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

Science.gov (United States)

Fegley, Bruce, Jr.

1990-01-01

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

Empiricism or self-consistent theory in chemical kinetics?

International Nuclear Information System (INIS)

Gutman, E.M.

2007-01-01

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

KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

International Nuclear Information System (INIS)

Yeh, G.T.; Iskra, G.A.

1995-01-01

This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

Modeling chemical kinetics graphically

NARCIS (Netherlands)

Heck, A.

2012-01-01

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

On the theory of time dilation in chemical kinetics

Science.gov (United States)

Baig, Mirza Wasif

2017-10-01

The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying basic theories of chemical kinetics, which are transition state theory, collision theory, RRKM and Marcus theory, with the special theory of relativity. Boltzmann constant and energy spacing between permitted quantum levels of molecules are quantum mechanically proved to be Lorentz variant. The relativistic statistical thermodynamics has been developed to explain quasi-equilibrium existing between reactants and activated complex. The newly formulated Lorentz transformation of the rate constant from Arrhenius equation, of the collision frequency and of the Eyring and Marcus equations renders the rate of reaction to be Lorentz variant. For a moving observer moving at fractions of the speed of light along the reaction coordinate, the transition state possess less kinetic energy to sweep translation over it. This results in the slower transformation of reactants into products and in a stretched time frame for the chemical reaction to complete. Lorentz transformation of the half-life equation explains time dilation of the half-life period of chemical reactions and proves special theory of relativity and presents theory in accord with each other. To demonstrate the effectiveness of the present theory, the enzymatic reaction of methylamine dehydrogenase and radioactive disintegration of Astatine into Bismuth are considered as numerical examples.

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

Science.gov (United States)

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.

Modeling of Scale-Dependent Bacterial Growth by Chemical Kinetics Approach

Directory of Open Access Journals (Sweden)

Haydee Martínez

2014-01-01

Full Text Available 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.

Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

Science.gov (United States)

Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

2016-02-01

Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complex Reaction Kinetics in Chemistry: A Unified Picture Suggested by Mechanics in Physics

Directory of Open Access Journals (Sweden)

Elena Agliari

2018-01-01

Full Text Available Complex biochemical pathways can be reduced to chains of elementary reactions, which can be described in terms of chemical kinetics. Among the elementary reactions so far extensively investigated, we recall the Michaelis-Menten and the Hill positive-cooperative kinetics, which apply to molecular binding and are characterized by the absence and the presence, respectively, of cooperative interactions between binding sites. However, there is evidence of reactions displaying a more complex pattern: these follow the positive-cooperative scenario at small substrate concentration, yet negative-cooperative effects emerge as the substrate concentration is increased. Here, we analyze the formal analogy between the mathematical backbone of (classical reaction kinetics in Chemistry and that of (classical mechanics in Physics. We first show that standard cooperative kinetics can be framed in terms of classical mechanics, where the emerging phenomenology can be obtained by applying the principle of least action of classical mechanics. Further, since the saturation function plays in Chemistry the same role played by velocity in Physics, we show that a relativistic scaffold naturally accounts for the kinetics of the above-mentioned complex reactions. The proposed formalism yields to a unique, consistent picture for cooperative-like reactions and to a stronger mathematical control.

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

Lunsford, J.L.

1977-10-01

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

Analysis of mechanism of complex chemical reaction taking radiation chemical purification of gases from impurities as an example

International Nuclear Information System (INIS)

Gerasimov, G.Ya.; Makarov, V.N.

1997-01-01

Algorithm of selecting optimal mechanism of complex chemical reaction, enabling to reduce the number of its stages, is suggested. Main steps of constructing the kinetic model of the medium are considered, taking the radiation chemical purification (using fast electron radiation) of gases (N 2 , CO 2 , O 2 and others) from impurities as an example. 17 refs., 3 figs., 2 tabs

Accounting for chemical kinetics in field scale transport calculations

International Nuclear Information System (INIS)

Bryan, N.D.

2005-01-01

The modelling of column experiments has shown that the humic acid mediated transport of metal ions is dominated by the non-exchangeable fraction. Metal ions enter this fraction via the exchangeable fraction, and may transfer back again. However, in both directions these chemical reactions are slow. Whether or not a kinetic description of these processes is required during transport calculations, or an assumption of local equilibrium will suffice, will depend upon the ratio of the reaction half-time to the residence time of species within the groundwater column. If the flow rate is sufficiently slow or the reaction sufficiently fast then the assumption of local equilibrium is acceptable. Alternatively, if the reaction is sufficiently slow (or the flow rate fast), then the reaction may be 'decoupled', i.e. removed from the calculation. These distinctions are important, because calculations involving chemical kinetics are computationally very expensive, and should be avoided wherever possible. In addition, column experiments have shown that the sorption of humic substances and metal-humate complexes may be significant, and that these reactions may also be slow. In this work, a set of rules is presented that dictate when the local equilibrium and decoupled assumptions may be used. In addition, it is shown that in all cases to a first approximation, the behaviour of a kinetically controlled species, and in particular its final distribution against distance at the end of a calculation, depends only upon the ratio of the reaction first order rate to the residence time, and hence, even in the region where the simplifications may not be used, the behaviour is predictable. In this way, it is possible to obtain an estimate of the migration of these species, without the need for a complex transport calculation. (orig.)

Chemical kinetics and oil shale process design

Energy Technology Data Exchange (ETDEWEB)

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.

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

International Nuclear Information System (INIS)

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

2016-01-01

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.

Catalyze and chemical inhibition of the R7T7 glass kinetics

International Nuclear Information System (INIS)

Gin, St.; Advocat, Th.

1997-01-01

This article highlights some phenomena likely to modify the glass alteration kinetics and/or the nature of the alteration products according to the chemical composition of the leaching water. It discusses experimental results showing that in neutral and basic media, the presence of inorganic anions or organic acid (simple carboxylic acid and humic acid) has relatively little effect on the long-term glass matrix alterability Actinide mobility appears to be more dependent on the concentration of complexing agents in the leaching solution. The behavior of phosphate ions, which may inhibit or catalyze the R7T7 glass alteration kinetics depending on the experimental conditions, is discussed; the gel microstructure can be related to the glass alteration kinetics by detailed examination of the alteration products. (authors)

pyJac: Analytical Jacobian generator for chemical kinetics

Science.gov (United States)

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

Chemical kinetics and combustion modeling

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Some concepts in condensed phase chemical kinetics

International Nuclear Information System (INIS)

Adelman, S.A.

1986-01-01

Some concepts in condensed phase chemical kinetics which have emerged from a recent rigorous statistical mechanical treatment of condensed phase chemical reaction dynamics (S.A. Adelman, Adv. Chem. Phys.53:61 (1983)) are discussed in simple physical terms

Chemical kinetics and modeling of planetary atmospheres

Science.gov (United States)

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.

Diameter dependent electron transfer kinetics in semiconductor-enzyme complexes.

Science.gov (United States)

Brown, Katherine A; Song, Qing; Mulder, David W; King, Paul W

2014-10-28

Excited state electron transfer (ET) is a fundamental step for the catalytic conversion of solar energy into chemical energy. To understand the properties controlling ET between photoexcited nanoparticles and catalysts, the ET kinetics were measured for solution-phase complexes of CdTe quantum dots and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) using time-resolved photoluminescence spectroscopy. Over a 2.0-3.5 nm diameter range of CdTe nanoparticles, the observed ET rate (kET) was sensitive to CaI concentration. To account for diameter effects on CaI binding, a Langmuir isotherm and two geometric binding models were created to estimate maximal CaI affinities and coverages at saturating concentrations. Normalizing the ET kinetics to CaI surface coverage for each CdTe diameter led to k(ET) values that were insensitive to diameter, despite a decrease in the free energy for photoexcited ET (ΔGET) with increasing diameter. The turnover frequency (TOF) of CaI in CdTe-CaI complexes was measured at several molar ratios. Normalization for diameter-dependent changes in CaI coverage showed an increase in TOF with diameter. These results suggest that k(ET) and H2 production for CdTe-CaI complexes are not strictly controlled by ΔG(ET) and that other factors must be considered.

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

Science.gov (United States)

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 H 2 combustion model.

CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

KAUST Repository

Tingas, Efstathios Al.

2018-03-11

Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53/325 species/reactions with N-chemistry) and the AramcoMech mechanism from NUI Galway (113/710 species/reactions without N-chemistry; Combustion and Flame 162:315-330, 2015). Although the two mechanisms provide qualitatively similar results (regarding ignition delay and profiles of temperature, of mass fractions and of explosive time scale), the 113/710 mechanism was shown to reproduce the experimental data with higher accuracy than the 53/325 mechanism. The present analysis explores the origin of the improved accuracy provided by the more complex kinetics mechanism. It is shown that the reactions responsible for the generation of the explosive time scale differ significantly. This is reflected to differences in the length of the chemical and thermal runaways and in the set of the most influential species.

Satl model lesson in chemical kinetics | Nazir | African Journal of ...

African Journals Online (AJOL)

Studies in order to pursue kinetics and mechanism of chemical reactions are a vital component of chemical literature. SATL literature is still not available for promoting this vital aspect of chemistry teaching. A lesson pertaining to this important issue has been developed and various parameters of kinetic studies are ...

Systematic Constraint Selection Strategy for Rate-Controlled Constrained-Equilibrium Modeling of Complex Nonequilibrium Chemical Kinetics

Science.gov (United States)

Beretta, Gian Paolo; Rivadossi, Luca; Janbozorgi, Mohammad

2018-04-01

Rate-Controlled Constrained-Equilibrium (RCCE) modeling of complex chemical kinetics provides acceptable accuracies with much fewer differential equations than for the fully Detailed Kinetic Model (DKM). Since its introduction by James C. Keck, a drawback of the RCCE scheme has been the absence of an automatable, systematic procedure to identify the constraints that most effectively warrant a desired level of approximation for a given range of initial, boundary, and thermodynamic conditions. An optimal constraint identification has been recently proposed. Given a DKM with S species, E elements, and R reactions, the procedure starts by running a probe DKM simulation to compute an S-vector that we call overall degree of disequilibrium (ODoD) because its scalar product with the S-vector formed by the stoichiometric coefficients of any reaction yields its degree of disequilibrium (DoD). The ODoD vector evolves in the same (S-E)-dimensional stoichiometric subspace spanned by the R stoichiometric S-vectors. Next we construct the rank-(S-E) matrix of ODoD traces obtained from the probe DKM numerical simulation and compute its singular value decomposition (SVD). By retaining only the first C largest singular values of the SVD and setting to zero all the others we obtain the best rank-C approximation of the matrix of ODoD traces whereby its columns span a C-dimensional subspace of the stoichiometric subspace. This in turn yields the best approximation of the evolution of the ODoD vector in terms of only C parameters that we call the constraint potentials. The resulting order-C RCCE approximate model reduces the number of independent differential equations related to species, mass, and energy balances from S+2 to C+E+2, with substantial computational savings when C ≪ S-E.

Elimination kinetic model for organic chemicals in earthworms.

NARCIS (Netherlands)

Dimitrova, N.; Dimitrov, S.; Georgieva, D.; van Gestel, C.A.M.; Hankard, P.; Spurgeon, D.J.; Li, H.; Mekenyan, O.

2010-01-01

Mechanistic understanding of bioaccumulation in different organisms and environments should take into account the influence of organism and chemical depending factors on the uptake and elimination kinetics of chemicals. Lipophilicity, metabolism, sorption (bioavailability) and biodegradation of

On improved understanding of plasma-chemical processes in complex low-temperature plasmas

Science.gov (United States)

Röpcke, Jürgen; Loffhagen, Detlef; von Wahl, Eric; Nave, Andy S. C.; Hamann, Stephan; van Helden, Jean-Piere H.; Lang, Norbert; Kersten, Holger

2018-05-01

Over the last years, chemical sensing using optical emission spectroscopy (OES) in the visible spectral range has been combined with methods of mid infrared laser absorption spectroscopy (MIR-LAS) in the molecular fingerprint region from 3 to 20 μm, which contains strong rotational-vibrational absorption bands of a large variety of gaseous species. This optical approach established powerful in situ diagnostic tools to study plasma-chemical processes of complex low-temperature plasmas. The methods of MIR-LAS enable to detect stable and transient molecular species in ground and excited states and to measure the concentrations and temperatures of reactive species in plasmas. Since kinetic processes are inherent to discharges ignited in molecular gases, high time resolution on sub-second timescales is frequently desired for fundamental studies as well as for process monitoring in applied research and industry. In addition to high sensitivity and good temporal resolution, the capacity for broad spectral coverage enabling multicomponent detection is further expanding the use of OES and MIR-LAS techniques. Based on selected examples, this paper reports on recent achievements in the understanding of complex low-temperature plasmas. Recently, a link with chemical modeling of the plasma has been provided, which is the ultimate objective for a better understanding of the chemical and reaction kinetic processes occurring in the plasma. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

Chemical kinetics of detonation in some liquid mixtures

Energy Technology Data Exchange (ETDEWEB)

Raikova, Vlada M.; Likholatov, Evgeny A. [Mendeleev University of Chemical Technology, Moscow (Russian Federation)

2005-09-01

The main objective of this work is to study the chemical kinetics of detonation reactions in some nitroester mixtures and solutions of nitrocompounds in concentrated nitric acid. The main source of information on chemical kinetics in the detonation wave was the experimental dependence of failure diameter on composition of mixtures. Calculations were carried out in terms of classic theory of Dremin using the SGKR computer code. Effective values for the activation energies and pre-exponential factors for detonation reactions in the mixtures under investigation have been defined. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

Chemical Kinetics of Progesterone Radioimmunoassay System

International Nuclear Information System (INIS)

Abdel-Fattah, A.A.; Moustsfs, K.A.; El-Kolally, M.T.

2004-01-01

Progesterone is one of the steroids secreted by the corpus Iuteum in females during the menstrual cycle, and in a much higher amount by the placenta during pregnancy. It is also secreted in a minor quantities by the adrenal cortex in both males and females. Measurement of serum progesterone represents one of diagnostic values in menstrual disorders and infertility. The progesterone radioimmunoassay is based on the competition between unlabelled progesterone and a fixed quantity of 125 I-labeled progesterone for a limited number of binding sites on progesterone specific antibody. Allowing for a fixed amount of magnetizable immunosorbent to react, the antigen-antibody complex is bound on solid particles which are then separated by magnetic rack, and the radioactivity of the solid phase was counted using gamma counter. In this work, the chemical kinetics of the assay was followed, where the specific rate constant (K) was calculated at 4 degree and 37 degree and the activation energy (E act ) were calculated and the reaction rate was deduced

Predicting in vivo effect levels for repeat-dose systemic toxicity using chemical, biological, kinetic and study covariates.

Science.gov (United States)

Truong, Lisa; Ouedraogo, Gladys; Pham, LyLy; Clouzeau, Jacques; Loisel-Joubert, Sophie; Blanchet, Delphine; Noçairi, Hicham; Setzer, Woodrow; Judson, Richard; Grulke, Chris; Mansouri, Kamel; Martin, Matthew

2018-02-01

In an effort to address a major challenge in chemical safety assessment, alternative approaches for characterizing systemic effect levels, a predictive model was developed. Systemic effect levels were curated from ToxRefDB, HESS-DB and COSMOS-DB from numerous study types totaling 4379 in vivo studies for 1247 chemicals. Observed systemic effects in mammalian models are a complex function of chemical dynamics, kinetics, and inter- and intra-individual variability. To address this complex problem, systemic effect levels were modeled at the study-level by leveraging study covariates (e.g., study type, strain, administration route) in addition to multiple descriptor sets, including chemical (ToxPrint, PaDEL, and Physchem), biological (ToxCast), and kinetic descriptors. Using random forest modeling with cross-validation and external validation procedures, study-level covariates alone accounted for approximately 15% of the variance reducing the root mean squared error (RMSE) from 0.96 log 10 to 0.85 log 10  mg/kg/day, providing a baseline performance metric (lower expectation of model performance). A consensus model developed using a combination of study-level covariates, chemical, biological, and kinetic descriptors explained a total of 43% of the variance with an RMSE of 0.69 log 10  mg/kg/day. A benchmark model (upper expectation of model performance) was also developed with an RMSE of 0.5 log 10  mg/kg/day by incorporating study-level covariates and the mean effect level per chemical. To achieve a representative chemical-level prediction, the minimum study-level predicted and observed effect level per chemical were compared reducing the RMSE from 1.0 to 0.73 log 10  mg/kg/day, equivalent to 87% of predictions falling within an order-of-magnitude of the observed value. Although biological descriptors did not improve model performance, the final model was enriched for biological descriptors that indicated xenobiotic metabolism gene expression, oxidative stress, and

Chemical Kinetic Modeling of 2-Methylhexane Combustion

KAUST Repository

Mohamed, Samah Y.

2015-03-30

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

Kinetics of chemical reactions initiated by hot atoms

International Nuclear Information System (INIS)

Firsova, L.P.

1977-01-01

Modern ideas about kinetics of chemical reactions of hot atoms are generalized. The main points of the phenomenological theories (''kinetic theory'' of Wolfgang-Estrup hot reactions and the theory of ''reactions integral probability'' of Porter) are given. Physico-chemical models of elastic and non-elastic collisions are considered which are used in solving Boltzmann integro-differential equations and stochastic equations in the Porter theory. The principal formulas are given describing probabilities or yields of chemical reactions, initiated with hot atoms, depending on the distribution functions of hot particles with respect to energy. Briefly described are the techniques and the results of applying the phenomenological theories for interpretation of the experimental data obtained during nuclear reactions with hot atoms, photochemical investigations, etc. 96 references are given

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

International Nuclear Information System (INIS)

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

1993-01-01

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

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

Science.gov (United States)

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…

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Equation-Free Computation to Accelerate Network-Free Stochastic Simulation of Chemical Kinetics.

Science.gov (United States)

Lin, Yen Ting; Chylek, Lily A; Lemons, Nathan W; Hlavacek, William S

2018-06-21

The chemical kinetics of many complex systems can be concisely represented by reaction rules, which can be used to generate reaction events via a kinetic Monte Carlo method that has been termed network-free simulation. Here, we demonstrate accelerated network-free simulation through a novel approach to equation-free computation. In this process, variables are introduced that approximately capture system state. Derivatives of these variables are estimated using short bursts of exact stochastic simulation and finite differencing. The variables are then projected forward in time via a numerical integration scheme, after which a new exact stochastic simulation is initialized and the whole process repeats. The projection step increases efficiency by bypassing the firing of numerous individual reaction events. As we show, the projected variables may be defined as populations of building blocks of chemical species. The maximal number of connected molecules included in these building blocks determines the degree of approximation. Equation-free acceleration of network-free simulation is found to be both accurate and efficient.

KinChem: A Computational Resource for Teaching and Learning Chemical Kinetics

Science.gov (United States)

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…

Chemical and kinetic equilibrations via radiative parton transport

International Nuclear Information System (INIS)

Zhang Bin; Wortman, Warner A

2011-01-01

A hot and dense partonic system can be produced in the early stage of a relativistic heavy ion collision. How it equilibrates is important for the extraction of Quark-Gluon Plasma properties. We study the chemical and kinetic equilibrations of the Quark-Gluon Plasma using a radiative transport model. Thermal and Color-Glass-Condensate motivated initial conditions are used. We observe that screened parton interactions always lead to partial pressure isotropization. Different initial pressure anisotropies result in the same asymptotic evolution. Comparison of evolutions with and without radiative processes shows that chemical equilibration interacts with kinetic equilibration and radiative processes can contribute significantly to pressure isotropization.

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

Science.gov (United States)

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

2018-06-13

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

Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

Science.gov (United States)

Lin, S H; Sahai, R; Eyring, H

1971-04-01

A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

CURRENT AND KINETIC HELICITY OF LONG-LIVED ACTIVITY COMPLEXES

International Nuclear Information System (INIS)

Komm, Rudolf; Gosain, Sanjay

2015-01-01

We study long-lived activity complexes and their current helicity at the solar surface and their kinetic helicity below the surface. The current helicity has been determined from synoptic vector magnetograms from the NSO/SOLIS facility, and the kinetic helicity of subsurface flows has been determined with ring-diagram analysis applied to full-disk Dopplergrams from NSO/GONG and SDO/HMI. Current and kinetic helicity of activity complexes follow the hemispheric helicity rule with mainly positive values (78%; 78%, respectively, with a 95% confidence level of 31%) in the southern hemisphere and negative ones (80%; 93%, respectively, with a 95% confidence level of 22% and 14%, respectively) in the northern hemisphere. The locations with the dominant sign of kinetic helicity derived from Global Oscillation Network Group (GONG) and SDO/HMI data are more organized than those of the secondary sign even if they are not part of an activity complex, while locations with the secondary sign are more fragmented. This is the case for both hemispheres even for the northern one where it is not as obvious visually due to the large amount of magnetic activity present as compared to the southern hemisphere. The current helicity shows a similar behavior. The dominant sign of current helicity is the same as that of kinetic helicity for the majority of the activity complexes (83% with a 95% confidence level of 15%). During the 24 Carrington rotations analyzed here, there is at least one longitude in each hemisphere where activity complexes occur repeatedly throughout the epoch. These ''active'' longitudes are identifiable as locations of strong current and kinetic helicity of the same sign

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

International Nuclear Information System (INIS)

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

2007-01-01

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

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

Science.gov (United States)

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

2007-06-16

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

Fundamental aspects of plasma chemical physics kinetics

CERN Document Server

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

2016-01-01

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

Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

National Research Council Canada - National Science Library

Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B

2002-01-01

Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...

Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

KAUST Repository

Eldeeb, Mazen A.

2016-08-30

A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

Hungarian University Students' Misunderstandings in Thermodynamics and Chemical Kinetics

Science.gov (United States)

Turanyi, Tamas; Toth, Zoltan

2013-01-01

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

Operational High Resolution Chemical Kinetics Simulation, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Numerical simulations of chemical kinetics are critical to addressing urgent issues in both the developed and developing world. Ongoing demand for higher resolution...

Chemical kinetic modeling of H{sub 2} applications

Energy Technology Data Exchange (ETDEWEB)

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

1995-09-01

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

Easy to use program “Simkine3” for simulating kinetic profiles of multi-step chemical Systems and optimisation of predictable rate coefficients therein

Directory of Open Access Journals (Sweden)

S.B. Jonnalagadda

2012-08-01

Full Text Available ‘Simkine3’, a Delphi based software is developed to simulate the kinetic schemes of complex reaction mechanisms involving multiple sequential and competitive elementary steps for homogeneous and heterogeneous chemical reactions. Simkine3 is designed to translate the user specified mechanism into chemical first-order differential equations (ODEs and optimise the estimated rate constants in such a way that simulated curves match the experimental kinetic profiles. TLSoda which uses backward differentiation method is utilised to solve resulting ODEs and Downhill Simplex method is used to optimise the estimated rate constants in a robotic way. An online help file is developed using HelpScrible Demo to guide the users of Simkine3. The versatility of the software is demonstrated by simulating the complex reaction between methylene violet and acidic bromate, a reaction which exhibits complex nonlinear kinetics. The new software is validated after testing it on a 19-step intricate mechanism involving 15 different species. The kinetic profiles of multiple simulated curves, illustrating the effect of initial concentrations of bromate, and bromide were matched with the corresponding experimental curves.DOI: http://dx.doi.org/10.4314/bcse.v26i2.10

Kinetic theory of nonlinear transport phenomena in complex plasmas

International Nuclear Information System (INIS)

Mishra, S. K.; Sodha, M. S.

2013-01-01

In contrast to the prevalent use of the phenomenological theory of transport phenomena, a number of transport properties of complex plasmas have been evaluated by using appropriate expressions, available from the kinetic theory, which are based on Boltzmann's transfer equation; in particular, the energy dependence of the electron collision frequency has been taken into account. Following the recent trend, the number and energy balance of all the constituents of the complex plasma and the charge balance on the particles is accounted for; the Ohmic loss has also been included in the energy balance of the electrons. The charging kinetics for the complex plasma comprising of uniformly dispersed dust particles, characterized by (i) uniform size and (ii) the Mathis, Rumpl, and Nordsieck power law of size distribution has been developed. Using appropriate expressions for the transport parameters based on the kinetic theory, the system of equations has been solved to investigate the parametric dependence of the complex plasma transport properties on the applied electric field and other plasma parameters; the results are graphically illustrated.

A kinetic model for chemical neurotransmission

Science.gov (United States)

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.

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

Science.gov (United States)

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

2011-01-01

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

Compactness and robustness: Applications in the solution of integral equations for chemical kinetics and electromagnetic scattering

Science.gov (United States)

Zhou, Yajun

This thesis employs the topological concept of compactness to deduce robust solutions to two integral equations arising from chemistry and physics: the inverse Laplace problem in chemical kinetics and the vector wave scattering problem in dielectric optics. The inverse Laplace problem occurs in the quantitative understanding of biological processes that exhibit complex kinetic behavior: different subpopulations of transition events from the "reactant" state to the "product" state follow distinct reaction rate constants, which results in a weighted superposition of exponential decay modes. Reconstruction of the rate constant distribution from kinetic data is often critical for mechanistic understandings of chemical reactions related to biological macromolecules. We devise a "phase function approach" to recover the probability distribution of rate constants from decay data in the time domain. The robustness (numerical stability) of this reconstruction algorithm builds upon the continuity of the transformations connecting the relevant function spaces that are compact metric spaces. The robust "phase function approach" not only is useful for the analysis of heterogeneous subpopulations of exponential decays within a single transition step, but also is generalizable to the kinetic analysis of complex chemical reactions that involve multiple intermediate steps. A quantitative characterization of the light scattering is central to many meteoro-logical, optical, and medical applications. We give a rigorous treatment to electromagnetic scattering on arbitrarily shaped dielectric media via the Born equation: an integral equation with a strongly singular convolution kernel that corresponds to a non-compact Green operator. By constructing a quadratic polynomial of the Green operator that cancels out the kernel singularity and satisfies the compactness criterion, we reveal the universality of a real resonance mode in dielectric optics. Meanwhile, exploiting the properties of

Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

Science.gov (United States)

Haryani, S.; Kurniawan, C.; Kasmui

2018-04-01

Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

Studies in Chemical Dynamics

International Nuclear Information System (INIS)

Rabitz, Herschel; Ho, Tak-San

2003-01-01

This final report draws together the research carried from February, 1986 through January, 2003 concerning a series of topics in chemical dynamics. The specific areas of study include molecular collisions, chemical kinetics, data inversion to extract potential energy surfaces, and model reduction of complex kinetic systems

Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

DEFF Research Database (Denmark)

Nielsen, Asbjørn Haaning; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

2003-01-01

A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...... be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m...... on continuous measurement of the reactants allowing the kinetics to be determined at varying reactant concentrations during the course of the experiment. The kinetics determined was simulated by a rate equation. The precision of the method was assessed in terms of the standard deviation of the kinetic...

Chemical kinetics and combustion modelling with CFX 4

Energy Technology Data Exchange (ETDEWEB)

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

1998-12-31

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

Chemical kinetics and combustion modelling with CFX 4

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

International Nuclear Information System (INIS)

Westbrook, C.K.

2000-01-01

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

Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

Science.gov (United States)

Barkalov, I. M.; Kiryukhin, D. P.

Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

Kinetic, spectroscopic and chemical modification study of iron release from transferrin; iron(III) complexation to adenosine triphosphate

International Nuclear Information System (INIS)

Thompson, C.P.

1985-01-01

Amino acids other than those that serve as ligands have been found to influence the chemical properties of transferrin iron. The catalytic ability of pyrophosphate to mediate transferrin iron release to a terminal acceptor is largely quenched by modification non-liganded histine groups on the protein. The first order rate constants of iron release for several partially histidine modified protein samples were measured. A statistical method was employed to establish that one non-liganded histidine per metal binding domain was responsible for the reduction in rate constant. These results imply that the iron mediated chelator, pyrophosphate, binds directly to a histidine residue on the protein during the iron release process. EPR spectroscopic results are consistent with this interpretation. Kinetic and amino acid sequence studies of ovotransferrin and lactoferrin, in addition to human serum transferrin, have allowed the tentative assignment of His-207 in the N-terminal domain and His-535 in the C-terminal domain as the groups responsible for the reduction in rate of iron release. The above concepts have been extended to lysine modified transferrin. Complexation of iron(II) to adenosine triphosphate (ATP) was also studied to gain insight into the nature of iron-ATP species present at physiological pH. 31 P NMR spectra are observed when ATP is presented in large excess

Bayesian inference of chemical kinetic models from proposed reactions

KAUST Repository

Galagali, Nikhil; Marzouk, Youssef M.

2015-01-01

© 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model

Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

Science.gov (United States)

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.

Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

Science.gov (United States)

Srinivas, Niranjan

hybridization, fraying, and branch migration, and provide a biophysical explanation of strand displacement kinetics. Our work paves the way for accurate modeling of strand displacement cascades, which would facilitate the simulation and construction of more complex molecular systems. In Chapters 3 and 4, we identify and overcome the crucial experimental challenges involved in using our general DNA-based technology for engineering dynamical behaviors in the test tube. In this process, we identify important design rules that inform our choice of molecular motifs and our algorithms for designing and verifying DNA sequences for our molecular implementation. We also develop flexible molecular strategies for "tuning" our reaction rates and stoichiometries in order to compensate for unavoidable non-idealities in the molecular implementation, such as imperfectly synthesized molecules and spurious "leak" pathways that compete with desired pathways. We successfully implement three distinct autocatalytic reactions, which we then combine into a de novo chemical oscillator. Unlike biological networks, which use sophisticated evolved molecules (like proteins) to realize such behavior, our test tube realization is the first to demonstrate that Watson-Crick base pairing interactions alone suffice for oscillatory dynamics. Since our design pipeline is general and applicable to any CRN, our experimental demonstration of a de novo chemical oscillator could enable the systematic construction of CRNs with other dynamic behaviors.

Mathematical study of chemical kinetics schemes. Application to air pollution models; Etude mathematique de schemas de cinetique chimique. Application a des modeles de pollution atmospherique

Energy Technology Data Exchange (ETDEWEB)

Billette, E.

1997-06-23

Complex chemical kinetics modelling is relevant in numerous fields related to the petroleum industry, for instance engine combustion, petrochemistry and atmospheric pollution. Many numerical difficulties are encountered in the computation of these models, mainly due to the large size, the non-linearity and the stiffness of the associated ordinary differential systems. We first studied systems that have an asymptotic behaviour which may be derived from an algebraic analysis. Then we reviewed different methods that make possible the reduction of size and stiffness for chemical kinetics-related differential systems, and suggest possible improvements for some of those methods. We also studied their application to atmospheric chemistry models. Finally, we started to extend those reduction methods to partial differential systems that include, in addition to chemical kinetics, other phenomena such as species emission, advection or diffusion. (author) 44 refs.

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

Science.gov (United States)

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

2016-06-01

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

Bayesian inference of chemical kinetic models from proposed reactions

KAUST Repository

Galagali, Nikhil

2015-02-01

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

Progress in Chemical Kinetic Modeling for Surrogate Fuels

Energy Technology Data Exchange (ETDEWEB)

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

2008-06-06

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

Some current problems in atmospheric ozone chemistry; role of chemical kinetics

Energy Technology Data Exchange (ETDEWEB)

Cox, R.A.

1987-03-01

A review is given on selected aspects of the reaction mechanisms of current interest in the chemistry of atmospheric ozone. Atmospheric ozone is produced and removed by a complex series of elementary gas-phase photochemical reactions involving O/sub x/, HO/sub x/, NO/sub x/, CIO/sub x/ and hydrocarbon species. At the present time there is a good knowledge of the basic processes involved in ozone chemistry in the stratosphere and the troposphere and the kinetics of most of the key reactions are well defined. There are a number of difficulties in the theoretical descriptions of observed ozone behaviour which may be due to uncertainties in the chemistry. Examples are the failure to predict present day ozone in the photochemically controlled region above 35 Km altitude and the large reductions in the ozone column in the Antartic Spring which has been observed in recent years. In the troposphere there is growing evidence that ozone and other trace gases have changed appreciably from pre-industrial concentrations, due to chemical reactions involving man-made pollutants. Quantitative investigation of the mechanisms by which these changes may occur requires a sound laboratory kinetics data base.

Chemical Kinetic Models for Advanced Engine Combustion

Energy Technology Data Exchange (ETDEWEB)

Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

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.

Iteration scheme for implicit calculations of kinetic and equilibrium chemical reactions in fluid dynamics

International Nuclear Information System (INIS)

Ramshaw, J.D.; Chang, C.H.

1995-01-01

An iteration scheme for the implicit treatment of equilibrium chemical reactions in partial equilibrium flow has previously been described. Here we generalize this scheme to kinetic reactions as well as equilibrium reactions. This extends the applicability of the scheme to problems with kinetic reactions that are fast in regions of the flow field but slow in others. The resulting scheme thereby provides a single unified framework for the implicit treatment of an arbitrary number of coupled equilibrium and kinetic reactions in chemically reacting fluid flow. 10 refs., 2 figs

Students' conceptions and misconceptions in chemical kinetics in ...

African Journals Online (AJOL)

The purpose of the study was to probe the conception and misconception of senior secondary (SS3) and University (US) chemistry students in chemical kinetics in Rivers State, Nigeria. The study sample was made up of 107 SS3 and 93 US students. Two main instruments were used to collect data for the study. They are the ...

Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

Science.gov (United States)

Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

The kinetics of nonequilibrium chain plasma-chemical oxidation in heterogeneous media

International Nuclear Information System (INIS)

Deminskii, M.A.; Potapkin, B.V.; Rusanov, V.D.

1994-01-01

The kinetics of oxidation of low-impurity components in air mixtures under heterogeneous conditions was studied. The principal kinetic features of the process were determined on the basis of theoretical analysis of plasma-chemical oxidation in heterogeneous media. The analysis also showed that low concentrations of impurities in liquid aerosol particles can be efficiently oxidized via a chain process induced by reactive species formed in the gas

Infrared absorption spectroscopy and chemical kinetics of free radicals

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

The modelling of direct chemical kinetic effects in turbulent flames

Energy Technology Data Exchange (ETDEWEB)

Lindstet, R.P. [Imperial College of Science, Technology and Medicine, London (United Kingdom). Dept. of Mechanical Engineering

2000-06-01

Combustion chemistry-related effects have traditionally been of secondary importance in the design of gas turbine combustors. However, the need to deal with issues such as flame stability, relight and pollutant emissions has served to bring chemical kinetics and the coupling of finite rate chemistry with turbulent flow fields to the centre of combustor design. Indeed, improved cycle efficiency and more stringent environmental legislation, as defined by the ICAO, are current key motivators in combustor design. Furthermore, lean premixed prevaporized (LPP) combustion systems, increasingly used for power generation, often operate close to the lean blow-off limit and are prone to extinction/reignition type phenomena. Thus, current key design issues require that direct chemical kinetic effects be accounted for accurately in any simulation procedure. The transported probability density function (PDF) approach uniquely offers the potential of facilitating the accurate modelling of such effects. The present paper thus assesses the ability of this technique to model kinetically controlled phenomena, such as carbon monoxide emissions and flame blow-off, through the application of a transported PDF method closed at the joint scalar level. The closure for the velocity field is at the second moment level, and a key feature of the present work is the use of comprehensive chemical kinetic mechanisms. The latter are derived from recent work by Lindstedt and co-workers that has resulted in a compact 141 reactions and 28 species mechanism for LNG combustion. The systematically reduced form used here features 14 independent C/H/O scalars, with the remaining species incorporated via steady state approximations. Computations have been performed for hydrogen/carbon dioxide and methane flames. The former (high Reynolds number) flames permit an assessment of the modelling of flame blow-off, and the methane flame has been selected to obtain an indication of the influence of differential

On mathematical modeling and numerical simulation of chemical kinetics in turbulent lean premixed combustion

Energy Technology Data Exchange (ETDEWEB)

Lilleberg, Bjorn

2011-07-01

This thesis investigates turbulent reacting lean premixed flows with detailed treatment of the chemistry. First, the fundamental equations which govern laminar and turbulent reacting flows are presented. A perfectly stirred reactor numerical code is developed to investigate the role of unmixedness and chemical kinetics in driving combustion instabilities. This includes both global single-step and detailed chemical kinetic mechanisms. The single-step mechanisms predict to some degree a similar behavior as the detailed mechanisms. However, it is shown that simple mechanisms can by themselves introduce instabilities. Magnussens Eddy Dissipation Concept (EDC) for turbulent combustion is implemented in the open source CFD toolbox OpenFOAM R for treatment of both fast and detailed chemistry. RANS turbulence models account for the turbulent compressible flow. A database of pre-calculated chemical time scales, which contains the influence of chemical kinetics, is coupled to EDC with fast chemistry to account for local extinction in both diffusion and premixed flames. Results are compared to fast and detailed chemistry calculations. The inclusion of the database shows significantly better results than the fast chemistry calculations while having a comparably small computational cost. Numerical simulations of four piloted lean premixed jet flames falling into the 'well stirred reactor/broken reaction zones' regime, with strong finite-rate chemistry effects, are performed. Measured and predicted scalars compare well for the two jets with the lowest velocities. The two jets with the highest velocities experience extinction and reignition, and the simulations are able to capture the decrease and increase of the OH mass fractions, but the peak values are higher than in the experiments. Also numerical simulations of a lean premixed lifted jet flame with high sensitivity to turbulence modeling and chemical kinetics are performed. Limitations of the applied turbulence and

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

KAUST Repository

Ciottoli, Pietro P.; Malpica Galassi, Riccardo; Lapenna, Pasquale E.; Leccese, G.; Bianchi, D.; Nasuti, F.; Creta, F.; Valorani, M.

2017-01-01

A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics

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

International Nuclear Information System (INIS)

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

2015-01-01

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. (paper)

Analyzing atmospheric kinetic pathways using PumpKin

Science.gov (United States)

Markosyan, A. H.; Luque, A.; Gordillo-Vázquez, F. J.; Ebert, U.

2013-09-01

In the present work we show the application of our software tool called PumpKin (pathway reduction method for plasma kinetic models) to find all principal pathways of atmospheric kinetic system, i.e. the dominant reaction sequences, in chemical reaction systems. The goal was to reduce a complex plasma chemistry model. Recent kinetic models of atmospheric chemistry, or any industrial application, contain thousands of chemical reactions and species. The main difficulty is that these reduced chemical pathways depend on timescales, electric field, temperature, pressure etc. PumpKin is a universal tool, which only requires from user the temporal profile of the densities of species and the reaction rates, as well the stoichiometric matrix of the system. Also, the user should specify the timescale of interest.

Modeling in applied sciences a kinetic theory approach

CERN Document Server

Pulvirenti, Mario

2000-01-01

Modeling complex biological, chemical, and physical systems, in the context of spatially heterogeneous mediums, is a challenging task for scientists and engineers using traditional methods of analysis Modeling in Applied Sciences is a comprehensive survey of modeling large systems using kinetic equations, and in particular the Boltzmann equation and its generalizations An interdisciplinary group of leading authorities carefully develop the foundations of kinetic models and discuss the connections and interactions between model theories, qualitative and computational analysis and real-world applications This book provides a thoroughly accessible and lucid overview of the different aspects, models, computations, and methodology for the kinetic-theory modeling process Topics and Features * Integrated modeling perspective utilized in all chapters * Fluid dynamics of reacting gases * Self-contained introduction to kinetic models * Becker–Doring equations * Nonlinear kinetic models with chemical reactions * Kinet...

Formulation, radiopharmaceutical kinetics and dosimetry of the 188Re(V)-DMSA complex

International Nuclear Information System (INIS)

Garcia S, L.; Ferro F, G.; Murphy, C.A. de; Pedraza L, M.; Azorin N, J.

1999-01-01

It was developed through experimental design (ANOVA), a formulation to prepare the 188 Re(V)-Dmsa complex. Likewise, there were realized studies of radiopharmaceutical kinetics and internal dosimetry in animals, its normal and with induced tumors, considering an open bi compartmental model using the MIRD methodology. The 188 Re(V)-Dmsa complex was obtained with a radiochemical purity greater than 95% incubating 30 min at 90 Centigrade under the following formulation: [SnCl 2 ] = 1.4 mg/ml, [ascorbic acid] = 0.5 mg/ml, p H = 2.0 - 3.0. The stability test of the formulation, shows that after 48 h of its preparation, does not produce radiolytic degradation neither chemical decomposition. The radiopharmaceutical kinetics data show an average residence time 7.2h, velocity constant α = 0.6508h -1 and β = 0.1046 h -1 with an apparent distribution volume 6.9 l. The main elimination via was renal and it was observed osseous caption with an accumulated activity 522.049 ± 62 MBq h (residence time 14.1094 ± 1.69h). In according with the dosimetric calculations, by each 37 MBq injected, the equivalent dose at the tumor was 9.67± 0.33 Sv/g, for an effective dose 0.292 ± 0.0017 mSv/MBq. The images obtained in the gamma camera of the mice with induced tumors, show that do not have significant accumulation in the metabolic organs. The caption in bone and in tumors induced of the 188 Re(V)-Dmsa complex, show its potential for be used as a palliative agent for pain in patients with osseous metastasis and in the treatment of tumors of soft tissue. (Author)

Heparin kinetics

International Nuclear Information System (INIS)

Swart, C.A.M. de.

