstrate the applicability and limitations of the scheme. Finally, we provide an estimate on the minimum number of moments necessary to obtain statistical significant data that would uniquely determine the dynamics of the underlying stochastic chemical kinetic system. The first two moments

  8. Analytical Derivation of Moment Equations in Stochastic Chemical Kinetics.

    PubMed

    Sotiropoulos, Vassilios; Kaznessis, Yiannis N

    2011-02-01

    The master probability equation captures the dynamic behavior of a variety of stochastic phenomena that can be modeled as Markov processes. Analytical solutions to the master equation are hard to come by though because they require the enumeration of all possible states and the determination of the transition probabilities between any two states. These two tasks quickly become intractable for all but the simplest of systems. Instead of determining how the probability distribution changes in time, we can express the master probability distribution as a function of its moments, and, we can then write transient equations for the probability distribution moments. In 1949, Moyal defined the derivative, or jump, moments of the master probability distribution. These are measures of the rate of change in the probability distribution moment values, i.e. what the impact is of any given transition between states on the moment values. In this paper we present a general scheme for deriving analytical moment equations for any N-dimensional Markov process as a function of the jump moments. Importantly, we propose a scheme to derive analytical expressions for the jump moments for any N-dimensional Markov process. To better illustrate the concepts, we focus on stochastic chemical kinetics models for which we derive analytical relations for jump moments of arbitrary order. Chemical kinetics models are widely used to capture the dynamic behavior of biological systems. The elements in the jump moment expressions are a function of the stoichiometric matrix and the reaction propensities, i.e the probabilistic reaction rates. We use two toy examples, a linear and a non-linear set of reactions, to demonstrate the applicability and limitations of the scheme. Finally, we provide an estimate on the minimum number of moments necessary to obtain statistical significant data that would uniquely determine the dynamics of the underlying stochastic chemical kinetic system. The first two moments

  9. Chemical kinetic and photochemical data for use in stratospheric modeling evaluation number 4: NASA panel for data evaluation

    NASA Technical Reports Server (NTRS)

    1981-01-01

    Evaluated sets of rate constants and photochemical cross sections compiled by the Panel are presented. The primary application of the data is in the modelling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  10. Stochastic kinetic mean field model

    NASA Astrophysics Data System (ADS)

    Erdélyi, Zoltán; Pasichnyy, Mykola; Bezpalchuk, Volodymyr; Tomán, János J.; Gajdics, Bence; Gusak, Andriy M.

    2016-07-01

    This paper introduces a new model for calculating the change in time of three-dimensional atomic configurations. The model is based on the kinetic mean field (KMF) approach, however we have transformed that model into a stochastic approach by introducing dynamic Langevin noise. The result is a stochastic kinetic mean field model (SKMF) which produces results similar to the lattice kinetic Monte Carlo (KMC). SKMF is, however, far more cost-effective and easier to implement the algorithm (open source program code is provided on http://skmf.eu website). We will show that the result of one SKMF run may correspond to the average of several KMC runs. The number of KMC runs is inversely proportional to the amplitude square of the noise in SKMF. This makes SKMF an ideal tool also for statistical purposes.

  11. A Kinetic-fluid Model

    SciTech Connect

    First Author = C.Z. Cheng; Jay R. Johnson

    1998-07-10

    A nonlinear kinetic-fluid model for high-beta plasmas with multiple ion species which can be applied to multiscale phenomena is presented. The model embeds important kinetic effects due to finite ion Larmor radius (FLR), wave-particle resonances, magnetic particle trapping, etc. in the framework of simple fluid descriptions. When further restricting to low frequency phenomena with frequencies less than the ion cyclotron frequency the kinetic-fluid model takes a simpler form in which the fluid equations of multiple ion species collapse into single-fluid density and momentum equations and a low frequency generalized Ohm's law. The kinetic effects are introduced via plasma pressure tensors for ions and electrons which are computed from particle distribution functions that are governed by the Vlasov equation or simplified plasma dynamics equations such as the gyrokinetic equation. The ion FLR effects provide a finite parallel electric field, a perpendicular velocity that modifies the ExB drift, and a gyroviscosity tensor, all of which are neglected in the usual one-fluid MHD description. Eigenmode equations are derived which include magnetosphere-ionosphere coupling effects for low frequency waves (e.g., kinetic/inertial Alfven waves and ballooning-mirror instabilities).

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

    ERIC Educational Resources Information Center

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

    2011-01-01

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

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

    ERIC Educational Resources Information Center

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

    2011-01-01

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

  14. Symmetry relations in chemical kinetics arising from microscopic reversibility.

    PubMed

    Adib, Artur B

    2006-01-20

    It is shown that the kinetics of time-reversible chemical reactions having the same equilibrium constant but different initial conditions are closely related to one another by a directly measurable symmetry relation analogous to chemical detailed balance. In contrast to detailed balance, however, this relation does not require knowledge of the elementary steps that underlie the reaction, and remains valid in regimes where the concept of rate constants is ill defined, such as at very short times and in the presence of low activation barriers. Numerical simulations of a model of isomerization in solution are provided to illustrate the symmetry under such conditions, and potential applications in protein folding or unfolding are pointed out.

  15. Active colloids in the context of chemical kinetics

    NASA Astrophysics Data System (ADS)

    Oshanin, G.; Popescu, M. N.; Dietrich, S.

    2017-03-01

    We study a mesoscopic model of a chemically active colloidal particle which on certain parts of its surface promotes chemical reactions in the surrounding solution. For reasons of simplicity and conceptual clarity, we focus on the case in which only electrically neutral species are present in the solution and on chemical reactions which are described by first order kinetics. Within a self-consistent approach we explicitly determine the steady state product and reactant number density fields around the colloid as functionals of the interaction potentials of the various molecular species in solution with the colloid. By using a reciprocal theorem, this allows us to compute and to interpret—in a transparent way in terms of the classical Smoluchowski theory of chemical kinetics—the external force needed to keep such a catalytically active colloid at rest (stall force) or, equivalently, the corresponding velocity of the colloid if it is free to move. We use the particular case of triangular-well interaction potentials as a benchmark example for applying the general theoretical framework developed here. For this latter case, we derive explicit expressions for the dependences of the quantities of interest on the diffusion coefficients of the chemical species, the reaction rate constant, the coverage by catalyst, the size of the colloid, as well as on the parameters of the interaction potentials. These expressions provide a detailed picture of the phenomenology associated with catalytically-active colloids and self-diffusiophoresis.

  16. Comparing microbial and chemical kinetics for modelling soil organic carbon decomposition using the DecoChem v1.0 and DecoBio v1.0 models

    NASA Astrophysics Data System (ADS)

    Xenakis, G.; Williams, M.

    2014-07-01

    Soil organic matter is a vast store of carbon, with a critical role in the global carbon cycle. Despite its importance, the dynamics of soil organic carbon decomposition, under the impact of climate change or changing litter inputs, are poorly understood. Current biogeochemical models usually lack microbial processes and thus miss an important feedback when considering the fate of carbon. Here we use a series of modelling experiments to evaluate two different model structures: one with a standard first-order kinetic representation of soil decomposition (DecoChem v1.0, hereafter chemical model) and one with control of soil decomposition through microbial activity (DecoBio v1.0, hereafter biological model). The biological model includes cycling of organic matter into and out of microbial biomass, and simulates the decay rate as a functional of microbial activity. We tested two hypotheses. First, we hypothesized different responses in the two models to increased litter inputs and glucose additions. In the microbial model we hypothesized that this perturbation would prime microbial activity and reduce soil carbon stocks; in the chemical model we expected this perturbation to increase C stocks. In the biological model, responses to changed litter quantity were more rapid, but with the residence time of soil C altering such that soil C stocks were buffered. However, in the biological model there was a strong response to increased glucose additions (i.e. changes in litter quality), with significant losses to soil C stocks over time, driven by priming. Secondly, we hypothesized that warming will stimulate decomposition in the chemical model and loss of C, but in the biological model soil C will be less sensitive to warming, due to complex microbial feedbacks. The numerical experiments supported this hypothesis, with the chemical model soil C residence times and steady-state C stocks adjusting strongly with temperature changes, extending over decades. On the other hand, the

  17. Investigation of the kinetic model equations.

    PubMed

    Liu, Sha; Zhong, Chengwen

    2014-03-01

    Currently the Boltzmann equation and its model equations are widely used in numerical predictions for dilute gas flows. The nonlinear integro-differential Boltzmann equation is the fundamental equation in the kinetic theory of dilute monatomic gases. By replacing the nonlinear fivefold collision integral term by a nonlinear relaxation term, its model equations such as the famous Bhatnagar-Gross-Krook (BGK) equation are mathematically simple. Since the computational cost of solving model equations is much less than that of solving the full Boltzmann equation, the model equations are widely used in predicting rarefied flows, multiphase flows, chemical flows, and turbulent flows although their predictions are only qualitatively right for highly nonequilibrium flows in transitional regime. In this paper the differences between the Boltzmann equation and its model equations are investigated aiming at giving guidelines for the further development of kinetic models. By comparing the Boltzmann equation and its model equations using test cases with different nonequilibrium types, two factors (the information held by nonequilibrium moments and the different relaxation rates of high- and low-speed molecules) are found useful for adjusting the behaviors of modeled collision terms in kinetic regime. The usefulness of these two factors are confirmed by a generalized model collision term derived from a mathematical relation between the Boltzmann equation and BGK equation that is also derived in this paper. After the analysis of the difference between the Boltzmann equation and the BGK equation, an attempt at approximating the collision term is proposed.

  18. Kinetic Modeling of Divertor Plasma

    NASA Astrophysics Data System (ADS)

    Ishiguro, Seiji; Hasegawa, Hiroki; Pianpanit, Theerasarn

    2015-11-01

    Particle-in-Cell (PIC) simulation with the Monte Carlo collisions and the cumulative scattering angle coulomb collision can present kinetic dynamics of divertor plasmas. We are developing two types of PIC codes. The first one is the three dimensional bounded PIC code where three dimensional kinetic dynamics of blob is studied and current flow structures related to sheath formation are unveiled. The second one is the one spatial three velocity space dimensional (1D3V) PIC code with the Monte Carlo collisions where formation of detach plasma is studied. First target of our research is to construct self-consistent full kinetic simulation modeling of the linear divertor simulation experiments. This work is performed with the support and under the auspices of NIFS Collaboration Research program (NIFS15KNSS059, NIFS14KNXN279, and NIFS13KNSS038) and the Research Cooperation Program on Hierarchy and Holism in Natural Science at NINS.

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

    SciTech Connect

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

    2008-08-28

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

  20. Chemical Kinetic and Aerodynamic Structures of Flames

    DTIC Science & Technology

    1992-06-11

    identification of the role of kinetics and system non- adiabaticity in flammability limits , and on adiabatic flame stabilization. These results are...stabilization and flammability, and supersonic combustion. .. SUIUECT TEUMS 15. NUMBE OF PAGESFlammability limit , flame extinction, hydrocarbon 55...flammability limits , and on adiabatic flame stabilization. These results are expected to be useful in the general interest of AFOSR in the fundamental and

  1. Models of fertilization kinetics

    PubMed Central

    Lehtonen, Jussi

    2015-01-01

    Fertilization functions describe how the number of realized fertilizations depends on gamete numbers or density. They provide insight into the fertilization process, and are important components in models on the evolution of reproductive and sex-specific traits. Existing fertilization functions generally examine the proportion of fertilized eggs as a function of sperm numbers or density in a given fertilization environment. Because these functions have been developed for species with highly diverged gametes, there is an inbuilt (and well justified) asymmetry in them: they treat eggs and sperm, and therefore the two sexes, differently. Although very useful, such functions cannot therefore be used to consistently model early stages in the evolution of the two sexes, or extant species where sex-specific gamete sizes and numbers are similar. Here, I derive fertilization functions that describe the fertilization process without making prior assumptions about the two sexes, and are therefore consistent under any level of gamete dimorphism. These functions are compatible with simpler fertilization functions under appropriate conditions. Such functions can be particularly useful in understanding the early stages in the differentiation of the two sexes, as well as its consequences, where the gametes from the two sexes should be treated on an equal basis. PMID:26473043

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

    ERIC Educational Resources Information Center

    Turanyi, Tamas; Toth, Zoltan

    2013-01-01

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

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

    ERIC Educational Resources Information Center

    Turanyi, Tamas; Toth, Zoltan

    2013-01-01

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

  4. Chemical kinetics computer program for static and flow reactions

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    General chemical kinetics computer program for complex gas mixtures has been developed. Program can be used for any homogeneous reaction in either one dimensional flow or static system. It is flexible, accurate, and easy to use. It can be used for any chemical system for which species thermodynamic data and reaction rate constant data are known.

  5. Kinetic Modeling of Microbiological Processes

    SciTech Connect

    Liu, Chongxuan; Fang, Yilin

    2012-08-26

    Kinetic description of microbiological processes is vital for the design and control of microbe-based biotechnologies such as waste water treatment, petroleum oil recovery, and contaminant attenuation and remediation. Various models have been proposed to describe microbiological processes. This editorial article discusses the advantages and limiation of these modeling approaches in cluding tranditional, Monod-type models and derivatives, and recently developed constraint-based approaches. The article also offers the future direction of modeling researches that best suit for petroleum and environmental biotechnologies.

  6. Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

    PubMed

    Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

    2015-05-07

    Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

  7. In silico prediction of percutaneous absorption and disposition kinetics of chemicals.

    PubMed

    Chen, Longjian; Han, Lujia; Saib, Ouarda; Lian, Guoping

    2015-05-01

    To develop in-silico model for predicting percutaneous absorption and disposition kinetics of chemicals in skin layers so as to facilitate the design of transdermal drug delivery systems and skin care products, and risk assessment of occupational or consumer exposure. A general-purpose computer model for simulating skin permeation, absorption and disposition kinetics in the stratum corneum, viable dermis and dermis has been developed. Equations have been proposed for determining the partition and diffusion properties of chemicals by considering molecular partition, binding and mobility in skin layers. In vitro skin penetration data of 12 chemicals was used to validate the model. The observed and simulated permeation and disposition in skin layers were compared for 12 tested chemicals. For most tested chemicals, the experimental and model results are in good agreement with the coefficient of determination >0.80 and relative root mean squared error <1.20. The disposition kinetic parameters of the maximum concentration and the area under the curve in the viable epidermis and dermis initially increased with hydrophobicity, but reached maxima and then decreased with further increase of hydrophobicity. By considering skin physiological structure and composition, the partition and diffusion properties of chemicals in skin layers are determined. This allows in-silico simulation of percutaneous permeation, absorption and disposition kinetics of wide chemical space. The model produced results in good agreement with experimental data of 12 chemicals, suggesting a much improved framework to support transdermal delivery of drug and cosmetic actives as well as integrated risk assessment.

  8. Free-Electron Lasers, Thermal Diffusion, Chemical Kinetics, and Surgery

    NASA Astrophysics Data System (ADS)

    Edwards, Glenn; Hutson, M. Shane

    2001-11-01

    Experiments demonstrate that the Mark-III FEL is a particularly effective tool for etching soft matter with remarkably little damage surrounding the site when tuned to wavelengths near 6.45 microns. Based on these observatons, human neuorsurgical and ophthalmic procedures were developed and have been performed successfully. A thermodynamic model was proposed to account for the wavelength dependence; however, the dynamics have not been well understood. We have theoretically investigated thermal diffusion and chemical kinetics in a system of alternating layers of protein and water as heated by a Mark-III FEL. The model is representative of cornea and the exposure conditions are comparable to previous experimental FEL investigations. A substantial temperature enhancement develops in the surface layer on the ten-nanosecond time scale. We consider the onset of both the helix-coil transition and chemical bond breaking of collagen in terms of the thermal, chemical, and structural properties of the system as well as laser wavelength and pulse structure.

  9. Detailed Chemical Kinetic Reaction Mechanisms for Incineration of Organophosphorus and Fluoro-Organophosphorus Compounds

    SciTech Connect

    Glaude, P A; Melius, C; Pitz, W J; Westbrook, C K

    2001-12-13

    A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a six-center molecular elimination reaction producing propene.

  10. Kinetic model of HIV infection

    SciTech Connect

    Zhdanov, V. P.

    2007-10-15

    Recent experiments clarifying the details of exhaustion of CD8 T cells specific to various strains of human immunodeficiency virus (HIV) are indicative of slow irreversible (on a one-year time scale) deterioration of the immune system. The conventional models of HIV kinetics do not take this effect into account. Removing this shortcoming, we show the likely influence of such changes on the escape of HIV from control of the immune system.

  11. A unified kinetic model for particle aggregation

    SciTech Connect

    Gardner, K.H.; Theis, T.L.

    1996-06-01

    Aggregation of submicrometer particles is a process with significant implications for the fate and transport of contaminants and major nutrients in many coastal, estuarine, and freshwater bodies as well as groundwater systems. A unified model has been developed that describes the kinetics of particle aggregation. The model is unique in the incorporation of surface chemical phenomena along with solution chemistry in the determination of the stability of a colloidal dispersion. The aggregation process is treated in a truly kinetic fashion, the main output from the model being the evolution of complete particle size distributions over time. The model was developed to interpret laboratory data and, as such, has the capacity to estimate a (variable) set of system parameters by fitting the size distribution over time data to that measured. It was found that the attachment distance, a parameter frequently approximated in practice, has a profound influence on the predicted aggregation kinetics as does the choice of a solid/solution interfacial model. Furthermore, simulation of relatively long-term aggregation, which was the principal focus of this work, indicates that values of the collision efficiency factor should be much smaller than those reported elsewhere in the literature.

  12. A kinetic-theory approach to turbulent chemically reacting flows

    NASA Technical Reports Server (NTRS)

    Chung, P. M.

    1976-01-01

    The paper examines the mathematical and physical foundations for the kinetic theory of reactive turbulent flows, discussing the differences and relation between the kinetic and averaged equations, and comparing some solutions of the kinetic equations obtained by the Green's function method with those obtained by the approximate bimodal method. The kinetic method described consists essentially in constructing the probability density functions of the chemical species on the basis of solutions of the Langevin stochastic equation for the influence of eddies on the behavior of fluid elements. When the kinetic equations are solved for the structure of the diffusion flame established in a shear layer by the bimodal method, discontinuities in gradients of the mean concentrations at the two flame edges appear. This is a consequence of the bimodal approximation of all distribution functions by two dissimilar half-Maxwellian functions, which is a very crude approximation. These discontinuities do not appear when the solutions are constructed by the Green's function method described here.

  13. Representing Model Inadequacy in Combustion Kinetics

    NASA Astrophysics Data System (ADS)

    Morrison, Rebecca E.; Moser, Robert D.

    2014-11-01

    An accurate description of the chemical processes involved in the oxidation of hydrocarbons may include hundreds of reactions and thirty or more chemical species. Kinetics models of these chemical mechanisms are often embedded in a fluid dynamics solver to represent combustion. Because the computational cost of such detailed mechanisms is so high, it is common practice to use drastically reduced mechanisms. But, this introduces modeling errors which may render the model inadequate. In this talk, we present a formulation of the model inadequacy in reduced models of hydrogen-methane combustion. Our goal is to account for the discrepancy between the high-fidelity model and its reduced version by incorporating an additive, linear, probabilistic inadequacy model. In effect, it is a random matrix, whose entries are characterized by probability distributions and which displays interesting properties due to conservation constraints. The distributions are calibrated via Bayesian inference using a hierarchical modeling scheme and high-dimensional MCMC. We apply this technique to a stand-alone reaction and also incorporate it within a one-dimensional laminar flame problem.

  14. Parameter Optimization of Nitriding Process Using Chemical Kinetics

    NASA Astrophysics Data System (ADS)

    Özdemir, İ. Bedii; Akar, Firat; Lippmann, Nils

    2016-12-01

    Using the dynamics of chemical kinetics, an investigation to search for an optimum condition for a gas nitriding process is performed over the solution space spanned by the initial temperature and gas composition of the furnace. For a two-component furnace atmosphere, the results are presented in temporal variations of gas concentrations and the nitrogen coverage on the surface. It seems that the exploitation of the nitriding kinetics can provide important feedback for setting the model-based control algorithms. The present work shows that when the nitrogen gas concentration is not allowed to exceed 6 pct, the Nad coverage can attain maximum values as high as 0.97. The time evolution of the Nad coverage also reveals that, as long as the temperature is above the value where nitrogen poisoning of the surface due to the low-temperature adsorption of excess nitrogen occurs, the initial ammonia content in the furnace atmosphere is much more important in the nitriding process than is the initial temperature.

  15. Kinetic models of conjugated metabolic cycles

    NASA Astrophysics Data System (ADS)

    Ershov, Yu. A.

    2016-01-01

    A general method is developed for the quantitative kinetic analysis of conjugated metabolic cycles in the human organism. This method is used as a basis for constructing a kinetic graph and model of the conjugated citric acid and ureapoiesis cycles. The results from a kinetic analysis of the model for these cycles are given.

  16. Chemical Kinetics of Polycyclic Aromatic Hydrocarbons in Comet Impacts

    NASA Astrophysics Data System (ADS)

    Kress, M. E.; McKay, C.; Tielens, A. G.; Frenklach, M.

    2004-12-01

    Polycyclic aromatic hydrocarbons (PAHs) are stable, robust organic compounds that would have been an important constituent of the early atmospheres of terrestrial planets. These strongly-bound molecules readily absorb ultraviolet light and may play a role in aerosol formation. PAHs are one of the predominant carriers of carbon in interstellar space, after CO. They are common in carbonaceous chondrites, and quite likely in comets as well. Impacts of volatile-rich planetesimals such as carbonaceous chondrites and comets would have been common during the late stages of planet formation. Theoretical studies of impact chemistry typically assume that the chemical composition of the post-impact material is given by thermodynamic equilibrium at 2000 K. These calculations also typically ignore the formation of aromatic compounds because the closure of the first aromatic ring is kinetically inhibited, although thermodynamically favorable at the temperatures and pressures of an impact fireball. Do the PAHs present in a comet or asteroid survive impact? If so, how are these PAHs modified during impact? To address these questions, we model the chemical kinetics of PAH survival, formation, growth and destruction within a parameter space consisting of impact fireball cooling timescales, pressures, temperatures, C/O ratios and other factors. The chemistry of PAHs has been well studied under conditions present in plug flow reactors and sooting flames (P ≈ 1atm, T≥ 1000 K). We hope that our results will motivate more experimental investigation of reaction mechanisms and rate coefficients for a broader range of temperatures and pressures than those heretofore studied for industrial applications. This work has been supported by the NASA Astrobiology Institute's Virtual Planetary Laboratory and the Institute for Geophysics and Planetary Physics at Lawrence Livermore National Laboratory.

  17. Chemical zonation in garnet: kinetics or chemical equilibrium?

    NASA Astrophysics Data System (ADS)

    Ague, Jay; Chu, Xu; Axler, Jennifer

    2015-04-01

    Chemical zonation in garnet is widely used to reconstruct the pressure (P), temperature (T), time (t), and fluid (f) histories of mountain belts. Zonation is thought to result largely from changing P - T - t - f conditions during growth as well as post-growth intracrystalline diffusion. Chemical zonation is conventionally interpreted to mean that at least some of the garnet interior was out of chemical equilibrium with the matrix during metamorphism. In this case, thermally-activated diffusion in garnet is too slow to equalize chemical potentials. However, in their groundbreaking paper, Tajčmanová et al. (2014) postulate that in high-grade rocks, chemical zonation may actually reflect attainment of equilibrium. In this scenario, diffusion is fast but viscous relaxation is slow such that the zonation patterns directly mirror internal pressure gradients within garnet. Such zoning would likely be very different than typical concentric growth zonation. Furthermore, Baumgartner et al. (2010) hypothesize that given significant variations in the molar volumes of garnet endmembers, diffusional relaxation may produce internal pressure gradients if the garnet behaves as a near constant-volume system. Consequently, growth zoning could be preserved by pressure variations within the garnet that equalize chemical potentials and slow or stop diffusion (i.e., the garnet is chemically heterogeneous but maintains internal chemical equilibrium due to the pressure variations). This mechanism predicts that areas of garnet with small compositional contrasts would undergo more diffusional relaxation than areas with large contrasts. Moreover, generation of large internal pressure gradients approaching 1 GPa would be expected to induce deformation (e.g., fracturing) in regions of large compositional gradients. Strongly growth-zoned amphibolite facies garnet from the Barrovian zones, Scotland (Ague and Baxter, 2007) shows neither of these features. The sharp compositional gradients are

  18. Kinetic models of immediate exchange

    NASA Astrophysics Data System (ADS)

    Heinsalu, Els; Patriarca, Marco

    2014-08-01

    We propose a novel kinetic exchange model differing from previous ones in two main aspects. First, the basic dynamics is modified in order to represent economies where immediate wealth exchanges are carried out, instead of reshufflings or uni-directional movements of wealth. Such dynamics produces wealth distributions that describe more faithfully real data at small values of wealth. Secondly, a general probabilistic trading criterion is introduced, so that two economic units can decide independently whether to trade or not depending on their profit. It is found that the type of the equilibrium wealth distribution is the same for a large class of trading criteria formulated in a symmetrical way with respect to the two interacting units. This establishes unexpected links between and provides a microscopic foundations of various kinetic exchange models in which the existence of a saving propensity is postulated. We also study the generalized heterogeneous version of the model in which units use different trading criteria and show that suitable sets of diversified parameter values with a moderate level of heterogeneity can reproduce realistic wealth distributions with a Pareto power law.

  19. Evidence of Structure Sensitivity in the Fischer-Tropsch Reaction on Model Cobalt Nanoparticles by Time-Resolved Chemical Transient Kinetics.

    PubMed

    Ralston, Walter T; Melaet, Gérôme; Saephan, Tommy; Somorjai, Gabor A

    2017-06-19

    The Fischer-Tropsch process, or the catalytic hydrogenation of carbon monoxide (CO), produces long chain hydrocarbons and offers an alternative to the use of crude oil for chemical feedstocks. The observed size dependence of cobalt (Co) catalysts for the Fischer-Tropsch reaction was studied with colloidally prepared Co nanoparticles and a chemical transient kinetics reactor capable of measurements under non-steady-state conditions. Co nanoparticles of 4.3 nm and 9.5 nm diameters were synthesized and tested under atmospheric pressure conditions and H2 /CO=2. Large differences in carbon coverage (ΘC ) were observed for the two catalysts: the 4.3 nm Co catalyst has a ΘC less than one while the 9.5 nm Co catalyst supports a ΘC greater than two. The monomer units present on the surface during reaction are identified as single carbon species for both sizes of Co nanoparticles, and the major CO dissociation site is identified as the B5 -B geometry. The difference in activity of Co nanoparticles was found to be a result of the structure sensitivity caused by the loss of these specific types of sites at smaller nanoparticle sizes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Improving Student Results in the Crystal Violet Chemical Kinetics Experiment

    ERIC Educational Resources Information Center

    Kazmierczak, Nathanael; Vander Griend, Douglas A.

    2017-01-01

    Despite widespread use in general chemistry laboratories, the crystal violet chemical kinetics experiment frequently suffers from erroneous student results. Student calculations for the reaction order in hydroxide often contain large asymmetric errors, pointing to the presence of systematic error. Through a combination of "in silico"…

  1. Improving Student Results in the Crystal Violet Chemical Kinetics Experiment

    ERIC Educational Resources Information Center

    Kazmierczak, Nathanael; Vander Griend, Douglas A.

    2017-01-01

    Despite widespread use in general chemistry laboratories, the crystal violet chemical kinetics experiment frequently suffers from erroneous student results. Student calculations for the reaction order in hydroxide often contain large asymmetric errors, pointing to the presence of systematic error. Through a combination of "in silico"…

  2. Chemical Kinetics at the Single-Molecule Level

    ERIC Educational Resources Information Center

    Levitus, Marcia

    2011-01-01

    For over a century, chemists have investigated the rates of chemical reactions using experimental conditions involving huge numbers of molecules. As a consequence, the description of the kinetics of the reaction in terms of average values was good enough for all practical purposes. From the pedagogical point of view, such a description misses the…

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

    ERIC Educational Resources Information Center

    Sozbilir, Mustafa; Pinarbasi, Tacettin; Canpolat, Nurtac

    2010-01-01

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

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

    ERIC Educational Resources Information Center

    Sozbilir, Mustafa; Pinarbasi, Tacettin; Canpolat, Nurtac

    2010-01-01

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

  5. Chemical Kinetics at the Single-Molecule Level

    ERIC Educational Resources Information Center

    Levitus, Marcia

    2011-01-01

    For over a century, chemists have investigated the rates of chemical reactions using experimental conditions involving huge numbers of molecules. As a consequence, the description of the kinetics of the reaction in terms of average values was good enough for all practical purposes. From the pedagogical point of view, such a description misses the…

  6. Hybrid framework for the simulation of stochastic chemical kinetics

    NASA Astrophysics Data System (ADS)

    Duncan, Andrew; Erban, Radek; Zygalakis, Konstantinos

    2016-12-01

    Stochasticity plays a fundamental role in various biochemical processes, such as cell regulatory networks and enzyme cascades. Isothermal, well-mixed systems can be modelled as Markov processes, typically simulated using the Gillespie Stochastic Simulation Algorithm (SSA) [25]. While easy to implement and exact, the computational cost of using the Gillespie SSA to simulate such systems can become prohibitive as the frequency of reaction events increases. This has motivated numerous coarse-grained schemes, where the "fast" reactions are approximated either using Langevin dynamics or deterministically. While such approaches provide a good approximation when all reactants are abundant, the approximation breaks down when one or more species exist only in small concentrations and the fluctuations arising from the discrete nature of the reactions become significant. This is particularly problematic when using such methods to compute statistics of extinction times for chemical species, as well as simulating non-equilibrium systems such as cell-cycle models in which a single species can cycle between abundance and scarcity. In this paper, a hybrid jump-diffusion model for simulating well-mixed stochastic kinetics is derived. It acts as a bridge between the Gillespie SSA and the chemical Langevin equation. For low reactant reactions the underlying behaviour is purely discrete, while purely diffusive when the concentrations of all species are large, with the two different behaviours coexisting in the intermediate region. A bound on the weak error in the classical large volume scaling limit is obtained, and three different numerical discretisations of the jump-diffusion model are described. The benefits of such a formalism are illustrated using computational examples.

  7. Hybrid framework for the simulation of stochastic chemical kinetics

    SciTech Connect

    Duncan, Andrew; Erban, Radek; Zygalakis, Konstantinos

    2016-12-01

    Stochasticity plays a fundamental role in various biochemical processes, such as cell regulatory networks and enzyme cascades. Isothermal, well-mixed systems can be modelled as Markov processes, typically simulated using the Gillespie Stochastic Simulation Algorithm (SSA) [25]. While easy to implement and exact, the computational cost of using the Gillespie SSA to simulate such systems can become prohibitive as the frequency of reaction events increases. This has motivated numerous coarse-grained schemes, where the “fast” reactions are approximated either using Langevin dynamics or deterministically. While such approaches provide a good approximation when all reactants are abundant, the approximation breaks down when one or more species exist only in small concentrations and the fluctuations arising from the discrete nature of the reactions become significant. This is particularly problematic when using such methods to compute statistics of extinction times for chemical species, as well as simulating non-equilibrium systems such as cell-cycle models in which a single species can cycle between abundance and scarcity. In this paper, a hybrid jump-diffusion model for simulating well-mixed stochastic kinetics is derived. It acts as a bridge between the Gillespie SSA and the chemical Langevin equation. For low reactant reactions the underlying behaviour is purely discrete, while purely diffusive when the concentrations of all species are large, with the two different behaviours coexisting in the intermediate region. A bound on the weak error in the classical large volume scaling limit is obtained, and three different numerical discretisations of the jump-diffusion model are described. The benefits of such a formalism are illustrated using computational examples.

  8. Chemkin-II: A Fortran chemical kinetics package for the analysis of gas-phase chemical kinetics

    SciTech Connect

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

    1989-09-01

    This document is the user's manual for the second-generation Chemkin package. Chemkin is a software package for whose purpose is to facilitate the formation, solution, and interpretation of problems involving elementary gas-phase chemical kinetics. It provides an especially flexible and powerful tool for incorporating complex chemical kinetics into simulations of fluid dynamics. The package consists of two major software components: an Interpreter and Gas-Phase Subroutine Library. The Interpreter is a program that reads a symbolic description of an elementary, user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Gas-Phase Subroutine Library. This library is a collection of about 100 highly modular Fortran subroutines that may be called to return information on equation of state, thermodynamic properties, and chemical production rates.

  9. A coke oven model including thermal decomposition kinetics of tar

    SciTech Connect

    Munekane, Fuminori; Yamaguchi, Yukio; Tanioka, Seiichi

    1997-12-31

    A new one-dimensional coke oven model has been developed for simulating the amount and the characteristics of by-products such as tar and gas as well as coke. This model consists of both heat transfer and chemical kinetics including thermal decomposition of coal and tar. The chemical kinetics constants are obtained by estimation based on the results of experiments conducted to investigate the thermal decomposition of both coal and tar. The calculation results using the new model are in good agreement with experimental ones.

  10. Chemical TOPAZ: Modifications to the heat transfer code TOPAZ: The addition of chemical reaction kinetics and chemical mixtures

    SciTech Connect

    Nichols, A.L. III.

    1990-06-07

    This is a report describing the modifications which have been made to the heat flow code TOPAZ to allow the inclusion of thermally controlled chemical kinetics. This report is broken into parts. The first part is an introduction to the general assumptions and theoretical underpinning that were used to develop the model. The second section describes the changes that have been implemented into the code. The third section is the users manual for the input for the code. The fourth section is a compilation of hints, common errors, and things to be aware of while you are getting started. The fifth section gives a sample problem using the new code. This manual addenda is written with the presumption that most readers are not fluent with chemical concepts. Therefore, we shall in this section endeavor to describe the requirements that must be met before chemistry can occur and how we have modeled the chemistry in the code.

  11. Chemical kinetic reaction mechanism for the combustion of propane

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1984-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  13. Spectral method for a kinetic swarming model

    SciTech Connect

    Gamba, Irene M.; Haack, Jeffrey R.; Motsch, Sebastien

    2015-04-28

    Here we present the first numerical method for a kinetic description of the Vicsek swarming model. The kinetic model poses a unique challenge, as there is a distribution dependent collision invariant to satisfy when computing the interaction term. We use a spectral representation linked with a discrete constrained optimization to compute these interactions. To test the numerical scheme we investigate the kinetic model at different scales and compare the solution with the microscopic and macroscopic descriptions of the Vicsek model. Lastly, we observe that the kinetic model captures key features such as vortex formation and traveling waves.

  14. Spectral method for a kinetic swarming model

    DOE PAGES

    Gamba, Irene M.; Haack, Jeffrey R.; Motsch, Sebastien

    2015-04-28

    Here we present the first numerical method for a kinetic description of the Vicsek swarming model. The kinetic model poses a unique challenge, as there is a distribution dependent collision invariant to satisfy when computing the interaction term. We use a spectral representation linked with a discrete constrained optimization to compute these interactions. To test the numerical scheme we investigate the kinetic model at different scales and compare the solution with the microscopic and macroscopic descriptions of the Vicsek model. Lastly, we observe that the kinetic model captures key features such as vortex formation and traveling waves.

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

    NASA Technical Reports Server (NTRS)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

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

  16. Infrared absorption spectroscopy and chemical kinetics of free radicals

    SciTech Connect

    Curl, R.F.; Glass, G.P.

    1993-12-01

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

  17. Chemical modelling of molecular sources

    NASA Astrophysics Data System (ADS)

    Nejad, L. A. M.; Millar, T. J.

    1987-09-01

    The authors present detailed results of a chemical kinetic model of the outer envelope (1016cm to 1018cm) of the carbon-rich star IRC +10216. The chemistry is driven by a combination of cosmic-ray ionization and ultraviolet radiation and, starting from 7 parent molecules injected into the envelope, the authors find that a complex chemistry ensues. Ion-molecule reactions can efficiently build hydrocarbon species and account for the observed abundances of CH3CN and HNC. Reactions involving CO may lead to observable abundances of oxygen-bearing molecules such as C3O, CH2CO and HCO+.

  18. Fourth-Order Vibrational Transition State Theory and Chemical Kinetics

    NASA Astrophysics Data System (ADS)

    Stanton, John F.; Matthews, Devin A.; Gong, Justin Z.

    2015-06-01

    Second-order vibrational perturbation theory (VPT2) is an enormously successful and well-established theory for treating anharmonic effects on the vibrational levels of semi-rigid molecules. Partially as a consequence of the fact that the theory is exact for the Morse potential (which provides an appropriate qualitative model for stretching anharmonicity), VPT2 calculations for such systems with appropriate ab initio potential functions tend to give fundamental and overtone levels that fall within a handful of wavenumbers of experimentally measured positions. As a consequence, the next non-vanishing level of perturbation theory -- VPT4 -- offers only slight improvements over VPT2 and is not practical for most calculations since it requires information about force constants up through sextic. However, VPT4 (as well as VPT2) can be used for other applications such as the next vibrational correction to rotational constants (the ``gammas'') and other spectroscopic parameters. In addition, the marriage of VPT with the semi-classical transition state theory of Miller (SCTST) has recently proven to be a powerful and accurate treatment for chemical kinetics. In this talk, VPT4-based SCTST tunneling probabilities and cumulative reaction probabilities are give for the first time for selected low-dimensional model systems. The prospects for VPT4, both practical and intrinsic, will also be discussed.

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

    SciTech Connect

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

    2010-03-14

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

  20. DNA as a universal substrate for chemical kinetics.

    PubMed

    Soloveichik, David; Seelig, Georg; Winfree, Erik

    2010-03-23

    Molecular programming aims to systematically engineer molecular and chemical systems of autonomous function and ever-increasing complexity. A key goal is to develop embedded control circuitry within a chemical system to direct molecular events. Here we show that systems of DNA molecules can be constructed that closely approximate the dynamic behavior of arbitrary systems of coupled chemical reactions. By using strand displacement reactions as a primitive, we construct reaction cascades with effectively unimolecular and bimolecular kinetics. Our construction allows individual reactions to be coupled in arbitrary ways such that reactants can participate in multiple reactions simultaneously, reproducing the desired dynamical properties. Thus arbitrary systems of chemical equations can be compiled into real chemical systems. We illustrate our method on the Lotka-Volterra oscillator, a limit-cycle oscillator, a chaotic system, and systems implementing feedback digital logic and algorithmic behavior.

  1. DNA as a universal substrate for chemical kinetics

    PubMed Central

    Soloveichik, David; Seelig, Georg; Winfree, Erik

    2010-01-01

    Molecular programming aims to systematically engineer molecular and chemical systems of autonomous function and ever-increasing complexity. A key goal is to develop embedded control circuitry within a chemical system to direct molecular events. Here we show that systems of DNA molecules can be constructed that closely approximate the dynamic behavior of arbitrary systems of coupled chemical reactions. By using strand displacement reactions as a primitive, we construct reaction cascades with effectively unimolecular and bimolecular kinetics. Our construction allows individual reactions to be coupled in arbitrary ways such that reactants can participate in multiple reactions simultaneously, reproducing the desired dynamical properties. Thus arbitrary systems of chemical equations can be compiled into real chemical systems. We illustrate our method on the Lotka–Volterra oscillator, a limit-cycle oscillator, a chaotic system, and systems implementing feedback digital logic and algorithmic behavior. PMID:20203007

  2. Kinetic models in industrial biotechnology - Improving cell factory performance.

    PubMed

    Almquist, Joachim; Cvijovic, Marija; Hatzimanikatis, Vassily; Nielsen, Jens; Jirstrand, Mats

    2014-07-01

    An increasing number of industrial bioprocesses capitalize on living cells by using them as cell factories that convert sugars into chemicals. These processes range from the production of bulk chemicals in yeasts and bacteria to the synthesis of therapeutic proteins in mammalian cell lines. One of the tools in the continuous search for improved performance of such production systems is the development and application of mathematical models. To be of value for industrial biotechnology, mathematical models should be able to assist in the rational design of cell factory properties or in the production processes in which they are utilized. Kinetic models are particularly suitable towards this end because they are capable of representing the complex biochemistry of cells in a more complete way compared to most other types of models. They can, at least in principle, be used to in detail understand, predict, and evaluate the effects of adding, removing, or modifying molecular components of a cell factory and for supporting the design of the bioreactor or fermentation process. However, several challenges still remain before kinetic modeling will reach the degree of maturity required for routine application in industry. Here we review the current status of kinetic cell factory modeling. Emphasis is on modeling methodology concepts, including model network structure, kinetic rate expressions, parameter estimation, optimization methods, identifiability analysis, model reduction, and model validation, but several applications of kinetic models for the improvement of cell factories are also discussed. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

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

    PubMed

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

    2016-01-01

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

  4. Kinetic modeling of non-ideal explosives

    SciTech Connect

    Fried, L E; Howard, W M; Souers, P C

    1999-03-01

    We have implemented a Wood-Kirkwood kinetic detonation model based on multi-species equations of state and multiple reaction rate laws. Finite rate laws are used for the slowest chemical reactions, while other reactions are given infinite rates and are kept in constant thermodynamic equilibrium. We model a wide range of ideal and non-ideal composite energetic materials. In addition, we develop an exp-6 equation of state for the product fluids that reproduces a wide range experimental shock Hugoniot and static compression data. For unreacted solids, including solid and liquid Al and Al{sub 2}O{sub 3}, we use a Murnaghan form for the equation of state. We find that we can replicate experimental detonation velocities to within a few per cent for a wide range of explosives, while obtaining good agreement with estimated reaction zone lengths. The detonation velocity as a function of charge radius is also correctly reproduced.

  5. [Study on Chemical Kinetic Effect of Dielectric Barrier Discharge Plasma].

    PubMed

    Zrang, Peng; Hong, Yan-ji; Shen, Shuang-yan; Ding, Xiao-yu; Ma, Di

    2015-03-01

    To reveal the mechanism of plasma (assisted the ignition process of methane/air further, schematic of dielectric barrier discharge plasma system with atmospheric air was designed and set up, the emission spectrum of dielectric barrier discharge plasma with atmospheric air was measured, and the active particles produced by the interaction of dielectric barrier discharge plasma with atmospheric air were analyzed with the spectrum technology, the ignition model and calculation methods of sensitivity analysis and reaction path analysis were given, effects of NO and O3 on the ignition delay time were simulated, and the chemical kinetics mechanism of NO and O3 assisted ignition was revealed via sensitivity analysis and reaction path analysis. The results show that main excited particles of N2 and O3 are generated via effect of plasma on the atmospheric air, which are converted into active particles of NO(ξ) and O3 in the end, the life of which are longer than any other active particles, effects of plasma on the ignition is simplified as effects of NO(ξ) and O3 on the ignition; NO and O3 could reduce the ignition delay time significantly, but the amplitude decrease with increase of the initial temperature, this is because the rate of ignition is decided by the oxidation rate of CH3, the oxidized pathway of CH3 is R155 and R156 for auto-ignition and their rates are slower when temperature is low, so the ignition delay time of methane/air is longer; NO could reduce the ignition delay time significantly because of the oxidized pathway of CH3 is changed to R327 CH3O2 + NO = CH3O + NO2, R328 CH3 + NO2 = CH3O + NO for NO(ξ) (assisted ignition process from R155 and R156 for auto-ignition; and the chemical kinetic effect is the dominating factor of O3 on the ignition and which change the reaction path.

  6. Kinetic Modelling of Transcription Elongation

    NASA Astrophysics Data System (ADS)

    O'Maoileidigh, Daibhid; Tadigotla, Vasisht; Sengupta, Anirvan; Epshtein, Vitaly; Ebright, Richard; Nudler, Evgeny; Ruckenstein, Andrei

    2006-03-01

    Transcription is the first step in gene expression and it is at this stage that most of genetic regulation occurs. The enzyme RNA polymerase (RNAP) walks along DNA creating an RNA transcript at a highly non-uniform rate. We discuss how many non-intuitive features of the system may be experimentally and physically motivated and present first a model, which agrees qualitatively with a host of experimental evidence. We also examine intrinsic pauses where it is thought that the RNAP will move backwards along the DNA template without changing the length of the RNA transcript. We describe a simplified kinetic scheme for the recovery of intrinsic pauses with the same degree of predictive power as our thermodynamic model (presented separately). The separation of timescales between the movement of the RNAP and global changes in the RNA secondary structure is seen to be crucial for the function of RNAP. This is essentially a model of a Brownian ratchet where RNAP executes a 1D random walk in a sequence dependent potential over a range determined by the co-transcriptional RNA fold for each transcript length

  7. Kinetic modelling of mitochondrial translation.

    PubMed

    Korla, Kalyani; Mitra, Chanchal K

    2014-01-01

    Mitochondrial genome contains 13 protein coding genes, all being part of the oxidative phosphorylation complexes. The process of translation of these protein coding mRNAs in mitochondrial matrix is a good miniature model of translation in cytoplasm. In this work, we have simulated three phases of mitochondrial translation viz. initiation, elongation and termination (including ribosome recycling). The kinetic equations for these phases have been deduced based on the information available in literature. Various factors involved in the process have been included explicitly. Kinetic simulation was done using Octave, open source software. Scripts were written individually for each phase. Initiation begins with mitoribosome, mRNA, fMet-tRNA and initiation factors. The final product of the initiation script, the initiation complex, was introduced as the start point in the successive step, i.e. elongation. Elongation is a particular extensive process where the various aminoacyl-tRNAs already present in the matrix check for matching with the triplet codon in A-site of mitoribosome. This script consists of two parts: one with the time behaviour of the factors involved in the molecular process (using ordinary differential equation solver) and the other including the reading of triplet codon on the mRNA and incorporating the corresponding aminoacyl-tRNA, and then at each step elongating the peptide chain (using loops and conditions). The peptide chain thus formed in the elongation step (in the loops and conditions segment) was released in the termination step. This was followed by mitoribosome recycling where the mitoribosome reached the native state and was ready for the next cycle of translation.

  8. The H-theorem for the chemical kinetic equations with discrete time and for their generalizations

    NASA Astrophysics Data System (ADS)

    Adzhiev, S.; Melikhov, I.; Vedenyapin, V.

    2017-01-01

    In this paper the generalizations of equations of chemical kinetics, including classical and quantum chemical kinetics, is considered. We make time discrete in these equations and prove the H-theorem.

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

    NASA Astrophysics Data System (ADS)

    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

  10. The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research

    SciTech Connect

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

    2008-07-16

    Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.

  11. Solute transport with multiple equilibrium-controlled or kinetically controlled chemical reactions

    USGS Publications Warehouse

    Friedly, John C.; Rubin, Jacob

    1992-01-01

    A new approach is applied to the problem of modeling solute transport accompanied by many chemical reactions. The approach, based on concepts of the concentration space and its stoichiometric subspaces, uses elements of the subspaces as primary dependent variables. It is shown that the resulting model equations are compact in form, isolate the chemical reaction expressions from flow expressions, and can be used for either equilibrium or kinetically controlled reactions. The implications of the results on numerical algorithms for solving the equations are discussed. The application of the theory is illustrated throughout with examples involving a simple but broadly representative set of reactions previously considered in the literature. Numerical results are presented for four interconnected reactions: a homogeneous complexation reaction, two sorption reactions, and a dissolution/precipitation reaction. Three cases are considered: (1) four kinetically controlled reactions, (2) four equilibrium-controlled reactions, and (3) a system with two kinetically controlled reactions and two equilibrium-controlled reactions.

  12. Kinetic Global Modeling of Rare Gas Lasers

    NASA Astrophysics Data System (ADS)

    Parsey, Guy; Verboncoeur, John; Christlieb, Andrew

    2016-10-01

    Akin to diode-pumped alkali metal lasers, electronically excited states of rare gases (e.g. Ar and Kr) have been shown to operate as chemically inert three-level gain media for an optically pumped laser system. As opposed to vaporization heating, these systems rely on electric discharge to efficiently maintain a population of metastable states acting as the bottom laser level. We propose that a modified electron energy distribution (EEDF) in the electric heating can tune optically pumped rare gas laser (OPRGL) efficiencies. The EEDF factors into all plasma phase chemistry within the underlying reaction network, and is assumed to be maintained by discharge and electron sources. Using parameter scanning methods within the kinetic global modeling framework (KGMf), optimized EEDFs are found for metastable production and increasing OPRGL operational efficiencies. Finally, we investigate the feasibility of using a modified EEDF to drive a rare gas laser system without optical pumping. Supported by AFOSR and an MSU SPG.

  13. Mesoscopic kinetic basis of macroscopic chemical thermodynamics: A mathematical theory.

    PubMed

    Ge, Hao; Qian, Hong

    2016-11-01

    Gibbs' macroscopic chemical thermodynamics is one of the most important theories in chemistry. Generalizing it to mesoscaled nonequilibrium systems is essential to biophysics. The nonequilibrium stochastic thermodynamics of chemical reaction kinetics suggested a free energy balance equation dF^{(meso)}/dt=E_{in}-e_{p} in which the free energy input rate E_{in} and dissipation rate e_{p} are both non-negative, and E_{in}≤e_{p}. We prove that in the macroscopic limit by merely allowing the molecular numbers to be infinite, the generalized mesoscopic free energy F^{(meso)} converges to φ^{ss}, the large deviation rate function for the stationary distributions. This generalized macroscopic free energy φ^{ss} now satisfies a balance equation dφ^{ss}(x)/dt=cmf(x)-σ(x), in which x represents chemical concentration. The chemical motive force cmf(x) and entropy production rate σ(x) are both non-negative, and cmf(x)≤σ(x). The balance equation is valid generally in isothermal driven systems and is different from mechanical energy conservation and the first law; it is actually an unknown form of the second law. Consequences of the emergent thermodynamic quantities and equalities are further discussed. The emergent "law" is independent of underlying kinetic details. Our theory provides an example showing how a macroscopic law emerges from a level below.

  14. Mesoscopic kinetic basis of macroscopic chemical thermodynamics: A mathematical theory

    NASA Astrophysics Data System (ADS)

    Ge, Hao; Qian, Hong

    2016-11-01

    Gibbs' macroscopic chemical thermodynamics is one of the most important theories in chemistry. Generalizing it to mesoscaled nonequilibrium systems is essential to biophysics. The nonequilibrium stochastic thermodynamics of chemical reaction kinetics suggested a free energy balance equation d F(meso)/d t =Ein-ep in which the free energy input rate Ein and dissipation rate ep are both non-negative, and Ein≤ep . We prove that in the macroscopic limit by merely allowing the molecular numbers to be infinite, the generalized mesoscopic free energy F(meso) converges to φss, the large deviation rate function for the stationary distributions. This generalized macroscopic free energy φss now satisfies a balance equation d φss(x ) /d t =cmf(x ) -σ (x ) , in which x represents chemical concentration. The chemical motive force cmf(x ) and entropy production rate σ (x ) are both non-negative, and cmf(x )≤σ (x ) . The balance equation is valid generally in isothermal driven systems and is different from mechanical energy conservation and the first law; it is actually an unknown form of the second law. Consequences of the emergent thermodynamic quantities and equalities are further discussed. The emergent "law" is independent of underlying kinetic details. Our theory provides an example showing how a macroscopic law emerges from a level below.

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

    SciTech Connect

    Pichon, S.; Black, G.; Simmie, J.M.; Curran, H.J.; Chaumeix, N.; Yahyaoui, M.; Donohue, R.

    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)

  16. Nucleation kinetics of diamond on carbide-forming substrates during chemical vapor deposition. 1: Transient nucleation stage

    SciTech Connect

    Liu, H.; Dandy, D.S.

    1996-03-01

    This paper presents a theoretical study on the initial stage of diamond nucleation during chemical vapor deposition. A kinetic model is developed to investigate the time evolution of diamond nucleation on carbide-forming substrates. The calculated results provide some insight into the effects of substrate materials, surface diffusion, and adsorption state on diamond nucleation kinetics.

  17. Improved Kinetic Models for High-Speed Combustion Simulation

    DTIC Science & Technology

    2008-06-01

    TYPE 3. DATES COVERED (From - To) June 2008 Final 18 May 2006 – 18 June 2008 4 . TITLE AND SUBTITLE IMPROVED KINETIC MODELS FOR HIGH-SPEED...44 4 Results and Discussion...19 4 . Multi-Step, Sequential Process Leading to Formation of Phenyl from Benzyl (Scheme 1) ....20 5. Generic Chemical Activation Reaction System

  18. KINETIC MODELING OF COUNTERFLOW DIFFUSION FLAMES OF BUTADIENE. (R828193)

    EPA Science Inventory

    A comprehensive, semi-detailed kinetic scheme was used to simulate the chemical structures of counterflow diffusion and fuel-rich premixed 1,3-butadiene flames, to better understand the formation of polycyclic aromatic hydrocarbons (PAH). The results showed that model predicti...

  19. Kinetics, Chemistry, and Morphology of Syngas Photoinitiated Chemical Vapor Deposition.

    PubMed

    Farhanian, Donya; De Crescenzo, Gregory; Tavares, Jason R

    2017-02-28

    Syngas is the product of gasification processes and is used for the production of petrochemicals. Little attention has been paid to its use in the production of oligomeric thin films under ambient conditions. Herein, the nature of the photoinitiated chemical vapor deposition of films made from syngas using high-wavelength ultraviolet light is discussed, including an exploration of the oligomeric films' structure, synthesis mechanism, and growth kinetics. Specifically, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry analyses provide insight into the chemical structure, illustrating the effect of photogenerated radicals in the formation of aliphatic, anhydride, and cyclic structures. The films are covalently bonded to the substrate and chemically uniform. Electron and atomic force microscopy identify an islandlike morphology for the deposit. These insights into the mechanism and structure are linked to processing parameters through a study on the effect of residence time and treatment duration on the deposition rate, as determined through profilometry.

  20. Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study.

    PubMed

    Shah, Bhavna; Mistry, Chirag; Shah, Ajay

    2013-04-01

    Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)-an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer-Emmett-Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions.

  1. Modeling of Reactor Kinetics and Dynamics

    SciTech Connect

    Matthew Johnson; Scott Lucas; Pavel Tsvetkov

    2010-09-01

    In order to model a full fuel cycle in a nuclear reactor, it is necessary to simulate the short time-scale kinetic behavior of the reactor as well as the long time-scale dynamics that occur with fuel burnup. The former is modeled using the point kinetics equations, while the latter is modeled by coupling fuel burnup equations with the kinetics equations. When the equations are solved simultaneously with a nonlinear equation solver, the end result is a code with the unique capability of modeling transients at any time during a fuel cycle.

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

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

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

  3. Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

    NASA Astrophysics Data System (ADS)

    Müller, Marcus; Li, Weihua; Orozco Rey, Juan Carlos; Welling, Ulrich

    2015-09-01

    Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies (”chemoepitaxy”). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer.

  4. Site-specific functionalization for chemical speciation of Cr(III) and Cr(VI) using polyaniline impregnated nanocellulose composite: equilibrium, kinetic, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Jain, Priyanka; Varshney, Shilpa; Srivastava, Shalini

    2017-07-01

    Site-specific functionalizations are the emergent attention for the enhancement of sorption latent of heavy metals. Limited chemistry has been applied for the fabrication of diafunctionalized materials having potential to tether both environmentally stable oxidation states of chromium (Cr(III) and Cr(VI). Polyaniline impregnated nanocellulose composite (PANI-NCC) has been fabricated using click chemistry and explored for the removal of Cr(III) and Cr(VI) from hydrological environment. The structure, stability, morphology, particle size, surface area, hydrophilicity, and porosity of fabricated PANI-NCC were characterized comprehensively using analytical techniques and mathematical tools. The maximum sorption performance of PANI-NCC was procured for (Cr(III): 47.06 mg g-1; 94.12 %) and (Cr(VI): 48.92 mg g-1; 97.84 %) by equilibrating 0.5 g sorbent dose with 1000 mL of 25 mg L-1 chromium conc. at pH 6.5 and 2.5 for Cr(III) and Cr(VI), respectively. The sorption data showed a best fit to the Langmuir isotherm and pseudo-second-order kinetic model. The negative value of ∆ G° (-8.59 and -11.16 kJ mol-1) and ∆ H° (66.46 × 10-1 and 17.84 × 10-1 kJ mol-1), and positive value of ∆ S° (26.66 and 31.46 J mol-1K-1) for Cr(III) and Cr(VI), respectively, reflect the spontaneous, feasibility, and exothermic nature of the sorption process. The application of fabricated PANI-NCC for removing both the forms of chromium in the presence of other heavy metals was also tested at laboratory and industrial waste water regime. These findings open up new avenues in the row of high performance, scalable, and economic nanobiomaterial for the remediation of both forms of chromium from water streams.