1983-01-01

The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)

Strain-induced structural changes and chemical reactions. 1: Thermomechanical and kinetic models

International Nuclear Information System (INIS)

Levitas, V.I.; Nesterenko, V.F.; Meyers, M.A.

1998-01-01

Strain-induced chemical reactions were observed recently (Nesterenko et al) in experiments in the shear band in both Ti-Si and Nb-Si mixtures. Reactions can start in the solid state or after melting of at least one component. One of the aims is to find theoretically whether there are possible macroscopic mechanisms of mechanical intensification of the above and other chemical reactions due to plastic shear in the solid state. Continuum thermodynamical theory of structural changes with an athermal kinetics, which includes martensitic phase transformations, plastic strain-induced chemical reactions and polymorphic transformations, is developed at finite strains. The theory includes kinematics, criterion of structural change and extremum principle for determination of all unknown variable parameters for the case with neglected elastic strains. Thermodynamically consistent kinetic theory of thermally activated structural changes is suggested. The concept of the effective temperature is introduced which takes into account that temperature can vary significantly (on 1,000 K) during the chemical reactions under consideration. The theory will be applied in Part 2 of the paper for the description of chemical reactions in the shear band

Dissociation kinetics of acyclic and macrocyclic polyaminopolycarboxylate complexes of yttrium

International Nuclear Information System (INIS)

Pathak, P.N.; Manchanda, V.K.

2000-01-01

Dissociation kinetics of Y III complexes of a linear as well as two macrocyclic polyaminopolycarboxylates, ethylenediamine diacetic acid (EDDA), 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid (K21DA) and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (K22DA) have been studied at a constant ionic strength (0.1 M) under varying (H + ) and temperatures. Cu II ion acts as the scavenger of the free ligand. Dissociation rate of Y III -K21DA is insensitive to Cu II and acetate (used as buffer anion) concentrations. Kinetic stability of the three complexes follow the order : Y III -K22DA>Y III -K21DA>Y III -EDDA. Enthalpies of activation for K21DA and K22DA complexes of Y III are also evaluated. Thermodynamic stability constant (log K) for Y III -K22DA complex is 10.81 ± 0.04. (author)

Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

Science.gov (United States)

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.

Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

International Nuclear Information System (INIS)

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

2010-01-01

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

Variable elimination in chemical reaction networks with mass-action kinetics

DEFF Research Database (Denmark)

Feliu, Elisenda; Wiuf, C.

2012-01-01

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

Surrogate models and optimal design of experiments for chemical kinetics applications

KAUST Repository

Bisetti, Fabrizio

2015-01-07

Kinetic models for reactive flow applications comprise hundreds of reactions describing the complex interaction among many chemical species. The detailed knowledge of the reaction parameters is a key component of the design cycle of next-generation combustion devices, which aim at improving conversion efficiency and reducing pollutant emissions. Shock tubes are a laboratory scale experimental configuration, which is widely used for the study of reaction rate parameters. Important uncertainties exist in the values of the thousands of parameters included in the most advanced kinetic models. This talk discusses the application of uncertainty quantification (UQ) methods to the analysis of shock tube data as well as the design of shock tube experiments. Attention is focused on a spectral framework in which uncertain inputs are parameterized in terms of canonical random variables, and quantities of interest (QoIs) are expressed in terms of a mean-square convergent series of orthogonal polynomials acting on these variables. We outline the implementation of a recent spectral collocation approach for determining the unknown coefficients of the expansion, namely using a sparse, adaptive pseudo-spectral construction that enables us to obtain surrogates for the QoIs accurately and efficiently. We first discuss the utility of the resulting expressions in quantifying the sensitivity of QoIs to uncertain inputs, and in the Bayesian inference key physical parameters from experimental measurements. We then discuss the application of these techniques to the analysis of shock-tube data and the optimal design of shock-tube experiments for two key reactions in combustion kinetics: the chain-brancing reaction H + O2 ←→ OH + O and the reaction of Furans with the hydroxyl radical OH.

Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

KAUST Repository

Eldeeb, Mazen A.; Jouzdani, Shirin; Wang, Zhandong; Sarathy, Mani; Akih-Kumgeh, Benjamin

2016-01-01

A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

Science.gov (United States)

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 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. 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.

Complexes between ovalbumin nanoparticles and linoleic acid: Stoichiometric, kinetic and thermodynamic aspects.

Science.gov (United States)

Sponton, Osvaldo E; Perez, Adrián A; Carrara, Carlos R; Santiago, Liliana G

2016-11-15

Stoichiometric, kinetic and thermodynamic aspects of complex formation between heat-induced aggregates of ovalbumin (ovalbumin nanoparticles, OVAn) and linoleic acid (LA) were evaluated. Extrinsic fluorescence data were fitted to modified Scatchard model yielding the following results: n: 49±2 LA molecules bound per OVA monomer unit and Ka: 9.80±2.53×10(5)M. Kinetic and thermodynamic properties were analyzed by turbidity measurements at different LA/OVA monomer molar ratios (21.5-172) and temperatures (20-40°C). An adsorption approach was used and a pseudo-second-order kinetics was found for LA-OVAn complex formation. This adsorption process took place within 1h. Thermodynamic parameters indicated that LA adsorption on OVAn was a spontaneous, endothermic and entropically-driven process, highlighting the hydrophobic nature of the LA and OVAn interaction. Finally, Atomic Force Microscopy imaging revealed that both OVAn and LA-OVAn complexes have a roughly rounded form with size lower than 100nm. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

DEFF Research Database (Denmark)

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

2007-01-01

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

Hydrogen exchange kinetics changes upon formation of the soybean trypsin inhibitor: trypsin complex

International Nuclear Information System (INIS)

Woodward, C.K.; Ellis, L.M.

1975-01-01

The hydrogen exchange kinetics of the complex of trypsin--soybean trypsin inhibitor (Kunitz) have been compared to the calculated sum of the exchange kinetics for the inhibitor and trypsin measured separately. The exchange rates observed for the complex are substantially less than the sum of the exchange rates in the two individual proteins. These results cannot be accounted for by changes in intermolecular or intramolecular hydrogen bonding. The decrease in exchange rates in the complex are ascribed to changes in solvent accessibility in the component proteins. (U.S.)

Complex boron redistribution kinetics in strongly doped polycrystalline-silicon/nitrogen-doped-silicon thin bi-layers

Energy Technology Data Exchange (ETDEWEB)

Abadli, S. [Department of Electrical Engineering, University Aout 1955, Skikda, 21000 (Algeria); LEMEAMED, Department of Electronics, University Mentouri, Constantine, 25000 (Algeria); Mansour, F. [LEMEAMED, Department of Electronics, University Mentouri, Constantine, 25000 (Algeria); Pereira, E. Bedel [CNRS-LAAS, 7 avenue du colonel Roche, 31077 Toulouse (France)

2012-10-15

We have investigated the complex behaviour of boron (B) redistribution process via silicon thin bi-layers interface. It concerns the instantaneous kinetics of B transfer, trapping, clustering and segregation during the thermal B activation annealing. The used silicon bi-layers have been obtained by low pressure chemical vapor deposition (LPCVD) method at 480 C, by using in-situ nitrogen-doped-silicon (NiDoS) layer and strongly B doped polycrystalline-silicon (P{sup +}) layer. To avoid long-range B redistributions, thermal annealing was carried out at relatively low-temperatures (600 C and 700 C) for various times ranging between 30 min and 2 h. To investigate the experimental secondary ion mass spectroscopy (SIMS) doping profiles, a redistribution model well adapted to the particular structure of two thin layers and to the effects of strong-concentrations has been established. The good adjustment of the simulated profiles with the experimental SIMS profiles allowed a fundamental understanding about the instantaneous physical phenomena giving and disturbing the complex B redistribution profiles-shoulders. The increasing kinetics of the B peak concentration near the bi-layers interface is well reproduced by the established model. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Prediction of Combustion Instability with Detailed Chemical Kinetics

Science.gov (United States)

2014-12-01

of combustion instability. The mechanisms used for methane oxidation are the GRI 1.2 set that comprises of 32 chemical species and 177 reactions. All...with a single step global reaction and the GRI -1.2 kinetics mechanism which contains 177 reactions. The paper is organized as follows, Section II...flame speeds10. GRI -1.2 is a more complete set of hydrocarbon reactions consisting of 177 reactions involving 32 species and was optimized for natural

Accuracy and precision of protein–ligand interaction kinetics determined from chemical shift titrations

International Nuclear Information System (INIS)

Markin, Craig J.; Spyracopoulos, Leo

2012-01-01

NMR-monitored chemical shift titrations for the study of weak protein–ligand interactions represent a rich source of information regarding thermodynamic parameters such as dissociation constants (K D ) in the micro- to millimolar range, populations for the free and ligand-bound states, and the kinetics of interconversion between states, which are typically within the fast exchange regime on the NMR timescale. We recently developed two chemical shift titration methods wherein co-variation of the total protein and ligand concentrations gives increased precision for the K D value of a 1:1 protein–ligand interaction (Markin and Spyracopoulos in J Biomol NMR 53: 125–138, 2012). In this study, we demonstrate that classical line shape analysis applied to a single set of 1 H– 15 N 2D HSQC NMR spectra acquired using precise protein–ligand chemical shift titration methods we developed, produces accurate and precise kinetic parameters such as the off-rate (k off ). For experimentally determined kinetics in the fast exchange regime on the NMR timescale, k off ∼ 3,000 s −1 in this work, the accuracy of classical line shape analysis was determined to be better than 5 % by conducting quantum mechanical NMR simulations of the chemical shift titration methods with the magnetic resonance toolkit GAMMA. Using Monte Carlo simulations, the experimental precision for k off from line shape analysis of NMR spectra was determined to be 13 %, in agreement with the theoretical precision of 12 % from line shape analysis of the GAMMA simulations in the presence of noise and protein concentration errors. In addition, GAMMA simulations were employed to demonstrate that line shape analysis has the potential to provide reasonably accurate and precise k off values over a wide range, from 100 to 15,000 s −1 . The validity of line shape analysis for k off values approaching intermediate exchange (∼100 s −1 ), may be facilitated by more accurate K D measurements from NMR

Accuracy and precision of protein-ligand interaction kinetics determined from chemical shift titrations.

Science.gov (United States)

Markin, Craig J; Spyracopoulos, Leo

2012-12-01

NMR-monitored chemical shift titrations for the study of weak protein-ligand interactions represent a rich source of information regarding thermodynamic parameters such as dissociation constants (K ( D )) in the micro- to millimolar range, populations for the free and ligand-bound states, and the kinetics of interconversion between states, which are typically within the fast exchange regime on the NMR timescale. We recently developed two chemical shift titration methods wherein co-variation of the total protein and ligand concentrations gives increased precision for the K ( D ) value of a 1:1 protein-ligand interaction (Markin and Spyracopoulos in J Biomol NMR 53: 125-138, 2012). In this study, we demonstrate that classical line shape analysis applied to a single set of (1)H-(15)N 2D HSQC NMR spectra acquired using precise protein-ligand chemical shift titration methods we developed, produces accurate and precise kinetic parameters such as the off-rate (k ( off )). For experimentally determined kinetics in the fast exchange regime on the NMR timescale, k ( off ) ~ 3,000 s(-1) in this work, the accuracy of classical line shape analysis was determined to be better than 5 % by conducting quantum mechanical NMR simulations of the chemical shift titration methods with the magnetic resonance toolkit GAMMA. Using Monte Carlo simulations, the experimental precision for k ( off ) from line shape analysis of NMR spectra was determined to be 13 %, in agreement with the theoretical precision of 12 % from line shape analysis of the GAMMA simulations in the presence of noise and protein concentration errors. In addition, GAMMA simulations were employed to demonstrate that line shape analysis has the potential to provide reasonably accurate and precise k ( off ) values over a wide range, from 100 to 15,000 s(-1). The validity of line shape analysis for k ( off ) values approaching intermediate exchange (~100 s(-1)), may be facilitated by more accurate K ( D ) measurements

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

KAUST Repository

Kuti, Olawole

2013-10-14

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

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

KAUST Repository

Kuti, Olawole; Nishida, Keiya; Sarathy, Mani; Zhu, Jingyu

2013-01-01

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

New Chemical Kinetics Approach for DSMC Applications to Nonequilibrium Flows, Phase II

Data.gov (United States)

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

New Chemical Kinetics Approach for DSMC Applications to Nonequilibrium Flows, Phase I

Data.gov (United States)

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

A network dynamics approach to chemical reaction networks

Science.gov (United States)

van der Schaft, A. J.; Rao, S.; Jayawardhana, B.

2016-04-01

A treatment of a chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption, the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a very simple derivation of a number of key results in the chemical reaction network theory, and which directly relates to the thermodynamics and port-Hamiltonian formulation of the system. Central in this formulation is the definition of a balanced Laplacian matrix on the graph of chemical complexes together with a resulting fundamental inequality. This immediately leads to the characterisation of the set of equilibria and their stability. Furthermore, the assumption of complex balancedness is revisited from the point of view of Kirchhoff's matrix tree theorem. Both the form of the dynamics and the deduced behaviour are very similar to consensus dynamics, and provide additional perspectives to the latter. Finally, using the classical idea of extending the graph of chemical complexes by a 'zero' complex, a complete steady-state stability analysis of mass action kinetics reaction networks with constant inflows and mass action kinetics outflows is given, and a unified framework is provided for structure-preserving model reduction of this important class of open reaction networks.

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

Science.gov (United States)

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 (E a ), 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. E a , 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.

Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

International Nuclear Information System (INIS)

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

2011-01-01

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.

Kinetic intermediates en route to the final serpin-protease complex: studies of complexes of α1-protease inhibitor with trypsin.

Science.gov (United States)

Maddur, Ashoka A; Swanson, Richard; Izaguirre, Gonzalo; Gettins, Peter G W; Olson, Steven T

2013-11-01

Serpin protein protease inhibitors inactivate their target proteases through a unique mechanism in which a major serpin conformational change, resulting in a 70-Å translocation of the protease from its initial reactive center loop docking site to the opposite pole of the serpin, kinetically traps the acyl-intermediate complex. Although the initial Michaelis and final trapped acyl-intermediate complexes have been well characterized structurally, the intermediate stages involved in this remarkable transformation are not well understood. To better characterize such intermediate steps, we undertook rapid kinetic studies of the FRET and fluorescence perturbation changes of site-specific fluorophore-labeled derivatives of the serpin, α1-protease inhibitor (α1PI), which report the serpin and protease conformational changes involved in transforming the Michaelis complex to the trapped acyl-intermediate complex in reactions with trypsin. Two kinetically resolvable conformational changes were observed in the reactions, ascribable to (i) serpin reactive center loop insertion into sheet A with full protease translocation but incomplete protease distortion followed by, (ii) full conformational distortion and movement of the protease and coupled serpin conformational changes involving the F helix-sheet A interface. Kinetic studies of calcium effects on the labeled α1PI-trypsin reactions demonstrated both inactive and low activity states of the distorted protease in the final complex that were distinct from the intermediate distorted state. These studies provide new insights into the nature of the serpin and protease conformational changes involved in trapping the acyl-intermediate complex in serpin-protease reactions and support a previously proposed role for helix F in the trapping mechanism.

Kinetic Modeling of Complex Catalytic Reactions Modélisation cinétique des réactions catalytiques complexes

Directory of Open Access Journals (Sweden)

Froment G. F.

2006-11-01

Full Text Available The paper deals with hydrocracking on metal-loaded zeolites. A fundamental approach is presented in which the detailed reaction network of the feed components of a complex feedstock is retained to a maximum extent. The kinetics are developed in terms of the elementary steps and single events involved in the reactions. Plausible assumptions and thermodynamic constraints limit the number of kinetic parameters. These do not depend on the chain length of the hydrocarbons and are not affected by the feed composition. Certainly, chemical analysis still imposes a certain degree of lumping of components and reaction networks, but not to the extent reflected by present day models. L'article traite de l'hydrocraquage sur des zéolites chargés en métaux. Dans l'approche fondamentale qui est présentée, le réseau de réaction des composants d'une charge complexe est retenu au maximum. La cinétique est établie en suivant pas à pas le déroulement et les étapes élémentaires des réactions. Des hypothèses plausibles et des contraintes thermodynamiques limitent le nombre de paramètres cinétiques. Ceux-ci ne dépendent pas de la longueur de la chaîne des hydrocarbures et ne sont pas affectés par la composition de la charge. L'analyse chimique impose bien sûr encore un certain agrégat des composants et des réseaux de réaction, mais moins que ne reflètent les modèles actuels.

Analysis of forward and inverse problems in chemical dynamics and spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Rabitz, H. [Princeton Univ., NJ (United States)

1993-12-01

The overall scope of this research concerns the development and application of forward and inverse analysis tools for problems in chemical dynamics and chemical kinetics. The chemical dynamics work is specifically associated with relating features in potential surfaces and resultant dynamical behavior. The analogous inverse research aims to provide stable algorithms for extracting potential surfaces from laboratory data. In the case of chemical kinetics, the focus is on the development of systematic means to reduce the complexity of chemical kinetic models. Recent progress in these directions is summarized below.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-30

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

ZnO nanostructures with tunable visible luminescence: Effects of kinetics of chemical reduction and annealing

Directory of Open Access Journals (Sweden)

R. Raji

2017-03-01

Full Text Available Highly crystalline ZnO nanoparticles were synthesized using a co-precipitation method. The morphology and optical properties of these nanoparticles are found to be highly sensitive to the growth parameters such as the concentration of reducing agent and annealing temperature. Indeed, the concentration of the reducing agent can alter the morphology of nanoparticles from quasi-spherical to rod-like and then to flower-like structures. Attempts were made to tune the emission wavelength over the visible region by varying the kinetics of chemical reduction and annealing. The possibility of tuning the emission in a visible range from orange to red and then to green by changing the nature of defects by annealing is also reported. Analysis of the Raman spectrum, with its intensity observed at 580 cm−1 corresponding to E1 (LO mode, revealed that the kinetics and thermodynamics of formation and growth of these nanoparticles determined the nature and density of the probable defects such as oxygen vacancies, interstitial zinc atoms and their complexes.

CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

KAUST Repository

Tingas, Efstathios Al.; Manias, Dimitris M.; Sarathy, Mani; Goussis, Dimitris A.

2018-01-01

Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53

Accuracy and precision of protein-ligand interaction kinetics determined from chemical shift titrations

Energy Technology Data Exchange (ETDEWEB)

Markin, Craig J.; Spyracopoulos, Leo, E-mail: leo.spyracopoulos@ualberta.ca [University of Alberta, Department of Biochemistry (Canada)

2012-12-15

NMR-monitored chemical shift titrations for the study of weak protein-ligand interactions represent a rich source of information regarding thermodynamic parameters such as dissociation constants (K{sub D}) in the micro- to millimolar range, populations for the free and ligand-bound states, and the kinetics of interconversion between states, which are typically within the fast exchange regime on the NMR timescale. We recently developed two chemical shift titration methods wherein co-variation of the total protein and ligand concentrations gives increased precision for the K{sub D} value of a 1:1 protein-ligand interaction (Markin and Spyracopoulos in J Biomol NMR 53: 125-138, 2012). In this study, we demonstrate that classical line shape analysis applied to a single set of {sup 1}H-{sup 15}N 2D HSQC NMR spectra acquired using precise protein-ligand chemical shift titration methods we developed, produces accurate and precise kinetic parameters such as the off-rate (k{sub off}). For experimentally determined kinetics in the fast exchange regime on the NMR timescale, k{sub off} {approx} 3,000 s{sup -1} in this work, the accuracy of classical line shape analysis was determined to be better than 5 % by conducting quantum mechanical NMR simulations of the chemical shift titration methods with the magnetic resonance toolkit GAMMA. Using Monte Carlo simulations, the experimental precision for k{sub off} from line shape analysis of NMR spectra was determined to be 13 %, in agreement with the theoretical precision of 12 % from line shape analysis of the GAMMA simulations in the presence of noise and protein concentration errors. In addition, GAMMA simulations were employed to demonstrate that line shape analysis has the potential to provide reasonably accurate and precise k{sub off} values over a wide range, from 100 to 15,000 s{sup -1}. The validity of line shape analysis for k{sub off} values approaching intermediate exchange ({approx}100 s{sup -1}), may be facilitated by

Symmetry Relations in Chemical Kinetics Arising from Microscopic Reversibility

Science.gov (United States)

Adib, Artur B.

2006-01-01

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.

Kinetics of thermal decomposition of γ-irradiated and unirradiated complexes of mandelhydroxamic acid

International Nuclear Information System (INIS)

Hassan, R.M.; Farid, T.; El-Bellihi, A.A.