  5. Site-specific functionalization for chemical speciation of Cr(III) and Cr(VI) using polyaniline impregnated nanocellulose composite: equilibrium, kinetic, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Jain, Priyanka; Varshney, Shilpa; Srivastava, Shalini

    2015-10-01

    Site-specific functionalizations are the emergent attention for the enhancement of sorption latent of heavy metals. Limited chemistry has been applied for the fabrication of diafunctionalized materials having potential to tether both environmentally stable oxidation states of chromium (Cr(III) and Cr(VI). Polyaniline impregnated nanocellulose composite (PANI-NCC) has been fabricated using click chemistry and explored for the removal of Cr(III) and Cr(VI) from hydrological environment. The structure, stability, morphology, particle size, surface area, hydrophilicity, and porosity of fabricated PANI-NCC were characterized comprehensively using analytical techniques and mathematical tools. The maximum sorption performance of PANI-NCC was procured for (Cr(III): 47.06 mg g-1; 94.12 %) and (Cr(VI): 48.92 mg g-1; 97.84 %) by equilibrating 0.5 g sorbent dose with 1000 mL of 25 mg L-1 chromium conc. at pH 6.5 and 2.5 for Cr(III) and Cr(VI), respectively. The sorption data showed a best fit to the Langmuir isotherm and pseudo-second-order kinetic model. The negative value of ∆ G° (-8.59 and -11.16 kJ mol-1) and ∆ H° (66.46 × 10-1 and 17.84 × 10-1 kJ mol-1), and positive value of ∆ S° (26.66 and 31.46 J mol-1K-1) for Cr(III) and Cr(VI), respectively, reflect the spontaneous, feasibility, and exothermic nature of the sorption process. The application of fabricated PANI-NCC for removing both the forms of chromium in the presence of other heavy metals was also tested at laboratory and industrial waste water regime. These findings open up new avenues in the row of high performance, scalable, and economic nanobiomaterial for the remediation of both forms of chromium from water streams.

  6. Summary of the LLNL one-dimensional transport-kinetics model of the troposphere and stratosphere: 1981

    SciTech Connect

    Wuebbles, D.J.

    1981-09-01

    Since the LLNL one-dimensional coupled transport and chemical kinetics model of the troposphere and stratosphere was originally developed in 1972 (Chang et al., 1974), there have been many changes to the model's representation of atmospheric physical and chemical processes. A brief description is given of the current LLNL one-dimensional coupled transport and chemical kinetics model of the troposphere and stratosphere.

  7. Kinetic model of network traffic

    NASA Astrophysics Data System (ADS)

    Antoniou, I.; Ivanov, V. V.; Kalinovsky, Yu. L.

    2002-05-01

    We present the first results on the application of the Prigogine-Herman kinetic approach (Kinetic Theory of Vehicular Traffic, American Elsevier Publishing Company, Inc., New York, 1971) to the network traffic. We discuss the solution of the kinetic equation for homogeneous time-independent situations and for the desired speed distribution function, obtained from traffic measurements analysis. For the log-normal desired speed distribution function the solution clearly shows two modes corresponding to individual flow patterns (low-concentration mode) and to collective flow patterns (traffic jam mode). For low-concentration situations we found almost linear dependence of the information flow versus the concentration and that the higher the average speed the lower the concentration at which the optimum flow takes place. When approaching the critical concentration there are no essential differences in the flow for different desired average speeds, whereas for the individual flow regions there are dramatic differences.

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

    SciTech Connect

    Santoro, Robers; Dryer, Frederick; Ju, Yiguang

    2013-09-30

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

  9. In vitro-in vivo extrapolation of quantitative hepatic biotransformation data for fish - I. A review of methods, and strategies for incorporating intrinsic clearance estimates into chemical kinetic models

    SciTech Connect

    Nichols, John W.; Schultz, Irv R.; Fitzsimmons, Patrick N..

    2006-06-10

    Mammalian researchers have developed a stepwise approach to predict in vivo hepatic clearance from measurements of in vitro hepatic metabolism. The resulting clearance estimates have been used to screen drug candidates, identify potential drug-drug interactions, investigate idiosyncratic drug responses, and support toxicology risk assessments. In this report we review these methods, discuss their potential application to studies with fish, and describe how extrapolated values could be incorporated into well-known compartmental kinetic models. Empirical equations that relate extrapolation factors to chemical log Kow are given to facilitate the incorporation of metabolism data into bioconcentration and bioaccumulation models. Because they explicitly incorporate the concept of clearance, compartmental clearance volume models are particularly well suited for incorporating hepatic clearance estimates. The manner in which these clearance values are incorporated into a given model depends, however, on the measurement frame of reference. Procedures for the incorporation of in vitro metabolism data into physiologically based toxicokinetic (PBTK) models are also described. Unlike most compartmental models, PBTK models are developed to describe the effects of metabolism in the tissue where it occurs. In addition, PBTK models are well suited to modeling metabolism in more than one tissue.

  10. Theory of homogeneous nucleation - A chemical kinetic view

    NASA Technical Reports Server (NTRS)

    Yang, C. H.; Qiu, H.

    1986-01-01

    A simple function with two undetermined parameters has been used in place of the Thomson-Gibbs relation to relate the activation energy of the vaporization reaction to cluster size. The parameters are iterated to assume optimum values in numerical computation so experimental data may be correlated. Calculations show this approach closely predicts and correlates available data for water, benzene, and ethanol. The nucleation formulism is redeveloped with an emphasis on the chemical kinetic view. Surface tension of the liquid and free energy of droplet formation are not used in its derivation.

  11. Theory of homogeneous nucleation - A chemical kinetic view

    NASA Technical Reports Server (NTRS)

    Yang, C. H.; Qiu, H.

    1986-01-01

    A simple function with two undetermined parameters has been used in place of the Thomson-Gibbs relation to relate the activation energy of the vaporization reaction to cluster size. The parameters are iterated to assume optimum values in numerical computation so experimental data may be correlated. Calculations show this approach closely predicts and correlates available data for water, benzene, and ethanol. The nucleation formulism is redeveloped with an emphasis on the chemical kinetic view. Surface tension of the liquid and free energy of droplet formation are not used in its derivation.

  12. Solutions of the chemical kinetic equations for initially inhomogeneous mixtures.

    NASA Technical Reports Server (NTRS)

    Hilst, G. R.

    1973-01-01

    Following the recent discussions by O'Brien (1971) and Donaldson and Hilst (1972) of the effects of inhomogeneous mixing and turbulent diffusion on simple chemical reaction rates, the present report provides a more extensive analysis of when inhomogeneous mixing has a significant effect on chemical reaction rates. The analysis is then extended to the development of an approximate chemical sub-model which provides much improved predictions of chemical reaction rates over a wide range of inhomogeneities and pathological distributions of the concentrations of the reacting chemical species. In particular, the development of an approximate representation of the third-order correlations of the joint concentration fluctuations permits closure of the chemical sub-model at the level of the second-order moments of these fluctuations and the mean concentrations.

  13. Assessing human variability in kinetics for exposures to multiple environmental chemicals: a physiologically based pharmacokinetic modeling case study with dichloromethane, benzene, toluene, ethylbenzene, and m-xylene.

    PubMed

    Valcke, Mathieu; Haddad, Sami

    2015-01-01

    The objective of this study was to compare the magnitude of interindividual variability in internal dose for inhalation exposure to single versus multiple chemicals. Physiologically based pharmacokinetic models for adults (AD), neonates (NEO), toddlers (TODD), and pregnant women (PW) were used to simulate inhalation exposure to "low" (RfC-like) or "high" (AEGL-like) air concentrations of benzene (Bz) or dichloromethane (DCM), along with various levels of toluene alone or toluene with ethylbenzene and xylene. Monte Carlo simulations were performed and distributions of relevant internal dose metrics of either Bz or DCM were computed. Area under the blood concentration of parent compound versus time curve (AUC)-based variability in AD, TODD, and PW rose for Bz when concomitant "low" exposure to mixtures of increasing complexities occurred (coefficient of variation (CV) = 16-24%, vs. 12-15% for Bz alone), but remained unchanged considering DCM. Conversely, AUC-based CV in NEO fell (15 to 5% for Bz; 12 to 6% for DCM). Comparable trends were observed considering production of metabolites (AMET), except for NEO's CYP2E1-mediated metabolites of Bz, where an increased CV was observed (20 to 71%). For "high" exposure scenarios, Cmax-based variability of Bz and DCM remained unchanged in AD and PW, but decreased in NEO (CV= 11-16% to 2-6%) and TODD (CV= 12-13% to 7-9%). Conversely, AMET-based variability for both substrates rose in every subpopulation. This study analyzed for the first time the impact of multiple exposures on interindividual variability in toxicokinetics. Evidence indicates that this impact depends upon chemical concentrations and biochemical properties, as well as the subpopulation and internal dose metrics considered.

  14. Viral kinetic modeling: state of the art

    DOE PAGES

    Canini, Laetitia; Perelson, Alan S.

    2014-06-25

    Viral kinetic modeling has led to increased understanding of the within host dynamics of viral infections and the effects of therapy. Here we review recent developments in the modeling of viral infection kinetics with emphasis on two infectious diseases: hepatitis C and influenza. We review how viral kinetic modeling has evolved from simple models of viral infections treated with a drug or drug cocktail with an assumed constant effectiveness to models that incorporate drug pharmacokinetics and pharmacodynamics, as well as phenomenological models that simply assume drugs have time varying-effectiveness. We also discuss multiscale models that include intracellular events in viralmore » replication, models of drug-resistance, models that include innate and adaptive immune responses and models that incorporate cell-to-cell spread of infection. Overall, viral kinetic modeling has provided new insights into the understanding of the disease progression and the modes of action of several drugs. In conclusion, we expect that viral kinetic modeling will be increasingly used in the coming years to optimize drug regimens in order to improve therapeutic outcomes and treatment tolerability for infectious diseases.« less

  15. Viral kinetic modeling: state of the art

    SciTech Connect

    Canini, Laetitia; Perelson, Alan S.

    2014-06-25

    Viral kinetic modeling has led to increased understanding of the within host dynamics of viral infections and the effects of therapy. Here we review recent developments in the modeling of viral infection kinetics with emphasis on two infectious diseases: hepatitis C and influenza. We review how viral kinetic modeling has evolved from simple models of viral infections treated with a drug or drug cocktail with an assumed constant effectiveness to models that incorporate drug pharmacokinetics and pharmacodynamics, as well as phenomenological models that simply assume drugs have time varying-effectiveness. We also discuss multiscale models that include intracellular events in viral replication, models of drug-resistance, models that include innate and adaptive immune responses and models that incorporate cell-to-cell spread of infection. Overall, viral kinetic modeling has provided new insights into the understanding of the disease progression and the modes of action of several drugs. In conclusion, we expect that viral kinetic modeling will be increasingly used in the coming years to optimize drug regimens in order to improve therapeutic outcomes and treatment tolerability for infectious diseases.

  16. Hard-sphere kinetic models for inert and reactive mixtures

    NASA Astrophysics Data System (ADS)

    Polewczak, Jacek

    2016-10-01

    I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A *, B *, in which the chemical reactions are of the type A+B\\rightleftharpoons {{A}\\ast}+{{B}\\ast} , with A * and B * being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided.

  17. Kinetic-effect models and their applications.

    PubMed

    Grevel, J

    1987-04-01

    This article focuses on mathematical models that analyze the time course of drug effects in humans. Any such model, whether parametric or nonparametric, is termed a kinetic-effect model (KEM). These models serve to describe (interpolation) and to predict (extrapolation) the effect-time profile. KEMs are applicable to many problems in pharmaceutics, pharmacology, and clinical pharmacology.

  18. Kinetic model for kraft pulping of hardwood

    SciTech Connect

    Giudici, R.; Park, S.W.

    1996-03-01

    A comprehensive model for the kraft pulping kinetics of Eucalyptus saligna hardwood is presented. Kinetic parameters were estimated by fitting the model to available experimental data taken from the literature over a range of process variables. The model takes into account the effect of hydroxide and sulfide concentration in the liquor as well as the temperature-time history of the cooking. Model predictions were successfully compared with an independent set of bench-scale plant data for lignin and carbohydrate dissolution. The model is able to predict quite well the trends of the process variables.

  19. The H-theorem for the physico-chemical kinetic equations with explicit time discretization

    NASA Astrophysics Data System (ADS)

    Adzhiev, S. Z.; Melikhov, I. V.; Vedenyapin, V. V.

    2017-09-01

    There is demonstrated in the present paper, that the H-theorem in the case of explicit time discretization of the physico-chemical kinetic equations, generally speaking, is not valid. We prove the H-theorem, when the system of the physico-chemical kinetic equations with explicit time discretization has the form of non-linear analogue of the Markov process with doubly stochastic matrix, and for more general cases. In these cases the proof is reduced to the proof of the H-theorem for Markov chains. The simplest discrete velocity models of the Boltzmann equation with explicit time discretization -the Carleman and Broadwell models are discussed and the H-theorem for them in the case of discrete time is proved.

  20. Thermoreversible associating polymer networks. I. Interplay of thermodynamics, chemical kinetics, and polymer physics.

    PubMed

    Hoy, Robert S; Fredrickson, Glenn H

    2009-12-14

    Hybrid molecular dynamics/Monte Carlo simulations are used to study melts of unentangled, thermoreversibly associating supramolecular polymers. In this first of a series of papers, we describe and validate a model that is effective in separating the effects of thermodynamics and chemical kinetics on the dynamics and mechanics of these systems, and is extensible to arbitrarily nonequilibrium situations and nonlinear mechanical properties. We examine the model's quiescent (and heterogeneous) dynamics, nonequilibrium chemical dynamics, and mechanical properties. Many of our results may be understood in terms of the crossover from diffusion-limited to kinetically limited sticky bond recombination, which both influences and is influenced by polymer physics, i.e., the connectivity of the parent chains.

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

    SciTech Connect

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

    1996-05-01

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

  2. Chemical kinetics of discharge-driven oxygen-iodine lasers

    NASA Astrophysics Data System (ADS)

    Azyazov, Valeriy N.; Kabir, Md. Humayun; Antonov, Ivan O.; Heaven, Michael C.

    2007-05-01

    Oxygen-iodine lasers that utilize electrical discharges to produce O II(a1Δ) are currently being developed. The discharge generators differ from those used in chemical oxygen-iodine lasers in that they produce significant amounts of atomic oxygen and traces of ozone. As a consequence of these differences, the chemical kinetics of the discharge laser are markedly different from those of a conventional chemical oxygen-iodine laser (COIL). The reactions of O with iodine include channels that are both beneficial and detrimental to the laser. The beneficial reactions result in the dissociation of I II while the detrimental processes cause direct and indirect removal of I(2P 1/2) (denoted I*, the upper level of the laser). We have examined kinetic processes relevant to the laser through studies of photo-initiated reactions in N IIO/CO II/I II mixtures. The reactions have been monitored using absorption spectroscopy, laser induced fluorescence and time-resolved emission spectroscopy. It has been established that deactivation of I* by O atoms is a critical energy loss process. We have determined a rate constant of (1.2+/-0.1)×10 -11 cm 3 s -1 for this reaction. As part of this effort the branching fraction for the formation of O II(a) from the reaction of O(1D) with N IIO was determined to be 0.38. This result has implications for lasers based on photolysis of O 3/N IIO/I II mixtures and the formation of O II(a) in the upper atmosphere.

  3. Classical Antiferromagnetism in Kinetically Frustrated Electronic Models

    NASA Astrophysics Data System (ADS)

    Sposetti, C. N.; Bravo, B.; Trumper, A. E.; Gazza, C. J.; Manuel, L. O.

    2014-05-01

    We study, by means of the density matrix renormalization group, the infinite U Hubbard model—with one hole doped away from half filling—in triangular and square lattices with frustrated hoppings, which invalidate Nagaoka's theorem. We find that these kinetically frustrated models have antiferromagnetic ground states with classical local magnetization in the thermodynamic limit. We identify the mechanism of this kinetic antiferromagnetism with the release of the kinetic energy frustration, as the hole moves in the established antiferromagnetic background. This release can occur in two different ways: by a nontrivial spin Berry phase acquired by the hole, or by the effective vanishing of the hopping amplitude along the frustrating loops.

  4. Chemical Kinetics Mechanism Reduction Based on Principal Component Analysis: Development and Testing of Some New Implementations

    DTIC Science & Technology

    2013-05-01

    prediction of propulsion system performance. In addition, programs employed in this study for screening the merit of reduced mechanisms were...development of system -specific gas-phase finite-rate chemical kinetics mechanisms is a significant part of these efforts (Anderson et al., 2010; Chen and...employed to model other combustion systems . The final step involves producing a “reduced” (or skeletal) mechanism from the detailed/full one

  5. Notes on the models of cadmium kinetics.

    PubMed

    Yan, Xiong

    2005-11-01

    This paper identifies several drawbacks in the models of absorption and desorption of cadmium presented by [Garcia-Gomez, C., Carbonell, G., 2004. Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches. Chemosphere 55, 869-878]. It then provides suggestions on improving the effectiveness of the model.

  6. Joint Non-kinetic Effects Model (JNEM)

    NASA Technical Reports Server (NTRS)

    Chamberlain, Robert G.; Metivier, Timothy

    2006-01-01

    This slide presentation reviews the development of the Joint Non-kinetic Effects Model (JNEM), which is tool to support Battle Command Training that links simulation-generated non-kinetic events and outcomes to Training Audience Command and Staff decisions. JNEM helps create the operating environment for the following population groups (P-groups): (1) Local Civilians on the Battlefield, (2) Inter-Governmental Organizations (3) Non-Governmental Organizations (4) Contractors on the battlefield.

  7. Algebraic operator approach to gas kinetic models

    NASA Astrophysics Data System (ADS)

    Il'ichov, L. V.

    1997-02-01

    Some general properties of the linear Boltzmann kinetic equation are used to present it in the form ∂ tϕ = - †Âϕ with the operators Âand† possessing some nontrivial algebraic properties. When applied to the Keilson-Storer kinetic model, this method gives an example of quantum ( q-deformed) Lie algebra. This approach provides also a natural generalization of the “kangaroo model”.

  8. Significance of xenobiotic metabolism for bioaccumulation kinetics of organic chemicals in Gammarus pulex.

    PubMed

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

    2012-03-20

    Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen (14)C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacrylate, malathion, chlorpyrifos, aldicarb, carbofuran, carbaryl, 2,4-dichlorophenol, 2,4,5-trichlorophenol, pentachlorophenol, 4-nitrobenzyl-chloride, 2,4-dichloroaniline, and sea-nine (4,5-dichloro-2-octyl-3-isothiazolone)). We detected and identified metabolites using HPLC with UV and radio-detection as well as high resolution mass spectrometry (LTQ-Orbitrap). Kinetics of uptake, biotransformation, and elimination of parent compounds and metabolites were modeled with a first-order one-compartment model. Bioaccumulation factors were calculated for parent compounds and metabolite enrichment factors for metabolites. Out of 19 detected metabolites, we identified seven by standards or accurate mass measurements and two via pathway analysis and analogies to other compounds. 1,2,3-Trichlorobenzene, imidacloprid, and 4,6-dinitro-o-cresol were not biotransformed. Dietary uptake contributed little to overall uptake. Differentiation between parent and metabolites increased accuracy of bioaccumulation parameters compared to total (14)C measurements. Biotransformation dominated toxicokinetics and strongly affected internal concentrations of parent compounds and metabolites. Many metabolites reached higher internal concentrations than their parents, characterized by large metabolite enrichment factors.

  9. From prelife to life: how chemical kinetics become evolutionary dynamics

    PubMed Central

    Chen, Irene A.

    2015-01-01

    Conspectus Life is that which evolves. Living systems are the products of evolutionary processes and are capable of undergoing further evolution. A crucial question for the origin of life is the following: when do chemical kinetics become evolutionary dynamics? In this paper we review properties of ‘prelife’ and discuss the transition from prelife to life. We describe prelife as a chemical system where activated monomers can co-polymerize into macromolecules (such as RNA). These macromolecules are information carriers. Their physical and chemical properties depend to a certain extent on their particular sequence of monomers. We consider prelife as a logical precursor of life, where macromolecules are formed by copolymerization, but they are not capable of replication. Prelife can undergo ‘prevolutionary dynamics’. There can be mutation, selection and cooperation. Prelife selection, however, is blunt: small differences in rate constants lead to small differences in abundance. Life emerges with the ability of replication. In the resulting evolutionary dynamics selection is sharp: small differences in rate constants can lead to large differences in abundance. We also study the competition of different ‘prelives’ and find that there can be selection for those systems which ultimately give rise to replication. The transition from prelife to life can occur over an extended period of time. There may not have been a single moment which marks the origin of life. Instead prelife seeds many attempts for the origin of life. Eventually life takes over and destroys prelife. PMID:22335792

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

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.

    1994-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.

    1994-01-01

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

  12. Some aspects of mathematical and chemical modeling of complex chemical processes

    NASA Technical Reports Server (NTRS)

    Nemes, I.; Botar, L.; Danoczy, E.; Vidoczy, T.; Gal, D.

    1983-01-01

    Some theoretical questions involved in the mathematical modeling of the kinetics of complex chemical process are discussed. The analysis is carried out for the homogeneous oxidation of ethylbenzene in the liquid phase. Particular attention is given to the determination of the general characteristics of chemical systems from an analysis of mathematical models developed on the basis of linear algebra.

  13. Ab initio Quantum Chemical Reaction Kinetics: Recent Applications in Combustion Chemistry (Briefing Charts)

    DTIC Science & Technology

    2015-06-28

    Charts 3. DATES COVERED (From - To) June 2015-June 2015 4. TITLE AND SUBTITLE AB INITIO QUANTUM CHEMICAL REACTION KINETICS: RECENT APPLICATIONS IN...Unlimited. 13. SUPPLEMENTARY NOTES Briefing Charts presented at 9th Int. Conf. Chemical Kinetics; Ghent, Belgium; 28 Jun 2015. PA#15351. 14. ABSTRACT...ghanshyam.vaghjiani@us.af.mil Ab initio Quantum Chemical Reaction Kinetics: Recent Applications in Combustion Chemistry Ghanshyam L. Vaghjiani* DISTRIBUTION A

  14. Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

    PubMed

    Otero, Toribio F

    2017-01-18

    In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (Ea), the reaction coefficient (k) and the reaction orders (α and β) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. Ea, k, α and β include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

  15. Algorithms, modelling and VO₂ kinetics.

    PubMed

    Capelli, Carlo; Carlo, Capelli; Cautero, Michela; Michela, Cautero; Pogliaghi, Silvia; Silvia, Pogliaghi

    2011-03-01

    This article summarises the pros and cons of different algorithms developed for estimating breath-by-breath (B-by-B) alveolar O(2) transfer (VO 2A) in humans. VO 2A is the difference between O(2) uptake at the mouth and changes in alveolar O(2) stores (∆ VO(2s)), which for any given breath, are equal to the alveolar volume change at constant FAO2/FAiO2 ∆VAi plus the O(2) alveolar fraction change at constant volume [V Ai-1(F Ai - F Ai-1) O2, where V (Ai-1) is the alveolar volume at the beginning of a breath. Therefore, VO 2A can be determined B-by-B provided that V (Ai-1) is: (a) set equal to the subject's functional residual capacity (algorithm of Auchincloss, A) or to zero; (b) measured (optoelectronic plethysmography, OEP); (c) selected according to a procedure that minimises B-by-B variability (algorithm of Busso and Robbins, BR). Alternatively, the respiratory cycle can be redefined as the time between equal FO(2) in two subsequent breaths (algorithm of Grønlund, G), making any assumption of V (Ai-1) unnecessary. All the above methods allow an unbiased estimate of VO2 at steady state, albeit with different precision. Yet the algorithms "per se" affect the parameters describing the B-by-B kinetics during exercise transitions. Among these approaches, BR and G, by increasing the signal-to-noise ratio of the measurements, reduce the number of exercise repetitions necessary to study VO2 kinetics, compared to A approach. OEP and G (though technically challenging and conceptually still debated), thanks to their ability to track ∆VO(2s) changes during the early phase of exercise transitions, appear rather promising for investigating B-by-B gas exchange.

  16. Adsorption studies of molasse's wastewaters on activated carbon: modelling with a new fractal kinetic equation and evaluation of kinetic models.

    PubMed

    Figaro, S; Avril, J P; Brouers, F; Ouensanga, A; Gaspard, S

    2009-01-30

    Adsorption kinetic of molasses wastewaters after anaerobic digestion (MSWD) and melanoidin respectively on activated carbon was studied at different pH. The kinetic parameters could be determined using classical kinetic equations and a recently published fractal kinetic equation. A linear form of this equation can also be used to fit adsorption data. Even with lower correlation coefficients the fractal kinetic equation gives lower normalized standard deviation values than the pseudo-second order model generally used to fit adsorption kinetic data, indicating that the fractal kinetic model is much more accurate for describing the kinetic adsorption data than the pseudo-second order kinetic model.

  17. Reduced and simplified chemical kinetics for air dissociation using Computational Singular Perturbation

    NASA Technical Reports Server (NTRS)

    Goussis, D. A.; Lam, S. H.; Gnoffo, P. A.

    1990-01-01

    The Computational Singular Perturbation CSP methods is employed (1) in the modeling of a homogeneous isothermal reacting system and (2) in the numerical simulation of the chemical reactions in a hypersonic flowfield. Reduced and simplified mechanisms are constructed. The solutions obtained on the basis of these approximate mechanisms are shown to be in very good agreement with the exact solution based on the full mechanism. Physically meaningful approximations are derived. It is demonstrated that the deduction of these approximations from CSP is independent of the complexity of the problem and requires no intuition or experience in chemical kinetics.

  18. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  19. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  20. Development of Detailed Kinetic Models for Fischer-Tropsch Fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Carstensen, H; Dean, A M

    2008-10-28

    Fischer-Tropsch (FT) fuels can be synthesized from a syngas stream generated by the gasification of biomass. As such they have the potential to be a renewable hydrocarbon fuel with many desirable properties. However, both the chemical and physical properties are somewhat different from the petroleum-based hydrocarbons that they might replace, and it is important to account for such differences when considering using them as replacements for conventional fuels in devices such as diesel engines and gas turbines. FT fuels generally contain iso-alkanes with one or two substituted methyl groups to meet the pour-point specifications. Although models have been developed for smaller branched alkanes such as isooctane, additional efforts are required to properly capture the kinetics of the larger branched alkanes. Recently, Westbrook et al. developed a chemical kinetic model that can be used to represent the entire series of n-alkanes from C{sub 1} to C{sub 16} (Figure 1). In the current work, the model is extended to treat 2,2,4,4,6,8,8-heptamethylnonane (HMN), a large iso-alkane. The same reaction rate rules used in the iso-octane mechanism were incorporated in the HMN mechanism. Both high and low temperature chemistry was included so that the chemical kinetic model would be applicable to advanced internal combustion engines using low temperature combustion strategies. The chemical kinetic model consists of 1114 species and 4468 reactions. Concurrently with this effort, work is underway to improve the details of specific reaction classes in the mechanism, guided by high-level electronic structure calculations. Attention is focused upon development of accurate rate rules for abstraction of the tertiary hydrogens present in branched alkanes and properly accounting for the pressure dependence of the ?-scission, isomerization, and R + O{sub 2} reactions.

  1. Propyl propionate methanolysis kinetics: experiment and modeling.

    PubMed

    Povarov, Vladimir G; Keresten, Andrey A

    2013-09-26

    In concentrated solutions, the reaction rate constant calculated from the law of mass action depends on a mixture composition. In this study, we suggest a new approach based on the dynamic equilibrium principle and modified equations of van Rysselberghe and de Donder. Experimental results obtained for propyl propionate methanolysis are in good agreement with calculated ones in the entire area of studied compositions. Such a method allows one to describe kinetics of reversible chemical reactions on both sides of the equilibrium.

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

    NASA Astrophysics Data System (ADS)

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

    1999-06-01

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

  3. Hybrid kinetic/fluid modeling of silicon nanoparticles dynamics in silane plasma discharges

    NASA Astrophysics Data System (ADS)

    Orlac'h, J.-M.; Giovangigli, V.; Novikova, T.; Cabarrocas, P. Roca i.

    2016-11-01

    We present a fully coupled self-consistent model for the evolution of nanoparticles in a plasma-enhanced chemical vapor deposition (PECVD) reactor. The plasma is treated as a fluid while the nanoparticles are handled kinetically. The plasma fluid model is derived from kinetic theory applied to multicomponent two-temperature chemically reactive polyatomic plasmas. The model has been implemented numerically for a silane-hydrogen plasma in the early stage of nanoparticles generation.

  4. An open-source chemical kinetics network: VULCAN

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    PubMed

    Nguyen, Thanh Lam; Stanton, John F

    2015-07-16

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

  6. KINETICS: A computer program to analyze chemical reaction data. Revision 2

    SciTech Connect

    Braun, R.L.; Burnham, A.K.