1992-01-01

The thermal decomposition of γ-irradiated and unirradiated complexes of mandelhydroxamic acid (HMA), Co (HMA) 2 .1/2H 2 O, Mn (HMA) 2 .2H 2 O, Ba (HMA) 2 .2H 2 O and Cd (HMA) 2 .2H 2 O have been studied thermogravimetrically (under isothermal conditions). The thermal dehydration of each complex occured in one step, while the decomposition of dehydrated complexes occured in two steps. The kinetic parameters for dehydration were computed by different models. The thermal dehydration is regulated by random nucleation A 3 for Co-, Mn-, and Cd-complexes and by phase-boundary (R 3 ) for Ba-complex. The effect of γ-irradiation on the kinetic parameters of thermal decomposition is discussed. Radiation did not modify the mechanism of the reaction but accelarated the dehydration steps in the case of Mn- and Co-complexes. (author) 7 refs.; 1 fig.; 4 tabs

The relationship between the Wigner-Weyl kinetic formalism and the complex geometrical optics method

OpenAIRE

Maj, Omar

2004-01-01

The relationship between two different asymptotic techniques developed in order to describe the propagation of waves beyond the standard geometrical optics approximation, namely, the Wigner-Weyl kinetic formalism and the complex geometrical optics method, is addressed. More specifically, a solution of the wave kinetic equation, relevant to the Wigner-Weyl formalism, is obtained which yields the same wavefield intensity as the complex geometrical optics method. Such a relationship is also disc...

Incorporation of chemical kinetic models into process control

International Nuclear Information System (INIS)

Herget, C.J.; Frazer, J.W.

1981-01-01

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

Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2, 3- dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex

Directory of Open Access Journals (Sweden)

Rajneesh Dutt Kaushik

2015-03-01

Full Text Available The formation of ternary intermediate unstable complex during the oxidation of aromatic amines by periodate ion catalysed by MnII has been proposed in case of some anilines. This paper is the first report on stopped-flow kinetic study and evaluation of stability constant of ternary complex forming in the MnII - catalysed periodate oxidation of 2, 3-dimethylaniline (D in acetone-water medium. Stop-flow spectrophotometric method was used to study the ternary complex formation and to determine its stability constant. The stop-flow trace shows the reaction to occur in two steps. The first step, which is presumably the formation of ternary complex, is relatively fast while the second stage is relatively quite slow. The stability constant evaluated for D - MnII - IO4- ternary complex by determining  equilibrium absorbance is (2.2 ± 1.0 × 105. Kinetics of ternary complex formation was defined by the rate law(A  under pseudo first order conditions. ln{[C2]eq / ( [C2]eq -[C2]} = kobs . t (A where, kobs is the pseudo first order rate constant, [C2] is concentration of ternary complex at given time t, and [C2]eq is the equilibrium concentration of ternary complex. © 2015 BCREC UNDIP. All rights reservedReceived: 3rd October 2014; Revised: 4th December 2014; Accepted: 15th December 2014How to Cite: Kaushik, R.D., Agarwal, R., Tyagi, P., Singh, O., Singh, J. (2015. Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2,3-dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 78-87. (doi:10.9767/bcrec.10.1.7621.78-87Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7621.78-87

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

Science.gov (United States)

Opila, Elizabeth J.

1994-01-01

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

Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation.

Science.gov (United States)

Michaels, Thomas C T; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M; Knowles, Tuomas P J

2018-04-20

Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation

Science.gov (United States)

Michaels, Thomas C. T.; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M.; Knowles, Tuomas P. J.

2018-04-01

Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

Science.gov (United States)

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.

Synthesis and thermal decomposition kinetics of Th(IV) complex with unsymmetrical Schiff base ligand

International Nuclear Information System (INIS)

Fan Yuhua; Bi Caifeng; Liu Siquan; Yang Lirong; Liu Feng; Ai Xiaokang

2006-01-01

A new unsymmetrical Schiff base ligand (H 2 LLi) was synthesized using L-lysine, o-vanillin and salicylaladyde. Thorium(IV) complex of this ligand [Th(H 2 L)(NO 3 )](NO 3 ) 2 x 3H 2 O have been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt = A x e -E/RT x 1/2 (1-α) x [-ln(1-α)] -1 . The kinetic parameters (E, A), activation entropy ΔS ≠ and activation free-energy ΔG ≠ were also calculated. (author)

Analysis on reduced chemical kinetic model of N-heptane for HCCI combustion. Paper no. IGEC-1-072

International Nuclear Information System (INIS)

Yao, M.; Zheng, Z.

2005-01-01

Because of high complexity coupled with multidimensional fluid dynamics, it is difficult to apply detailed chemical kinetic model to simulate practical engines. A reduced model of n-heptane has been developed on the basic of detailed mechanism by sensitivity analysis and reaction path analysis of every stage of combustion. The new reduced mechanism consists of 35 species and 41 reactions, and it is effective in engine condition. The results show that it gives predictions similar to the detailed model in ignition timing, in-cylinder temperature and pressure. Furthermore, the reduced mechanism can be used to simulate boundary condition of partial combustion in good agreement with the detailed mechanism. (author)

Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

Czech Academy of Sciences Publication Activity Database

Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

2014-01-01

Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

Chemical kinetics on thermal decompositions of cumene hydroperoxide in cumene studied by calorimetry: An overview

Energy Technology Data Exchange (ETDEWEB)

Duh, Yih-Shing, E-mail: yihshingduh@yahoo.com.tw [Department of Occupation Safety and Health, Jen-Teh Junior College of Medicine, Nursing and Management, Miaoli, 35664, Taiwan, ROC (China); Department of Safety, Health and Environmental Engineering, National United University, No. 1 Lien-Da, Miaoli, 36052, Taiwan, ROC (China)

2016-08-10

Highlights: • Chemical kinetics on thermal decompositions of CHP are conducted and summarized. • Kinetics agrees well between data from DSC and adiabatic calorimetry. • Ea is determined to be about 120 kJ mol{sup −1} by various calorimetry. • LogA (A in s{sup −1}) is determined to be about 11.8 by various calorimetry. - Abstract: Study on chemical kinetics related to the thermal decomposition of cumene hydoperoxide (CHP) in cumene is summarized in this work. It is of great importance to gather and compare the differences between these kinetic parameters for further substantial applications in the chemical industry and process safety. CHP has been verified to possess an autocatalytic behavior by using microcalorimetry (such as TAM and C-80) operated at isothermal mode in the temperature range from 70 °C to 120 °C. However, it exhibits a reaction of n-th order detected by non-isothermal DSC scanning and adiabatic calorimeter. By the isothermal aging tests, activation energy and frequency factor in logA(s{sup −1}) were averaged to be (117.3 ± 5.9) kJ mol{sup −1}and (11.4 ± 0.3), respectively. Kinetic parameters acquired from data of interlaboratories by using heat-flow calorimetry, the averaged activation energy and frequency factor in logA(s{sup −1}) were (119.3 ± 11.3) kJ mol{sup −1}and (12.0 ± 0.2), respectively. On the analogy of results from adiabatic calorimetry, the activation energy and frequency factor in logA(s{sup −1}) were respectively averaged to be (122.4 ± 9.2) kJ mol{sup −1}and (11.8 ± 0.8). Five sets of kinetic models in relation to autocatalytic reactions are collected and discussed as well.

Estimation of apparent kinetic parameters of polymer pyrolysis with complex thermal degradation behavior

International Nuclear Information System (INIS)

Srimachai, Taranee; Anantawaraskul, Siripon

2010-01-01

Full text: Thermal degradation behavior during polymer pyrolysis can typically be described using three apparent kinetic parameters (i.e., pre-exponential factor, activation energy, and reaction order). Several efficient techniques have been developed to estimate these apparent kinetic parameters for simple thermal degradation behavior (i.e., single apparent pyrolysis reaction). Unfortunately, these techniques cannot be directly extended to the case of polymer pyrolysis with complex thermal degradation behavior (i.e., multiple concurrent reactions forming single or multiple DTG peaks). In this work, we proposed a deconvolution method to determine the number of apparent reactions and estimate three apparent kinetic parameters and contribution of each reaction for polymer pyrolysis with complex thermal degradation behavior. The proposed technique was validated with the model and experimental pyrolysis data of several polymer blends with known compositions. The results showed that (1) the number of reaction and (2) three apparent kinetic parameters and contribution of each reaction can be estimated reasonably. The simulated DTG curves with estimated parameters also agree well with experimental DTG curves. (author)

Kinetics of the reactions of hydrated electrons with metal complexes

International Nuclear Information System (INIS)

Korsse, J.

1983-01-01

The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

Heterogeneous chemical kinetics by modulated molecular beam mass spectrometry: limitations of technique

International Nuclear Information System (INIS)

Olander, D.R.

1977-01-01

The advantages and limitations of modulated molecular beam, mass spectrometry as applied to the study of heterogeneous chemical kinetics are reviewed. The process of deducing a model of the surface reaction from experimental data is illustrated by analysis of the hydrogen reduction of uranium dioxide

Study of kinetics and mechanism of diazo compound reactions using nuclear chemical polarization

International Nuclear Information System (INIS)

Gragerov, I.P.; Levit, A.F.; Kiprianova, L.A.; Buchachenko, A.L.; Sterleva, T.G.

1975-01-01

It has been established that at the rate-determining steps of the radical reactions in which aniline interacts with isoamyl nitrite and substituted diazo salts interact with sodium methylate, tertiary fatty amines, or phosphinic acid, no transfer of a single electron occurs. The processes of single electron transfer do not seem to play a decisive role in the kinetics of most transformations of diazo compounds. Chemical nuclear polarization is shown to be suitable for kinetic studies of fast radical processes

Chemical kinetics in H2O and D2O under hydrothermal conditions

International Nuclear Information System (INIS)

Ghandi, K.; Alcorn, C.D.; Legate, G.; Percival, P.W.; Brodovitch, J.-C.

2010-01-01

Muonium (Mu = μ + e - ) is a light analogue of the H-atom. Studies of Mu chemical kinetics have been extended to supercritical water, a medium in some designs of future generation nuclear reactors. The Supercritical-Water-Cooled Reactor (SCWR) would operate at higher temperatures than current pressurized water-cooled reactors, and the lack of knowledge of water radiolysis under supercritical conditions constitutes a technology gap for SCWR development. Accurate modeling of chemistry in a SCWR requires data on kinetics of reactions involved in the radiolysis of water. In this paper, we first review our measurements of kinetics in H 2 O and then describe new data for D 2 O under sub- and supercritical conditions. (author)

The Teaching and Learning of Chemical Kinetics Supported with MS Excel

Science.gov (United States)

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

2013-01-01

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

Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

International Nuclear Information System (INIS)

Fux, P.

1984-06-01

A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

H2-dependent attachment kinetics and shape evolution in chemical vapor deposition graphene growth

Science.gov (United States)

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.

An optimized chemical kinetic mechanism for HCCI combustion of PRFs using multi-zone model and genetic algorithm

International Nuclear Information System (INIS)

Neshat, Elaheh; Saray, Rahim Khoshbakhti

2015-01-01

Highlights: • A new chemical kinetic mechanism for PRFs HCCI combustion is developed. • New mechanism optimization is performed using genetic algorithm and multi-zone model. • Engine-related combustion and performance parameters are predicted accurately. • Engine unburned HC and CO emissions are predicted by the model properly. - Abstract: Development of comprehensive chemical kinetic mechanisms is required for HCCI combustion and emissions prediction to be used in engine development. The main purpose of this study is development of a new chemical kinetic mechanism for primary reference fuels (PRFs) HCCI combustion, which can be applied to combustion models to predict in-cylinder pressure and exhaust CO and UHC emissions, accurately. Hence, a multi-zone model is developed for HCCI engine simulation. Two semi-detailed chemical kinetic mechanisms those are suitable for premixed combustion are used for n-heptane and iso-octane HCCI combustion simulation. The iso-octane mechanism contains 84 species and 484 reactions and the n-heptane mechanism contains 57 species and 296 reactions. A simple interaction between iso-octane and n-heptane is considered in new mechanism. The multi-zone model is validated using experimental data for pure n-heptane and iso-octane. A new mechanism is prepared by combination of these two mechanisms for n-heptane and iso-octane blended fuel, which includes 101 species and 594 reactions. New mechanism optimization is performed using genetic algorithm and multi-zone model. Mechanism contains low temperature heat release region, which decreases with increasing octane number. The results showed that the optimized chemical kinetic mechanism is capable of predicting engine-related combustion and performance parameters. Also after implementing the optimized mechanism, engine unburned HC and CO emissions predicted by the model are in good agreement with the corresponding experimental data

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions

International Nuclear Information System (INIS)

Avlyanov, Zh.K.; Kabanov, N.M.; Zezin, A.B.; Askarov, M.A.

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions

EFFECTS OF SIMPLIFIED CHEMICAL KINETIC MODEL ON THE MICRO-FLAME STRUCTURE AND TEMPERATURE OF THE LEAN PREMIXED METHANE-AIR MIXTURES

Directory of Open Access Journals (Sweden)

JUNJIE CHEN

2015-07-01

Full Text Available The effect of simplified chemical kinetic model on the micro-flame structure, central axis and wall temperatures were investigated with different one-step global chemical kinetic mechanisms following Mantel, Duterque and Fernández-Tarrazo models. Numerical investigations of the premixed methane-air flame in the micro-channel and lean conditions were carried out to compare and analyze the effect of the comprehensive chemical kinetic mechanisms. The results indicate that one-step global chemical kinetic mechanism affects both the micro-flame shape and the combustion temperature. Among three simulation models, Mantel model allows a stable micro-flame with a bamboo shoot form, which anchor at the inlet. Duterque model gives a stable elongated micro-flame with a considerable ignition delay, and a dead zone with fluid accumulation is observed at the entrance, which may explain the very high combustion temperature and the fast reaction rate obtained, despite the micro-flame development presents a very hot spot and causes a broadening of the combustion zone. Fernández-Tarrazo model results in a rapid extinction and doesn't seem to take all the kinetic behavior into account for the appropriate micro-combustion simulations.

A computational environment for creating and testing reduced chemical kinetic mechanisms

Energy Technology Data Exchange (ETDEWEB)

Montgomery, C.J.; Swensen, D.A.; Harding, T.V.; Cremer, M.A.; Bockelie, M.J. [Reaction Engineering International, Salt Lake City, UT (USA)

2002-02-01

This paper describes software called computer assisted reduced mechanism problem solving environment (CARM-PSE) that gives the engineer the ability to rapidly set up, run and examine large numbers of problems comparing detailed and reduced (approximate) chemistry. CARM-PSE integrates the automatic chemical mechanism reduction code CARM and the codes that simulate perfectly stirred reactors and plug flow reactors into a user-friendly computational environment. CARM-PSE gives the combustion engineer the ability to easily test chemical approximations over many hundreds of combinations of inputs in a multidimensional parameter space. The demonstration problems compare detailed and reduced chemical kinetic calculations for methane-air combustion, including nitrogen oxide formation, in a stirred reactor and selective non-catalytic reduction of NOx, in coal combustion flue gas.

Continuum-Kinetic Hybrid Framework for Chemically Reacting Flows

Data.gov (United States)

National Aeronautics and Space Administration — Predictive modeling of chemically reacting flows is essential for the design and optimization of future hypersonic vehicles. During atmospheric re-entry, complex...

Estimation of beech pyrolysis kinetic parameters by Shuffled Complex Evolution.

Science.gov (United States)

Ding, Yanming; Wang, Changjian; Chaos, Marcos; Chen, Ruiyu; Lu, Shouxiang

2016-01-01

The pyrolysis kinetics of a typical biomass energy feedstock, beech, was investigated based on thermogravimetric analysis over a wide heating rate range from 5K/min to 80K/min. A three-component (corresponding to hemicellulose, cellulose and lignin) parallel decomposition reaction scheme was applied to describe the experimental data. The resulting kinetic reaction model was coupled to an evolutionary optimization algorithm (Shuffled Complex Evolution, SCE) to obtain model parameters. To the authors' knowledge, this is the first study in which SCE has been used in the context of thermogravimetry. The kinetic parameters were simultaneously optimized against data for 10, 20 and 60K/min heating rates, providing excellent fits to experimental data. Furthermore, it was shown that the optimized parameters were applicable to heating rates (5 and 80K/min) beyond those used to generate them. Finally, the predicted results based on optimized parameters were contrasted with those based on the literature. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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.

Lightning talk slide for "SLACKHA: Software Library for Accelerating Chemical Kinetics on Hybrid Architectures"

OpenAIRE

Niemeyer, Kyle; Sung, Chih-Jen

2018-01-01

Lightning talk slide describing the "SLACKHA: Software Library for Accelerating Chemical Kinetics on Hybrid Architectures" project at the 2018 NSF SI2 PI meeting: https://si2-pi-community.github.io/2018-meeting/

Thermodynamic and kinetic characterization of a zirconium chelate

International Nuclear Information System (INIS)

Stumpf, H.O.; Ekman, M.F.; Souza, R.F.; Costa, V.H.; Dick, Y.P.

1980-01-01

The chemical preparation, composition and characteristics of a zirconium complex with hemateine was studied. Hematein is the common name of an organic compound containing hydroxy-aromatic and hydroxyquinonic groups. The stability constant of this complex was determined spectrophotometrically. Other thermodynamic parameters for the complex formation were also determined; the effect of temperature on these parameters was examined. Reaction kinetics was investigated, as well as the charge of reacting species for the formation of the activated complex. (C.L.B.) [pt

BGK-type models in strong reaction and kinetic chemical equilibrium regimes

International Nuclear Information System (INIS)

Monaco, R; Bianchi, M Pandolfi; Soares, A J

2005-01-01

A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

The complex interaction between marine debris and toxic chemicals in the ocean.

Science.gov (United States)

Engler, Richard E

2012-11-20

Marine debris, especially plastic debris, is widely recognized as a global environmental problem. There has been substantial research on the impacts of plastic marine debris, such as entanglement and ingestion. These impacts are largely due to the physical presence of plastic debris. In recent years there has been an increasing focus on the impacts of toxic chemicals as they relate to plastic debris. Some plastic debris acts as a source of toxic chemicals: substances that were added to the plastic during manufacturing leach from plastic debris. Plastic debris also acts as a sink for toxic chemicals. Plastic sorbs persistent, bioaccumulative, and toxic substances (PBTs), such as polychlorinated biphenyls (PCBs) and dioxins, from the water or sediment. These PBTs may desorb when the plastic is ingested by any of a variety of marine species. This broad look at the current research suggests that while there is significant uncertainty and complexity in the kinetics and thermodynamics of the interaction, plastic debris appears to act as a vector transferring PBTs from the water to the food web, increasing risk throughout the marine food web, including humans. Because of the extremely long lifetime of plastic and PBTs in the ocean, prevention strategies are vital to minimizing these risks.

Biodegradation testing of hydrophobic chemicals in mixtures at low concentrations – covering the chemical space of petroleum hydrocarbons

DEFF Research Database (Denmark)

Birch, Heidi; Hammershøj, Rikke Høst; Mayer, Philipp

Petroleum products are complex mixtures of varying composition containing thousands of hydrocarbons each with their own physicochemical properties and degradation kinetics. One approach for risk assessment of these products is therefore to group the hydrocarbons by carbon number and chemical class...... i.e. hydrocarbon blocks. However, the biodegradation kinetic data varies in quantity and quality for the different hydrocarbon blocks, hampering the characterization of their fate properties. In this study, biodegradation kinetics of a large number of hydrocarbons aiming to cover the chemical space...... of petroleum hydrocarbons, were therefore determined at ng/L to µg/L concentrations in surface water, seawater and activated sludge filtrate. Two hydrocarbon mixtures were prepared, comprising a total of 53 chemicals including paraffins, naphthenics and aromatic hydrocarbons from C8 to C20. Passive dosing from...

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

Science.gov (United States)

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

Science.gov (United States)

Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

2011-01-01

In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

Directory of Open Access Journals (Sweden)

James Bland

2013-12-01

Full Text Available The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM. The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C2H4, followed by dissociation of o-QM to the C6H6 isomers benzene and fulvene (+ CO. At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

Investigating High-School Chemical Kinetics: The Greek Chemistry Textbook and Students' Difficulties

Science.gov (United States)

Gegios, Theodoros; Salta, Katerina; Koinis, Spyros

2017-01-01

In this study we present an analysis of how the structure and content of the Greek school textbook approaches the concepts of chemical kinetics, and an investigation of the difficulties that 11th grade Greek students face regarding these concepts. Based on the structure and content of the Greek textbook, a tool was developed and applied to…

VULCAN: An Open-source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

Energy Technology Data Exchange (ETDEWEB)

Tsai, Shang-Min; Grosheintz, Luc; Kitzmann, Daniel; Heng, Kevin [University of Bern, Center for Space and Habitability, Sidlerstrasse 5, CH-3012, Bern (Switzerland); Lyons, James R. [Arizona State University, School of Earth and Space Exploration, Bateman Physical Sciences, Tempe, AZ 85287-1404 (United States); Rimmer, Paul B., E-mail: shang-min.tsai@space.unibe.ch, E-mail: kevin.heng@csh.unibe.ch, E-mail: jimlyons@asu.edu [University of St. Andrews, School of Physics and Astronomy, St. Andrews, KY16 9SS (United Kingdom)

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 and 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.