    1994-09-01

    KINETICS (Version 3.2) is a copyrighted, user-friendly kinetics analysis computer program designed for reactions such-as kerogen or polymer decomposition. It can fit rate parameters to chemical reaction data (rate or cumulative reacted) measured at a series of constant temperatures, constant heating rates, or arbitrary thermal histories. The program uses two models with conversion-dependent Azrhenius parameters and two models with activation energy distributions. The discrete distribution model fits an average frequency factor and relative fractions and activation energies for up to 25 parallel, fast-order reactions. The Gaussian distribution model fits a frequency factor, activation energy, Gaussian distribution parameter, and reaction order for up to 3 parallel reactions. For both distribution models, if the experiments are at a series of constant heating rates, the program uses a very fast approximate fitting procedure to determine possible initial parameter-estimates for the subsequent nonlinear regression analysis. This increases the probability that the regression analysis will properly. converge with a minimum of computer time. Once convergence is reached by the discrete model, the parameter space is further systematically searched to achieve global convergence. With the Gaussian model, the calculated rates or integrals can be convoluted with an experimental tracer signal during the nonlinear regression to account for dispersion effects often found in real chemical reaction data. KINETICS can also be used in an application mode to calculate reaction rates and integrals for previously determined Gaussian or discrete, parameters, using an arbitrary thermal history. Four additional models have been incorporated for the kinetics analysis of polymers and other materials, including some kerogens, which have a reaction-rate profile that is narrower than that for a single first-order reaction.

  7. Acetylcholine receptor: channel-opening kinetics evaluated by rapid chemical kinetic and single-channel current measurements.

    PubMed Central

    Udgaonkar, J. B.; Hess, G. P.

    1987-01-01

    from the regulatory site, and a carbamoylcholine concentration-dependent, but voltage-independent, time constant interpreted to represent the rate constant for channel opening (k0). An analysis of the mean closed time data on the basis of the minimum model gives values for K1 and k0 of 0.6 mM and 440 s-1, respectively, with carbamoylcholine as the activating ligand. The values obtained for K1, phi (= kc/k0), J, and alpha from the single-channel current measurements using electroplax are in good agreement with the values obtained from the chemical kinetic measurements using receptor-rich vesicles prepared from the same cells. These results confirm the assumed basic agreement between two entirely different methodologies and underlie the strategy of using the two techniques to obtain complementary information in time and ligand-concentration regions where only one or the other technique can be used. This agreement between results allows estimates to be made of the ko values, for both acetylcholine and suberyldicholine, from the phi values obtained from the chemical kinetic measurements and the kc values obtained in single-channel current measurements. PMID:2447965

  8. Chemical kinetics of octane sensitivity in a spark-ignition engine (Chemical Kinetics of Octane Sensitivity in a Spark Ignition Engine)

    DOE PAGES

    Westbrook, Charles K.; Mehl, Marco; Pitz, William J.; ...

    2016-07-11

    This article uses a chemical kinetic modeling approach to study the influences of fuel molecular structure on Octane Sensitivity (OS) in Spark Ignition (SI) engines. Octane Sensitivity has the potential to identify fuels that can be used in next-generation high compression, turbocharged SI engines to avoid unwanted knocking conditions and extend the range of operating conditions that can be used in such engines. While the concept of octane numbers of different fuels has been familiar for many years, the variations of their values and their role in determining Octane Sensitivity have not been addressed previously in terms of the basicmore » structures of the fuel molecules. In particular, the importance of electron delocalization on low temperature hydrocarbon reactivity and its role in determining OS in engine fuel is described here for the first time. Finally, the role of electron delocalization on fuel reactivity and Octane Sensitivity is illustrated for a very wide range of engine fuel types, including n-alkane, 1-olefin, n-alcohol, and n-alkyl benzenes, and the unifying features of these fuels and their common trends, using existing detailed chemical kinetic reaction mechanisms that have been collected and unified to produce an overall model with unprecedented capabilities.« less

  9. Chemical kinetics of octane sensitivity in a spark-ignition engine (Chemical Kinetics of Octane Sensitivity in a Spark Ignition Engine)

    SciTech Connect

    Westbrook, Charles K.; Mehl, Marco; Pitz, William J.; Sjöberg, Magnus

    2016-07-11

    This article uses a chemical kinetic modeling approach to study the influences of fuel molecular structure on Octane Sensitivity (OS) in Spark Ignition (SI) engines. Octane Sensitivity has the potential to identify fuels that can be used in next-generation high compression, turbocharged SI engines to avoid unwanted knocking conditions and extend the range of operating conditions that can be used in such engines. While the concept of octane numbers of different fuels has been familiar for many years, the variations of their values and their role in determining Octane Sensitivity have not been addressed previously in terms of the basic structures of the fuel molecules. In particular, the importance of electron delocalization on low temperature hydrocarbon reactivity and its role in determining OS in engine fuel is described here for the first time. Finally, the role of electron delocalization on fuel reactivity and Octane Sensitivity is illustrated for a very wide range of engine fuel types, including n-alkane, 1-olefin, n-alcohol, and n-alkyl benzenes, and the unifying features of these fuels and their common trends, using existing detailed chemical kinetic reaction mechanisms that have been collected and unified to produce an overall model with unprecedented capabilities.

  10. Chemical kinetics of octane sensitivity in a spark-ignition engine (Chemical Kinetics of Octane Sensitivity in a Spark Ignition Engine)

    SciTech Connect

    Westbrook, Charles K.; Mehl, Marco; Pitz, William J.; Sjöberg, Magnus

    2016-07-11

    This article uses a chemical kinetic modeling approach to study the influences of fuel molecular structure on Octane Sensitivity (OS) in Spark Ignition (SI) engines. Octane Sensitivity has the potential to identify fuels that can be used in next-generation high compression, turbocharged SI engines to avoid unwanted knocking conditions and extend the range of operating conditions that can be used in such engines. While the concept of octane numbers of different fuels has been familiar for many years, the variations of their values and their role in determining Octane Sensitivity have not been addressed previously in terms of the basic structures of the fuel molecules. In particular, the importance of electron delocalization on low temperature hydrocarbon reactivity and its role in determining OS in engine fuel is described here for the first time. Finally, the role of electron delocalization on fuel reactivity and Octane Sensitivity is illustrated for a very wide range of engine fuel types, including n-alkane, 1-olefin, n-alcohol, and n-alkyl benzenes, and the unifying features of these fuels and their common trends, using existing detailed chemical kinetic reaction mechanisms that have been collected and unified to produce an overall model with unprecedented capabilities.

  11. Simple Model of Protein Folding Kinetics

    NASA Astrophysics Data System (ADS)

    Zwanzig, Robert

    1995-10-01

    A simple model of the kinetics of protein folding is presented. The reaction coordinate is the "correctness" of a configuration compared with the native state. The model has a gap in the energy spectrum, a large configurational entropy, a free energy barrier between folded and partially folded states, and a good thermodynamic folding transition. Folding kinetics is described by a master equation. The folding time is estimated by means of a local thermodynamic equilibrium assumption and then is calculated both numerically and analytically by solving the master equation. The folding time has a maximum near the folding transition temperature and can have a minimum at a lower temperature.

  12. Chemical Kinetics in Support of Syngas Turbine Combustion

    SciTech Connect

    Dryer, Frederick

    2007-07-31

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

  13. A Piagetian Learning Cycle for Introductory Chemical Kinetics.

    ERIC Educational Resources Information Center

    Batt, Russell H.

    1980-01-01

    Described is a Piagetian learning cycle based on Monte Carlo modeling of several simple reaction mechanisms. Included are descriptions of learning cycle phases (exploration, invention, and discovery) and four BASIC-PLUS computer programs to be used in the explanation of chemical reacting systems. (Author/DS)

  14. Tropospheric chemical models

    NASA Technical Reports Server (NTRS)

    Prinn, R. G.

    1992-01-01

    The differences in atmospheric composition over the globe and the short- and long-term variations in this composition are the net effect of several atmospheric and biospheric processes: biospheric emissions, atmospheric circulation, atmospheric chemical transformations and finally deposition back to the surface. Accurate and realistic atmospheric chemistry and circulation models are essential to interpret the observed global distributions and trends of atmospheric species in terms of these underlying processes. Comparisons between model predictions and observations test current understanding of these processes and models used in conjunction with inverse methods allow deductions of the rates of these processes from the observations. With the planned inclusion of at least CO and CH4 observations on the Earth Observing System (EOS) satellites, together with the large global data set expected from in situ observations under the International Global Atmospheric Chemistry (IGAC) Project, the further development of global three-dimensional high-resolution atmospheric chemistry and circulation models in order to interpret this new data is a high-priority endeavor.

  15. Chemistry Resolved Kinetic Flow Modeling of TATB Based Explosives

    SciTech Connect

    Vitello, P A; Fried, L E; Howard, W M; Levesque, G; Souers, P C

    2011-07-21

    Detonation waves in insensitive, TATB based explosives are believed to have multi-time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. They use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. They term their model chemistry resolved kinetic flow as CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. A HE-validation suite of model simulations compared to experiments at ambient, hot, and cold temperatures has been developed. They present here a new rate model and comparison with experimental data.

  16. Modeling recrystallization kinetics during strip rolling

    SciTech Connect

    Sun, W.P.; Hawbolt, E.B.; Meadowcroft, T.R.

    1995-01-01

    In order to simulate the microstructural evolution during hot strip rolling, double-hit compression tests have been carried out on plain carbon steels. Using the softening data obtained by these tests, mathematical models were developed to predict the overall kinetics of static recrystallization under roughing and finishing mill conditions. These models include the effects of deformation temperature, applied strain, strain rate and initial austenite grain size. Predictions based on these models are in reasonable agreement with the present experimental results.

  17. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  18. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  19. Chemical earth models

    NASA Astrophysics Data System (ADS)

    Javoy, Marc

    1999-10-01

    This article presents a critical review of method, concepts and prejudices used bv modelists of the Earth's chemical composition over approximate the last fifty years and of the resulting compositions. Brief descriptions are given of admitted accretion mechanisms, of the starting materials most often considered and of the major parameters and recurrent concepts: 'reduced" state, mantle homogeneity vs heterogeneity, 'low pressure' core formation, 'great impact', refractory, lithophile, siderophile, compatible, incompatible character of elements, depleted and degassed mantle, Urey ratio, as well as the description of a commonly-used instrument, possibly harmful to Iogic, the famous Ockham's razor. Differences between models are now restricted to the lower mantle composition:the 'primary' (before crust differentiation) upper mentle varies little from model to model and the idea of a 10-15% combined Si-O-S concentration as representing the necessary light elements in the core is gaining more and more ground. The dominant type of model derives more or less directly from the CI cabonaceous composition by complete devolatilization and reduction. Its mantle is homogeneous and convecting mainly in a one-level mode, in accordence with dominant geophysicists' views but in rather strong disagreement with geochemical data and models which insist on the strong decoupling between lower and upper mantle. Its low Si excess is generally supposed to have been absorbed by the core, whereas its high refractory lithophile element (RLE) content creates mass balance problems relative to presently observed mantle and crust concentrations. The alternative type is a two-lavel mantle with a Si and Fe-rich, RLE-poor, lower mantle, previously based mainly on seismic and mineral physics data, and now also on geochemical and cosmochemical arguments.

  20. Exploring Secondary Students' Understanding of Chemical Kinetics through Inquiry-Based Learning Activities

    ERIC Educational Resources Information Center

    Chairam, Sanoe; Klahan, Nutsuda; Coll, Richard K.

    2015-01-01

    This research is trying to evaluate the feedback of Thai secondary school students to inquiry-based teaching and learning methods, exemplified by the study of chemical kinetics. This work used the multiple-choice questions, scientifically practical diagram and questionnaire to assess students' understanding of chemical kinetics. The findings…

  1. Preservice Science Teachers' Attitudes towards Chemistry and Misconceptions about Chemical Kinetics

    ERIC Educational Resources Information Center

    Çam, Aylin; Topçu, Mustafa Sami; Sülün, Yusuf

    2015-01-01

    The present study investigates preservice science teachers' attitudes towards chemistry; their misconceptions about chemical kinetics; and relationships between pre-service science teachers' attitudes toward chemistry and misconceptions about chemical kinetics were examined. The sample of this study consisted of 81 freshman pre-service science…

  2. KinChem: A Computational Resource for Teaching and Learning Chemical Kinetics

    ERIC Educational Resources Information Center

    da Silva, Jose´ Nunes, Jr.; Sousa Lima, Mary Anne; Silva Sousa, Eduardo Henrique; Oliveira Alexandre, Francisco Serra; Melo Leite, Antonio Jose´, Jr.

    2014-01-01

    This paper presents a piece of educational software covering a comprehensive number of topics of chemical kinetics, which is available free of charge in Portuguese and English. The software was developed to support chemistry educators and students in the teaching-learning process of chemical kinetics by using animations, calculations, and…

  3. KinChem: A Computational Resource for Teaching and Learning Chemical Kinetics

    ERIC Educational Resources Information Center

    da Silva, Jose´ Nunes, Jr.; Sousa Lima, Mary Anne; Silva Sousa, Eduardo Henrique; Oliveira Alexandre, Francisco Serra; Melo Leite, Antonio Jose´, Jr.

    2014-01-01

    This paper presents a piece of educational software covering a comprehensive number of topics of chemical kinetics, which is available free of charge in Portuguese and English. The software was developed to support chemistry educators and students in the teaching-learning process of chemical kinetics by using animations, calculations, and…

  4. Exploring Secondary Students' Understanding of Chemical Kinetics through Inquiry-Based Learning Activities

    ERIC Educational Resources Information Center

    Chairam, Sanoe; Klahan, Nutsuda; Coll, Richard K.

    2015-01-01

    This research is trying to evaluate the feedback of Thai secondary school students to inquiry-based teaching and learning methods, exemplified by the study of chemical kinetics. This work used the multiple-choice questions, scientifically practical diagram and questionnaire to assess students' understanding of chemical kinetics. The findings…

  5. Identifying Alternative Conceptions of Chemical Kinetics among Secondary School and Undergraduate Students in Turkey

    ERIC Educational Resources Information Center

    Cakmakci, Gultekin

    2010-01-01

    This study identifies some alternative conceptions of chemical kinetics held by secondary school and undergraduate students (N = 191) in Turkey. Undergraduate students who participated are studying to become chemistry teachers when they graduate. Students' conceptions about chemical kinetics were elicited through a series of written tasks and…

  6. Identifying Alternative Conceptions of Chemical Kinetics among Secondary School and Undergraduate Students in Turkey

    ERIC Educational Resources Information Center

    Cakmakci, Gultekin

    2010-01-01

    This study identifies some alternative conceptions of chemical kinetics held by secondary school and undergraduate students (N = 191) in Turkey. Undergraduate students who participated are studying to become chemistry teachers when they graduate. Students' conceptions about chemical kinetics were elicited through a series of written tasks and…

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

    ERIC Educational Resources Information Center

    Bain, Kinsey; Towns, Marcy H.

    2016-01-01

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

  8. Preservice Science Teachers' Attitudes towards Chemistry and Misconceptions about Chemical Kinetics

    ERIC Educational Resources Information Center

    Çam, Aylin; Topçu, Mustafa Sami; Sülün, Yusuf

    2015-01-01

    The present study investigates preservice science teachers' attitudes towards chemistry; their misconceptions about chemical kinetics; and relationships between pre-service science teachers' attitudes toward chemistry and misconceptions about chemical kinetics were examined. The sample of this study consisted of 81 freshman pre-service science…

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

    ERIC Educational Resources Information Center

    Bain, Kinsey; Towns, Marcy H.

    2016-01-01

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

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

    SciTech Connect

    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.

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

    SciTech Connect

    Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K.

    2010-05-15

    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. (author)

  12. A numerical scheme for optimal transition paths of stochastic chemical kinetic systems

    SciTech Connect

    Liu Di

    2008-10-01

    We present a new framework for finding the optimal transition paths of metastable stochastic chemical kinetic systems with large system size. The optimal transition paths are identified to be the most probable paths according to the Large Deviation Theory of stochastic processes. Dynamical equations for the optimal transition paths are derived using the variational principle. A modified Minimum Action Method (MAM) is proposed as a numerical scheme to solve the optimal transition paths. Applications to Gene Regulatory Networks such as the toggle switch model and the Lactose Operon Model in Escherichia coli are presented as numerical examples.

  13. Development of a chemical kinetic model for a biosolids fluidized-bed gasifier and the effects of operating parameters on syngas quality.

    PubMed

    Champion, Wyatt M; Cooper, C David; Mackie, Kevin R; Cairney, Paul

    2014-02-01

    In an effort to decrease the land disposal of sewage sludge biosolids and to recover energy, gasification has become a viable option for the treatment of waste biosolids. The process of gasification involves the drying and devolatilization and partial oxidation of biosolids, followed closely by the reduction of the organic gases and char in a single vessel. The products of gasification include a gaseous fuel composed largely of N2, H2O, CO2, CO, H2, CH4, and tars, as well as ash and unburned solid carbon. A mathematical model was developed using published devolatilization, oxidation, and reduction reactions, and calibrated using data from three different experimental studies of laboratory-scale fluidized-bed sewage sludge gasifiers reported in the literature. The model predicts syngas production rate, composition, and temperature as functions of the biosolids composition and feed rate, the air input rate, and gasifier bottom temperature. Several data sets from the three independent literature sources were reserved for model validation, with a focus placed on five species of interest (CO, CO2, H2, CH4, and C6H6). The syngas composition predictions from the model compared well with experimental results from the literature. A sensitivity analysis on the most important operating parameters of a gasifier (bed temperature and equivalence ratio) was performed as well, with the results of the analysis offering insight into the operations of a biosolids gasifier.

  14. Kinetic modeling of active plasma resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Oberrath, Jens

    2016-09-01

    The term ``active plasma resonance spectroscopy'' (APRS) refers to a plasma diagnostic method which employs the natural ability of plasmas to resonate close to the plasma frequency. Essential for this method is an appropriate model to determine the relation between the resonance parameters and demanded plasma parameters. Measurements with these probes in plasmas of a few Pa typically show a broadening of the spectrum that cannot be predicted by a fluid model. Thus, a kinetic model is necessary. A general kinetic model of APRS probes, which can be described in electorstatic approximation, valid for all pressures has been presented. This model is used to analyze the dynamic behavior of such probes by means of functional analytic methods. One of the main results is, that the system response function Y (ω) is given in terms of the matrix elements of the resolvent of the dynamic operator evaluated for values on the imaginary axis. The spectrum of this operator is continuous which implies a new phenomenon related to anomalous or non-collisional dissipation. Based on the scalar product, which is motivated by the kinetic free energy, the non-collisional damping can be interpreted: In a periodic state, the probe constantly emits plasma waves which propagate to ``infinity''. The free energy simply leaves the ``observation range'' of the probe which is recorded as damping. The kinetic damping, which depends on the mean kinetic energy of the electrons, is responsible for the broadening of a resonance peak in the measured spectrum of APRS probes. The ultimate goal is to determine explicit formulas for the relation between the broadening of the resonance peak and the ``equivalent electron temperature'', especially in the case of the spherical Impedance Probe and the Multipole Resonance Probe. Gratitude is expressed to the internal funding of Leuphana University, the BMBF via PluTO+, the DFG via Collaborative Research Center TR 87, and the Ruhr University Research School.

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

    PubMed

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

    2016-05-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

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

  18. Chemistry resolved kinetic flow modeling of TATB based explosives

    NASA Astrophysics Data System (ADS)

    Vitello, Peter; Fried, Laurence E.; William, Howard; Levesque, George; Souers, P. Clark

    2012-03-01

    Detonation waves in insensitive, TATB-based explosives are believed to have multiple time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. We term our model chemistry resolved kinetic flow, since CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. We present here two variants of our new rate model and comparison with hot, ambient, and cold experimental data for PBX 9502.

  19. Chemical kinetic studies on dry sorbents. Final report. [Sodium bicarbonate

    SciTech Connect

    Davis, W.T.; Keener, T.C.

    1982-02-15

    The scope of this research investigation has included a review of potential additives suitable for dry flue-gas desulfurization (FGD) and a bench scale laboratory study to determine the chemical kinetics for the reaction of five different sorbents with sulfur dioxide. The sorbents chosen included sodium bicarbonate (NaHCO/sub 3/), soda ash (Na/sub 2/CO/sub 3/), trona, lime (CaO) and hydrated lime (Ca(OH)/sub 2/). This study has shown that: (1) The reaction rate increases with temperature for soda ash and calcium oxide. The reaction temperature has an inverse effect on sodium bicarbonate and trona due, primarily, to the simultaneous thermal activation reaction. The calcium hydroxide-SO/sub 2/ reaction increased up to 550/sup 0/F, and then decreased, due to uneven gas flow distribution. (2) The reaction rates for soda ash, calcium oxide and calcium hydroxide were increased by decreasing their particle size. This effect was not confirmed for sodium bicarbonate and trona where reaction temperature was the most important reaction parameter. (3) Reaction with soda ash was found to be limited by the presence of an impervious ash layer which prevented interparticle gaseous diffusion. Calcium oxide and calcium hydroxide were found to be limited by a slow chemical reaction rate. Results on the rate-limiting steps for sodium bicarbonate and trona were inconclusive because of the simultaneous thermal activation reaction. (4) The effect of thermal activation was to increase the reaction rate for sodium bicarbonate and trona at lower temperatures. This effect was less pronounced at higher temperatures. (5) Results obtained for nitric oxide show limited adsorption for the five sorbents tested as compared to the finding for sulfur dioxide.

  20. Kinetics model development of cocoa bean fermentation

    NASA Astrophysics Data System (ADS)

    Kresnowati, M. T. A. P.; Gunawan, Agus Yodi; Muliyadini, Winny

    2015-12-01

    Although Indonesia is one of the biggest cocoa beans producers in the world, Indonesian cocoa beans are oftenly of low quality and thereby frequently priced low in the world market. In order to improve the quality, adequate post-harvest cocoa processing techniques are required. Fermentation is the vital stage in series of cocoa beans post harvest processing which could improve the quality of cocoa beans, in particular taste, aroma, and colours. During the fermentation process, combination of microbes grow producing metabolites that serve as the precursors for cocoa beans flavour. Microbial composition and thereby their activities will affect the fermentation performance and influence the properties of cocoa beans. The correlation could be reviewed using a kinetic model that includes unstructured microbial growth, substrate utilization and metabolic product formation. The developed kinetic model could be further used to design cocoa bean fermentation process to meet the expected quality. Further the development of kinetic model of cocoa bean fermentation also serve as a good case study of mixed culture solid state fermentation, that has rarely been studied. This paper presents the development of a kinetic model for solid-state cocoa beans fermentation using an empirical approach. Series of lab scale cocoa bean fermentations, either natural fermentations without starter addition or fermentations with mixed yeast and lactic acid bacteria starter addition, were used for model parameters estimation. The results showed that cocoa beans fermentation can be modelled mathematically and the best model included substrate utilization, microbial growth, metabolites production and its transport. Although the developed model still can not explain the dynamics in microbial population, this model can sufficiently explained the observed changes in sugar concentration as well as metabolic products in the cocoa bean pulp.

  1. Modelling the effect of ascorbic acid, sodium metabisulphite and sodium chloride on the kinetic responses of lactic acid bacteria and yeasts in table olive storage using a specifically implemented Quasi-chemical primary model.

    PubMed

    Echevarria, R; Bautista-Gallego, J; Arroyo-López, F N; Garrido-Fernández, A

    2010-04-15

    The goal of this work was to apply the Quasi-chemical primary model (a system of four ordinary differential equations that derives from a hypothetical four-step chemical mechanism involving an antagonistic metabolite) in the study of the evolution of yeast and lactic acid bacteria populations during the storage of Manzanilla-Aloreña table olives subjected to different mixtures of ascorbic acid, sodium metabisulphite and NaCl. Firstly, the Quasi-chemical model was applied to microbial count data to estimate the growth-decay biological parameters. The model accurately described the evolution of both populations during storage, providing detailed information on the microbial behaviour. Secondly, these parameters were used as responses and analysed according to a mixture design experiment (secondary model). The contour lines of the corresponding response surfaces clearly disclosed the relationships between growth and environmental conditions, showing the stimulating and inhibitory effect of ascorbic acid and sodium metabisulphite, respectively, on both populations of microorganisms. This work opens new possibilities for the potential use of the Quasi-chemical primary model in the study of table olive fermentations.

  2. Modeling inhomogeneous DNA replication kinetics.

    PubMed

    Gauthier, Michel G; Norio, Paolo; Bechhoefer, John

    2012-01-01

    In eukaryotic organisms, DNA replication is initiated at a series of chromosomal locations called origins, where replication forks are assembled proceeding bidirectionally to replicate the genome. The distribution and firing rate of these origins, in conjunction with the velocity at which forks progress, dictate the program of the replication process. Previous attempts at modeling DNA replication in eukaryotes have focused on cases where the firing rate and the velocity of replication forks are homogeneous, or uniform, across the genome. However, it is now known that there are large variations in origin activity along the genome and variations in fork velocities can also take place. Here, we generalize previous approaches to modeling replication, to allow for arbitrary spatial variation of initiation rates and fork velocities. We derive rate equations for left- and right-moving forks and for replication probability over time that can be solved numerically to obtain the mean-field replication program. This method accurately reproduces the results of DNA replication simulation. We also successfully adapted our approach to the inverse problem of fitting measurements of DNA replication performed on single DNA molecules. Since such measurements are performed on specified portion of the genome, the examined DNA molecules may be replicated by forks that originate either within the studied molecule or outside of it. This problem was solved by using an effective flux of incoming replication forks at the model boundaries to represent the origin activity outside the studied region. Using this approach, we show that reliable inferences can be made about the replication of specific portions of the genome even if the amount of data that can be obtained from single-molecule experiments is generally limited.

  3. Textbook Deficiencies: Ambiguities in Chemical Kinetics Rates and Rate Constants

    NASA Astrophysics Data System (ADS)

    Quisenberry, Keith T.; Tellinghuisen, Joel

    2006-03-01

    Balanced chemical reactions often have at least some stoichiometry coefficients that are not unity. To avoid ambiguity in defining the kinetics rate for a reaction, the IUPAC has established the convention, rate = (1/ν i )/(d[A i ]/d t ) relating the reaction rate to the rate of change of concentration of any reactant or product A i and its stoichiometry number ν i (negative for reactants, positive for products). The rate is a product of the rate constant k and some function of the concentrations of reactants and products that must be determined experimentally. While most general chemistry textbooks correctly state this convention, most also proceed to ignore it in subsequent development, particularly in the use of integrated rate laws and the definition of the reaction half-life. We recommend that in future editions, authors make it clear that (i) the reaction rate and rate constant cannot be defined unambiguously without explicitly stating the reaction for which they apply and therefore (ii) the relation between the half-life, which is a physical property of the reaction system, and the rate constant depends upon how the reaction is written. The errors have arisen in part because most texts simply state the integrated rate expressions for first- and second-order reactions without deriving them. It is both appropriate and easy to include such derivations in texts oriented toward students intending careers in science, engineering, and medicine.

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

    USGS Publications Warehouse

    Ross, D.S.

    2006-01-01

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

  5. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    PubMed

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

  6. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    NASA Astrophysics Data System (ADS)

    Li, Tiejun; Lin, Feng

    2016-04-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis-Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes.

  7. Viral kinetic modeling: state of the art.

    PubMed

    Canini, Laetitia; Perelson, Alan S

    2014-10-01

    Viral kinetic (VK) modeling has led to increased understanding of the within host dynamics of viral infections and the effects of therapy. Here we review recent developments in the modeling of viral infection kinetics with emphasis on two infectious diseases: hepatitis C and influenza. We review how VK modeling has evolved from simple models of viral infections treated with a drug or drug cocktail with an assumed constant effectiveness to models that incorporate drug pharmacokinetics and pharmacodynamics, as well as phenomenological models that simply assume drugs have time varying-effectiveness. We also discuss multiscale models that include intracellular events in viral replication, models of drug-resistance, models that include innate and adaptive immune responses and models that incorporate cell-to-cell spread of infection. Overall, VK modeling has provided new insights into the understanding of the disease progression and the modes of action of several drugs. We expect that VK modeling will be increasingly used in the coming years to optimize drug regimens in order to improve therapeutic outcomes and treatment tolerability for infectious diseases.

  8. Modeling the Kinetics of Root Gravireaction

    NASA Astrophysics Data System (ADS)

    Kondrachuk, Alexander V.; Starkov, Vyacheslav N.

    2011-02-01

    The known "sun-flower equation" (SFE), which was originally proposed to model root circumnutating, was used to describe the simplest tip root graviresponse. Two forms of the SFE (integro-differential and differential-delayed) were solved, analyzed and compared with each other. The numerical solutions of these equations were found to be matching with arbitrary accuracy. The analysis of the solutions focused on time-lag effects on the kinetics of tip root bending. The results of the modeling are in good correlation with an experiment at the initial stages of root tips graviresponse. Further development of the model calls for its systematic comparison with some specially designed experiments, which would include measuring the kinetics of root tip bending before gravistimulation over the period of time longer than the time lag.

  9. Use of a pressuremeter to measure the kinetics of carbon dioxide evolution in chemically leavened wheat flour dough.

    PubMed

    Bellido, Guillermo G; Scanlon, Martin G; Sapirstein, Harry D; Page, John H

    2008-11-12

    Among a number of impediments to a wider use of chemical leavening agents in bakery applications is the lack of standardized instrumentation capable of providing information on the rates of CO2 production from chemical leaveners in a format that is meaningful to both the technologist (i.e., the dough rate of reaction or DRR) and the researcher (e.g., in terms of fundamental unitskmol CO2 per kg of dough per s). This paper presents an original methodology to carry out the DRR test using a commercial pressuremeter, the Gassmart apparatus, and to model the kinetics of CO2 evolution of chemically leavened dough. Lean formula doughs were leavened at 27 and 39 degrees C with four chemical leavening systems containing sodium bicarbonate and one of four leavening acids, sodium acid pyrophosphate 40 (SAPP), adipic acid (ADA), potassium acid tartrate (KAT), and glucono-delta-lactone (GDL). Chemical kinetics theory was used to gain an insight into the reaction mechanisms responsible for the evolution of carbon dioxide from the leaveners. A first-order reaction kinetics model was found to be suitable for describing the neutralizing properties of GDL and ADA leavening systems, whereas a first-order reaction kinetics model for irreversible parallel reactions better described the leavening properties of the acidic salts KAT and SAPP.

  10. Reduction of chemical reaction models

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  11. The chemical shock tube as a tool for studying high-temperature chemical kinetics

    NASA Technical Reports Server (NTRS)

    Brabbs, Theodore A.

    1986-01-01

    Although the combustion of hydrocarbons is our primary source of energy today, the chemical reactions, or pathway, by which even the simplest hydro-carbon reacts with atmospheric oxygen to form CO2 and water may not always be known. Furthermore, even when the reaction pathway is known, the reaction rates are always under discussion. The shock tube has been an important and unique tool for building a data base of reaction rates important in the combustion of hydrocarbon fuels. The ability of a shock wave to bring the gas sample to reaction conditions rapidly and homogeneously makes shock-tube studies of reaction kinetics extremely attractive. In addition to the control and uniformity of reaction conditions achieved with shock-wave methods, shock compression can produce gas temperatures far in excess of those in conventional reactors. Argon can be heated to well over 10 000 K, and temperatures around 5000 K are easily obtained with conventional shock-tube techniques. Experiments have proven the validity of shock-wave theory; thus, reaction temperatures and pressures can be calculated from a measurement of the incident shock velocity. A description is given of the chemical shock tube and auxiliary equipment and of two examples of kinetic experiments conducted in a shock tube.

  12. Chemical Kinetics of the Growth and Destruction of PAHs in Circumstellar Environments

    NASA Astrophysics Data System (ADS)

    Kress, M. E.; Tielens, A. G. G. M.; Frenklach, M. E.

    2004-12-01

    Polycyclic aromatic hydrocarbons (PAHs) are one of the predominant carriers of carbon in interstellar space, after CO. PAHs are also observed in circumstellar environments (e.g. GL 618 and the Red Rectangle). The presence of PAHs in stellar outflows, in the ISM and in meteorites raise several important questions: are meteoritic PAHs inherited from late-type stars? Are these compounds modified in the solar nebula, and if so, how, where and when? Can the abundances and varieties of PAHs in stellar outflows give more insight into the evolution of stars off the main sequence through the planetary nebula stage? To this end, we are modeling the chemical kinetics of PAH formation, growth and destruction within a parameter space of outflow timescales, pressures, temperatures, C/O ratios and other factors to address these questions. The chemical kinetics of PAHs has been well studied at the higher temperatures of plug flow reactors and sooting flames (> 1000 K), and we base our chemical model upon these studies. We hope that our results will motivate more detailed experimental studies of PAH chemistry at the lower temperatures and pressures characteristic of circumstellar environments. This work has been supported by NASA Astrobiology Institute's Virtual Planetary Laboratory and the Institute for Geophysics and Planetary Physics at Lawrence Livermore National Laboratory.

  13. Minimal curvature trajectories: Riemannian geometry concepts for slow manifold computation in chemical kinetics

    NASA Astrophysics Data System (ADS)

    Lebiedz, Dirk; Reinhardt, Volkmar; Siehr, Jochen

    2010-09-01

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

  14. Equivalence of on-Lattice Stochastic Chemical Kinetics with the Well-Mixed Chemical Master Equation in the Limit of Fast Diffusion.

    PubMed

    Stamatakis, Michail; Vlachos, Dionisios G

    2011-12-14

    Well-mixed and lattice-based descriptions of stochastic chemical kinetics have been extensively used in the literature. Realizations of the corresponding stochastic processes are obtained by the Gillespie stochastic simulation algorithm and lattice kinetic Monte Carlo algorithms, respectively. However, the two frameworks have remained disconnected. We show the equivalence of these frameworks whereby the stochastic lattice kinetics reduces to effective well-mixed kinetics in the limit of fast diffusion. In the latter, the lattice structure appears implicitly, as the lumped rate of bimolecular reactions depends on the number of neighbors of a site on the lattice. Moreover, we propose a mapping between the stochastic propensities and the deterministic rates of the well-mixed vessel and lattice dynamics that illustrates the hierarchy of models and the key parameters that enable model reduction.

  15. Kinetic modeling of non-ideal explosives with CHEETAH

    SciTech Connect

    Fried, L E; Howard, W M; Souers, P C

    1998-08-06

    We report an implementation of the Wood-Kirkwood kinetic detonation model based on multi-species equations of state and multiple reaction rate laws. Finite rate laws are used for the slowest chemical reactions. Other reactions are given infinite rates and are kept in constant thermodynamic equilibrium. We model a wide range of ideal and non-ideal composite energetic materials. We find that we can replicate experimental detonation velocities to within a few per cent, while obtaining good agreement with estimated reaction zone lengths. The detonation velocity as a function of charge radius is also correctly reproduced.

  16. Kinetic Models with Randomly Perturbed Binary Collisions

    NASA Astrophysics Data System (ADS)

    Bassetti, Federico; Ladelli, Lucia; Toscani, Giuseppe

    2011-02-01

    We introduce a class of Kac-like kinetic equations on the real line, with general random collisional rules which, in some special cases, identify models for granular gases with a background heat bath (Carrillo et al. in Discrete Contin. Dyn. Syst. 24(1):59-81, 2009), and models for wealth redistribution in an agent-based market (Bisi et al. in Commun. Math. Sci. 7:901-916, 2009). Conditions on these collisional rules which guarantee both the existence and uniqueness of equilibrium profiles and their main properties are found. The characterization of these stationary states is of independent interest, since we show that they are stationary solutions of different evolution problems, both in the kinetic theory of rarefied gases (Cercignani et al. in J. Stat. Phys. 105:337-352, 2001; Villani in J. Stat. Phys. 124:781-822, 2006) and in the econophysical context (Bisi et al. in Commun. Math. Sci. 7:901-916, 2009).

  17. Application of Photoacoustic Effect to Chemical Kinetics in Solution.

    NASA Astrophysics Data System (ADS)

    Cheng, Huy-Zu.

    The application of the pulsed photoacoustic technique (PA) to the study of chemical kinetics in very dilute solutions is demonstrated with three different reactions: A bidental ligand substitution of 1,2-bi(diphenylphosphino) ethane on the five-coordinate cobalt dithiolene complex, a nucleophilic addition of tributyl phosphite to (p-(dimethylamino)triphenyl)methyl cation, and an enzyme catalyzed reduction of nicotinamide adenine dinucleotide by glucose-6-phosphate. Photoacoustic detection is shown to be 100 times more sensitive than spectrophotometric detection. As a consequence, it allows one to use lower reactant concentrations so that the time scale for the corresponding fast reactions can be lengthened. The pulsed PA technique also provides an alternative method for the direct determination of reverse rate constants and equilibrium constants of reactions. Moreover, Michaelis constants of biochemical reactions, especially for enzymes whose K_{rm m} values is below 1.0 muM, can be measured more accurately using photoacoustic detection than using spectrophotometric detection. Additionally, the pulsed PA method can be very valuable for the study of reactions that are restricted by the low solubility, availability, or high cost of reactants. The sensitivity of the PA method is found to be limited by the background signal resulting from solvents. Photoacoustic signals generated in strongly absorbing media are also studied and results are in agreement with the theory developed by G. J. Diebold. From the time profile of the acoustic signal, the absorption coefficient of strongly absorbing medium can be determined provided the sound speed is known. Since the pulse shape of the acoustic transient depends upon the relative density and the acoustic velocity of the transparent and the strongly absorbing media, the physical properties of the transparent medium can also be determined with the use of the PA technique.

  18. Application of Chemical Kinetics to Deterioration of Foods.

    ERIC Educational Resources Information Center

    Labuza, T. P.

    1984-01-01

    Possible modes of food deterioration (such as microbial decay, nonenzymatic browning, senescence, lipid oxidation) are reviewed. A basic mathematical approach to the kinetics of food deterioration, kinetic approach to accelerating shelf-life deterioration, and shelf-life predictions are discussed. (JN)

  19. Application of Chemical Kinetics to Deterioration of Foods.

    ERIC Educational Resources Information Center

    Labuza, T. P.

    1984-01-01

    Possible modes of food deterioration (such as microbial decay, nonenzymatic browning, senescence, lipid oxidation) are reviewed. A basic mathematical approach to the kinetics of food deterioration, kinetic approach to accelerating shelf-life deterioration, and shelf-life predictions are discussed. (JN)

  20. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics.

    PubMed

    Bazant, Martin Z

    2013-05-21

    Advances in the fields of catalysis and electrochemical energy conversion often involve nanoparticles, which can have kinetics surprisingly different from the bulk material. Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create variations that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend not only on the order parameter but also on its gradients at phase boundaries. Reaction-driven phase transformations are common in electrochemistry, when charge transfer is accompanied by ion intercalation or deposition in a solid phase. Examples abound in Li-ion, metal-air, and lead-acid batteries, as well as metal electrodeposition-dissolution. Despite complex thermodynamics, however, the standard kinetic model is the Butler-Volmer equation, based on a dilute solution approximation. The Marcus theory of charge transfer likewise considers isolated reactants and neglects elastic stress, configurational entropy, and other nonidealities in condensed phases. The limitations of existing theories recently became apparent for the Li-ion battery material LixFePO4 (LFP). It has a strong tendency to separate into Li-rich and Li-poor solid phases, which scientists believe limits its performance. Chemists first modeled phase separation in LFP as an isotropic "shrinking core" within each particle, but experiments later revealed striped phase boundaries on the active crystal facet. This raised the question: What is the reaction rate at a surface undergoing a phase transformation? Meanwhile, dramatic rate enhancement was attained with LFP nanoparticles, and classical battery models could not predict the roles of phase separation and surface modification. In this Account, I present a general theory of chemical kinetics, developed over

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

  3. Kinetic effects in edge plasma: kinetic modeling for edge plasma and detached divertor

    NASA Astrophysics Data System (ADS)

    Takizuka, T.

    2017-03-01

    Detached divertor is considered a solution for the heat control in magnetic-confinement fusion reactors. Numerical simulations using the comprehensive divertor codes based on the plasma fluid modeling are indispensable for the design of the detached divertor in future reactors. Since the agreement in the results between detached-divertor experiments and simulations has been rather fair but not satisfactory, further improvement of the modeling is required. The kinetic effect is one of key issues for improving the modeling. Complete kinetic behaviors are able to be simulated by the kinetic modeling. In this paper at first, major kinetic effects in edge plasma and detached divertor are listed. One of the most powerful kinetic models, particle-in-cell (PIC) model, is described in detail. Several results of PIC simulations of edge-plasma kinetic natures are presented. Future works on PIC modeling and simulation for the deeper understanding of edge plasma and detached divertor are discussed.

  4. Making Models of Chemical Compounds.

    ERIC Educational Resources Information Center

    Hoehn, Robert G.

    1992-01-01

    Describes the benefits and techniques of having students create models of chemical compounds. This hands-on approach uses colored paper and other inexpensive materials to construct the models. A step-by-step approach provides objectives, materials, an explanation on how to calculate chemical ratios, procedures, follow-up activities, and a resource…

  5. Melting behavior of typical thermoplastic materials--an experimental and chemical kinetics study.

    PubMed

    Wang, Nan; Tu, Ran; Ma, Xin; Xie, Qiyuan; Jiang, Xi

    2013-11-15

    A medium-scale melting experiment rig was designed and constructed in this study. A detailed experimental study was conducted on the melting behavior and the chemical kinetic characteristics of three typical thermoplastic materials, including polypropylene (PP), polyethylene (PE) and polystyrene (PS). It is observed that the thermal decomposition of the thermoplastic materials mainly consists of three stages: the initial heating stage, the melting-dominated stage and the gasification-dominated stage. Melting of the materials examined takes place within a certain temperature range. The melting temperature of PS is the lowest, moreover, it takes the shortest time to be completely liquefied. To quantitatively represent the chemical kinetics, an nth-order reaction model was employed to interpret the thermal decomposition behavior of the materials. The calculated reaction order is largely in accordance with the small-scale thermal gravimetric analysis (TGA). The small difference between the results and TGA data suggests that there are some limitations in the small-scale experiments in simulating the behavior of thermoplastic materials in a thermal hazard. Therefore, investigating the thermal physical and chemical properties of the thermoplastic materials and their thermal hazard prevention in medium or large-scale experiments is necessary for the fire safety considerations of polymer materials. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    NASA Astrophysics Data System (ADS)

    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.

  7. Predicting chemical kinetics with computational chemistry: is QOO&(H)rarr;HOQO important in fuel ignition?

    NASA Astrophysics Data System (ADS)

    Green, William H.; Wijaya, Catherina D.; Yelvington, Paul E.; Sumathi, R.

    An overview of predictive chemical kinetics is presented, with an application to the simulation and design of homogeneous charge compression ignition (HCCI) engines. The engine simulations are sensitive to the details of hydroperoxyalkyl (QOOH) radical chemistry, which are only partially understood, and there is a significant discrepancy between the simulations and experiment that limits the usefulness of the simulations. One possible explanation is that QOOH decomposes by other channels not considered in existing combustion chemistry models. Rate constants for one of these neglected channels, the intramolecular radical attack on the QOOH peroxide linkage to form hydroxyalkoxyl (HOQO) radicals, are predicted using quantum chemistry (CBS-QB3), to test whether or not this proposed channel can explain the observed discrepancies in the engine simulations. Although this channel has a significant rate, the competing attack on the other O atom in the peroxide to form a cyclic ether+OH is computed to be an order of magnitude faster, so the HOQO channel does not appear to be fast enough to explain the discrepancy. Definitive judgement on the importance of this reaction channel will require a careful reconsideration of all the coupled chemically activated QOOH reaction channels using modern predictive chemical kinetics software.

  8. Prediction of Combustion Instability with Detailed Chemical Kinetics

    DTIC Science & Technology

    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

  9. Kinetic modeling in PET imaging of hypoxia

    PubMed Central

    Li, Fan; Joergensen, Jesper T; Hansen, Anders E; Kjaer, Andreas

    2014-01-01

    Tumor hypoxia is associated with increased therapeutic resistance leading to poor treatment outcome. Therefore the ability to detect and quantify intratumoral oxygenation could play an important role in future individual personalized treatment strategies. Positron Emission Tomography (PET) can be used for non-invasive mapping of tissue oxygenation in vivo and several hypoxia specific PET tracers have been developed. Evaluation of PET data in the clinic is commonly based on visual assessment together with semiquantitative measurements e.g. standard uptake value (SUV). However, dynamic PET contains additional valuable information on the temporal changes in tracer distribution. Kinetic modeling can be used to extract relevant pharmacokinetic parameters of tracer behavior in vivo that reflects relevant physiological processes. In this paper, we review the potential contribution of kinetic analysis for PET imaging of hypoxia. PMID:25250200

  10. ACCURACY AND COST CONSIDERATIONS IN CHOOSING A CHEMICAL MECHANISM FOR OPERATIONAL USE IN AQ MODELS

    EPA Science Inventory

    There are several contemporary chemical kinetic mechanisms available for use in tropospheric air quality simulation models, with varying degrees of condensation of the chemical reaction pathways. Likewise, there are several different numerical solution methods available to use w...

  11. ACCURACY AND COST CONSIDERATIONS IN CHOOSING A CHEMICAL MECHANISM FOR OPERATIONAL USE IN AQ MODELS

    EPA Science Inventory

    There are several contemporary chemical kinetic mechanisms available for use in tropospheric air quality simulation models, with varying degrees of condensation of the chemical reaction pathways. Likewise, there are several different numerical solution methods available to use w...

  12. Kinetic and hydrodynamic models of chemotactic aggregation

    NASA Astrophysics Data System (ADS)

    Chavanis, Pierre-Henri; Sire, Clément

    2007-10-01

    We derive general kinetic and hydrodynamic models of chemotactic aggregation that describe certain features of the morphogenesis of biological colonies (like bacteria, amoebae, endothelial cells or social insects). Starting from a stochastic model defined in terms of N coupled Langevin equations, we derive a nonlinear mean-field Fokker-Planck equation governing the evolution of the distribution function of the system in phase space. By taking the successive moments of this kinetic equation and using a local thermodynamic equilibrium condition, we derive a set of hydrodynamic equations involving a damping term. In the limit of small frictions, we obtain a hyperbolic model describing the formation of network patterns (filaments) and in the limit of strong frictions we obtain a parabolic model which is a generalization of the standard Keller-Segel model describing the formation of clusters (clumps). Our approach connects and generalizes several models introduced in the chemotactic literature. We discuss the analogy between bacterial colonies and self-gravitating systems and between the chemotactic collapse and the gravitational collapse (Jeans instability). We also show that the basic equations of chemotaxis are similar to nonlinear mean-field Fokker-Planck equations so that a notion of effective generalized thermodynamics can be developed.

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

    SciTech Connect

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

    2009-10-01

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

  14. Cluster kinetics model for mixtures of glassformers

    NASA Astrophysics Data System (ADS)

    Brenskelle, Lisa A.; McCoy, Benjamin J.

    2007-10-01

    For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied.

  15. Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

    NASA Astrophysics Data System (ADS)

    Zaera, Francisco

    2017-05-01

    In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H2 with O2 and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. Sections 6 and 7 of this review deal with the advances made in the use of molecular beams with

  16. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

    NASA Technical Reports Server (NTRS)

    Bittker, David A.; Radhakrishnan, Krishnan

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  17. A simplified kinetic model for an autopoietic synthesis of micelles

    NASA Astrophysics Data System (ADS)

    Chizmadzhew, Yuri A.; Maestro, Marco; Mavelli, Fabio

    1994-08-01

    Recently, some chemical systems have been implemented which have an autopoietic behaviour according to Varela and Maturana's definition. They consist of micelles or reversed micelles which are able to produce their building material inside themselves, and, in such a way reproduce themselves. For one of these systems we have elaborated a kinetic model to rationalize the long lag phase and the abrupt rate increase displayed during the autopietic process of micellar self-replication. The theoretical predictions are in good agreement with the experimental observations available to date.

  18. Kinetic modeling of the polar wind

    NASA Astrophysics Data System (ADS)

    Tam, S. W. Y.; Chang, T.; Pierrard, V.

    2007-11-01

    The polar wind, a plasma outflow along open geomagnetic field lines from the Earth's ionosphere, has been the subject of many theoretical studies. Since the proposal of its existence more than 30 years ago, the polar wind has been described by various theoretical modeling approaches. In this paper, we first describe the two traditional modeling approaches for the classical polar wind: moment-based models and collisionless kinetic calculations; and discuss how other models of the outflow were formed by combining these two traditional approaches. We then discuss how kinetic calculations have been improved to take into account the effects of Coulomb collisions, which may contribute to the formation of double-peaked H+ velocity distributions in the polar wind. As observations of escaping O+ fluxes have guided theoreticians to go beyond the classical polar wind description, we discuss how models were modified or constructed in order to take into account the various non-classical effects, including those due to photoelectrons, which may also provide an explanation for the satellite observations of day night asymmetries in addition to the acceleration of the O+ ions.

  19. Autoignition chemistry of the hexane isomers: An experimental and kinetic modeling study

    SciTech Connect

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

    1995-06-01

    Autoignition of the five distinct isomers of hexane is studied experimentally under motored engine conditions and computationally using a detailed chemical kinetic reaction mechanism. Computed and experimental results are compared and used to help understand the chemical factors leading to engine knock in spark-ignited engines and the molecular structure factors contributing to octane rating for hydrocarbon fuels. The kinetic model reproduces observed variations in critical compression ratio with fuel structure, and it also provides intermediate and final product species concentrations in very dose agreement with observed results. In addition, the computed results provide insights into the kinetic origins of fuel octane sensitive.

  20. Chemistry Resolved Kinetic Flow Modeling of TATB Based Explosives

    NASA Astrophysics Data System (ADS)

    Vitello, Peter; Fried, Lawrence; Howard, Mike; Levesque, George; Souers, Clark

    2011-06-01

    Detonation waves in insensitive, TATB based explosives are believed to have multi-time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to ALE hydrodynamics codes to model detonations. We term our model chemistry resolved kinetic flow as CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculate EOS values based on the concentrations. A validation suite of model simulations compared to recent high fidelity metal push experiments at ambient and cold temperatures has been developed. We present here a study of multi-time scale kinetic rate effects for these experiments. Prepared by LLNL under Contract DE-AC52-07NA27344.

  1. VULCAN: An Open-source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K, using a reduced C-H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing its output versus the disequilibrium-chemistry calculations of Moses et al. and Rimmer & Helling. It reproduces the models of HD 189733b and HD 209458b by Moses et al., which employ a network with nearly 1600 reactions. We also use VULCAN to examine the theoretical trends produced when the temperature-pressure profile and carbon-to-oxygen ratio are varied. Assisted by a sensitivity test designed to identify the key reactions responsible for producing a specific molecule, we revisit the quenching approximation and find that it is accurate for methane but breaks down for acetylene, because the disequilibrium abundance of acetylene is not directly determined by transport-induced quenching, but is rather indirectly controlled by the disequilibrium abundance of methane. Therefore we suggest that the quenching approximation should be used with caution and must always be checked against a chemical kinetics calculation. A one-dimensional model atmosphere with 100 layers, computed using VULCAN, typically takes several minutes to complete. VULCAN is part of the Exoclimes Simulation Platform (ESP; exoclime.net) and publicly available at https://github.com/exoclime/VULCAN.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. Thermodynamic and kinetic modeling of transcriptional pausing.

    PubMed

    Tadigotla, Vasisht R; O Maoiléidigh, Dáibhid; Sengupta, Anirvan M; Epshtein, Vitaly; Ebright, Richard H; Nudler, Evgeny; Ruckenstein, Andrei E

    2006-03-21

    We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC). Our algorithm is based on the thermodynamic stability of the EC along the DNA template calculated from the sequence-dependent free energy of DNA-DNA, DNA-RNA, and RNA-RNA base pairing associated with (i) the translocational and size fluctuations of the transcription bubble; (ii) changes in the associated DNA-RNA hybrid; and (iii) changes in the cotranscriptional RNA secondary structure upstream of the RNA exit channel. The calculations involve no adjustable parameters except for a cutoff used to discriminate paused from nonpaused complexes. When applied to 100 experimental pauses in transcription elongation by Escherichia coli RNA polymerase on 10 DNA templates, the approach produces statistically significant results. We also present a kinetic model for the rate of recovery of backtracked paused complexes. A crucial ingredient of our model is the incorporation of kinetic barriers to backtracking resulting from steric clashes of EC with the cotranscriptionally generated RNA secondary structure, an aspect not included explicitly in previous attempts at modeling the transcription elongation process.

  4. Thermodynamic and kinetic modeling of transcriptional pausing

    PubMed Central

    Tadigotla, Vasisht R.; Maoiléidigh, Dáibhid Ó; Sengupta, Anirvan M.; Epshtein, Vitaly; Ebright, Richard H.; Nudler, Evgeny; Ruckenstein, Andrei E.

    2006-01-01

    We present a statistical mechanics approach for the prediction of backtracked pauses in bacterial transcription elongation derived from structural models of the transcription elongation complex (EC). Our algorithm is based on the thermodynamic stability of the EC along the DNA template calculated from the sequence-dependent free energy of DNA–DNA, DNA–RNA, and RNA–RNA base pairing associated with (i) the translocational and size fluctuations of the transcription bubble; (ii) changes in the associated DNA–RNA hybrid; and (iii) changes in the cotranscriptional RNA secondary structure upstream of the RNA exit channel. The calculations involve no adjustable parameters except for a cutoff used to discriminate paused from nonpaused complexes. When applied to 100 experimental pauses in transcription elongation by Escherichia coli RNA polymerase on 10 DNA templates, the approach produces statistically significant results. We also present a kinetic model for the rate of recovery of backtracked paused complexes. A crucial ingredient of our model is the incorporation of kinetic barriers to backtracking resulting from steric clashes of EC with the cotranscriptionally generated RNA secondary structure, an aspect not included explicitly in previous attempts at modeling the transcription elongation process. PMID:16537373

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

    SciTech Connect

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

    2008-02-08

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

  6. High-Pressure Turbulent Flame Speeds and Chemical Kinetics of Syngas Blends with and without Impurities

    SciTech Connect

    Peterson, Eric; Mathieu, Olivier; Morones, Anibal; Ravi, Sankar; Keesee, Charles; Hargis, Joshua; Vivanco, Jose

    2014-12-01

    This Topical Report documents the first year of the project, from October 1, 2013 through September 30, 2014. Efforts for this project included experiments to characterize the atmospheric-pressure turbulent flame speed vessel over a range of operating conditions (fan speeds and turbulent length scales). To this end, a new LDV system was acquired and set up for the detailed characterization of the turbulence field. Much progress was made in the area of impurity kinetics, which included a numerical study of the effect of impurities such as NO2, NO, H2S, and NH3 on ignition delay times and laminar flame speeds of syngas blends at engine conditions. Experiments included a series of laminar flame speed measurements for syngas (CO/H2) blends with various levels of CH4 and C2H6 addition, and the results were compared to the chemical kinetics model of NUI Galway. Also, a final NOx kinetics mechanism including ammonia was assembled, and a journal paper was written and is now in press. Overall, three journal papers and six conference papers related to this project were published this year. Finally, much progress was made on the design of the new high-pressure turbulent flame speed facility. An overall design that includes a venting system was decided upon, and the detailed design is in progress.

  7. Wealth redistribution in conservative linear kinetic models

    NASA Astrophysics Data System (ADS)

    Toscani, G.

    2009-10-01

    We introduce and discuss kinetic models for wealth distribution which include both taxation and uniform redistribution. The evolution of the continuous density of wealth obeys a linear Boltzmann equation where the background density represents the action of an external subject on the taxation mechanism. The case in which the mean wealth is conserved is analyzed in full details, by recovering the analytical form of the steady states. These states are probability distributions of convergent random series of a special structure, called perpetuities. Among others, Gibbs distribution appears as steady state in case of total taxation and uniform redistribution.

  8. Promoting Higher-Order Thinking Skills: Uses of Mathcad and Classical Chemical Kinetics to Foster Student Development

    NASA Astrophysics Data System (ADS)

    Zielinski, Theresa Julia

    1995-07-01

    Mathematical models play an important role in physical chemistry. This paper describes the use of Mathcad software in a series of exercises that explore the mathematical models for reversible first order and series first order reactions. In this approach students learn to use the Mathcad software while exploring kinetics models in an open ended format. Other objectives of the exercises include helping students to develop higher order thinking skills and to foster deeper chemical thinking processes. The method uses the Perry model of student development as the pedagogical framework. This approach to teaching chemical kinetics is an easily implemented alternative to traditional lecture presentations. This is important as retention of material learned through immediate use of the learning in teaching others rises to 90% in group work. The student pair interaction that these exercises require provides the opportunity for teaching that increases learning. Positive student responses to the method and the advantages of this approach are given in the paper.