First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study.

Science.gov (United States)

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

A KDE-Based Random Walk Method for Modeling Reactive Transport With Complex Kinetics in Porous Media

Science.gov (United States)

Sole-Mari, Guillem; Fernà ndez-Garcia, Daniel; Rodríguez-Escales, Paula; Sanchez-Vila, Xavier

2017-11-01

In recent years, a large body of the literature has been devoted to study reactive transport of solutes in porous media based on pure Lagrangian formulations. Such approaches have also been extended to accommodate second-order bimolecular reactions, in which the reaction rate is proportional to the concentrations of the reactants. Rather, in some cases, chemical reactions involving two reactants follow more complicated rate laws. Some examples are (1) reaction rate laws written in terms of powers of concentrations, (2) redox reactions incorporating a limiting term (e.g., Michaelis-Menten), or (3) any reaction where the activity coefficients vary with the concentration of the reactants, just to name a few. We provide a methodology to account for complex kinetic bimolecular reactions in a fully Lagrangian framework where each particle represents a fraction of the total mass of a specific solute. The method, built as an extension to the second-order case, is based on the concept of optimal Kernel Density Estimator, which allows the concentrations to be written in terms of particle locations, hence transferring the concept of reaction rate to that of particle location distribution. By doing so, we can update the probability of particles reacting without the need to fully reconstruct the concentration maps. The performance and convergence of the method is tested for several illustrative examples that simulate the Advection-Dispersion-Reaction Equation in a 1-D homogeneous column. Finally, a 2-D application example is presented evaluating the need of fully describing non-bilinear chemical kinetics in a randomly heterogeneous porous medium.

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

NARCIS (Netherlands)

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

2006-01-01

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

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

Science.gov (United States)

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

1995-06-01

This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

Fast Search and Adaptive Resolution for Complex Particle Kinetics

Science.gov (United States)

Larson, David J.

2005-10-01

A new plasma simulation algorithm, intended to bridge the gap between Eulerian fluid and kinetic regimes, is now being used for a variety of applications in ICF and weapon effects. The CPK method (Complex Particle Kinetic) concept [1] uses an ensemble of macro-particles with a Gaussian spatial profile and a Mawellian velocity distribution to represent particle distributions in phase space. Time evolution is modeled by a combination of Lagrangian motion and internal evolution within each individual macro-particle. Collisional particle-particle interactions [2] are facilitated by sorting particles into bins depending of the particle size. Different bin levels are connected by a linked list. Searching for neighboring particles is highly efficient because the search is limited to particles in neighboring bins with the possibility of interaction. The bin structure also allows the computation of various spatial moments at different resolutions. Combining the results of the moment calculations yields information on where and when increased resolution is necessary. We will present details of the particle binning process along with progress towards our goal of simulating the transition from continuum to fully kinetic physics. [1] D. W. Hewett, J. Comp. Phys. 189 (2003). [2] D. J. Larson, J. Comp. Phys. 188 (2003).

Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

Science.gov (United States)

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

Quantum chemical investigation of levofloxacin-boron complexes: A computational approach

Science.gov (United States)

Sayin, Koray; Karakaş, Duran

2018-04-01

Quantum chemical calculations are performed over some boron complexes with levofloxacin. Boron complex with fluorine atoms are optimized at three different methods (HF, B3LYP and M062X) with 6-31 + G(d) basis set. The best level is determined as M062X/6-31 + G(d) by comparison of experimental and calculated results of complex (1). The other complexes are optimized by using the best level. Structural properties, IR and NMR spectrum are examined in detail. Biological activities of mentioned complexes are investigated by some quantum chemical descriptors and molecular docking analyses. As a result, biological activities of complex (2) and (4) are close to each other and higher than those of other complexes. Additionally, NLO properties of mentioned complexes are investigated by some quantum chemical parameters. It is found that complex (3) is the best candidate for NLO applications.

Application of adjustable pulse lasers to studying rapid reaction kinetics of excited lanthanide complexing

Energy Technology Data Exchange (ETDEWEB)

Gruzdev, V.P. (Gosudarstvennyj Opticheskij Inst., Leningrad (USSR))

1983-12-01

Using some europium (3) ion complexes new possibilities to be opened by application of adjustable pulse lasers for studying rapid reactions of electron-excited metal ion complexing are demonstrated. The 6Zh rhodamine pulse laser is used as a source of nonequilibrium photoexcitation of an array of Eu/sup 3 +/ complexes in the luminescent kinetic spectroscopy method. The following results are obtained: for the first time the rate of reaction of acetate ion substitution for water molecules of an excited (/sup 5/D/sub 0/) ion of Eu/sup 3 +/ was measured to be (0.7+-0.2)x10/sup 7/ s/sup -1/; using direct experiments the lower limit for the rate of transition of one isomeric form of the excited Eu x EDTA complex into another one in an aqueous solution is determined to be 5x10/sup 5/ s/sup -1/ at 295 K; the kinetics of the excitation energy migration beteen aqueous solvates of Eu/sup 3 +/ and EuxEDTA complexes is investigated.

Is case-based learning an effective teaching strategy to challenge students' alternative conceptions regarding chemical kinetics?

Science.gov (United States)

Yalçınkaya, Eylem; Taştan-Kırık, Özgecan; Boz, Yezdan; Yıldıran, Demet

2012-07-01

Background: Case-based learning (CBL) is simply teaching the concept to the students based on the cases. CBL involves a case, which is a scenario based on daily life, and study questions related to the case, which allows students to discuss their ideas. Chemical kinetics is one of the most difficult concepts for students in chemistry. Students have generally low levels of conceptual understanding and many alternative conceptions regarding it. Purpose: This study aimed to explore the effect of CBL on dealing with students' alternative conceptions about chemical kinetics. Sample: The sample consists of 53 high school students from one public high school in Turkey. Design and methods : Nonequivalent pre-test and post-test control group design was used. Reaction Rate Concept Test and semi-structured interviews were used for data collection. Convenience sampling technique was followed. For data analysis, the independent samples t-test and ANOVA was performed. Results : Both concept test and interview results showed that students instructed with cases had better understanding of core concepts of chemical kinetics and had less alternative conceptions related to the subject matter compared to the control group students, despite the fact that it was impossible to challenge all the alternative conceptions in the experimental group. Conclusions: CBL is an effective teaching method for challenging students' alternative conceptions in the context of chemical kinetics. Since using cases in small groups and whole class discussions has been found to be an effective way to cope with the alternative conceptions, it can be applied to other subjects and grade levels in high schools with a higher sample size. Furthermore, the effect of this method on academic achievement, motivation and critical thinking skills are other variables that can be investigated for future studies in the subject area of chemistry.

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

Science.gov (United States)

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…

Chemical kinetic insights into the ignition dynamics of n-hexane

KAUST Repository

Tingas, Alexandros

2017-10-13

Normal alkanes constitute a significant fraction of transportation fuels, and are the primary drivers of ignition processes in gasoline and diesel fuels. Low temperature ignition of n-alkanes is driven by a complex sequence of oxidation reactions, for which detailed mechanisms are still being developed. The current study explores the dynamics of low-temperature ignition of n-hexane/air mixtures, and identifies chemical pathways that characterize the combustion process. Two chemical kinetic mechanisms were selected as a comparative study in order to better understand the role of specific reaction sequences in ignition dynamics: one mechanism including a new third sequential O2 addition reaction pathways (recently proposed by Wang et al. 2017), while the other without (Zhang et al. 2015). The analysis is conducted by applying tools generated from the computational singular perturbation (CSP) approach to two distinct ignition phenomena: constant volume and compression ignition. In both cases, the role of the third sequential O2 addition reactions proves to be significant, although it is found to be much more pronounced in the constant volume cases compared to the HCCI. In particular, in the constant volume ignition case, reactions present in the third sequential O2 addition reaction pathways (e.g., KDHP  →  products + OH) contribute significantly to the explosivity of the mixture; when accounted for along with reactions P(OOH)2 + O2  →  OOP(OOH)2 and OOP(OOH)2  →  KDHP + OH, they decrease ignition delay time of the mixture by up to 40%. Under HCCI conditions, in the first-stage ignition, the third-O2 addition reactions contribute to the process, although their role decays with time and becomes negligible at the end of the first stage. The second ignition stage is dominated almost exclusively by hydrogen-related chemistry.

Kinetics of the Dynamical Information Shannon Entropy for Complex Systems

International Nuclear Information System (INIS)

Yulmetyev, R.M.; Yulmetyeva, D.G.

1999-01-01

Kinetic behaviour of dynamical information Shannon entropy is discussed for complex systems: physical systems with non-Markovian property and memory in correlation approximation, and biological and physiological systems with sequences of the Markovian and non-Markovian random noises. For the stochastic processes, a description of the information entropy in terms of normalized time correlation functions is given. The influence and important role of two mutually dependent channels of the entropy change, correlation (creation or generation of correlations) and anti-correlation (decay or annihilation of correlation) is discussed. The method developed here is also used in analysis of the density fluctuations in liquid cesium obtained from slow neutron scattering data, fractal kinetics of the long-range fluctuation in the short-time human memory and chaotic dynamics of R-R intervals of human ECG. (author)

Features in chemical kinetics. I. Signatures of self-emerging dimensional reduction from a general format of the evolution law.

Science.gov (United States)

Nicolini, Paolo; Frezzato, Diego

2013-06-21

Simplification of chemical kinetics description through dimensional reduction is particularly important to achieve an accurate numerical treatment of complex reacting systems, especially when stiff kinetics are considered and a comprehensive picture of the evolving system is required. To this aim several tools have been proposed in the past decades, such as sensitivity analysis, lumping approaches, and exploitation of time scales separation. In addition, there are methods based on the existence of the so-called slow manifolds, which are hyper-surfaces of lower dimension than the one of the whole phase-space and in whose neighborhood the slow evolution occurs after an initial fast transient. On the other hand, all tools contain to some extent a degree of subjectivity which seems to be irremovable. With reference to macroscopic and spatially homogeneous reacting systems under isothermal conditions, in this work we shall adopt a phenomenological approach to let self-emerge the dimensional reduction from the mathematical structure of the evolution law. By transforming the original system of polynomial differential equations, which describes the chemical evolution, into a universal quadratic format, and making a direct inspection of the high-order time-derivatives of the new dynamic variables, we then formulate a conjecture which leads to the concept of an "attractiveness" region in the phase-space where a well-defined state-dependent rate function ω has the simple evolution ω[over dot]=-ω(2) along any trajectory up to the stationary state. This constitutes, by itself, a drastic dimensional reduction from a system of N-dimensional equations (being N the number of chemical species) to a one-dimensional and universal evolution law for such a characteristic rate. Step-by-step numerical inspections on model kinetic schemes are presented. In the companion paper [P. Nicolini and D. Frezzato, J. Chem. Phys. 138, 234102 (2013)] this outcome will be naturally related to the

FUNDAMENTAL KINETICS OF SUPERCRITICAL COAL LIQUEFACTION: EFFECT OF CATALYSTS AND HYDROGEN-DONOR SOLVENTS; FINAL

International Nuclear Information System (INIS)

Benjamin J. McCoy; J.M. Smith

1998-01-01

This report outlines a distribution kinetics approach to macromolecular reactions that has been applied to several processes. The objective was to develop an understanding of high-temperature, dense-phase thermolytic processes for complex macromolecular systems, such as coal. Experiments and theory are described for chemical models that simulate depolymerization of coal. The approach has been exceptionally successful for the model macromolecular systems. Development of a novel chemical reaction engineering analysis, based on distribution kinetics, was a major accomplishment of the current research

On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

NARCIS (Netherlands)

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

2013-01-01

Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the

Synthesis, X-ray crystallography, spectroscopy, electrochemistry, thermal and kinetic study of uranyl Schiff base complexes

Czech Academy of Sciences Publication Activity Database

Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal

2013-01-01

Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013

Slow manifolds in chemical kinetics

International Nuclear Information System (INIS)

Shahzad, M.; Haq, I. U.; Sultan, F.; Wahab, A.; Faizullah, F.; Rahman, G. U.

2016-01-01

Modelling the chemical system, especially for complex and higher dimensional problems, gives an easy way to handle the ongoing reaction process with respect to time. Here, we will consider some of the newly developed computational methods commonly used for model reductions in a chemical reaction. An effective (simple) method is planned to measure the low dimensional manifold, which reduces the higher dimensional system in such a way that it may not affect the precision of the whole mechanism. The phase flow of the solution trajectories near the equilibrium point is observed while the initial approximation is measured with the spectral quasi equilibrium manifold, which starts from the equilibrium point. To make it an invariant curve, the approximated curve is first refined a certain number of times using the method of invariant grids. The other way of getting the reduced data in the low dimensional manifold is possible through the intrinsic low dimensional manifold. Then, we compare these two invariant curves given by both the methods. Finally, the idea is extended to the higher dimensional manifold, where more number of progress variables will be added. (author)

Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

International Nuclear Information System (INIS)

Kelley, D.

1990-01-01

The kinetics of the reactions of C 2 H 5 radical with Co(NH 3 ) 5 X 2+ , Ru(NH 3 ) 5 X 2+ , and Co(dmgH) 2 (X) (Y) (X = Br, Cl, N 3 , SCN; Y = H 2 O, CH 3 CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with β-Ni(cyclam) 2+ were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ were studied. Activation parameters were obtained for the unimolecular homolysis of C 2 H 5 Ni(cyclam)H 2 O 2+ . Kinetic and thermodynamic data obtained from these reactions were compared with those for the σ-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ complexes were studied by monitoring the formation of the oxygen insertion product RO 2 Ni(cyclam)H 2 O 2+ . The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-02-08

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

Characterization of the pharmacokinetics of gasoline using PBPK modeling with a complex mixtures chemical lumping approach.

Science.gov (United States)

Dennison, James E; Andersen, Melvin E; Yang, Raymond S H

2003-09-01

Gasoline consists of a few toxicologically significant components and a large number of other hydrocarbons in a complex mixture. By using an integrated, physiologically based pharmacokinetic (PBPK) modeling and lumping approach, we have developed a method for characterizing the pharmacokinetics (PKs) of gasoline in rats. The PBPK model tracks selected target components (benzene, toluene, ethylbenzene, o-xylene [BTEX], and n-hexane) and a lumped chemical group representing all nontarget components, with competitive metabolic inhibition between all target compounds and the lumped chemical. PK data was acquired by performing gas uptake PK studies with male F344 rats in a closed chamber. Chamber air samples were analyzed every 10-20 min by gas chromatography/flame ionization detection and all nontarget chemicals were co-integrated. A four-compartment PBPK model with metabolic interactions was constructed using the BTEX, n-hexane, and lumped chemical data. Target chemical kinetic parameters were refined by studies with either the single chemical alone or with all five chemicals together. o-Xylene, at high concentrations, decreased alveolar ventilation, consistent with respiratory irritation. A six-chemical interaction model with the lumped chemical group was used to estimate lumped chemical partitioning and metabolic parameters for a winter blend of gasoline with methyl t-butyl ether and a summer blend without any oxygenate. Computer simulation results from this model matched well with experimental data from single chemical, five-chemical mixture, and the two blends of gasoline. The PBPK model analysis indicated that metabolism of individual components was inhibited up to 27% during the 6-h gas uptake experiments of gasoline exposures.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. K Krishna Kishore. Articles written in Journal of Chemical Sciences. Volume 113 Issue 4 August 2001 pp 351-359 Physical and Theoretical. Mechanism of oxidation of L-methionine by iron(III)-1,10-phenanthroline complex - A kinetic study · P Vani K Krishna Kishore R ...

Event-by-event extraction of kinetic and chemical freeze-out properties in the CBM experiment

Energy Technology Data Exchange (ETDEWEB)

Vovchenko, Volodymyr [Goethe University, Frankfurt am Main (Germany); Frankfurt Institute for Advanced Studies, Frankfurt am Main (Germany); GSI Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Taras Shevchenko University, Kyiv (Ukraine); Kisel, Ivan [Goethe University, Frankfurt am Main (Germany); Frankfurt Institute for Advanced Studies, Frankfurt am Main (Germany); GSI Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Anchishkin, Dmitry [Taras Shevchenko University, Kyiv (Ukraine); Bogolyubov Institute for Theoretical Physics, Kyiv (Ukraine); Collaboration: CBM-Collaboration

2015-07-01

The future CBM experiment at FAIR is designed to study properties of strongly interacting matter produced in heavy-ion collisions at high baryon densities. It will employ high intensity beams and large acceptance detectors. One important task is to extract the thermal parameters of matter at stages of kinetic and chemical freeze-out from the observed data. The extraction of thermal parameters is implemented as a package within the CBMROOT framework. The kinetic freeze-out temperature and the inverse slope of charged pions are extracted from their measured momentum spectra with appropriate correction on acceptance and reconstruction efficiency. The parameters of the chemical freeze-out are extracted by fitting the measured particle ratios in the framework of Hadron Resonance Gas model. The procedures can be used to perform analysis on event-by-event as well as on the inclusive spectra level.

Charge-transfer complexes between p-toluidine and iodine in solution: a kinetic study

International Nuclear Information System (INIS)

Beggiato, G.; Casalbore, G.; Marconi, G.; Baraldi, C.

1985-01-01

The kinetics of charge-transfer interaction between p-toluidine and iodine in methylene chloride was investigated in depth. The thermal process of formation of the 'inner' complex was found to proceed to an equilibrium. The photochemical process follows a different reaction coordinate, going through the formation of an exciplex between the excited 'outer' complex and the amine ground state. In both cases the same ionic complex (Am 2 I + I - 3 , where Am stands for p-toluidine) was detected as the final product. (Author)

Reduced chemical kinetic mechanisms for hydrocarbon fuels

International Nuclear Information System (INIS)

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

1999-01-01

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

Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

International Nuclear Information System (INIS)

Tabushi, I.; Yoshizawa, A.

1986-01-01

Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

The Characterization of Cognitive Processes Involved in Chemical Kinetics Using a Blended Processing Framework

Science.gov (United States)

Bain, Kinsey; Rodriguez, Jon-Marc G.; Moon, Alena; Towns, Marcy H.

2018-01-01

Chemical kinetics is a highly quantitative content area that involves the use of multiple mathematical representations to model processes and is a context that is under-investigated in the literature. This qualitative study explored undergraduate student integration of chemistry and mathematics during problem solving in the context of chemical…

GPU-accelerated atmospheric chemical kinetics in the ECHAM/MESSy (EMAC) Earth system model (version 2.52)

Science.gov (United States)

Alvanos, Michail; Christoudias, Theodoros

2017-10-01

This paper presents an application of GPU accelerators in Earth system modeling. We focus on atmospheric chemical kinetics, one of the most computationally intensive tasks in climate-chemistry model simulations. We developed a software package that automatically generates CUDA kernels to numerically integrate atmospheric chemical kinetics in the global climate model ECHAM/MESSy Atmospheric Chemistry (EMAC), used to study climate change and air quality scenarios. A source-to-source compiler outputs a CUDA-compatible kernel by parsing the FORTRAN code generated by the Kinetic PreProcessor (KPP) general analysis tool. All Rosenbrock methods that are available in the KPP numerical library are supported.Performance evaluation, using Fermi and Pascal CUDA-enabled GPU accelerators, shows achieved speed-ups of 4. 5 × and 20. 4 × , respectively, of the kernel execution time. A node-to-node real-world production performance comparison shows a 1. 75 × speed-up over the non-accelerated application using the KPP three-stage Rosenbrock solver. We provide a detailed description of the code optimizations used to improve the performance including memory optimizations, control code simplification, and reduction of idle time. The accuracy and correctness of the accelerated implementation are evaluated by comparing to the CPU-only code of the application. The median relative difference is found to be less than 0.000000001 % when comparing the output of the accelerated kernel the CPU-only code.The approach followed, including the computational workload division, and the developed GPU solver code can potentially be used as the basis for hardware acceleration of numerous geoscientific models that rely on KPP for atmospheric chemical kinetics applications.

The first experimental confirmation of the fractional kinetics containing the complex-power-law exponents: Dielectric measurements of polymerization reactions

Science.gov (United States)

Nigmatullin, R. R.; Arbuzov, A. A.; Salehli, F.; Giz, A.; Bayrak, I.; Catalgil-Giz, H.