  9. H2-dependent attachment kinetics and shape evolution in chemical vapor deposition graphene growth

    NASA Astrophysics Data System (ADS)

    Meca, Esteban; Shenoy, Vivek B.; Lowengrub, John

    2017-09-01

    Experiments on graphene growth through chemical vapor deposition (CVD) involving methane (CH4) and hydrogen (H2) gases reveal a complex shape evolution and a non-monotonic dependence on the partial pressure of H2 ({{p}{{\\text{H}2}}} ). To explain these intriguing observations, we develop a microkinetic model for the stepwise decomposition of CH4 into mobile radicals and consider two possible mechanisms of attachment to graphene crystals: CH radicals to hydrogen-decorated edges of the crystals and C radicals to bare crystal edges. We derive an effective mass flux and an effective kinetic coefficient, both of which depend on {{p}{{\\text{H}2}}} , and incorporate these into a phase field model. The model reproduces both the non-monotonic dependence on {{p}{{\\text{H}2}}} and the characteristic shapes of graphene crystals observed in experiments. At small {{p}{{\\text{H}2}}} , growth is limited by the kinetics of attachment while at large {{p}{{\\text{H}2}}} growth is limited because the effective mass flux is small. We also derive a simple analytical model that captures the non-monotone behavior, enables the two mechanisms of attachment to be distinguished and provides guidelines for CVD growth of defect-free 2D crystals.

  10. A generalized Fisher equation and its utility in chemical kinetics.

    PubMed

    Ross, John; Fernández Villaverde, Alejandro; Banga, Julio R; Vázquez, Sara; Morán, Federico

    2010-07-20

    A generalized Fisher equation (GFE) relates the time derivative of the average of the intrinsic rate of growth to its variance. The GFE is an exact mathematical result that has been widely used in population dynamics and genetics, where it originated. Here we demonstrate that the GFE can also be useful in other fields, specifically in chemistry, with models of two chemical reaction systems for which the mechanisms and rate coefficients correspond reasonably well to experiments. A bad fit of the GFE can be a sign of high levels of measurement noise; for low or moderate levels of noise, fulfillment of the GFE is not degraded. Hence, the GFE presents a noise threshold that may be used to test the validity of experimental measurements without requiring any additional information. In a different approach information about the system (model) is included in the calculations. In that case, the discrepancy with the GFE can be used as an optimization criterion for the determination of rate coefficients in a given reaction mechanism.

  11. A generalized Fisher equation and its utility in chemical kinetics

    PubMed Central

    Ross, John; Villaverde, Alejandro Fernández; Banga, Julio R.; Vázquez, Sara; Morán, Federico

    2010-01-01

    A generalized Fisher equation (GFE) relates the time derivative of the average of the intrinsic rate of growth to its variance. The GFE is an exact mathematical result that has been widely used in population dynamics and genetics, where it originated. Here we demonstrate that the GFE can also be useful in other fields, specifically in chemistry, with models of two chemical reaction systems for which the mechanisms and rate coefficients correspond reasonably well to experiments. A bad fit of the GFE can be a sign of high levels of measurement noise; for low or moderate levels of noise, fulfillment of the GFE is not degraded. Hence, the GFE presents a noise threshold that may be used to test the validity of experimental measurements without requiring any additional information. In a different approach information about the system (model) is included in the calculations. In that case, the discrepancy with the GFE can be used as an optimization criterion for the determination of rate coefficients in a given reaction mechanism. PMID:20615992

  12. Multiple-relaxation-time lattice Boltzmann kinetic model for combustion

    NASA Astrophysics Data System (ADS)

    Xu, Aiguo; Lin, Chuandong; Zhang, Guangcai; Li, Yingjun

    2015-04-01

    To probe both the hydrodynamic nonequilibrium (HNE) and thermodynamic nonequilibrium (TNE) in the combustion process, a two-dimensional multiple-relaxation-time (MRT) version of lattice Boltzmann kinetic model (LBKM) for combustion phenomena is presented. The chemical energy released in the progress of combustion is dynamically coupled into the system by adding a chemical term to the LB kinetic equation. Aside from describing the evolutions of the conserved quantities, the density, momentum, and energy, which are what the Navier-Stokes model describes, the MRT-LBKM presents also a coarse-grained description on the evolutions of some nonconserved quantities. The current model works for both subsonic and supersonic flows with or without chemical reaction. In this model, both the specific-heat ratio and the Prandtl number are flexible, the TNE effects are naturally presented in each simulation step. The model is verified and validated via well-known benchmark tests. As an initial application, various nonequilibrium behaviors, including the complex interplays between various HNEs, between various TNEs, and between the HNE and TNE, around the detonation wave in the unsteady and steady one-dimensional detonation processes are preliminarily probed. It is found that the system viscosity (or heat conductivity) decreases the local TNE, but increases the global TNE around the detonation wave, that even locally, the system viscosity (or heat conductivity) results in two kinds of competing trends, to increase and to decrease the TNE effects. The physical reason is that the viscosity (or heat conductivity) takes part in both the thermodynamic and hydrodynamic responses.

  13. Multiple-relaxation-time lattice Boltzmann kinetic model for combustion.

    PubMed

    Xu, Aiguo; Lin, Chuandong; Zhang, Guangcai; Li, Yingjun

    2015-04-01

    To probe both the hydrodynamic nonequilibrium (HNE) and thermodynamic nonequilibrium (TNE) in the combustion process, a two-dimensional multiple-relaxation-time (MRT) version of lattice Boltzmann kinetic model (LBKM) for combustion phenomena is presented. The chemical energy released in the progress of combustion is dynamically coupled into the system by adding a chemical term to the LB kinetic equation. Aside from describing the evolutions of the conserved quantities, the density, momentum, and energy, which are what the Navier-Stokes model describes, the MRT-LBKM presents also a coarse-grained description on the evolutions of some nonconserved quantities. The current model works for both subsonic and supersonic flows with or without chemical reaction. In this model, both the specific-heat ratio and the Prandtl number are flexible, the TNE effects are naturally presented in each simulation step. The model is verified and validated via well-known benchmark tests. As an initial application, various nonequilibrium behaviors, including the complex interplays between various HNEs, between various TNEs, and between the HNE and TNE, around the detonation wave in the unsteady and steady one-dimensional detonation processes are preliminarily probed. It is found that the system viscosity (or heat conductivity) decreases the local TNE, but increases the global TNE around the detonation wave, that even locally, the system viscosity (or heat conductivity) results in two kinds of competing trends, to increase and to decrease the TNE effects. The physical reason is that the viscosity (or heat conductivity) takes part in both the thermodynamic and hydrodynamic responses.

  14. A Kinetic Model of Active Extensile Bundles

    NASA Astrophysics Data System (ADS)

    Goldstein, Daniel; Chakraborty, Bulbul; Baskaran, Aparna

    Recent experiments in active filament networks reveal interesting rheological properties (Dan Chen: APS March Meeting 2015 D49.00001). This system consumes ATP to produce an extensile motion in bundles of microtubules. This extension then leads to self generated stresses and spontaneous flows. We propose a minimal model where the activity is modeled by self-extending bundles that are part of a cross linked network. This network can reorganize itself through buckling of extending filaments and merging events that alter the topology of the network. We numerically simulate this minimal kinetic model and examine the emergent rheological properties and determine how stresses are generated by the extensile activity. We will present results that focus on the effects of confinement and network connectivity of the bundles on stress fluctuations and response of an active gel.

  15. Chemical uncertainties in modeling hot Jupiters atmospheres

    NASA Astrophysics Data System (ADS)

    Hebrard, Eric; Domagal-Goldman, Shawn

    2015-11-01

    Most predictions and interpretations of observations in beyond our Solar System have occurred through the use of 1D photo-thermo-chemical models. Their predicted atmospheric compositions are highly dependent on model parameters. Chemical reactions are based on empirical parameters that must be known at temperatures ranging from 100 K to above 2500 K and at pressures from millibars to hundreds of bars. Obtained from experiments, calculations and educated-guessed estimations, these parameters are always evaluated with substantial uncertainties. However, although of practical use, few models of exoplanetary atmospheres have considered these underlying chemical uncertainties and their consequences. Recent progress has been made recently that allow us to (1) evaluate the accuracy and precision of 1D models of planetary atmospheres, with quantifiable uncertainties on their predictions for the atmospheric composition and associated spectral features, (2) identify the ‘key parameters’ that contribute the most to the models predictivity and should therefore require further experimental or theoretical analysis, (3) reduce and optimize complex chemical networks for their inclusion in multidimensional atmospheric models.First, a global sampling approach based on low discrepancy sequences has been applied in order to propose error bars on simulations of the atmospheres HD 209458b and HD 189733b, using a detailed kinetic model derived from applied combustion models that was methodically validated over a range of temperatures and pressures typical for these hot Jupiters. A two-parameters temperature-dependent uncertainty factor has been assigned to each considered rate constant. Second, a global sensitivity approach based on high dimensional model representations (HDMR) has been applied in order to identify those reactions which make the largest contributions to the overall uncertainty of the simulated results. The HDMR analysis has been restricted to the most important

  16. On Kinetics Modeling of Vibrational Energy Transfer

    NASA Technical Reports Server (NTRS)

    Gilmore, John O.; Sharma, Surendra P.; Cavolowsky, John A. (Technical Monitor)

    1996-01-01

    Two models of vibrational energy exchange are compared at equilibrium to the elementary vibrational exchange reaction for a binary mixture. The first model, non-linear in the species vibrational energies, was derived by Schwartz, Slawsky, and Herzfeld (SSH) by considering the detailed kinetics of vibrational energy levels. This model recovers the result demanded at equilibrium by the elementary reaction. The second model is more recent, and is gaining use in certain areas of computational fluid dynamics. This model, linear in the species vibrational energies, is shown not to recover the required equilibrium result. Further, this more recent model is inconsistent with its suggested rate constants in that those rate constants were inferred from measurements by using the SSH model to reduce the data. The non-linear versus linear nature of these two models can lead to significant differences in vibrational energy coupling. Use of the contemporary model may lead to significant misconceptions, especially when integrated in computer codes considering multiple energy coupling mechanisms.

  17. On Kinetics Modeling of Vibrational Energy Transfer

    NASA Technical Reports Server (NTRS)

    Gilmore, John O.; Sharma, Surendra P.; Cavolowsky, John A. (Technical Monitor)

    1996-01-01

    Two models of vibrational energy exchange are compared at equilibrium to the elementary vibrational exchange reaction for a binary mixture. The first model, non-linear in the species vibrational energies, was derived by Schwartz, Slawsky, and Herzfeld (SSH) by considering the detailed kinetics of vibrational energy levels. This model recovers the result demanded at equilibrium by the elementary reaction. The second model is more recent, and is gaining use in certain areas of computational fluid dynamics. This model, linear in the species vibrational energies, is shown not to recover the required equilibrium result. Further, this more recent model is inconsistent with its suggested rate constants in that those rate constants were inferred from measurements by using the SSH model to reduce the data. The non-linear versus linear nature of these two models can lead to significant differences in vibrational energy coupling. Use of the contemporary model may lead to significant misconceptions, especially when integrated in computer codes considering multiple energy coupling mechanisms.

  18. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    NASA Technical Reports Server (NTRS)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  19. Reduction Kinetics of a CasO4 Based Oxygen Carrier for Chemical-Looping Combustion

    NASA Astrophysics Data System (ADS)

    Xiao, R.; Song, Q. L.; Zheng, W. G.; Deng, Z. Y.; Shen, L. H.; Zhang, M. Y.

    The CaSO4 based oxygen carrier has been proposed as an alternative low cost oxygen carrier for Chemical-looping combustion (CLC) of coal. The reduction of CaSO4 to CaS is an important step for the cyclic process of reduction/oxidation in CLC of coal with CaSO4 based oxygen carrier. Thermodynamic analysis of CaSO4 oxygen carrier with CO based on the principle of Gibbs free energy minimization show that the essentially high purity of CO2 can be obtained, while the solid product is CaS instead of CaO. The intrinsic reduction kinetics of a CaSO4 based oxygen carrier with CO was investigated in a differential fixed bed reactor. The effects of gas partial pressure (20%-70%) and temperature (880-950°C) on the reduction were investigated. The reduction was described with shrinking unreacted core model. Experimental results of CO partial pressure on the solid conversion show that the reduction of fresh oxygen carriers is of first order with respect to the CO partial pressure. Both chemical reaction control and product layer diffusion control determine the reduction rate. The dependences of reaction rate constant and effective diffusivity with temperature were both obtained. The kinetic equation well predicted the experimental data.

  20. A Case Study in Chemical Kinetics: The OH + CO Reaction.

    ERIC Educational Resources Information Center

    Weston, Ralph E., Jr.

    1988-01-01

    Reviews some important properties of the bimolecular reaction between the hydroxyl radical and carbon monoxide. Investigates the kinetics of the reaction, the temperature and pressure dependence of the rate constant, the state-to-state dynamics of the reaction, and the reverse reaction. (MVL)

  1. A Case Study in Chemical Kinetics: The OH + CO Reaction.

    ERIC Educational Resources Information Center

    Weston, Ralph E., Jr.

    1988-01-01

    Reviews some important properties of the bimolecular reaction between the hydroxyl radical and carbon monoxide. Investigates the kinetics of the reaction, the temperature and pressure dependence of the rate constant, the state-to-state dynamics of the reaction, and the reverse reaction. (MVL)

  2. A kinetic model of adsorption on solid surfaces

    NASA Astrophysics Data System (ADS)

    Aoki, Kazuo; Giovangigli, Vincent; Hattori, Masanari

    2016-11-01

    A kinetic model describing physisorption and chemisorption of gas particles on a crystal surface is introduced. A single kinetic equation is used to model gas and physisorbed particles interacting with an average potential and colliding with phonons. This equation is coupled to a kinetic equation describing localized chemisorbed species. A modified kinetic entropy is introduced for the coupled system and the H theorem is established. Using a fluid scaling and the Chapman-Enskog asymptotic method, fluid boundary conditions for the physisorbed and chemisorbed species are derived from the kinetic model.

  3. Kinetic models of tissue fusion processes

    NASA Astrophysics Data System (ADS)

    Pearce, John A.; Thomsen, Sharon L.

    1992-06-01

    Recent studies of tissue fusion (welding) processes have reported temperature ranges but have not carefully analyzed critical exposure time data. Electron microscopic (EM) studies suggest that the fusion process in blood vessels may be dominated by random re-entwinement of thermally dissociated adventitial collagen fibrils (Type I) during the end stage heating and early cooling phases. At the light microscopic level, this bonding process is reflected by the formation of an amorphous coagulum of thermally coagulated adventitial collagen at the anastomotic site. We have constructed a numerical model of the vessel welding process, assuming CO2 laser impingement, and used it to simulate quantitative histologic data obtained from successful welds of rat femoral and canine brachial arteries (unpublished data). The model estimates smooth muscle and collagen damage based on kinetic thermal damage analysis and water loss boundaries as a function of irradiation beam parameters and heating time. Both heating and cooling phases are simulated. The results illustrate the importance of the damage kinetics and local heat transfer phenomena to the weld characteristics realized.

  4. Hydration kinetics modeling of Portland cement considering the effects of curing temperature and applied pressure

    SciTech Connect

    Lin Feng Meyer, Christian

    2009-04-15

    A hydration kinetics model for Portland cement is formulated based on thermodynamics of multiphase porous media. The mechanism of cement hydration is discussed based on literature review. The model is then developed considering the effects of chemical composition and fineness of cement, water-cement ratio, curing temperature and applied pressure. The ultimate degree of hydration of Portland cement is also analyzed and a corresponding formula is established. The model is calibrated against the experimental data for eight different Portland cements. Simple relations between the model parameters and cement composition are obtained and used to predict hydration kinetics. The model is used to reproduce experimental results on hydration kinetics, adiabatic temperature rise, and chemical shrinkage of different cement pastes. The comparisons between the model reproductions and the different experimental results demonstrate the applicability of the proposed model, especially for cement hydration at elevated temperature and high pressure.

  5. Glassy dynamics of kinetically constrained models

    NASA Astrophysics Data System (ADS)

    Ritort, F.; Sollich, P.

    2003-06-01

    We review the use of kinetically constrained models (KCMs) for the study of dynamics in glassy systems. The characteristic feature of KCMs is that they have trivial, often non-interacting, equilibrium behaviour but interesting slow dynamics due to restrictions on the allowed transitions between configurations. The basic question which KCMs ask is therefore how much glassy physics can be understood without an underlying 'equilibrium glass transition'. After a brief review of glassy phenomenology, we describe the main model classes, which include spin-facilitated (Ising) models, constrained lattice gases, models inspired by cellular structures such as soap froths, models obtained via mappings from interacting systems without constraints, and finally related models such as urn, oscillator, tiling and needle models. We then describe the broad range of techniques that have been applied to KCMs, including exact solutions, adiabatic approximations, projection and mode-coupling techniques, diagrammatic approaches and mappings to quantum systems or effective models. Finally, we give a survey of the known results for the dynamics of KCMs both in and out of equilibrium, including topics such as relaxation time divergences and dynamical transitions, nonlinear relaxation, ageing and effective temperatures, cooperativity and dynamical heterogeneities, and finally non-equilibrium stationary states generated by external driving. We conclude with a discussion of open questions and possibilities for future work.

  6. Modeling of turbulent chemical reaction

    NASA Technical Reports Server (NTRS)

    Chen, J.-Y.

    1995-01-01

    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  7. Gas phase chemical kinetics at high temperature of carbonaceous molecules: application to circumstellar envelopes

    NASA Astrophysics Data System (ADS)

    Biennier, L.; Gardez, A.; Saidani, G.; Georges, R.; Rowe, B.; Reddy, K. P. J.

    2011-05-01

    Circumstellar shells of evolved stars are a theater of extremely rich physical and chemical processes. More than seventy molecules of varied nature have been identified in the envelopes through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals and a significant number are unique to the circumstellar medium. However, observational data remain scarce and more than half of the detected species have been observed in only one object, the nearby carbon star IRC + 10216. Chemical kinetic models are needed to describe the formation of molecules in evolved circumstellar outflows. Upcoming terrestrial telescopes such as ALMA will increase the spatial resolution by several orders of magnitude and provide a wealth of data. The determination of relevant laboratory kinetics data is critical to keep up with the development of the observations and of the refinement of chemical models. Today, the majority of reactions studied in the laboratory are the ones involved in combustion and concerning light hydrocarbons. Our objective is to provide the scientific community with rate coefficients of reactions between abundant species in these warm environments. Cyanopolyynes from HC_2N to HC_9N have all been detected in carbon rich circumstellar envelopes in up to 10 sources for HC_3N. Neutral-neutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures. Our approach aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high enthalpy source (Moudens et al. 2011) with a flow tube and a pulsed laser photolysis and laser induced fluorescence system to probe the undergoing chemical reactions. The high enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane, propene

  8. The effects of consistent chemical kinetics calculations on the pressure-temperature profiles and emission spectra of hot Jupiters

    NASA Astrophysics Data System (ADS)

    Drummond, B.; Tremblin, P.; Baraffe, I.; Amundsen, D. S.; Mayne, N. J.; Venot, O.; Goyal, J.

    2016-10-01

    In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure-temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in cases of strong chemical disequilibrium, consistent calculations can lead to differences in the P-T profile of up to 100 K compared to the P-T profile derived assuming chemical equilibrium. This temperature change can, in turn, have important consequences for the chemical abundances themselves as well as for the simulated emission spectra. In particular, we find that performing the chemical kinetics calculation consistently can reduce the overall impact of non-equilibrium chemistry on the observable emission spectrum of hot Jupiters. Simulated observations derived from non-consistent models could thus yield the wrong interpretation. We show that this behaviour is due to the non-consistent models violating the energy budget balance of the atmosphere.

  9. Optimization of chemical reactor feed by simulations based on a kinetic approach.

    PubMed

    Guinand, Charles; Dabros, Michal; Roduit, Bertrand; Meyer, Thierry; Stoessel, Francis

    2014-10-01

    Chemical incidents are typically caused by loss of control, resulting in runaway reactions or process deviations in different stages of the production. In the case of fed-batch reactors, the problem generally encountered is the accumulation of heat. This is directly related to the temperature of the process, the reaction kinetics and adiabatic temperature rise, which is the maximum temperature attainable in the event of cooling failure. The main possibility to control the heat accumulation is the use of a well-controlled adapted feed. The feed rate can be adjusted by using reaction and reactor dynamic models coupled to Model Predictive Control. Thereby, it is possible to predict the best feed profile respecting the safety constraints.

  10. Detailed Kinetic Modeling of Gasoline Surrogate Mixtures

    SciTech Connect

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

    2009-03-09

    Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. It is generally agreed that their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. In this work, a recently revised version of the kinetic model by the authors is used to analyze the combustion behavior of several components relevant to gasoline surrogate formulation. Particular attention is devoted to linear and branched saturated hydrocarbons (PRF mixtures), olefins (1-hexene) and aromatics (toluene). Model predictions for pure components, binary mixtures and multi-component gasoline surrogates are compared with recent experimental information collected in rapid compression machine, shock tube and jet stirred reactors covering a wide range of conditions pertinent to internal combustion engines. Simulation results are discussed focusing attention on the mixing effects of the fuel components.

  11. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs

    NASA Astrophysics Data System (ADS)

    Chia, A.; Tan, K. C.; Pawela, Ł.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  12. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs.

    PubMed

    Chia, A; Tan, K C; Pawela, Ł; Kurzyński, P; Paterek, T; Kaszlikowski, D

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013)], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  13. General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

  14. Chemical gas-dynamics beyond Wang Chang-Uhlenbeck's kinetics

    SciTech Connect

    Kolesnichenko, Evgeniy G.; Gorbachev, Yuriy E.

    2014-12-09

    Wang Chang-Uhlenbeck equation does not give possibility to take into account intermolecular processes such as redistribution of the energy among different degrees of freedom. The modification of the generalized Wang Chang-Uhlenbeck equation including such processes is proposed. It allows to study for instance the kinetics of non-radiative transitions. Limitations of this approach are connected with the requirements of absence of polarization of rotational momentum and phases of intermolecular vibrations.

  15. Chemical gas-dynamics beyond Wang Chang-Uhlenbeck's kinetics

    NASA Astrophysics Data System (ADS)

    Kolesnichenko, Evgeniy G.; Gorbachev, Yuriy E.

    2014-12-01

    Wang Chang-Uhlenbeck equation does not give possibility to take into account intermolecular processes such as redistribution of the energy among different degrees of freedom. The modification of the generalized Wang Chang-Uhlenbeck equation including such processes is proposed. It allows to study for instance the kinetics of non-radiative transitions. Limitations of this approach are connected with the requirements of absence of polarization of rotational momentum and phases of intermolecular vibrations.

  16. Leaching Kinetics of Atrazine and Inorganic Chemicals in Tilled and Orchard Soils

    NASA Astrophysics Data System (ADS)

    Szajdak, Lech W.; Lipiec, Jerzy; Siczek, Anna; Nosalewicz, Artur; Majewska, Urszula

    2014-04-01

    The aim of this study was to verify first-order kinetic reaction rate model performance in predicting of leaching of atrazine and inorganic compounds (K+1, Fe+3, Mg+2, Mn+2, NH4 +, NO3 - and PO4 -3) from tilled and orchard silty loam soils. This model provided an excellent fit to the experimental concentration changes of the compounds vs. time data during leaching. Calculated values of the first-order reaction rate constants for the changes of all chemicals were from 3.8 to 19.0 times higher in orchard than in tilled soil. Higher first-order reaction constants for orchard than tilled soil correspond with both higher total porosity and contribution of biological pores in the former. The first order reaction constants for the leaching of chemical compounds enables prediction of the actual compound concentration and the interactions between compound and soil as affected by management system. The study demonstrates the effectiveness of simultaneous chemical and physical analyses as a tool for the understanding of leaching in variously managed soils.

  17. Model colloid system for interfacial sorption kinetics

    NASA Astrophysics Data System (ADS)

    Salipante, Paul; Hudson, Steven

    2014-11-01

    Adsorption kinetics of nanometer scale molecules, such as proteins at interfaces, is usually determined through measurements of surface coverage. Their small size limits the ability to directly observe individual molecule behavior. To better understand the behavior of nanometer size molecules and the effect on interfacial kinetics, we use micron size colloids with a weak interfacial interaction potential as a model system. Thus, the interaction strength is comparable to many nanoscale systems (less than 10 kBT). The colloid-interface interaction potential is tuned using a combination of depletion, electrostatic, and gravitational forces. The colloids transition between an entropically trapped adsorbed state and a desorbed state through Brownian motion. Observations are made using an LED-based Total Internal Reflection Microscopy (TIRM) setup. The observed adsorption and desorption rates are compared theoretical predictions based on the measured interaction potential and near wall particle diffusivity. This experimental system also allows for the study of more complex dynamics such as nonspherical colloids and collective effects at higher concentrations.

  18. Kinetic modelling of heterogeneous catalytic systems

    NASA Astrophysics Data System (ADS)

    Stamatakis, Michail

    2015-01-01

    The importance of heterogeneous catalysis in modern life is evidenced by the fact that numerous products and technologies routinely used nowadays involve catalysts in their synthesis or function. The discovery of catalytic materials is, however, a non-trivial procedure, requiring tedious trial-and-error experimentation. First-principles-based kinetic modelling methods have recently emerged as a promising way to understand catalytic function and aid in materials discovery. In particular, kinetic Monte Carlo (KMC) simulation is increasingly becoming more popular, as it can integrate several sources of complexity encountered in catalytic systems, and has already been used to successfully unravel the underlying physics of several systems of interest. After a short discussion of the different scales involved in catalysis, we summarize the theory behind KMC simulation, and present the latest KMC computational implementations in the field. Early achievements that transformed the way we think about catalysts are subsequently reviewed in connection to latest studies of realistic systems, in an attempt to highlight how the field has evolved over the last few decades. Present challenges and future directions and opportunities in computational catalysis are finally discussed.

  19. Population balance modeling of antibodies aggregation kinetics.

    PubMed

    Arosio, Paolo; Rima, Simonetta; Lattuada, Marco; Morbidelli, Massimo

    2012-06-21

    The aggregates morphology and the aggregation kinetics of a model monoclonal antibody under acidic conditions have been investigated. Growth occurs via irreversible cluster-cluster coagulation forming compact, fractal aggregates with fractal dimension of 2.6. We measured the time evolution of the average radius of gyration, , and the average hydrodynamic radius, , by in situ light scattering, and simulated the aggregation kinetics by a modified Smoluchowski's population balance equations. The analysis indicates that aggregation does not occur under diffusive control, and allows quantification of effective intermolecular interactions, expressed in terms of the Fuchs stability ratio (W). In particular, by introducing a dimensionless time weighed on W, the time evolutions of measured under various operating conditions (temperature, pH, type and concentration of salt) collapse on a single master curve. The analysis applies also to data reported in the literature when growth by cluster-cluster coagulation dominates, showing a certain level of generality in the antibodies aggregation behavior. The quantification of the stability ratio gives important physical insights into the process, including the Arrhenius dependence of the aggregation rate constant and the relationship between monomer-monomer and cluster-cluster interactions. Particularly, it is found that the reactivity of non-native monomers is larger than that of non-native aggregates, likely due to the reduction of the number of available hydrophobic patches during aggregation.

  20. Kinetic Models for the Trading of Goods

    NASA Astrophysics Data System (ADS)

    Toscani, Giuseppe; Brugna, Carlo; Demichelis, Stefano

    2013-05-01

    In this paper we introduce kinetic equations for the evolution of the probability distribution of two goods among a huge population of agents. The leading idea is to describe the trading of these goods by means of some fundamental rules in price theory, in particular by using Cobb-Douglas utility functions for the binary exchange, and the Edgeworth box for the description of the common exchange area in which utility is increasing for both agents. This leads to a Boltzmann-type equation in which the post-interaction variables depend in a nonlinear way from the pre-interaction ones. Other models will be derived, by suitably linearizing this Boltzmann equation. In presence of uncertainty in the exchanges, it is shown that the solution to some of the linearized kinetic equations develop Pareto tails, where the Pareto index depends on the ratio between the gain and the variance of the uncertainty. In particular, the result holds true for the solution of a drift-diffusion equation of Fokker-Planck type, obtained from the linear Boltzmann equation as the limit of quasi-invariant trades.

  1. Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

    NASA Astrophysics Data System (ADS)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  2. Kinetic model of excess activated sludge thermohydrolysis.