2007-01-01

For the first time we achieved incontestable evidence that the real process of dielectric relaxation during the polymerization reaction of polyvinylpyrrolidone (PVP) is described in terms of the fractional kinetic equations containing complex-power-law exponents. The possibility of the existence of the fractional kinetics containing non-integer complex-power-law exponents follows from the general theory of dielectric relaxation that has been suggested recently by one of the authors (R.R.N). Based on the physical/geometrical meaning of the fractional integral with complex exponents there is a possibility to develop a general theory of dielectric relaxation based on the self-similar (fractal) character of the reduced (averaged) microprocesses that take place in the mesoscale region. This theory contains some essential predictions related to existence of the non-integer power-law kinetics and the results of this paper can be considered as the first confirmation of existence of the kinetic phenomena that are described by fractional derivatives with complex-power-law exponents. We want to stress here that with the help of a new complex fitting function for the complex permittivity it becomes possible to describe the whole process for real and imaginary parts simultaneously throughout the admissible frequency range (30 Hz-13 MHz). The fitting parameters obtained for the complex permittivity function for three temperatures (70, 90 and 110 °C) confirm in general the picture of reaction that was known qualitatively before. They also reveal some new features, which improve the interpretation of the whole polymerization process. We hope that these first results obtained in the paper will serve as a good stimulus for other researches to find the traces of the existence of new fractional kinetics in other relaxation processes unrelated to the dielectric relaxation. These results should lead to the reconsideration and generalization of irreversibility and kinetic phenomena that

Chemical kinetics in H{sub 2}O and D{sub 2}O under hydrothermal conditions

Energy Technology Data Exchange (ETDEWEB)

Ghandi, K.; Alcorn, C.D.; Legate, G. [Mount Allison Univ., Sackville, New Brunswick (Canada); Percival, P.W.; Brodovitch, J.-C. [Simon Fraser Univ., Burnaby, British Columbia (Canada)

2010-07-01

Muonium (Mu = μ{sup +}e{sup -}) is a light analogue of the H-atom. Studies of Mu chemical kinetics have been extended to supercritical water, a medium in some designs of future generation nuclear reactors. The Supercritical-Water-Cooled Reactor (SCWR) would operate at higher temperatures than current pressurized water-cooled reactors, and the lack of knowledge of water radiolysis under supercritical conditions constitutes a technology gap for SCWR development. Accurate modeling of chemistry in a SCWR requires data on kinetics of reactions involved in the radiolysis of water. In this paper, we first review our measurements of kinetics in H{sub 2}O and then describe new data for D{sub 2}O under sub- and supercritical conditions. (author)

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

International Nuclear Information System (INIS)

Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

2011-01-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

Science.gov (United States)

Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

2011-03-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

for simulating kinetic profiles of multi-step chemical systems

African Journals Online (AJOL)

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waves and Belousov-Zhabotinsky type reactions have complex reaction mechanisms ... A pre-processor code for a sequence of chemical reactions is .... mechanism only as the text file using any editor that support text format, (iv) the reactant.

Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

Energy Technology Data Exchange (ETDEWEB)

Asadi, Zahra; Nasrollahi, Rahele; Ranjkeshshorkaei, Mohammad; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Chemistry Dept.; Dusek, Michal; Fejfarova, Karla [ASCR, Prague (Czech Republic). Inst. of Physics

2016-05-15

Uranyl(VI) complexes, [UO{sub 2}(X-saloph)(solvent)], where saloph denotes N,N{sup '}-bis(salicylidene)-1,2-phenylenediamine and X = NO{sub 2}, Cl, Me, H; were synthesized and characterized by 61H NMR, IR, UV-Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO{sub 2}(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO{sub 2}(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

Thermodynamic stability and kinetic inertness of a Gd-DTPA bisamide complex grafted onto gold nanoparticles.

Science.gov (United States)

Mogilireddy, Vijetha; Déchamps-Olivier, Isabelle; Alric, Christophe; Laurent, Gautier; Laurent, Sophie; Vander Elst, Luce; Muller, Robert; Bazzi, Rana; Roux, Stéphane; Tillement, Olivier; Chuburu, Françoise

2015-01-01

Gold nanoparticles coated by gadolinium (III) chelates (Au@DTDTPA) where DTDTPA is a dithiolated bisamide derivative of diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), constituted contrast agents for both X-ray computed tomography and magnetic resonance imaging. In an MRI context, highly stable Gd(3+) complexes are needed for in vivo applications. Thus, knowledge of the thermodynamic stability and kinetic inertness of these chelates, when grafted onto gold nanoparticles, is crucial since bisamide DTPA chelates are usually less suited for Gd(3+) coordination than DTPA. Therefore, these parameters were evaluated by means of potentiometric titrations and relaxivity measurements. The results showed that, when the chelates were grafted onto the nanoparticle, not only their thermodynamic stability but also their kinetic inertness were improved. These positive effects were correlated to the chelate packing at the nanoparticle surface that stabilized the corresponding Gd(3+) complexes and greatly enhanced their kinetic inertness. Copyright © 2014 John Wiley & Sons, Ltd.

Chemical kinetics and transport processes in supercritical fluid extraction of coal. Final report, August 10, 1990--December 30, 1992

Energy Technology Data Exchange (ETDEWEB)

McCoy, B.J.; Smith, J.M.; Wang, M.; Zhang, C.J.

1993-02-01

The overall objective of this project was to study the supercritical fluid extraction of hydrocarbons from coal. Beyond the practical concern of deriving products from coal, the research has provided insights into the structure, properties, and reactivities of coal. Information on engineering fundamentals of coal thermolysis and extraction, including physical and chemical processes, is presented in this final report. To accomplish the goals of the project we developed continuous-flow experiments for fixed-bed samples of coal that allow two types of analysis of the extract: continuous spectrophotometric absorbance measurements of the lumped concentration of extract, and chromatographic determinations of molecular-weight distributions as a function of time. Thermolysis of coal yields a complex mixture of many extract products whose molecular-weight distribution (MWD) varies with time for continuous-flow, semibatch experiments. The flow reactor with a differential, fixed bed of coal particles contacted by supercritical t-butanol was employed to provide dynamic MWD data by means of HPLC gel permeation chromatography of the extract. The experimental results, time-dependent MWDs of extract molecules, were interpreted by a novel mathematical model based on continuous-mixture kinetics for thermal cleavage of chemical bonds in the coal network. The parameters for the MWDs of extractable groups in the coal and the rate constants for one- and two-fragment reaction are determined from the experimental data. The significant effect of temperature on the kinetics of the extraction was explained in terms of one- and two-fragment reactions in the coal.

Health and environmental effects of complex chemical mixtures: proceedings

Energy Technology Data Exchange (ETDEWEB)

1985-01-01

The Office of Health and Environmental Research (OHER) of the Department of Energy supports a broad long-term research program on human health and environmental effects from potential exposure to energy-related complex chemical mixtures. The program seeks basic mechanistic data on the effects of complex mixtures at the cellular, molecular, and whole animal levels to aid in predicting human health effects and seeks ecological data on biological and physical transformations in the mixtures, concentrations of the mixtures in various compartments of the environment, and potential routes for human exposure to these mixtures (e.g., food chain). On June 17-18, 1985, OHER held its First Annual Technical Meeting on the Complex Chemical Mixtures Program in Chicago, IL. The primary purpose of the meeting was to enable principal investigators to report the research status and accomplishments of ongoing complex chemical mixture studies supported by OHER. To help focus future research directions round table discussions were conducted.

Water-chemical regime of a fast reactor ower complex

International Nuclear Information System (INIS)

Musikhin, R.N.; Piskunov, E.M.; Samarkin, A.A.; Yurchenko, D.S.

1983-01-01

Some peculiarities of water-chemical regime of a power compleX in Shevchenko are considered. The complex comprises a desalination unit, a gas-masout heating-and-power plant and the BN-350 reactor. The compleX is used for the production of electric and thermal energy and fresh water. The power complex peculiarity is the utilization of disalinated seawater in a technological cycle along with highly mineralized seawater with a total salt content of 13.5 g/l (for cooling) in heat exchanges. A regime of ammoniacal correction of feed water was used as a basic water-chemical regime in the initial period of the BN-350 steam generator operation. Deposits composed mainly of iron oxide slime were observed on steam generator surfaces during the operation under these conditions. A conclusion is made that the regime with chelating agent providing steam generator safe operation without chemical cleaning is the most expedient one

Kinetics and equilibria for the formation of a new DNA metal-intercalator: the cyclic polyamine Neotrien/copper(II) complex.

Science.gov (United States)

Biver, Tarita; Secco, Fernando; Tinè, Maria Rosaria; Venturini, Marcella

2004-01-01

A study has been performed of the kinetics and equilibria involved in complex formation between the macrocyclic polyamine 2,5,8,11-tetraaza[12]-[12](2,9)[1,10]-phenanthrolinophane (Neotrien) and Cu(II) in acidic aqueous solution and ionic strength 0.5 M (NaCl), by means of the stopped-flow method and UV spectrophotometry. Spectrophotometric titrations and kinetic experiments revealed that the binding of Cu(II) to Neotrien gives rise to several 1:1 complexes differing in their degree of protonation. Under the experimental hydrogen ion concentration range investigated, complexation occurs by two parallel paths: (a) M2+ + (H4L)4+ (MH4L)6+ and (b) M2+ + (H3L)3+ (MH3L)5+. The rate constants values found for complex formation, by paths (a) and (b), are much lower than the values expected from water exchange at copper(II) and other amine/Cu(II) complexation kinetic constants. Kinetic experiments at different NaCl concentrations indicated that this finding was not due to chloride ion competition in complex formation with Neotrien, but it was related to a ring rigidity effect. As the phenanthroline moiety could, in principle, interact with nucleic acids by intercalation or external binding, some preliminary measurements concerned with the possible interactions occurring between the Cu(II)/Neotrien complex and calf thymus DNA (CT-DNA) have also been carried out. The absorption spectra of the Cu(II)/Neotrien complex change upon addition of CT-DNA at pH 7.0, revealing the occurrence of complex-nucleic acid interactions. Moreover, fluorescence titrations, carried out by adding the Cu(II)/Neotrien complex to CT-DNA, previously saturated with ethidium bromide (EB), show that the Cu(II)/Neotrien complex is able to displace EB from DNA, suggesting the complex is able to intercalate into the polynucleotide and then to cleave the phosphodiester bond of DNA.

Scramjet Combustor Simulations Using Reduced Chemical Kinetics for Practical Fuels

Science.gov (United States)

2003-12-01

JP-8 kinetics and soot models into the UNICORN CFD code (Montgomery et al., 2003a) NSF Phase I and II SBIRs for development of a computer-assisted...the consequent large relative ratio of communication to computation, which increases as the number of processors increases. Table 6. CPU Times for 2-D...divided by diameter QSS quasi-steady state REI Reaction Engineering International UNICORN UNsteady Ignition and COmbustion with ReactioNs VULCAN Viscous Upwind aLgorithm for Complex flow ANalysis

A kinetic study of the redox reactions of complex cyanides of iron, molybdenum and tungsten with compounds of the group VI A elements

International Nuclear Information System (INIS)

Dennis, C.R.

1981-01-01

The kinetic study arises out of the fact that few is known about redox kinetics of complex cyanides of molybdenum and tungsten. The redox kinetics of the complex cyanides of iron with organic and inorganic compounds are well known in organic chemistry. This comparitive study is done to obtain more information on redox reactions of complex cyanides of molybdenum and tungsten considering its greater applicability in organic and inorganic chemistry because of the propitious reduction potential of this complex cyanide in acidic and alkaline mediums. Various redox systems are kinetically investigated regarding the influence of the oxidising agent, reducing agent hydrogen ions and alkaline-metal ions on the reaction rate. A reaction mechanism is proposed for every system

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

NARCIS (Netherlands)

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

2012-01-01

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

GPU-accelerated atmospheric chemical kinetics in the ECHAM/MESSy (EMAC Earth system model (version 2.52

Directory of Open Access Journals (Sweden)

M. Alvanos

2017-10-01

Full Text Available This paper presents an application of GPU accelerators in Earth system modeling. We focus on atmospheric chemical kinetics, one of the most computationally intensive tasks in climate–chemistry model simulations. We developed a software package that automatically generates CUDA kernels to numerically integrate atmospheric chemical kinetics in the global climate model ECHAM/MESSy Atmospheric Chemistry (EMAC, used to study climate change and air quality scenarios. A source-to-source compiler outputs a CUDA-compatible kernel by parsing the FORTRAN code generated by the Kinetic PreProcessor (KPP general analysis tool. All Rosenbrock methods that are available in the KPP numerical library are supported.Performance evaluation, using Fermi and Pascal CUDA-enabled GPU accelerators, shows achieved speed-ups of 4. 5 ×  and 20. 4 × , respectively, of the kernel execution time. A node-to-node real-world production performance comparison shows a 1. 75 ×  speed-up over the non-accelerated application using the KPP three-stage Rosenbrock solver. We provide a detailed description of the code optimizations used to improve the performance including memory optimizations, control code simplification, and reduction of idle time. The accuracy and correctness of the accelerated implementation are evaluated by comparing to the CPU-only code of the application. The median relative difference is found to be less than 0.000000001 % when comparing the output of the accelerated kernel the CPU-only code.The approach followed, including the computational workload division, and the developed GPU solver code can potentially be used as the basis for hardware acceleration of numerous geoscientific models that rely on KPP for atmospheric chemical kinetics applications.

Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

DEFF Research Database (Denmark)

Sørensen, Thomas Just; Tropiano, Manuel; Kenwright, Alan M.

2017-01-01

Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques. The photo...... and lanthanide(III) centres in these molecules inhibits the efficient sensitisation of europium. We conclude that the intramolecular collisions required for efficient Dexter energy transfer from the sensitiser to the lanthanide(III) centre can be prevented by steric congestion....

Chemometrics as a tool to analyse complex chemical mixtures

DEFF Research Database (Denmark)

Christensen, J. H.

Chemical characterisation of contaminant mixtures is important for environmental forensics and risk assessment. The great challenge in future research lies in develop- ing suitable, rapid, reliable and objective methods for analysis of the composition of complex chemical mixtures. This thesis...... describes the development of such methods for assessing the identity (chemical fingerprinting) and fate (e.g. biodegradation) of petroleum hydrocarbon mixtures. The methods comply with the general concept that suitable methods must be rapid and inexpensive, objective with limited human in- tervention...... and at the same time must consider a substantial fraction of compounds in the complex mixture. A combination of a) limited sample preparation, b) rapid chemical screening analysis, c) fast and semi-automatic pre-processing, d) compre- hensive multivariate statistical data analysis and e) objective data evaluation...

Spectrophotometric Analysis of the Kinetic of Pd(II Chloride Complex Ions Sorption Process from Diluted Aqua Solutions Using Commercially Available Activated Carbon

Directory of Open Access Journals (Sweden)

Wojnicki M.

2017-12-01

Full Text Available In this paper, results of adsorption kinetic studies of Pd(II chloride complex ions on activated carbon Organosrob 10 CO are presented. Spectorphotometrical method was applied to investigate the process. Kinetic model was proposed, and fundamental thermodynamic parameters were determined. Proposed kinetic model describes well observed phenomenon in the studied range of concentration of Pd(II chloride complex ions as well, as concentration of activated carbon.

Kinetic stability of the dysprosium(3) complex with tetraazaporphine in acetic acid-water and acetic acid-methanol mixtures

International Nuclear Information System (INIS)

Khelevina, O.G.; Vojnov, A.A.

1999-01-01

Water-soluble dysprosium tetraazaporphine with acetylacetonate-ion as extraligand is synthesized for the first time. Its kinetic stability in acetic acid solutions is investigated. It is shown that the complex is dissociated with formation of free tetraazaporphine. Kinetic parameters of dissociation reaction are determined [ru

Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

National Research Council Canada - National Science Library

Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

2000-01-01

... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

Global minimum profile error (GMPE) - a least-squares-based approach for extracting macroscopic rate coefficients for complex gas-phase chemical reactions.

Science.gov (United States)

Duong, Minh V; Nguyen, Hieu T; Mai, Tam V-T; Huynh, Lam K

2018-01-03

Master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) has shown to be a powerful framework for modeling kinetic and dynamic behaviors of a complex gas-phase chemical system on a complicated multiple-species and multiple-channel potential energy surface (PES) for a wide range of temperatures and pressures. Derived from the ME time-resolved species profiles, the macroscopic or phenomenological rate coefficients are essential for many reaction engineering applications including those in combustion and atmospheric chemistry. Therefore, in this study, a least-squares-based approach named Global Minimum Profile Error (GMPE) was proposed and implemented in the MultiSpecies-MultiChannel (MSMC) code (Int. J. Chem. Kinet., 2015, 47, 564) to extract macroscopic rate coefficients for such a complicated system. The capability and limitations of the new approach were discussed in several well-defined test cases.

Chemical speciation of L-glutamine complexes with Co(II), Ni(II) and ...

African Journals Online (AJOL)

The trend in the variation of stability constants of the complexes with mole fraction of the surfactant is attributed to the compartmentalization of complexation equilibria. Distribution of species and effect of influential parameters on chemical speciation have also been presented. KEY WORDS: Chemical speciation, complex ...

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals

Energy Technology Data Exchange (ETDEWEB)

Curl, Robert F; Glass, Graham

2004-11-01

This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

Gas phase chemical kinetics at high temperature of carbonaceous molecules: application to circumstellar envelopes

Science.gov (United States)

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

Kinetics of electrically and chemically induced swelling in polyelectrolyte gels

Science.gov (United States)

Grimshaw, P. E.; Nussbaum, J. H.; Grodzinsky, A. J.; Yarmush, M. L.

1990-09-01

Controlled swelling and shrinking of polyelectrolyte gels is useful for regulating the transport of solutes into, out of, and through these materials. A macroscopic continuum model is presented to predict the kinetics of swelling in polyelectrolyte gel membranes induced by augmentation of electrostatic swelling forces arising from membrane fixed charge groups. The model accounts for ionic transport within the membrane, electrodiffusion phenomena, dissociation of membrane charge groups, intramembrane fluid flow, and mechanical deformation of the membrane matrix. Model predictions are compared with measurements of chemically and electrically induced swelling and shrinking in crosslinked polymethacrylic acid (PMAA) membranes. Large, reversible changes in PMAA membrane hydration were observed after changing the bath pH or by applying an electric field to modify the intramembrane ionic environment and fixed charge density. A relatively slow swelling process and more rapid shrinking for both chemical and electrical modulation of the intramembrane pH are observed. The model indicates that retardation of membrane swelling is dominated by diffusion-limited reaction of H+ ions with membrane charge groups, and that the more rapid shrinking is limited primarily by mechanical processes.

Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

Czech Academy of Sciences Publication Activity Database

Asadi, Z.; Nasrollahi, R.; Dušek, Michal; Fejfarová, Karla; Ranjkeshshorkaei, M.; Firuzabadi, F.D.

2016-01-01

Roč. 13, č. 5 (2016), 913-924 ISSN 1735-207X R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Schiff base complex * kinetic study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.407, year: 2016

Reactive chemicals and process hazards

International Nuclear Information System (INIS)

Surianarayanan, M.

2016-01-01

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

Study of chemical changes in pasteurised orange juice during shelf-life: A fingerprinting-kinetics evaluation of the volatile fraction.

Science.gov (United States)

Wibowo, Scheling; Grauwet, Tara; Kebede, Biniam Tamiru; Hendrickx, Marc; Van Loey, Ann

2015-09-01

The current work used fingerprinting-kinetics for the first time to monitor shelf-life changes in a low-pH, pasteurised, shelf-stable product, more particular in orange juice. Orange juice samples were stored as a function of time at four different storage temperatures (20, 28, 35 and 42°C). To obtain insight into chemical changes in the volatile food fraction, samples were fingerprinted with headspace GC-MS. The objectives of this work were twofold: (i) to identify major chemical changes of pasteurised orange juice during shelf-life and (ii) to study the kinetics of selected shelf-life compounds in the context of accelerated shelf-life testing (ASLT). At 20°C, changes in terpenes and a decrease in aldehydes were observed. Oxides and sulphur compounds increased and esters decreased at increased storage temperatures (at 28°C and above). Concerning ASLT, four volatile compounds had clear temperature and time dependent kinetics within the investigated temperature range. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theory of First Order Chemical Kinetics at the Critical Point of Solution.

Science.gov (United States)

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.

Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

Science.gov (United States)

Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

2017-09-01

The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

Science.gov (United States)

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.

Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

Science.gov (United States)

Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

2007-01-01

A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

Thermodynamically consistent model calibration in chemical kinetics

Directory of Open Access Journals (Sweden)

Goutsias John

2011-05-01

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

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

DEFF Research Database (Denmark)

Dederichs, Anne

Carbon monoxide is treated as one of the most common and dangerous of gases evolving in fires. Modeling the formation of the toxic gas CO from in fire enclosures using detailed chemical kinetics is the topic of this manuscript. A semi-empirical model is developed to study the formation of CO from......, the model separately treats the process of pyrolysis and combustion. For under ventilated conditions and at high temperatures during pyrolysis it is found that the process of pyrolysation strongly influences the formation of CO in fire. CO2 follows the same trend....