    PubMed

    Imbierowicz, Mirosław; Chacuk, Andrzej

    2012-11-01

    Thermal hydrolysis of excess activated sludge suspensions was carried at temperatures ranging from 423 K to 523 K and under pressure 0.2-4.0 MPa. Changes of total organic carbon (TOC) concentration in a solid and liquid phase were measured during these studies. At the temperature 423 K, after 2 h of the process, TOC concentration in the reaction mixture decreased by 15-18% of the initial value. At 473 K total organic carbon removal from activated sludge suspension increased to 30%. It was also found that the solubilisation of particulate organic matter strongly depended on the process temperature. At 423 K the transfer of TOC from solid particles into liquid phase after 1 h of the process reached 25% of the initial value, however, at the temperature of 523 K the conversion degree of 'solid' TOC attained 50% just after 15 min of the process. In the article a lumped kinetic model of the process of activated sludge thermohydrolysis has been proposed. It was assumed that during heating of the activated sludge suspension to a temperature in the range of 423-523 K two parallel reactions occurred. One, connected with thermal destruction of activated sludge particles, caused solubilisation of organic carbon and an increase of dissolved organic carbon concentration in the liquid phase (hydrolysate). The parallel reaction led to a new kind of unsolvable solid phase, which was further decomposed into gaseous products (CO(2)). The collected experimental data were used to identify unknown parameters of the model, i.e. activation energies and pre-exponential factors of elementary reactions. The mathematical model of activated sludge thermohydrolysis appropriately describes the kinetics of reactions occurring in the studied system.

  3. Chemical Process Modeling and Control.

    ERIC Educational Resources Information Center

    Bartusiak, R. Donald; Price, Randel M.

    1987-01-01

    Describes some of the features of Lehigh University's (Pennsylvania) process modeling and control program. Highlights the creation and operation of the Chemical Process Modeling and Control Center (PMC). Outlines the program's philosophy, faculty, technical program, current research projects, and facilities. (TW)

  4. Finding the chemistry in biomass pyrolysis: Millisecond chemical kinetics and visualization

    NASA Astrophysics Data System (ADS)

    Krumm, Christoph

    Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first- ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Through this technique, a transition is identified, known as the reactive melting point, between low and high temperature depolymerization. The transition between two mechanisms of cellulose decompositions unifies the mechanisms that govern low temperature char formation, intermediate pyrolysis conditions, and high temperature gas formation. The conditions under which biomass undergoes pyrolysis, including modes of heat transfer, have been shown to significantly affect the distribution of biorenewable chemical and fuel products. High-speed photography is used to observe the liftoff of initially crystalline cellulose particles when impinged on a heated surface, known as the Leidenfrost effect for room-temperature liquids. Order

  5. A combined spectroscopic and plasma chemical kinetic analysis of ionospheric samarium releases

    NASA Astrophysics Data System (ADS)

    Holmes, Jeffrey M.; Dressler, Rainer A.; Pedersen, Todd R.; Caton, Ronald G.; Miller, Daniel

    2017-05-01

    Two rocket-borne releases of samarium vapor in the upper atmosphere occurred in May 2013, as part of the Metal Oxide Space Clouds experiment. The releases were characterized by a combination of optical and RF diagnostic instruments located at the Roi-Namur launch site and surrounding islands and atolls. The evolution of the optical spectrum of the solar-illuminated cloud was recorded with a spectrograph covering a 400-800 nm spectral range. The spectra exhibit two distinct spectral regions centered at 496 and 636 nm within which the relative intensities change insignificantly. The ratio between the integrated intensities within these regions, however, changes with time, suggesting that they are associated with different species. With the help of an equilibrium plasma spectral model we attribute the region centered at 496 nm to neutral samarium atoms (Sm I radiance) and features peaking at 649 nm to a molecular species. No evidence for structure due to Sm+ (Sm II) is identified. The persistence of the Sm I radiance suggests a high dissociative recombination rate for the chemi-ionization product, SmO+. A one-dimensional plasma chemical kinetic model of the evolution of the density ratio NSmO/NSm(t) demonstrates that the molecular feature peaking at 649 nm can be attributed to SmO radiance. SmO+ radiance is not identified. By adjusting the Sm vapor mass of the chemical kinetic model input to match the evolution of the total electron density determined by ionosonde data, we conclude that less than 5% of the payload samarium was vaporized.

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

    SciTech Connect

    Schnoerr, David; Sanguinetti, Guido; Grima, Ramon

    2014-08-28

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

  7. Discussion of the Separation of Chemical and Relaxational Kinetics of Chemically Activated Intermediates in Master Equation Simulations.

    PubMed

    Döntgen, Malte; Leonhard, Kai

    2017-03-02

    Chemical activation of intermediates, such as hydrogen abstraction products, is emerging as a basis for a fully new reaction type: hot β-scission. While for thermally equilibrated intermediates chemical kinetics are typically orders of magnitude slower than relaxational kinetics, chemically activated intermediates raise the issue of inseparable chemical and relaxational kinetics. Here, this separation problem is discussed in the framework of master equation simulations, proposing three cases often encountered in chemistry: insignificant chemical activation, predominant chemical activation, and the transition between these two limits. These three cases are illustrated via three example systems: methoxy (CH3Ȯ), diazenyl (ṄNH), and methyl formate radicals (CH3OĊO). For diazenyl, it is found that hot β-scission fully replaces the sequence of hydrogen abstraction and β-scission of thermally equilibrated diazenyl. Building on the example systems, a rule of thumb is proposed that can be used to intuitively judge the significance of hot β-scission: if the reverse hydrogen abstraction barrier height is comparable to or larger than the β-scission barrier height, hot β-scission should be considered in more detail.

  8. Logarithmic relaxation in a kinetically constrained model.

    PubMed

    Moreno, Angel J; Colmenero, Juan

    2006-07-07

    We present Monte Carlo simulations on a coarse-grained model for relaxation in binary mixtures. The liquid structure is substituted by a three-dimensional array of cells. A spin variable is assigned to each cell, with values 0 or 1 denoting, respectively, unexcited and excited local states in a mobility field. Change in local mobility (spin flip) is permitted according to kinetic constraints determined by the mobilities of neighboring cells. We introduce two types of cells ("fast" and "slow") with very different rates for spin flip. Fast cells display anomalous relaxation, characterized by a concave-to-convex crossover in dynamic correlators by changing temperature or composition. At intermediate state points logarithmic relaxation is observed over three time decades. These results display striking analogies with dynamic correlators reported in recent simulations on polymer blends.

  9. Chemical vapor deposition modeling for high temperature materials

    NASA Technical Reports Server (NTRS)

    Goekoglu, Sueleyman

    1992-01-01

    The formalism for the accurate modeling of chemical vapor deposition (CVD) processes has matured based on the well established principles of transport phenomena and chemical kinetics in the gas phase and on surfaces. The utility and limitations of such models are discussed in practical applications for high temperature structural materials. Attention is drawn to the complexities and uncertainties in chemical kinetics. Traditional approaches based on only equilibrium thermochemistry and/or transport phenomena are defended as useful tools, within their validity, for engineering purposes. The role of modeling is discussed within the context of establishing the link between CVD process parameters and material microstructures/properties. It is argued that CVD modeling is an essential part of designing CVD equipment and controlling/optimizing CVD processes for the production and/or coating of high performance structural materials.

  10. Aerosol kinetic code "AERFORM": Model, validation and simulation results

    NASA Astrophysics Data System (ADS)

    Gainullin, K. G.; Golubev, A. I.; Petrov, A. M.; Piskunov, V. N.

    2016-06-01

    The aerosol kinetic code "AERFORM" is modified to simulate droplet and ice particle formation in mixed clouds. The splitting method is used to calculate condensation and coagulation simultaneously. The method is calibrated with analytic solutions of kinetic equations. Condensation kinetic model is based on cloud particle growth equation, mass and heat balance equations. The coagulation kinetic model includes Brownian, turbulent and precipitation effects. The real values are used for condensation and coagulation growth of water droplets and ice particles. The model and the simulation results for two full-scale cloud experiments are presented. The simulation model and code may be used autonomously or as an element of another code.

  11. Kinetic modelling of vinyl ester resin polymerization

    SciTech Connect

    Dhulipala, R.; Kreig. G.; Hawley, M.C.

    1993-12-31

    The study of kinetics offers a substantional incentive in the endeavor to manufacture polymer matrix composites at high speeds. The study enables one to optimize the curing cycle based on the specific curing characteristics of the resin and also makes it possible to simulate the curing process. This paper reports the results of the modelling of the thermal curing of the vinyl ester resin. The parameters for the proposed model have been calculated based on conversion-vs-data generated at various temperatures and Benzoyl peroxide (initiator) concentrations. The extent of cure of the resin mixture was determined using Fourier Transform Infrared Spectroscopy. In this model the termination rate constant is considered to drop with extent of cure until a limiting value is reached. The limiting value is a consequence of the active chain ends possessing a degree of mobility due to the propagation reaction even though the translational motion of the growing for radicals in increasingly restricted with conversion. Good agreements is observed between the model predictions and the experimental data.

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

    PubMed

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

    2010-03-25

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

  13. Ab initio determination of kinetics for atomic layer deposition modeling

    NASA Astrophysics Data System (ADS)

    Remmers, Elizabeth M.

    A first principles model is developed to describe the kinetics of atomic layer deposition (ALD) systems. This model requires no fitting parameters, as it is based on the reaction pathways, structures, and energetics obtained from quantum-chemical studies. Using transition state theory and partition functions from statistical mechanics, equilibrium constants and reaction rates can be calculated. Several tools were created in Python to aid in the calculation of these quantities, and this procedure was applied to two systems- zinc oxide deposition from diethyl zinc (DEZ) and water, and alumina deposition from trimethyl aluminum (TMA) and water. A Gauss-Jordan factorization is used to decompose the system dynamics, and the resulting systems of equations are solved numerically to obtain the temporal concentration profiles of these two deposition systems.

  14. CHEMKIN2. General Gas-Phase Chemical Kinetics

    SciTech Connect

    Rupley, F.M.

    1992-01-24

    CHEMKIN is a high-level tool for chemists to use to describe arbitrary gas-phase chemical reaction mechanisms and systems of governing equations. It remains, however, for the user to select and implement a solution method; this is not provided. It consists of two major components: the Interpreter and the Gas-phase Subroutine Library. The Interpreter reads a symbolic description of an arbitrary, user-specified chemical reaction mechanism. A data file is generated which forms a link to the Gas-phase Subroutine Library, a collection of about 200 modular subroutines which may be called to return thermodynamic properties, chemical production rates, derivatives of thermodynamic properties, derivatives of chemical production rates, or sensitivity parameters. Both single and double precision versions of CHEMKIN are included. Also provided is a set of FORTRAN subroutines for evaluating gas-phase transport properties such as thermal conductivities, viscosities, and diffusion coefficients. These properties are an important part of any computational simulation of a chemically reacting flow. The transport properties subroutines are designed to be used in conjunction with the CHEMKIN Subroutine Library. The transport properties depend on the state of the gas and on certain molecular parameters. The parameters considered are the Lennard-Jones potential well depth and collision diameter, the dipole moment, the polarizability, and the rotational relaxation collision number.

  15. A new kinetic model for human iodine metabolism

    SciTech Connect

    Ficken, V.J.; Allen, E.W.; Adams, G.D.

    1985-05-01

    A new kinetic model of iodine metabolism incorporating preferential organification of tyrosil (TYR) residues of thyroglobulin is developed and evaluated for euthyroid (n=5) and hyperthyroid (n=11) subjects. Iodine and peripheral T4 metabolims were measured with oral /sup 131/I-NaI and intravenous /sup 125/I-74 respectively. Data (obtained over 10 days) and kinetic model are analyzed using the SAAM27 program developed by Berman (1978). Compartment rate constants (mean rate per hour +- ISD) are tabulated in this paper. Thyroid and renal iodide clearance compare favorably with values reported in the literature. TYR rate constants were not unique; however, values obtained are within the range of rate constants determined from the invitro data reported by others. Intraluminal iodine as coupled TYR is predicted to be 21% for euthyroid and 59% for hyperthyroid subjects compared to analytical chemical methods of 30% and 51% respectively determined elsewhere. The authors plan to evaluate this model as a method of predicting the thyroid radiation dose from orally administered I/sup 131/.

  16. NASA Data Evaluation: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies

    NASA Astrophysics Data System (ADS)

    Burkholder, J. B.; Sander, S. P.; Abbatt, J.; Barker, J. R.; Fleming, E. L.; Friedl, R.; Huie, R. E.; Jackman, C. H.; Kolb, C. E., Jr.; Kurylo, M. J., III; Orkin, V. L.; Wine, P. H.

    2014-12-01

    Atmospheric chemistry models must include a large number of processes to accurately describe the temporal and spatial behavior of atmospheric composition. They require a wide range of chemical and physical data (parameters) that describe elementary gas-phase and heterogeneous processes. The review and evaluation of chemical and physical data has, therefore, played an important role in the development of chemical models and in their use in environmental assessment activities. The NASA data panel was originally established in 1977 by the NASA Upper Atmosphere Research Program Office to provide a critical evaluation of kinetic and photochemical data for use in laboratory studies and in atmospheric modeling of stratospheric ozone. Today, the NASA data panel evaluations have a broader atmospheric focus and include Ox, O(1D), singlet O2, HOx, NOx, Organic, FOx, ClOx, BrOx, IOx, SOx, and Na reactions, three-body reactions, equilibrium constants, photochemistry, aqueous chemistry, heterogeneous chemistry and processes, and thermodynamic parameters. The 2011 evaluation (JPL 10-6 available at http://jpldataeval.jpl.nasa.gov.) includes the comprehensive coverage of ~670 bimolecular reactions, 75 three-body reactions, 24 equilibrium constants, 215 photochemical species, 355 aqueous and heterogeneous processes, thermodynamic parameters for 590 species, and over 4000 literature citations. Each evaluation includes (1) recommended values (e.g. rate coefficients, absorption cross sections, and uptake coefficients) with estimated uncertainty factors and (2) a note describing the available experimental and theoretical data and explanation for the recommendation. As new studies have become available over the years the recommendations are critically reviewed and updated as warranted (the next evaluation is scheduled for release in early 2015). This presentation provides an overview of the NASA data panel evaluation process and the methodology used to estimate uncertainties. Examples on

  17. Incorporating qualitative knowledge in enzyme kinetic models using fuzzy logic.

    PubMed

    Lee, B; Yen, J; Yang, L; Liao, J C

    1999-03-20

    Modeling of metabolic pathway dynamics requires detailed kinetic equations at the enzyme level. In particular, the kinetic equations must account for metabolite effectors that contribute significantly to the pathway regulation in vivo. Unfortunately, most kinetic rate laws available in the literature do not consider all the effectors simultaneously, and much kinetic information exists in a qualitative or semiquantitative form. In this article, we present a strategy to incorporate such information into the kinetic equation. This strategy uses fuzzy logic-based factors to modify algebraic rate laws that account for partial kinetic characteristics. The parameters introduced by the fuzzy factors are then optimized by use of a hybrid of simplex and genetic algorithms. The resulting model provides a flexible form that can simulate various kinetic behaviors. Such kinetic models are suitable for pathway modeling without complete enzyme mechanisms. Three enzymes in Escherichia coli central metabolism are used as examples: phosphoenolpyruvate carboxylase; phosphoenolpyruvate carboxykinase; and pyruvate kinase I. Results show that, with fuzzy logic-augmented models, the kinetic data can be much better described. In particular, complex behavior, such as allosteric inhibition, can be captured using fuzzy rules. The resulting models, even though they do not provide additional physical meaning in enzyme mechanisms, allow the model to incorporate semiquantitative information in metabolic pathway models.

  18. A Kinetic Model for the Ruhrstahl Heraeus (RH) Degassing Process

    NASA Astrophysics Data System (ADS)

    van Ende, Marie-Aline; Kim, Young-Min; Cho, Mun-Kyu; Choi, Juhan; Jung, In-Ho

    2011-06-01

    A kinetic model (effective equilibrium reaction zone model) was developed to simulate the decarburization reaction in the Ruhrstahl Heraeus (RH) degassing process. The model assumes that the chemical reactions reach equilibrium in the designated effective reaction volumes near the reaction interfaces. After the RH degassing process was divided into various reaction zones, the effective reaction volumes of each reaction zone were expressed as a function of the process conditions based on the physical descriptions of the reaction mechanisms. The influence of the chemical reaction between the RH slag and the RH steel to the decarburization phenomena was considered for the first time. The calculated C and O profiles by the present model are in good agreement with the industrial operation data for various steel compositions and process conditions. RH slag can serve as an oxygen reservoir to supply O during the RH decarburization process, which induces the observed deviation of the C and O contents from their ideal stoichiometric trajectory. The present model provides an efficient tool to understand the RH degassing process.

  19. A Chemical Kinetics Network for Lightning and Life in Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Rimmer, P. B.; Helling, Ch

    2016-05-01

    There are many open questions about prebiotic chemistry in both planetary and exoplanetary environments. The increasing number of known exoplanets and other ultra-cool, substellar objects has propelled the desire to detect life and prebiotic chemistry outside the solar system. We present an ion-neutral chemical network constructed from scratch, Stand2015, that treats hydrogen, nitrogen, carbon, and oxygen chemistry accurately within a temperature range between 100 and 30,000 K. Formation pathways for glycine and other organic molecules are included. The network is complete up to H6C2N2O3. Stand2015 is successfully tested against atmospheric chemistry models for HD 209458b, Jupiter, and the present-day Earth using a simple one-dimensional photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting for CO2, H2, CO, and O2, but do not agree for water and atomic oxygen. We use the network to simulate an experiment where varied chemical initial conditions are irradiated by UV light. The result from our simulation is that more glycine is produced when more ammonia and methane is present. Very little glycine is produced in the absence of any molecular nitrogen and oxygen. This suggests that the production of glycine is inhibited if a gas is too strongly reducing. Possible applications and limitations of the chemical kinetics network are also discussed.

  20. Chemical kinetic considerations for postflame synthesis of carbon nanotubes in premixed flames using a support catalyst

    SciTech Connect

    Gopinath, Prarthana; Gore, Jay

    2007-11-15

    Multiwalled carbon nanotubes (MWCNTs) on a grid supported cobalt nanocatalyst were grown, by exposing it to combustion gases from ethylene/air rich premixed flames. Ten equivalence ratios ({phi}) were investigated, as follows: 1.37, 1.44, 1.47, 1.50, 1.55, 1.57, 1.62, 1.75, 1.82, and 1.91. MWCNT growth could be observed for the range of equivalence ratios between 1.45 and 1.75, with the best yield restricted to the range 1.5-1.6. A one-dimensional premixed flame code with a postflame heat loss model, including detailed chemistry, was used to estimate the gas phase chemical composition that favors MWCNT growth. The results of the calculations show that the mixture, including the water gas shift reaction, is not even in partial chemical equilibrium. Therefore, past discussions of compositional parameters that relate to optimum carbon nanotube (CNT) growth are revised to include chemical kinetic effects. Specifically, rapid departures of the water gas shift reaction from partial equilibrium and changes in mole fraction ratios of unburned C{sub 2} hydrocarbons to hydrogen correlate well with experimentally observed CNT yields. (author)

  1. Integrating chemical kinetic rate equations by selective use of stiff and nonstiff methods

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, K.

    1985-01-01

    The effect of switching between nonstiff and stiff methods on the efficiency of algorithms for integrating chemical kinetic rate equations was examined. Different integration methods were tested by application of the packaged code LSODE to four practical combustion kinetics problems. The problems describe adiabatic, and homogeneous gas phase combustion reactions. It is shown that selective use of nonstiff and stiff methods in different regimes of a typical batch combustion problem is faster than the use of either method for the entire problem. The implications which result in the development of fast integration techniques for combustion kinetic rate equations are discussed.

  2. A comparison of the efficiency of numerical methods for integrating chemical kinetic rate equations

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, K.

    1984-01-01

    The efficiency of several algorithms used for numerical integration of stiff ordinary differential equations was compared. The methods examined included two general purpose codes EPISODE and LSODE and three codes (CHEMEQ, CREK1D and GCKP84) developed specifically to integrate chemical kinetic rate equations. The codes were applied to two test problems drawn from combustion kinetics. The comparisons show that LSODE is the fastest code available for the integration of combustion kinetic rate equations. It is shown that an iterative solution of the algebraic energy conservation equation to compute the temperature can be more efficient then evaluating the temperature by integrating its time-derivative.

  3. Integrating chemical kinetic rate equations by selective use of stiff and nonstiff methods

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, K.

    1985-01-01

    The effect of switching between nonstiff and stiff methods on the efficiency of algorithms for integrating chemical kinetic rate equations is presented. Different integration methods are tested by application of the packaged code LSODE to four practical combustion kinetics problems. The problems describe adiabatic, homogeneous gas-phase combustion reactions. It is shown that selective use of nonstiff and stiff methods in different regimes of a typical batch combustion problem is faster than the use of either method for the entire problem. The implications of this result to the development of fast integration techniques for combustion kinetic rate equations are discussed.

  4. Shear-Driven Reconnection in Kinetic Models

    NASA Astrophysics Data System (ADS)

    Black, C.; Antiochos, S. K.; Germaschewski, K.; Karpen, J. T.; DeVore, C. R.; Bessho, N.

    2015-12-01

    The explosive energy release in solar eruptive phenomena is believed to be due to magnetic reconnection. In the standard model for coronal mass ejections (CME) and/or solar flares, the free energy for the event resides in the strongly sheared magnetic field of a filament channel. The pre-eruption force balance consists of an upward force due to the magnetic pressure of the sheared field countered by a downward tension due to overlying unsheared field. Magnetic reconnection disrupts this force balance; therefore, it is critical for understanding CME/flare initiation, to model the onset of reconnection driven by the build-up of magnetic shear. In MHD simulations, the application of a magnetic-field shear is a trivial matter. However, kinetic effects are dominant in the diffusion region and thus, it is important to examine this process with PIC simulations as well. The implementation of such a driver in PIC methods is challenging, however, and indicates the necessity of a true multiscale model for such processes in the solar environment. The field must be sheared self-consistently and indirectly to prevent the generation of waves that destroy the desired system. Plasma instabilities can arise nonetheless. In the work presented here, we show that we can control this instability and generate a predicted out-of-plane magnetic flux. This material is based upon work supported by the National Science Foundation under Award No. AGS-1331356.

  5. Kinetic modelling of krypton fluoride laser systems

    SciTech Connect

    Jancaitis, K.S.

    1983-11-01

    A kinetic model has been developed for the KrF* rare gas halide laser system, specifically for electron-beam pumped mixtures of krypton, fluorine, and either helium or argon. The excitation produced in the laser gas by the e-beam was calculated numerically using an algorithm checked by comparing the predicted ionization yields in the pure rare gases with their experimental values. The excitation of the laser media by multi-kilovolt x-rays was also modeled and shown to be similar to that produced by high energy electrons. A system of equations describing the transfer of the initial gas excitation into the laser upper level was assembled using reaction rate constants from both experiment and theory. A one-dimensional treatment of the interaction of the laser radiation with the gas was formulated which considered spontaneous and stimulated emission and absorption. The predictions of this model were in good agreement with the fluorescence signals and gain and absorption measured experimentally.

  6. Growth kinetics and inhibition of growth of chemical vapor deposited thin tungsten films on silicon from tungsten hexafluoride

    NASA Astrophysics Data System (ADS)

    Leusink, G. J.; Kleijn, C. R.; Oosterlaken, T. G. M.; Janssen, G. C. A. M.; Radelaar, S.

    1992-07-01

    The growth kinetics and inhibition of growth of chemical vapor deposited thin W films on Si(100) from WF6 was studied with in situ growth stress and reflectivity measurements and ex situ weight gain measurements. A systematic series of experiments at varying WF6 flow, total pressure, and temperature show that the thickening kinetics and inhibition of the growth are controlled by two processes: WF6 diffusion through the gas phase and Si diffusion through the thickening columnar film. The steady state growth kinetics are controlled by WF6 diffusion in the gas phase whereas inhibition of the growth occurs at the transition from WF6 gas diffusion limited to Si solid state diffusion limited growth. A simple model based on WF6 gas phase diffusion and Si solid state diffusion is presented which gives a quantitative description of the experimental results.

  7. Modeling Large Zinc Isotope Fractionations Associated with Reaction Kinetics

    NASA Astrophysics Data System (ADS)

    Black, J. R.; John, S.; Kavner, A.

    2009-12-01

    Often multiple processes govern isotope fractionation during a chemical reaction, such as the mass-transport, equilibrium and reaction kinetics between reactants and products. Here we use experimental electrochemical techniques to control the mass-transport and reaction kinetics of the electrodeposition reaction: Zn2+ + 2e- = Zn(s); and model the isotopic fractionation measured to resolve the underlying mechanisms of fractionation. Zn was plated on a rotating disc electrode at various applied overpotentials, rotation rates and temperatures. Electroplated Zn was recovered in acid for analysis of the stable isotope composition by multi-collector ICP-MS. The isotopic composition (66Zn/64Zn) of plated metal is reported relative to the stock solution. A large range of Δ66Znsample-stock is observed, with increasing fractionation at higher rotation rates (Fig. 1A), and lower overpotentials (Fig. 1B). Models of electrochemical kinetics, show that these variables control the relative rates of precipitation and diffusion, as defined by the Koutecky-Levich equation [Bard and Faulkner (2001), Electrochemical Methods, John Wiley & Sons]. Using this equation to interpret our data shows that all the data fall along a systematic trend (Fig. 1C) with smaller fractionations in the mass-transport limited regime and larger fractionations produced under electrochemical kinetic control. We extend the Koutecky-Levich model to predict isotope fractionation during electrochemical processes as a function of mass-dependent diffusion (Fig. 2A); standard rate constant (Fig. 2B); and transfer coefficient, describing reaction barrier symmetry (Fig. 2C). A comparison of the model and our data shows that diffusive and equilibrium fractionation alone (Fig. 2A-B) cannot reproduce the trends in our data, but a mass-dependence in α can explain our observations. However, the predicted fractionation is very sensitive to the magnitude of k0 (Fig. 2C). This model predicts how isotope fractionation

  8. Reflected kinetics model for nuclear space reactor kinetics and control scoping calculations

    SciTech Connect

    Washington, K.E.

    1986-05-01

    The objective of this research is to develop a model that offers an alternative to the point kinetics (PK) modelling approach in the analysis of space reactor kinetics and control studies. Modelling effort will focus on the explicit treatment of control drums as reactivity input devices so that the transition to automatic control can be smoothly done. The proposed model is developed for the specific integration of automatic control and the solution of the servo mechanism problem. The integration of the kinetics model with an automatic controller will provide a useful tool for performing space reactor scoping studies for different designs and configurations. Such a tool should prove to be invaluable in the design phase of a space nuclear system from the point of view of kinetics and control limitations.

  9. A hybrid computer program for rapidly solving flowing or static chemical kinetic problems involving many chemical species

    NASA Technical Reports Server (NTRS)

    Mclain, A. G.; Rao, C. S. R.

    1976-01-01

    A hybrid chemical kinetic computer program was assembled which provides a rapid solution to problems involving flowing or static, chemically reacting, gas mixtures. The computer program uses existing subroutines for problem setup, initialization, and preliminary calculations and incorporates a stiff ordinary differential equation solution technique. A number of check cases were recomputed with the hybrid program and the results were almost identical to those previously obtained. The computational time saving was demonstrated with a propane-oxygen-argon shock tube combustion problem involving 31 chemical species and 64 reactions. Information is presented to enable potential users to prepare an input data deck for the calculation of a problem.