Chemical structure and dynamics: Annual report 1993

Energy Technology Data Exchange (ETDEWEB)

Colson, S.D.

1994-07-01

The Chemical Structure and Dynamics program responds to the need for a fundamental, molecular-level understanding of chemistry at the wide variety of environmentally-important interfaces. The research program is built around the established relationship between structure, thermodynamics, and kinetics. This research effort continues to evolve into a program of rigorous studies of fundamental molecular processes in model systems (e.g., well-characterized surfaces, single-component solutions, clusters, and biological molecules), and studies of complex systems found in the environment. Experimental studies of molecular and supramolecular structures and thermodynamics are key to understanding the nature of matter, and lead to direct comparison with computational results. Kinetic and mechanistic measurements, combined with real-time dynamics measurements of atomic and molecular motions during chemical reactions, provide for a molecular-level description of chemical reactions. The anticipated results of this work are the achievement of a quantitative understanding of chemical processes at complex interfaces, the development of new techniques for the detection and measurement of species at such interfaces, and the interpretation and extrapolation of the observations in terms of models of interfacial chemistry. The Chemical Structure and Dynamics research program includes five areas described in detail in this report: Reaction mechanisms at solid interfaces; Solution and solution interfaces; Structure and dynamics of biological systems; Analytical methods development; and atmospheric chemistry. Extended abstracts are presented for 23 studies.

Learning reduced kinetic Monte Carlo models of complex chemistry from molecular dynamics.

Science.gov (United States)

Yang, Qian; Sing-Long, Carlos A; Reed, Evan J

2017-08-01

We propose a novel statistical learning framework for automatically and efficiently building reduced kinetic Monte Carlo (KMC) models of large-scale elementary reaction networks from data generated by a single or few molecular dynamics simulations (MD). Existing approaches for identifying species and reactions from molecular dynamics typically use bond length and duration criteria, where bond duration is a fixed parameter motivated by an understanding of bond vibrational frequencies. In contrast, we show that for highly reactive systems, bond duration should be a model parameter that is chosen to maximize the predictive power of the resulting statistical model. We demonstrate our method on a high temperature, high pressure system of reacting liquid methane, and show that the learned KMC model is able to extrapolate more than an order of magnitude in time for key molecules. Additionally, our KMC model of elementary reactions enables us to isolate the most important set of reactions governing the behavior of key molecules found in the MD simulation. We develop a new data-driven algorithm to reduce the chemical reaction network which can be solved either as an integer program or efficiently using L1 regularization, and compare our results with simple count-based reduction. For our liquid methane system, we discover that rare reactions do not play a significant role in the system, and find that less than 7% of the approximately 2000 reactions observed from molecular dynamics are necessary to reproduce the molecular concentration over time of methane. The framework described in this work paves the way towards a genomic approach to studying complex chemical systems, where expensive MD simulation data can be reused to contribute to an increasingly large and accurate genome of elementary reactions and rates.

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

International Nuclear Information System (INIS)

Li, Tiejun; Lin, Feng

2016-01-01

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. (paper)

NMR of α-synuclein–polyamine complexes elucidates the mechanism and kinetics of induced aggregation

Science.gov (United States)

Fernández, Claudio O; Hoyer, Wolfgang; Zweckstetter, Markus; Jares-Erijman, Elizabeth A; Subramaniam, Vinod; Griesinger, Christian; Jovin, Thomas M

2004-01-01

The aggregation of α-synuclein is characteristic of Parkinson's disease (PD) and other neurodegenerative synucleinopathies. The 140-aa protein is natively unstructured; thus, ligands binding to the monomeric form are of therapeutic interest. Biogenic polyamines promote the aggregation of α-synuclein and may constitute endogenous agents modulating the pathogenesis of PD. We characterized the complexes of natural and synthetic polyamines with α-synuclein by NMR and assigned the binding site to C-terminal residues 109–140. Dissociation constants were derived from chemical shift perturbations. Greater polyamine charge (+2 → +5) correlated with increased affinity and enhancement of fibrillation, for which we propose a simple kinetic mechanism involving a dimeric nucleation center. According to the analysis, polyamines increase the extent of nucleation by ∼104 and the rate of monomer addition ∼40-fold. Significant secondary structure is not induced in monomeric α-synuclein by polyamines at 15°C. Instead, NMR reveals changes in a region (aa 22–93) far removed from the polyamine binding site and presumed to adopt the β-sheet conformation characteristic of fibrillar α-synuclein. We conclude that the C-terminal domain acts as a regulator of α-synuclein aggregation. PMID:15103328

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

KAUST Repository

Atef, Nour

2017-02-05

Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Moreover, 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. Furthermore, new alternative isomerization pathways for peroxy-alkyl hydroperoxide (ȮOQOOH) 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. These 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.

Some Considerations on the Fundamentals of Chemical Kinetics: Steady State, Quasi-Equilibrium, and Transition State Theory

Science.gov (United States)

Perez-Benito, Joaquin F.

2017-01-01

The elementary reaction sequence A ? I ? Products is the simplest mechanism for which the steady-state and quasi-equilibrium kinetic approximations can be applied. The exact integrated solutions for this chemical system allow inferring the conditions that must fulfill the rate constants for the different approximations to hold. A graphical…

Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Mass transfer with complex reversible chemical reactions. II: Parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, Geert; van Beckum, F.P.H.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Mass transfer with complex reversible chemical reactions. II: parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, van F.P.H.; van Swaaij, W.P.M.

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Analysis of chemical reaction kinetics of depredating organic pollutants from secondary effluent of wastewater treatment plant in constructed wetlands.

Science.gov (United States)

Wang, Hao; Jiang, Dengling; Yang, Yong; Cao, Guoping

2013-01-01

Four subsurface constructed wetlands were built to treat the secondary effluent of a wastewater treatment plant in Tangshan, China. The chemical pollutant indexes of chemical oxygen demand (COD) were analyzed to evaluate the removal efficiency of organic pollutants from the secondary effluent of the wastewater treatment plant. In all cases, the subsurface constructed wetlands were efficient in treating organic pollutants. Under the same hydraulic loading condition, the horizontal flow wetlands exhibited better efficiency of COD removal than vertical flow wetlands: the removal rates in horizontal flow wetlands could be maintained at 68.4 ± 2.42% to 92.2 ± 1.61%, compared with 63.8 ± 1.19% to 85.0 ± 1.25% in the vertical flow wetlands. Meanwhile, the chemical reaction kinetics of organic pollutants was analyzed, and the results showed that the degradation courses of the four subsurface wetlands all corresponded with the first order reaction kinetics to a large extent.

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

International Nuclear Information System (INIS)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO 3 solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at [HNO 3 ]=1-6 mol/l as well as inhibiting effect at [HNO 3 ]=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined

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

KAUST Repository

Ciottoli, Pietro P.

2017-08-14

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

Noise-Induced Modulation of the Relaxation Kinetics around a Non-Equilibrium Steady State of Non-Linear Chemical Reaction Networks

OpenAIRE

Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

2011-01-01

Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confi...

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

International Nuclear Information System (INIS)

Sun, Hongjie; Yan, Feng; Yu, Hao; Su, W.H.

2015-01-01

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

A network dynamics approach to chemical reaction networks

NARCIS (Netherlands)

van der Schaft, Abraham; Rao, S.; Jayawardhana, B.

2016-01-01

A treatment of chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a

Preparation, characterization, and kinetics of thermolysis of nickel and copper nitrate complexes with 2,2 Prime -bipyridine ligand

Energy Technology Data Exchange (ETDEWEB)

Kumar, Dinesh; Kapoor, I.P.S. [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Singh, Gurdip, E-mail: gsingh4us@yahoo.com [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Froehlich, Roland [Institut fuer Organische Chemie, Universitaet Muenster, D-48149 Muenster (Germany)

2012-10-10

Graphical abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine, nitrate and water ligands have been prepared and characterized by single crystal X-ray diffraction, FT-IR and CHN analyses. Thermolysis was performed by using TG, DTA and ignition delay measurements. The kinetics of thermolysis were also evaluated. Highlights: Black-Right-Pointing-Pointer Preparation and characterization of Ni and Cu nitrate complexes have been reported. Black-Right-Pointing-Pointer Thermolysis has been carried out using TG-DTA and ignition delay measurements. Black-Right-Pointing-Pointer Their thermal decomposition pathways have been proposed. Black-Right-Pointing-Pointer Oxides residues as end product of thermolysis were revealed by XRD patterns. Black-Right-Pointing-Pointer Kinetics of their isothermal decomposition was evaluated. - Abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine (bipy) as a N donor and nitrate and water as oxygen donor ligands of the general formula [M(NO{sub 3})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 3}](NO{sub 3}), where M = Ni and Cu, have been obtained from the corresponding metal nitrate salts. These complexes were characterized by X-ray crystallography, FT-IR, and CHN analysis. Both the complexes have been found to be six coordinated. Their thermal decomposition behaviour was investigated by TG, DTA, and ignition delay measurements. TG-DTA examinations of these complexes revealed multistep thermal decomposition. The corresponding metal oxide residues obtained after thermolysis were identified from their X-ray diffraction patterns (XRD). Kinetics of isothermal decomposition of the complexes was established from both the model-fitting as well as isoconversional methods.

Effect of physical, chemical and electro-kinetic properties of pumice samples on radiation shielding properties of pumice material

International Nuclear Information System (INIS)

Tapan, Mücip; Yalçın, Zeynel; İçelli, Orhan; Kara, Hüsnü; Orak, Salim; Özvan, Ali; Depci, Tolga

2014-01-01

Highlights: • Radiation shielding properties of pumice materials are studied. • The relationship between physical, chemical and electro-kinetic properties pumice samples is identified. • The photon atomic parameters are important for the absorber peculiarity of the pumices. - Abstract: Pumice has been used in cement, concrete, brick, and ceramic industries as an additive and aggregate material. In this study, some gamma-ray photon absorption parameters such as the total mass attenuation coefficients, effective atomic number and electronic density have been investigated for six different pumice samples. Numerous values of energy related parameters from low energy (1 keV) to high energy (100 MeV) were calculated using WinXCom programme. The relationship between radiation shielding properties of the pumice samples and their physical, chemical and electro-kinetic properties was evaluated using simple regression analysis. Simple regression analysis indicated a strong correlation between photon energy absorption parameters and density and SiO 2 , Fe 2 O 3 , CaO, MgO, TiO 2 content of pumice samples in this study. It is found that photon energy absorption parameters are not related to electro-kinetic properties of pumice samples

Abstracts Book of Jubilee Scientific Assembly of Polish Chemical Society and Association of Engineers and Technicians of Chemical Industry

International Nuclear Information System (INIS)

2000-01-01

Scientific Assemblies of Polish Chemical Society and Association of Engineers and Technicians of Chemical Industry are most important chemical discussion forum organised annually in Poland. Basic as well as application studies in all chemical branches have been extensively presented. The next subjects was proposed as sections and symposia topics: organic chemistry, physical chemistry (chemical kinetics, catalysis, thermodynamics), membranes and membrane processes, biological chemistry, biotechnology, metalorganic compounds and complexes, polymer chemistry, crystallochemical study, spectroscopy in nowadays chemistry, supramolecular chemistry, chemistry and technology of coal, high-energetic materials, environment protection, didactics in chemistry, radiation chemistry, photochemistry, electrochemistry, chemistry and technology of carbohydrates, theoretical and computer chemistry, young scientists forum, history of chemistry

Effects of chemical kinetics and starting material regeneration on the efficiency of an iodine laser amplifier

International Nuclear Information System (INIS)

Fisk, G.A.

1977-05-01

A model of the chemical kinetics occurring in an iodine laser amplifier is presented and used to calculate the degree to which the starting material is consumed as a result of laser operation. The cost of purchasing new starting material is estimated and shown to be prohibitive. A scheme for regenerating the starting material from the species present in the amplifier after lasing is proposed. It is shown that the estimated efficiency of this chemical regeneration process is appreciably higher than the projected optimum efficiency of the pumping process

Mass transfer with complex reversible chemical reactions—I. Single reversible chemical reaction

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1989-01-01

An improved numerical technique was used in order to develop an absorption model with which it is possible to calculate rapidly absorption rates for the phenomenon of mass transfer accompanied by a complex reversible chemical reaction. This model can be applied for the calculation of the mass

Reduced chemical kinetic mechanisms for NOx emission prediction in biomass combustion

DEFF Research Database (Denmark)

Houshfar, Ehsan; Skreiberg, Øyvind; Glarborg, Peter

2012-01-01

Because of the complex composition of biomass, the chemical mechanism contains many different species and therefore a large number of reactions. Although biomass gas‐phase combustion is fairly well researched and understood, the proposed mechanisms are still complex and need very long computational...... time and powerful hardware resources. A reduction of the mechanism for biomass volatile oxidation has therefore been performed to avoid these difficulties. The selected detailed mechanism in this study contains 81 species and 703 elementary reactions. Necessity analysis is used to determine which...... reactions and chemical species, that is, 35 species and 198 reactions, corresponding to 72% reduction in the number of reactions and, therefore, improving the computational time considerably. Yet, the model based on the reduced mechanism predicts correctly concentrations of NOx and CO that are essentially...

A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

Science.gov (United States)

Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

2016-09-21

Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

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

International Nuclear Information System (INIS)

Liu Di

2008-01-01

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

Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

Science.gov (United States)

Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

2008-07-01

We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

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

Science.gov (United States)

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.

Application of Chemical Kinetics to Deterioration of Foods.

Science.gov (United States)

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)

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO/sub 3/ solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at (HNO/sub 3/)=1-6 mol/l as well as inhibiting effect at (HNO/sub 3/)=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined.

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions.

Science.gov (United States)

Chang, Yi Kuo; Chang, Juu En; Chiang, Li Choung

2003-08-01

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS). Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.

Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

KAUST Repository

Bisetti, Fabrizio

2012-06-01

Recent trends in hydrocarbon fuel research indicate that the number of species and reactions in chemical kinetic mechanisms is rapidly increasing in an effort to provide predictive capabilities for fuels of practical interest. In order to cope with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix. The components of the approach are described in detail and applied to the ignition of stoichiometric methane-air and iso-octane-air mixtures, here described by two widely adopted chemical kinetic mechanisms. The approach is found to be robust even at relatively large time steps and the global error displays a nominal third-order convergence. The performance of the approach is improved by utilising an adaptive algorithm for the selection of the Krylov subspace size, which guarantees an approximation to the matrix exponential within user-defined error tolerance. The Krylov projection of the Jacobian matrix onto a low-dimensional space is interpreted as a local model reduction with a well-defined error control strategy. Finally, the performance of the approach is discussed with regard to the optimal selection of the parameters governing the accuracy of its individual components. © 2012 Copyright Taylor and Francis Group, LLC.

Coping with Complexity Model Reduction and Data Analysis

CERN Document Server

Gorban, Alexander N

2011-01-01

This volume contains the extended version of selected talks given at the international research workshop 'Coping with Complexity: Model Reduction and Data Analysis', Ambleside, UK, August 31 - September 4, 2009. This book is deliberately broad in scope and aims at promoting new ideas and methodological perspectives. The topics of the chapters range from theoretical analysis of complex and multiscale mathematical models to applications in e.g., fluid dynamics and chemical kinetics.

Non-isothermal degradation and evaluation of kinetic parameters of some Schiff base metal complexes

International Nuclear Information System (INIS)

Mishra, A.P.; Soni, Monika

2008-01-01

Thermal decomposition of VO (II)-methyl isobutyl ketone-nicotinamide, VO (II)-2-furfurylidine-3,4-dichloroaniline, Co(II)-4-dimethyl amino benzylidine-3-chloro-4-fluoroaniline, VO(II)-2-pyridine carboxylidine-4-aminobenzoic acid complexes have been carried out by thermogravimetric method. The TG curves of complexes were recorded at a uniform rate of 20 deg C/min in nitrogen. The thermogram of the three VO(II) complexes exhibit single stage decomposition whereas the Co(II) complex shows a double stage decomposition. Various kinetic parameters i. e., energy of activation (E), entropy (AS) and frequency factor (Z) have been evaluated by using Coats-Redfern and Piloyan-Novikova equations and their comparable values are reported. The order of thermal stability of first decomposition stage is as: 4=2>1>3. (author)

Revealing chemical processes and kinetics of drug action within single living cells via plasmonic Raman probes.

Science.gov (United States)

Li, Shan-Shan; Guan, Qi-Yuan; Meng, Gang; Chang, Xiao-Feng; Wei, Ji-Wu; Wang, Peng; Kang, Bin; Xu, Jing-Juan; Chen, Hong-Yuan

2017-05-23

Better understanding the drug action within cells may extend our knowledge on drug action mechanisms and promote new drugs discovery. Herein, we studied the processes of drug induced chemical changes on proteins and nucleic acids in human breast adenocarcinoma (MCF-7) cells via time-resolved plasmonic-enhanced Raman spectroscopy (PERS) in combination with principal component analysis (PCA). Using three popular chemotherapy drugs (fluorouracil, cisplatin and camptothecin) as models, chemical changes during drug action process were clearly discriminated. Reaction kinetics related to protein denaturation, conformational modification, DNA damage and their associated biomolecular events were calculated. Through rate constants and reaction delay times, the different action modes of these drugs could be distinguished. These results may provide vital insights into understanding the chemical reactions associated with drug-cell interactions.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Science.gov (United States)

Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

2018-03-01

Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Directory of Open Access Journals (Sweden)

Marc Philippe

2018-01-01

Full Text Available Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the “true” chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

Kinetic studies of chemical shrinkage and residual stress formation in thermoset epoxy adhesives under confined curing conditions

Science.gov (United States)

Schumann, M.; Geiß, P. L.

2015-05-01

Faultless processing of thermoset polymers in demanding applications requires a profound mastering of the curing kinetics considering both the physico-chemical changes in the transition from the liquid to the solid state and the consolidation of the polymers network in the diffusion controlled curing regime past the gel point. Especially in adhesive joints shrinkage stress occurring at an early state of the curing process under confined conditions is likely to cause defects due to local debonding and thus reduce their strength and durability1. Rheometry is considered the method of choice to investigate the change of elastic and viscous properties in the progress of curing. Drawbacks however relate to experimental challenges in accessing the full range of kinetic parameters of thermoset resins with low initial viscosity from the very beginning of the curing reaction to the post-cure consolidation of the polymer due to the formation of secondary chemical bonds. Therefore the scope of this study was to interrelate rheological data with results from in-situ measurements of the shrinkage stress formation in adhesive joints and with the change of refractive index in the progress of curing. This combination of different methods has shown to be valuable in gaining advanced insight into the kinetics of the curing reaction. The experimental results are based on a multi component thermoset epoxy-amine adhesive.

Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics.

Science.gov (United States)

Masunov, Artëm E; Wait, Elizabeth E; Atlanov, Arseniy A; Vasu, Subith S

2017-05-18

In oxy-fuel combustion, the pure oxygen (O 2 ), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2 O) are free from pollution by nitrogen oxides. Moreover, high pressures result in the near-liquid density of CO 2 at supercritical state (sCO 2 ). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. To assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of the carbon dioxide molecule. All transition states and reactant and product complexes are reported for three reactions: H 2 CO + HO 2 → HCO + H 2 O 2 (R1), 2HO 2 → H 2 O 2 + O 2 (R2), and CO + OH → CO 2 + H (R3). In reaction R3, covalent binding of CO 2 to the OH radical and then the CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to the bimolecular OH + CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol and is expected to accelerate the reaction. In the case of hydroperoxyl self-reaction 2HO 2 → H 2 O 2 + O 2 the intermediates, containing covalent bonds to CO 2 are found not to be competitive. However, the spectator CO 2 molecule can stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates is also discovered in the H 2 CO + HO 2 → HCO + H 2 O 2 reaction, but these species lead to substantially higher activation barriers, which makes them unlikely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilizes the transition state and reduces the reaction barrier. These results indicate that the CO 2 environment is likely to have a catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2 .

From simple to complex and backwards. Chemical reactions under very high pressure

International Nuclear Information System (INIS)

Bini, Roberto; Ceppatelli, Matteo; Citroni, Margherita; Schettino, Vincenzo

2012-01-01

Highlights: ► High pressure reactivity of several molecular systems. ► Reaction kinetics and dynamics in high density conditions. ► Key role of optical pumping and electronic excitation. ► Perspectives for the synthesis of hydrogen. - Abstract: High pressure chemical reactions of molecular systems are discussed considering the various factors that can affect the reactivity. These include steric hindrance and geometrical constraints in the confined environment of crystals at high pressure, changes of the free energy landscape with pressure, photoactivation by two-photon absorption, local and collective effects. A classification of the chemical reactions at high pressure is attempted on the basis of the prevailing factors.