  10. Students' Systematic Errors When Solving Kinetic and Chemical Equilibrium Problems.

    ERIC Educational Resources Information Center

    BouJaoude, Saouma

    Although students' misconceptions about the concept of chemical equilibrium has been the focus of numerous investigations, few have investigated students' systematic errors when solving equilibrium problems at the college level. Students (n=189) enrolled in the second semester of a first year chemistry course for science and engineering majors at…

  11. Kinetic modeling and sensitivity analysis of plasma-assisted combustion

    NASA Astrophysics Data System (ADS)

    Togai, Kuninori

    Plasma-assisted combustion (PAC) is a promising combustion enhancement technique that shows great potential for applications to a number of different practical combustion systems. In this dissertation, the chemical kinetics associated with PAC are investigated numerically with a newly developed model that describes the chemical processes induced by plasma. To support the model development, experiments were performed using a plasma flow reactor in which the fuel oxidation proceeds with the aid of plasma discharges below and above the self-ignition thermal limit of the reactive mixtures. The mixtures used were heavily diluted with Ar in order to study the reactions with temperature-controlled environments by suppressing the temperature changes due to chemical reactions. The temperature of the reactor was varied from 420 K to 1250 K and the pressure was fixed at 1 atm. Simulations were performed for the conditions corresponding to the experiments and the results are compared against each other. Important reaction paths were identified through path flux and sensitivity analyses. Reaction systems studied in this work are oxidation of hydrogen, ethylene, and methane, as well as the kinetics of NOx in plasma. In the fuel oxidation studies, reaction schemes that control the fuel oxidation are analyzed and discussed. With all the fuels studied, the oxidation reactions were extended to lower temperatures with plasma discharges compared to the cases without plasma. The analyses showed that radicals produced by dissociation of the reactants in plasma plays an important role of initiating the reaction sequence. At low temperatures where the system exhibits a chain-terminating nature, reactions of HO2 were found to play important roles on overall fuel oxidation. The effectiveness of HO2 as a chain terminator was weakened in the ethylene oxidation system, because the reactions of C 2H4 + O that have low activation energies deflects the flux of O atoms away from HO2. For the

  12. Recent Results in Quantum Chemical Kinetics from High Resolution Spectroscopy

    SciTech Connect

    Quack, Martin

    2007-12-26

    We outline the approach of our group to derive intramolecular kinetic primary processes from high resolution spectroscopy. We then review recent results on intramolecular vibrational redistribution (IVR) and on tunneling processes. Examples are the quantum dynamics of the C-H-chromophore in organic molecules, hydrogen bond dynamics in (HF){sub 2} and stereomutation dynamics in H{sub 2}O{sub 2} and related chiral molecules. We finally discuss the time scales for these and further processes which range from 10 fs to more than seconds in terms of successive symmetry breakings, leading to the question of nuclear spin symmetry and parity violation as well as the question of CPT symmetry.

  13. Enhancing conjugation rate of antibodies to carboxylates: Numerical modeling of conjugation kinetics in microfluidic channels and characterization of chemical over-exposure in conventional protocols by quartz crystal microbalance

    PubMed Central

    Asiaei, Sasan; Smith, Brendan

    2015-01-01

    This research reports an improved conjugation process for immobilization of antibodies on carboxyl ended self-assembled monolayers (SAMs). The kinetics of antibody/SAM binding in microfluidic heterogeneous immunoassays has been studied through numerical simulation and experiments. Through numerical simulations, the mass transport of reacting species, namely, antibodies and crosslinking reagent, is related to the available surface concentration of carboxyl ended SAMs in a microchannel. In the bulk flow, the mass transport equation (diffusion and convection) is coupled to the surface reaction between the antibodies and SAM. The model developed is employed to study the effect of the flow rate, conjugating reagents concentration, and height of the microchannel. Dimensionless groups, such as the Damköhler number, are used to compare the reaction and fluidic phenomena present and justify the kinetic trends observed. Based on the model predictions, the conventional conjugation protocol is modified to increase the yield of conjugation reaction. A quartz crystal microbalance device is implemented to examine the resulting surface density of antibodies. As a result, an increase in surface density from 321 ng/cm2, in the conventional protocol, to 617 ng/cm2 in the modified protocol is observed, which is quite promising for (bio-) sensing applications. PMID:26697125

  14. Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

    DTIC Science & Technology

    2009-05-01

    decomposition by several advanced oxidation processes. Chemosphere , 41, 1271-1277. 5. Bier, E.L., Singh, J., Li, Z.M., Comfort, S.D., Shea, P.J...G.M., 2001a. The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton’s reagent. J. Hazard. Mater., 87, 171 -186. 45...oxidation by Fenton’s reagent. Chemosphere , 45, 85-90. 22. Duesterberg, C.K., Waite, T.D., 2006. Process optimization of fenton oxidation using kinetic

  15. Modeling the kinetics of carbon coagulation in explosives detonation

    NASA Astrophysics Data System (ADS)

    Ree, F. H.; Viecelli, J. A.; Glosli, J. N.

    1998-05-01

    A typical insensitive high explosive such as LX-17 has a large carbon content. The detonation behavior of these explosives is affected by a slow coagulation of carbon atoms by diffusion and their possible transformation from one chemical bonding type to another. We have used the Brenner bond order potential to compute the melting line of diamond at high pressure and high temperature by molecular dynamics and Monte Carlo simulations, with the goal to refine the potential for the study of the kinetics of the graphite diamond transition. The slow diffusion-controlled kinetics of carbon clusters has been examined by including a time-dependent surface correction to the Gibbs free energy of these clusters in the nonequilibrium CHEQ code. We also propose a new explosive burn model which incorporates a partial release of the heat of detonation in a fast reaction zone, followed by a diffusion-limited release of the remaining energy. Hydrodynamic applications of the new burn model to LX-17 show that computed expansion and compression results both agree closely with experimental data.

  16. Fully implicit kinetic modelling of collisional plasmas

    SciTech Connect

    Mousseau, Vincent Andrew

    1996-05-01

    This dissertation describes a numerical technique, Matrix-Free Newton Krylov, for solving a simplified Vlasov-Fokker-Planck equation. This method is both deterministic and fully implicit, and may not have been a viable option before current developments in numerical methods. Results are presented that indicate the efficiency of the Matrix-Free Newton Krylov method for these fully-coupled, nonlinear integro-differential equations. The use and requirement for advanced differencing is also shown. To this end, implementations of Chang-Cooper differencing and flux limited Quadratic Upstream Interpolation for Convective Kinematics (QUICK) are presented. Results are given for a fully kinetic ion-electron problem with a self consistent electric field calculated from the ion and electron distribution functions. This numerical method, including advanced differencing, provides accurate solutions, which quickly converge on workstation class machines. It is demonstrated that efficient steady-state solutions can be achieved to the non-linear integro-differential equation, obtaining quadratic convergence, without incurring the large memory requirements of an integral operator. Model problems are presented which simulate plasma impinging on a plate with both high and low neutral particle recycling typical of a divertor in a Tokamak device. These model problems demonstrate the performance of the new solution method.

  17. Thrust optimization of nozzle contour including finite rate chemical kinetics

    NASA Astrophysics Data System (ADS)

    Rao, G. V. R.; Dang, A. L.

    1992-07-01

    Within the restraints of length and exit area it is desirable to contour nozzles for optimum thrust. Calculus of variations is employed to define the exit flow of the nozzle that fits the requirement, and then, the Method of Characteristics (MOC) is used to compute the nozzle contour that would deliver the desired exit flow. High velocities of the exhaust gases and finite chemical reaction rates of the component species complicate the procedure since the thermodynamic state conditions depend upon the residence time along each stream tube. The present method develops the nozzle contour by applying the optimization procedure for each stream tube taking into account the rate of production of the chemical species along the streamline.

  18. Kinetic Requirements for Spatiotemporal Chemical Imaging with Fluorescent Nanosensors.

    PubMed

    Meyer, Daniel; Hagemann, Annika; Kruss, Sebastian

    2017-04-25

    Fluorescent nanosensors are powerful tools for basic research and bioanalytical applications. Individual nanosensors are able to detect single molecules, while ensembles of nanosensors can be used to measure the bulk concentration of an analyte. Collective imaging of multiple nanosensors could provide both spatial and temporal chemical information from the nano- to the microscale. This type of chemical imaging with nanosensors would be very attractive to study processes such as chemical signaling between cells (e.g., neurons). So far, it is not understood what processes are resolvable (concentration, time, space) and how optimal sensors should be designed. Here, we develop a theoretical framework to simulate the fluorescence image of arrays of nanosensors in response to a concentration gradient. For that purpose, binding and unbinding of the analyte is simulated for each single nanosensor by using a Monte Carlo simulation and varying rate constants (kon, koff). Multiple nanosensors are arranged on a surface and exposed to a concentration pattern cA(x,y,t) of an analyte. We account for the resolution limit of light microscopy (Abbe limit) and the acquisition speed and resolution of optical setups and determine the resulting response images ΔI(x,y,t). Consequently, we introduce terms for the spatial and temporal resolution and simulate phase diagrams for different rate constants that allow us to predict how a sensor should be designed to provide a desired spatial and temporal resolution. Our results show, for example, that imaging of neurotransmitter release requires rate constants of kon = 10(6) M(-1) s(-1)and koff = 10(2) s(-1) in many scenarios, which corresponds to high dissociation constants of Kd > 100 μM. This work predicts if a given fluorescent nanosensor array (rate constants, size, shape, geometry, density) is able to resolve fast concentration changes such as neurotransmitter release from cells. Additionally, we provide rational design principles to

  19. A dynamic physicochemical model for chemical phosphorus removal.

    PubMed

    Hauduc, H; Takács, I; Smith, S; Szabo, A; Murthy, S; Daigger, G T; Spérandio, M

    2015-04-15

    A dynamic physico-chemical model for chemical phosphorus removal in wastewater is presented as a tool to optimize chemical dosing simultaneously while ensuring compliant effluent phosphorus concentration. This new model predicts the kinetic and stoichiometric variable processes of precipitation of hydrous ferric oxides (HFO), phosphates adsorption and co-precipitation. It is combined with chemical equilibrium and physical precipitation reactions in order to model observed bulk dynamics in terms of pH. The model is calibrated and validated based on previous studies and experimental data from Smith et al. (2008) and Szabo et al. (2008) as a first step for full-plant implementation. The simulation results show that the structure of the model describes adequately the mechanisms of adsorption and co-precipitation of phosphate species onto HFO and that the model is robust under various experimental conditions.

  20. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    PubMed

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  1. Automatic network coupling analysis for dynamical systems based on detailed kinetic models.

    PubMed

    Lebiedz, Dirk; Kammerer, Julia; Brandt-Pollmann, Ulrich

    2005-10-01

    We introduce a numerical complexity reduction method for the automatic identification and analysis of dynamic network decompositions in (bio)chemical kinetics based on error-controlled computation of a minimal model dimension represented by the number of (locally) active dynamical modes. Our algorithm exploits a generalized sensitivity analysis along state trajectories and subsequent singular value decomposition of sensitivity matrices for the identification of these dominant dynamical modes. It allows for a dynamic coupling analysis of (bio)chemical species in kinetic models that can be exploited for the piecewise computation of a minimal model on small time intervals and offers valuable functional insight into highly nonlinear reaction mechanisms and network dynamics. We present results for the identification of network decompositions in a simple oscillatory chemical reaction, time scale separation based model reduction in a Michaelis-Menten enzyme system and network decomposition of a detailed model for the oscillatory peroxidase-oxidase enzyme system.

  2. Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

    NASA Astrophysics Data System (ADS)

    Roden, Eric E.

    2004-08-01

    Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to

  3. Including Bioconcentration Kinetics for the Prioritization and Interpretation of Regulatory Aquatic Toxicity Tests of Highly Hydrophobic Chemicals.

    PubMed

    Kwon, Jung-Hwan; Lee, So-Young; Kang, Hyun-Joong; Mayer, Philipp; Escher, Beate I

    2016-11-01

    Worldwide, regulations of chemicals require short-term toxicity data for evaluating hazards and risks of the chemicals. Current data requirements on the registration of chemicals are primarily based on tonnage and do not yet consider properties of chemicals. For example, short-term ecotoxicity data are required for chemicals with production volume greater than 1 or 10 ton/y according to REACH, without considering chemical properties. Highly hydrophobic chemicals are characterized by low water solubility and slow bioconcentration kinetics, which may hamper the interpretation of short-term toxicity experiments. In this work, internal concentrations of highly hydrophobic chemicals were predicted for standard acute ecotoxicity tests at three trophic levels, algae, invertebrate, and fish. As demonstrated by comparison with maximum aqueous concentrations at water solubility, chemicals with an octanol-water partition coefficient (Kow) greater than 10(6) are not expected to reach sufficiently high internal concentrations for exerting effects within the test duration of acute tests with fish and invertebrates, even though they might be intrinsically toxic. This toxicity cutoff was explained by the slow uptake, i.e., by kinetics, not by thermodynamic limitations. Predictions were confirmed by data entries of the OECD's screening information data set (SIDS) (n = 746), apart from a few exceptions concerning mainly organometallic substances and those with inconsistency between water solubility and Kow. Taking error propagation and model assumptions into account, we thus propose a revision of data requirements for highly hydrophobic chemicals with log Kow > 7.4: Short-term toxicity tests can be limited to algae that generally have the highest uptake rate constants, whereas the primary focus of the assessment should be on persistence, bioaccumulation, and long-term effects.

  4. Do arbuscular mycorrhizal fungi affect cadmium uptake kinetics, subcellular distribution and chemical forms in rice?

    PubMed

    Li, Hui; Luo, Na; Zhang, Li Jun; Zhao, Hai Ming; Li, Yan Wen; Cai, Quan Ying; Wong, Ming Hung; Mo, Ce Hui

    2016-11-15

    Rice (Oryza sativa L.) plants were inoculated with two species of arbuscular mycorrhizal fungi (AMF) - Rhizophagus intraradices (RI) and Funneliformis mosseae (FM) and grown for 60days to ensure strong colonization. Subsequently, a short-term hydroponic experiment was carried out to investigate the effects of AMF on cadmium (Cd) uptake kinetics, subcellular distribution and chemical forms in rice exposed to six Cd levels (0, 0.005, 0.01, 0.025, 0.05, 0.1mM) for three days. The results showed that the uptake kinetics of Cd fitted the Michaelis-Menten model well (R(2)>0.89). AMF significantly decreased the Cd concentrations both in shoots and roots in Cd solutions. Furthermore, the decrement of Cd concentrations by FM was significantly higher than RI treatment in roots. AMF reduced the Cd concentrations markedly in the cell wall fractions at high Cd substrate (≥0.025mM). The main subcellular fraction contributed to Cd detoxification was cell wall at low Cd substrate (<0.05mM), while vacuoles at high Cd substrate (≥0.05mM). Moreover, the concentrations and proportions of Cd in inorganic and water-soluble form also reduced by AMF colonization at high Cd substrate (≥0.05mM), both in shoots and roots. This suggested that AMF could convert Cd into inactive forms which were less toxic. Therefore, AMF could enhance rice resistance to Cd through altering subcellular distribution and chemical forms of Cd in rice.

  5. A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

    NASA Technical Reports Server (NTRS)

    Gokoglu, S. A.; Kuczmarski, M. A.

    1993-01-01

    Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

  6. Kinetic model for phenolic compound oxidation by Fenton's reagent.

    PubMed

    De Heredia, J B; Torregrosa, J; Dominguez, J R; Peres, J A

    2001-10-01

    A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.

  7. First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study.

    PubMed

    Van Speybroeck, Veronique; De Wispelaere, Kristof; Van der Mynsbrugge, Jeroen; Vandichel, Matthias; Hemelsoet, Karen; Waroquier, Michel

    2014-11-07

    To optimally design next generation catalysts a thorough understanding of the chemical phenomena at the molecular scale is a prerequisite. Apart from qualitative knowledge on the reaction mechanism, it is also essential to be able to predict accurate rate constants. Molecular modeling has become a ubiquitous tool within the field of heterogeneous catalysis. Herein, we review current computational procedures to determine chemical kinetics from first principles, thus by using no experimental input and by modeling the catalyst and reacting species at the molecular level. Therefore, we use the methanol-to-olefin (MTO) process as a case study to illustrate the various theoretical concepts. This process is a showcase example where rational design of the catalyst was for a long time performed on the basis of trial and error, due to insufficient knowledge of the mechanism. For theoreticians the MTO process is particularly challenging as the catalyst has an inherent supramolecular nature, for which not only the Brønsted acidic site is important but also organic species, trapped in the zeolite pores, must be essentially present during active catalyst operation. All these aspects give rise to specific challenges for theoretical modeling. It is shown that present computational techniques have matured to a level where accurate enthalpy barriers and rate constants can be predicted for reactions occurring at a single active site. The comparison with experimental data such as apparent kinetic data for well-defined elementary reactions has become feasible as current computational techniques also allow predicting adsorption enthalpies with reasonable accuracy. Real catalysts are truly heterogeneous in a space- and time-like manner. Future theory developments should focus on extending our view towards phenomena occurring at longer length and time scales and integrating information from various scales towards a unified understanding of the catalyst. Within this respect molecular

  8. An Experimental and Kinetic Modeling Study of Methyl Decanoate Combustion

    SciTech Connect

    Sarathy, S M; Thomson, M J; Pitz, W J; Lu, T

    2010-02-19

    Biodiesel is typically a mixture of long chain fatty acid methyl esters for use in compression ignition engines. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This research study presents new combustion data for methyl decanoate in an opposed-flow diffusion flame. An improved detailed chemical kinetic model for methyl decanoate combustion is developed, which serves as the basis for deriving a skeletal mechanism via the direct relation graph method. The novel skeletal mechanism consists of 648 species and 2998 reactions. This mechanism well predicts the methyl decanoate opposed-flow diffusion flame data. The results from the flame simulations indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.

  9. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    SciTech Connect

    Naik, C; Westbrook, C K; Herbinet, O; Pitz, W J; Mehl, M

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  10. Physical and numerical sources of computational inefficiency in integration of chemical kinetic rate equations: Etiology, treatment and prognosis

    NASA Technical Reports Server (NTRS)

    Pratt, D. T.; Radhakrishnan, K.

    1986-01-01

    The design of a very fast, automatic black-box code for homogeneous, gas-phase chemical kinetics problems requires an understanding of the physical and numerical sources of computational inefficiency. Some major sources reviewed in this report are stiffness of the governing ordinary differential equations (ODE's) and its detection, choice of appropriate method (i.e., integration algorithm plus step-size control strategy), nonphysical initial conditions, and too frequent evaluation of thermochemical and kinetic properties. Specific techniques are recommended (and some advised against) for improving or overcoming the identified problem areas. It is argued that, because reactive species increase exponentially with time during induction, and all species exhibit asymptotic, exponential decay with time during equilibration, exponential-fitted integration algorithms are inherently more accurate for kinetics modeling than classical, polynomial-interpolant methods for the same computational work. But current codes using the exponential-fitted method lack the sophisticated stepsize-control logic of existing black-box ODE solver codes, such as EPISODE and LSODE. The ultimate chemical kinetics code does not exist yet, but the general characteristics of such a code are becoming apparent.

  11. Enskog-like kinetic models for vehicular traffic

    SciTech Connect

    Klar, A.; Wegener, R.

    1997-04-01

    In the present paper a general criticism of kinetic equations for vehicular traffic is given. The necessity of introducing an Enskog-type correction into these equations is shown. An Enskog-like kinetic traffic flow equation is presented and fluid dynamic equations are derived. This derivation yields new coefficients for the standard fluid dynamic equations of vehicular traffic. Numerical simulations for inhomogeneous traffic flow situations are shown together with a comparison between kinetic and fluid dynamics models.

  12. Reflected kinetics model for nuclear space reactor kinetics and control scoping calculations

    SciTech Connect

    Washington, K.E.

    1986-01-01

    Renewed interest in space nuclear applications has motivated the study of a specialized reactor kinetics model. Consideration of a kinetics model favorable for study of the feasibility of automatic control of these devices is warranted. The need to bridge this gap between reactor kinetics and automatic control in conjunction with the control drum design characteristic of next generation paper space reactors inspired the development of a new Reflected Kinetics (RK) model. An extension of the conventional point-kinetics (PK) model was done in order to explicitly correlate reactivity and the reflector/absorber control drums characteristic of space nuclear reactor designs. Open-loop computations and numerical comparison to analytic PK equations indicated that the RK model is a functional alternative to equivalent bare point kinetics in the analysis of moderate transients. Variations in the RK reflector-to-core transfer probabilities and coolant flow rate do indeed drive the transient differently than the lumped insertion of equivalent reactivity amounts in the core. These computations illustrated the potential importance of the utilization of variable coolant flow rate to aid control in space reactor systems limited by minimal drum reactivity worth. Additionally the Doppler reactivity shutdown mechanism was concluded to be the primarily reliable means of safety shutdown in such systems. The structure of the RK equations proved to be advantageous for integration of automatic control.

  13. Fully Kinetic versus Reduced-kinetic Modeling of Collisionless Plasma Turbulence

    NASA Astrophysics Data System (ADS)

    Grošelj, Daniel; Cerri, Silvio S.; Bañón Navarro, Alejandro; Willmott, Christopher; Told, Daniel; Loureiro, Nuno F.; Califano, Francesco; Jenko, Frank

    2017-09-01

    We report the results of a direct comparison between different kinetic models of collisionless plasma turbulence in two spatial dimensions. The models considered include a first-principles fully kinetic (FK) description, two widely used reduced models (gyrokinetic (GK) and hybrid-kinetic (HK) with fluid electrons), and a novel reduced gyrokinetic approach (KREHM). Two different ion beta ({β }i) regimes are considered: 0.1 and 0.5. For {β }i=0.5, good agreement between the GK and FK models is found at scales ranging from the ion to the electron gyroradius, thus providing firm evidence for a kinetic Alfvén cascade scenario. In the same range, the HK model produces shallower spectral slopes, presumably due to the lack of electron Landau damping. For {β }i=0.1, a detailed analysis of spectral ratios reveals a slight disagreement between the GK and FK descriptions at kinetic scales, even though kinetic Alfvén fluctuations likely still play a significant role. The discrepancy can be traced back to scales above the ion gyroradius, where the FK and HK results seem to suggest the presence of fast magnetosonic and ion Bernstein modes in both plasma beta regimes, but with a more notable deviation from GK in the low-beta case. The identified practical limits and strengths of reduced-kinetic approximations, compared here against the FK model on a case-by-case basis, may provide valuable insight into the main kinetic effects at play in turbulent collisionless plasmas, such as the solar wind.

  14. The release behavior and kinetic evaluation of tramadol HCl from chemically cross linked Ter polymeric hydrogels

    PubMed Central

    2013-01-01

    Background and the purpose of the study Hydrogels, being stimuli responsive are considered to be effective for targeted and sustained drug delivery. The main purpose for this work was to study the release behavior and kinetic evaluation of Tramadol HCl from chemically cross linked ter polymeric hydrogels. Methods Ter-polymers of methacrylate, vinyl acetate and acrylic acid cross linked with ethylene glycol dimethacrylate (EGDMA) were prepared by free radical polymerization. The drug release rates, dynamic swelling behavior and pH sensitivity of hydrogels ranging in composition from 1-10 mol% EGDMA were studied. Tramadol HCl was used as model drug substance. The release behavior was investigated at pH 8 where all formulations exhibited non-Fickian diffusion mechanism. Results and major conclusion Absorbency was found to be more than 99% indicating good drug loading capability of these hydrogels towards the selected drug substance. Formulations designed with increasing amounts of EGDMA had a decreased equilibrium media content as well as media penetrating velocity and thus exhibited a slower drug release rate. Fitting of release data to different kinetic models indicate that the kinetic order shifts from the first to zero order as the concentration of drug was increased in the medium, showing gradual independency of drug release towards its concentration. Formulations with low drug content showed best fitness with Higuchi model whereas those with higher concentration of drug followed Hixson-Crowell model with better correlation values indicating that the drug release from these formulations depends more on change in surface area and diameter of tablets than that on concentration of the drug. Release exponent (n) derived from Korse-Meyer Peppas equation implied that the release of Tramadol HCl from these formulations was generally non-Fickian (n > 0.5 > 1) showing swelling controlled mechanism. The mechanical strength and controlled release capability of the

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

    NASA Technical Reports Server (NTRS)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

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

  17. Chemical-kinetic problems of future NASA missions

    NASA Technical Reports Server (NTRS)

    Park, Chul; Howe, John T.; Jaffe, Richard L.; Candler, Graham V.

    1991-01-01

    Thermochemical nonequilibrium in the shock layer surrounding vehicles entering the atmospheres of earth and Mars at superescape velocities is studied, deriving reaction rate coefficients that reproduce experimental data obtained in shock tubes. Thermodynamic properties and emitted radiation intensities are obtained for shock tube flow and flow in a shock layer over a blunt body. The results indicate that the viscous layer of the ablation product over an ablating heat shield is likely to be in chemical nonequilbrium. For earth entry flight, the thickness of the nonequilbrium region is between and 2 cm at the expected peak radiation point in the aerobraking trajectory, For Martian entry flight it is between 8 and 23 cm. For the earth entry case, nonequilibrium phenomena reduce radiative heating rate, while the opposite occurs for the Martian case. The radiative heat transfer rates are significant for the Mars entry conditions at entry velocities equal to or greater than 7 km/s.

  18. Modulation of a ligand's energy landscape and kinetics by the chemical environment.

    PubMed

    Held, Martin; Imhof, Petra; Keller, Bettina G; Noé, Frank

    2012-11-26

    Understanding how the chemical environment modulates the predominant conformations and kinetics of flexible molecules is a core interest of biochemistry and a prerequisite for the rational design of synthetic catalysts. This study combines molecular dynamics simulation and Markov state models (MSMs) to a systematic computational strategy for investigating the effect of the chemical environment of a molecule on its conformations and kinetics. MSMs allow quantities to be computed that are otherwise difficult to access, such as the metastable sets, their free energies, and the relaxation time scales related to the rare transitions between metastable states. Additionally, MSMs are useful to identify observables that may act as sensors for the conformational or binding state of the molecule, thus guiding the design of experiments. In the present study, the conformation dynamics of UDP-GlcNAc are studied in vacuum, water, water + Mg(2+), and in the protein UDP-GlcNAc 2-epimerase. It is found that addition of Mg(2+) significantly affects the conformational stability, thermodynamics, and kinetics of UDP-GlcNAc. In particular, the slowest structural process, puckering of the GlcNAc sugar, depends on the overall conformation of UDP-GlcNAc and may thus act as a sensor of whether Mg(2+) is bound or not. Interestingly, transferring the molecule from vacuum to water makes the protein-binding conformations UDP-GlcNAc first accessible, while adding Mg(2+) further stabilizes them by specifically associating to binding-competent conformations. While Mg(2+) is not cocrystallized in the UDP-GlcNAc 2-epimerase complex, the selectively stabilized Mg(2+)/UDP-GlcNAc complex may be a template for the bound state, and Mg(2+) may accompany the binding-competent ligand conformation to the binding pocket. This serves as a possible explanation of the enhanced epimerization rate in the presence of Mg(2+). This role of Mg(2+) has previously not been described and opens the question whether

  19. Assessment of two-temperature kinetic model for ionizing air

    NASA Technical Reports Server (NTRS)

    Park, Chul

    1987-01-01

    A two-temperature chemical-kinetic model for air is assessed by comparing theoretical results with existing experimental data obtained in shock-tubes, ballistic ranges, and flight experiments. In the model, named the TTv model, one temperature (T) is assumed to characterize the heavy-particle translational and molecular rotational energies, and another temperature (Tv) to characterize the molecular vibrational, electron translational, and electronic excitation energies. The theoretical results for nonequilibrium air flow in shock tubes are obtained using the computer code STRAP (Shock-Tube Radiation Program), and for flow along the stagnation streamline in the shock layer over spherical bodies using the newly developed code STRAP (Stagnation-Point Radiation Program). Substantial agreement is shown between the theoretical and experimental results for relaxation times and radiative heat fluxes. At very high temperatures the spectral calculations need further improvement. The present agreement provides strong evidence that the two-temperature model characterizes principal features of nonequilibrium air flow. New theoretical results using the model are presented for the radiative heat fluxes at the stagnation point of a 6-m-radius sphere, representing an aeroassisted orbital transfer vehicle, over a range of free-stream conditions. Assumptions, approximations, and limitations of the model are discussed.

  20. Chemical mechanism of lysophosphatidylcholine: lysophosphatidylcholine acyltransferase from rabbit lung. pH-dependence of kinetic parameters.

    PubMed Central

    Pérez-Gil, J; Martín, J; Acebal, C; Arche, R

    1990-01-01

    Lysophosphatidylcholine: lysophosphatidylcholine acyltransferase is an enzyme that catalyses two reactions: hydrolysis of lysophosphatidylcholine and transacylation between two molecules of lysophosphatidylcholine to give disaturated phosphatidylcholine. Following the kinetic model previously proposed for this enzyme [Martín, Pérez-Gil, Acebal & Arche (1990) Biochem. J. 266, 47-53], the values of essential pK values in free enzyme and substrate-enzyme complexes have now been determined. The chemical mechanism of catalysis was dependent on the deprotonation of a histidine residue with pK about 5.7. This result was supported by the perturbation of pK values by addition of organic solvent. Very high and exothermic enthalpy of ionization was measured, indicating that a conformational re-arrangement in the enzyme accompanies the ionization of the essential histidine residue. These results, as well as the results from previous studies, enabled the proposal of a chemical mechanism for the enzymic reactions catalysed by lysophosphatidylcholine: lysophosphatidylcholine acyltransferase from rabbit lung. PMID:2241908