Understanding the reaction kinetics to optimize graphene growth on Cu by chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Kraus, Juergen; Boebel, Lena; Zwaschka, Gregor; Guenther, Sebastian [Technische Universitaet Muenchen, Zentralinstitut fuer Katalyseforschung, Chemie Department, Physikalische Chemie mit Schwerpunkt Katalyse, Garching (Germany)

2017-11-15

Understanding and controlling the growth kinetics of graphene is a prerequisite to synthesize this highly wanted material by chemical vapor deposition on Cu, e.g. for the construction of ultra-stable electron transparent membranes. It is reviewed that Cu foils contain a considerable amount of carbon in the bulk which significantly exceeds the expected amount of thermally equilibrated dissolved carbon in Cu and that this carbon must be removed before any high quality graphene may be grown. Starting with such conditioned Cu foils, systematic studies of the graphene growth kinetics in a reactive CH{sub 4}/H{sub 2} atmosphere allow to extract the following meaningful data: prediction of the equilibrium constant of the graphene formation reaction within a precision of a factor of two, the confirmation that the graphene growth proceeds from a C(ad)-phase on Cu which is in thermal equilibrium with the reactive gas phase, its apparent activation barrier and finally the prediction of the achievable growth velocity of the growing graphene flakes during chemical vapor deposition. As a result of the performed study, growth parameters are identified for the synthesis of high quality monolayer graphene with single crystalline domains of 100-1000 μm in diameter within a reasonable growth time. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Interaction of 2-aminopyrimidine with dichloro-[1-alkyl-2-(naphthylazo imidazole]palladium(II complexes : Kinetic and mechanistic studies

Directory of Open Access Journals (Sweden)

Saha Sushanta

2007-10-01

Full Text Available Abstract Background The anticancer properties of cisplatin and palladium(II complexes stem from the ability of the cis-MCl2 fragment to bind to DNA bases. However, cisplatin also interacts with non-cancer cells, mainly through bonding molecules containing -SH groups, resulting in nephrotoxicity. This has aroused interest in the design of palladium(II complexes of improved activity and lower toxicity. The reaction of DNA bases with palladium(II complexes with chelating N,N/donors of the cis-MCl2 configuration constitutes a model system that may help explore the mechanism of cisplatin's anticancer activity. Heterocyclic compounds are found widely in nature and are essential to many biochemical processes. Amongst these naturally occurring compounds, the most thoroughly studied is that of pyrimidine. This was one of the factors that encouraged this study into the kinetics and mechanism of the interaction of 2-aminopyrimidine (2-NH2-Pym with dichloro-{1-alkyl-2-(α-naphthylazoimidazole}palladium(II [Pd(α-NaiRCl2, 1] and dichloro-{1-alkyl-2-(β-naphthylazoimidazole}palladium(II [Pd(β-NaiRCl2, 2] complexes where the alkyl R = Me (a, Et (b, or Bz (c. Results 2-NH2-Pym reacts with 1a, 1b, and 1c to yield [{1-alkyl-2-(α-naphthylazoimidazole}bis(2-aminopyrimidine]palladium(II (3a, 3b, 3c dichloride and with 2a, 2b, and 2c to yield [{1-alkyl-2-(β-naphthylazoimidazole}bis(2-aminopyrimidine]palladium(II (4a, 4b, 4c dichloride in an acetonitrile (MeCN medium. The products were characterized using spectroscopic techniques (FT-IR, UV-Vis, NMR. The ligand substitution reactions follow second order kinetics – first order dependence on the concentration of the Pd(II complex and 2-NH2-Pym. Addition of LiCl to the reaction does not influence its rate. The thermodynamic parameters (standard enthalpy of activation, Δ‡H° and standard entropy of activation, Δ‡S° were determined from variable temperature kinetic studies. The magnitude of the second order

Chemical Kinetic Influences of Alkyl Chain Structure on the High Pressure and Temperature Oxidation of a Representative Unsaturated Biodiesel: Methyl Nonenoate.

Science.gov (United States)

Fridlyand, Aleksandr; Goldsborough, S Scott; Brezinsky, Kenneth

2015-07-16

The high pressure and temperature oxidation of methyl trans-2-nonenoate, methyl trans-3-nonenoate, 1-octene, and trans-2-octene are investigated experimentally to probe the influence of the double bond position on the chemical kinetics of long esters and alkenes. Single pulse shock tube experiments are performed in the ranges p = 3.8-6.2 MPa and T = 850-1500 K, with an average reaction time of 2 ms. Gas chromatographic measurements indicate increased reactivity for trans-2-octene compared to 1-octene, whereas both methyl nonenoate isomers have reactivities similar to that of 1-octene. A difference in the yield of stable intermediates is observed for the octenes when compared to the methyl nonenoates. Chemical kinetic models are developed with the aid of the Reaction Mechanism Generator to interpret the experimental results. The models are created using two different base chemistry submodels to investigate the influence of the foundational chemistry (i.e., C0-C4), whereas Monte Carlo simulations are performed to examine the quality of agreement with the experimental results. Significant uncertainties are found in the chemistry of unsaturated esters with the double bonds located close to the ester groups. This work highlights the importance of the foundational chemistry in predictive chemical kinetics of biodiesel combustion at engine relevant conditions.

Actinide phosphonate complexes in aqueous solutions

International Nuclear Information System (INIS)

Nash, K.L.

1993-01-01

Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO 3 H 2 ) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described

Study on synthesis, kit formulation and chemical kinetics of dissociation of 99mTc labeled PnAO biotin complex

International Nuclear Information System (INIS)

Afshan, A.; Jafri, S.R.A.; Maecke, H.

2004-01-01

Full text: A bifunctional ligand of PnAO-biotin has recently been synthesized, with a better percentage yield of 63% in the presence of newly developed coupling agent 0-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexaflorophos phate (HATU). Then lyophilized kit with 150μg of PnAObiotin has been developed and labeled with high specific activity of technetium-99m (2500-3000MBq) to get maximum radiochemical purity of 99mTc-PnAO-biotin complex i.e. > 97%. The association of avidin and streptavidin is among the strongest known non-covalent protein ligand interaction Ka 1015 M-1 and 1013 M-1 respectively. We measured the dissociation rate constant of PnAO-biotin from avidin and streptavidin challenged with excess of cold biotin. For the separation of bound and free-labeled biotin we employed ultrafilteration technique. The results of these experiments demonstrated that the non-covalent binding between 99mTc-PnAO-biotin with avidin and 99mTc-PnAO-biotin with streptavidin is more than 99%. Both biotin-binding proteins exhibited a faster initial phase and the rate of dissociation of 99mTc-PnAO-biotin with avidin is found to be 8.2x10-8 at 250C and 2.6x10-7 at 370C while the rate of dissociation 99mTc-PnAO-biotin from streptavidin is found to be 6x10-7 at 250C and 1.06x10-6 at 370C. The in-vitro study of the kinetics of dissociation exhibits the strong interaction of 99mTc-PnAO-biotin complex with both proteins, which suggests that this bifunctional PnAO-biotin ligand can be used for tumor localization with monoclonal antibodies to achieve high tumor to non-tumor ratio. (author)

Comparison of different chemical kinetic mechanisms of methane combustion in an internal combustion engine configuration

OpenAIRE

Ennetta Ridha; Hamdi Mohamed; Said Rachid

2008-01-01

Three chemical kinetic mechanisms of methane combustion were tested and compared using the internal combustion engine model of Chemkin 4.02 [1]: one-step global reaction mechanism, four-step mechanism, and the standard detailed scheme GRIMECH 3.0. This study shows good concordances, especially between the four-step and the detailed mechanisms in the prediction of temperature and main species profiles. But reduced schemes were incapables to predict pollutant emissions in an internal combustion...

CHMTRNS, Non-Equilibrium Chemical Transport Code

International Nuclear Information System (INIS)

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

1998-01-01

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

Stochastic chemical kinetics theory and (mostly) systems biological applications

CERN Document Server

Érdi, Péter; Lente, Gabor

2014-01-01

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

Simultaneous determination of thermodynamic and kinetic parameters of aminopolycarbonate complexes of cobalt(II) and nickel(II) based on isothermal titration calorimetry data.

Science.gov (United States)

Tesmar, Aleksandra; Wyrzykowski, Dariusz; Muñoz, Eva; Pilarski, Bogusław; Pranczk, Joanna; Jacewicz, Dagmara; Chmurzyński, Lech

2017-04-01

The influence of the different side chain residues on the thermodynamic and kinetic parameters for complexation reactions of the Co 2 + and Ni 2 + ions has been investigated by using the isothermal titration calorimetry (ITC) technique supported by potentiometric titration data. The study was concerned with the 2 common tripodal aminocarboxylate ligands, namely, nitrilotriacetic acid and N-(2-hydroxyethyl) iminodiacetic acid. Calorimetric measurements (ITC) were run in the 2-(N-morpholino)ethanesulfonic acid hydrate (2-(N-morpholino) ethanesulfonic acid), piperazine-N,N'-bis(2-ethanesulfonic acid), and dimethylarsenic acid buffers (0.1 mol L -1 , pH 6) at 298.15 K. The quantification of the metal-buffer interactions and their incorporation into the ITC data analysis enabled to obtain the pH-independent and buffer-independent thermodynamic parameters (K, ΔG, ΔH, and ΔS) for the reactions under study. Furthermore, the kinITC method was applied to obtain kinetic information on complexation reactions from the ITC data. Correlations, based on kinetic and thermodynamic data, between the kinetics of formation of Co 2 + and Ni 2 + complexes and their thermodynamic stabilities are discussed. Copyright © 2016 John Wiley & Sons, Ltd.

Kinetics of methane fermentation yield in biogas reactors: Genetic variation and association with chemical composition in maize

International Nuclear Information System (INIS)

Grieder, Christoph; Mittweg, Greta; Dhillon, Baldev S.; Montes, Juan M.; Orsini, Elena; Melchinger, Albrecht E.

2012-01-01

Maize (Zea mays L.) is the most competitive crop for methane production in Germany. Methane fermentation yield per unit of dry matter (MFY) is a determinant of methane yield, but little information is available on this trait. Our objectives were to investigate the kinetics of MFY during fermentation of maize, estimate quantitative-genetic parameters for different traits related to MFY and examine the relationship of MFY with chemical composition and silage quality. Whole-plant material of 16 inbreds and their 32 testcrosses was analyzed for MFY over 35 days of fermentation using a discontinuous laboratory assay. Data were also generated on chemical composition and in vitro digestible organic matter (IVDOM). Significant genotypic variances and high heritabilities were observed for MFY at early fermentation stages (up to 5 days) probably due to different concentrations of easily degradable chemical components. However, genotypic variances and heritability of MFY reduced as fermentation progressed, because of complete or partial degradation of all chemical components. Further, there were strong correlations of MFY with chemical components at early fermentation stages but not at later stages. Therefore, MFY at later stages, which is closer to potential MFY, does not seem to be amenable to selection. High heritability of IVDOM and its strong correlation with MFY in testcrosses indicated its possible use for preliminary or indirect selection. Keeping in view the magnitude of genetic variance that was low for MFY and high for dry matter yield (DMY), the other component of methane yield, more emphasis on breeding for DMY seems appropriate. -- Highlights: ► We investigated methane fermentation yield (MFY) of diverse germplasm of maize. ► The kinetics of MFY and its correlations with chemical composition were examined. ► Genetic variance and heritability for MFY decreased with fermentation time. ► Complete fermentation (35 d) reduced correlations of MFY with chemical

Coordination kinetics of different metal ions with the amidoximated polyacrylonitrile nanofibrous membranes and catalytic behaviors of their complexes

Energy Technology Data Exchange (ETDEWEB)

Li, Fu; Dong, Yong Chun; Kang, Wei Min; Cheng, Bowen; Qu, Xiang; Cui, Guixin [School of Textiles, Tianjin Polytechnic University, Tianjin (China)

2016-12-15

Two transition metal ions (Fe{sup 3+} and Cu{sup 2+}) and a rare earth metal ion (Ce{sup 3+}) were selected to coordinate with amidoximated polyacrylonitrile (PAN) nanofibrous membrane for preparing three metal modified PAN nanofibrous membrane complexes (M-AO-n-PANs, M = Fe, Cu, or Ce) as the heterogeneous Fenton catalysts for the dye degradation in water under visible irradiation. The coordination kinetics of three metal ions with modified PAN nanofibrous membranes was studied and the catalytic properties of the resulting complexes were also compared. The results indicated that increasing metal ion concentrations in solution or higher coordination temperature led to a significant increase in metal content, particularly in Fe and Cu contents of the complexes. Their coordination process could be described using Langmuir isotherm and pseudo-second-order kinetic equations. Moreover, Fe-AO-n-PAN had the best photocatalytic efficiency for the dye degradation in acidic medium, but a lower photocatalytic activity than Cu-AO-n-PAN in alkali medium.

Determination of rhenium in ores of complex composition by the kinetic method

Energy Technology Data Exchange (ETDEWEB)

Pavlova, L G; Gurkina, T V [Kazakhskij Gosudarstvennyj Univ., Alma-Ata (USSR); Tsentral' naya Lab. Yuzhno-Kazakhstanskogo Geologicheskogo Upravleniya, Alma-Ata (USSR))

1979-09-01

The kinetic rhenium determination method is proposed based on rhenium catalytic effect in the reaction of malachite green with thiourea. The accompanying elements, excluding molybdenum, do not interfere with the rhenium determination at their concentration of up to 0.1 M. The interfering influence of molybdenum can be eliminated by addition of tartaric acid to the solution up to the concentration of 0.1 M. This enables to determine rhenium in presence of 1000-fold quantity of molybdenum. The method is applicable for the analysis of complex copper-zinc sulphide ores.

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

Science.gov (United States)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

A CHEMICAL KINETICS NETWORK FOR LIGHTNING AND LIFE IN PLANETARY ATMOSPHERES

International Nuclear Information System (INIS)

Rimmer, P. B.; Helling, Ch

2016-01-01

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 CO 2 , H 2 , CO, and O 2 , 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.

A CHEMICAL KINETICS NETWORK FOR LIGHTNING AND LIFE IN PLANETARY ATMOSPHERES

Energy Technology Data Exchange (ETDEWEB)

Rimmer, P. B.; Helling, Ch, E-mail: pr33@st-andrews.ac.uk [School of Physics and Astronomy, University of St Andrews, St Andrews, KY16 9SS (United Kingdom)

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 CO{sub 2}, H{sub 2}, CO, and O{sub 2}, 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.

Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

Energy Technology Data Exchange (ETDEWEB)

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

1998-12-31

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

Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Ligand sphere conversions in terminal carbide complexes

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

2016-01-01

Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first...... example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also...... demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction...

Use of Measured Species Class Concentrations with Chemical Kinetic Modeling for the Prediction of Autoxidation and Deposition of Jet Fuels (Postprint)

National Research Council Canada - National Science Library

Kuprowicz, Nicholas J; Zabarnick, Steven; West, Zachary J; Ervin, Jamie S

2007-01-01

.... In the present work, a chemical kinetic mechanism developed previously is refined to include the roles of key fuel species classes, such as phenols, reactive sulfur species, dissolved metals, and hydroperoxides...

Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

Science.gov (United States)

Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

2016-04-01

Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

Directory of Open Access Journals (Sweden)

Junfeng Yang

2012-01-01

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

Hybrid framework for the simulation of stochastic chemical kinetics

International Nuclear Information System (INIS)

Duncan, Andrew; Erban, Radek; Zygalakis, Konstantinos

2016-01-01

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.

Hybrid framework for the simulation of stochastic chemical kinetics

Science.gov (United States)

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.

Hybrid framework for the simulation of stochastic chemical kinetics

Energy Technology Data Exchange (ETDEWEB)

Duncan, Andrew, E-mail: a.duncan@imperial.ac.uk [Department of Mathematics, Imperial College, South Kensington Campus, London, SW7 2AZ (United Kingdom); Erban, Radek, E-mail: erban@maths.ox.ac.uk [Mathematical Institute, University of Oxford, Radcliffe Observatory Quarter, Woodstock Road, Oxford, OX2 6GG (United Kingdom); Zygalakis, Konstantinos, E-mail: k.zygalakis@ed.ac.uk [School of Mathematics, University of Edinburgh, Peter Guthrie Tait Road, Edinburgh, EH9 3FD (United Kingdom)

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.

Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

International Nuclear Information System (INIS)

Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

2009-01-01

Stirred-flow cell experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments

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

Science.gov (United States)

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

2016-07-27

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

The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

Science.gov (United States)

Doktorov, Alexander B

2015-08-21

Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

Sorption kinetics and microbial biodegradation activity of hydrophobic chemicals in sewage sludge: Model and measurements based on free concentrations

NARCIS (Netherlands)

Artola-Garicano, E.; Borkent, I.; Damen, K.; Jager, T.; Vaes, W.H.J.

2003-01-01

In the current study, a new method is introduced with which the rate-limiting factor of biodegradation processes of hydrophobic chemicals in organic and aqueous systems can be determined. The novelty of this approach lies in the combination of a free concentration-based kinetic model with

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Science.gov (United States)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation

Chemical Editing of Macrocyclic Natural Products and Kinetic Profiling Reveal Slow, Tight-Binding Histone Deacetylase Inhibitors with Picomolar Affinities

DEFF Research Database (Denmark)

Kitir, Betül; Maolanon, Alex R.; Ohm, Ragnhild G.

2017-01-01

medicines. Therefore, detailed mechanistic information and precise characterization of the chemical probes used to investigate the effects of HDAC enzymes are vital. We interrogated Nature's arsenal of macrocyclic nonribosomal peptide HDAC inhibitors by chemical synthesis and evaluation of more than 30...... natural products and analogues. This furnished surprising trends in binding affinities for the various macrocycles, which were then exploited for the design of highly potent class I and IIb HDAC inhibitors. Furthermore, thorough kinetic investigation revealed unexpected inhibitory mechanisms of important...

Exact results in nonequilibrium statistical mechanics: Formalism and applications in chemical kinetics and single-molecule free energy estimation

Science.gov (United States)

Adib, Artur B.

In the last two decades or so, a collection of results in nonequilibrium statistical mechanics that departs from the traditional near-equilibrium framework introduced by Lars Onsager in 1931 has been derived, yielding new fundamental insights into far-from-equilibrium processes in general. Apart from offering a more quantitative statement of the second law of thermodynamics, some of these results---typified by the so-called "Jarzynski equality"---have also offered novel means of estimating equilibrium quantities from nonequilibrium processes, such as free energy differences from single-molecule "pulling" experiments. This thesis contributes to such efforts by offering three novel results in nonequilibrium statistical mechanics: (a) The entropic analog of the Jarzynski equality; (b) A methodology for estimating free energies from "clamp-and-release" nonequilibrium processes; and (c) A directly measurable symmetry relation in chemical kinetics similar to (but more general than) chemical detailed balance. These results share in common the feature of remaining valid outside Onsager's near-equilibrium regime, and bear direct applicability in protein folding kinetics as well as in single-molecule free energy estimation.

Kinetic Study of the Chemical Vapor Deposition of Tantalum in Long Narrow Channels

DEFF Research Database (Denmark)

Mugabi, James Atwoki; Eriksen, Søren; Petrushina, Irina

2016-01-01

A kinetic study of the chemical vapor deposition of tantalum in long narrow channels is done to optimize the industrial process for the manufacture of tantalum coated plate heat exchangers. The developed model fits well at temperatures between 750 and 850 °C, and in the pressure range of25–990 mbar....... According to the model, the predominant tantalum growth species is TaCl3. The temperature is shown to have a pronounced effect onthe morphology and rate of deposition of the tantalum and an apparent change in deposition mechanism occurs between 850–900 °C, resulting in the deposition rate at 900 °C being...

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

Science.gov (United States)

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

2013-01-01

unexplored intermediate temperature combustion pathways of 25DMF. Hydroxyl radical addition to the furan ring is highlighted as an important fuel consuming reaction, leading to the formation of methyl vinyl ketone and acetyl radical. The chemically activated recombination of HȮ2 or CH3Ȯ2 with the 5-methyl-2-furanylmethyl radical, forming a 5-methyl-2-furylmethanoxy radical and ȮH or CH3Ȯ radical is also found to exhibit significant control over ignition delay times, as well as being important reactions in the prediction of species profiles in a JSR. Kinetics for the abstraction of a hydrogen atom from the alkyl side-chain of the fuel by molecular oxygen and HȮ2 radical are found to be sensitive in the estimation of ignition delay times for fuel-air mixtures from temperatures of 820–1200 K. At intermediate temperatures, the resonantly stabilised 5-methyl-2-furanylmethyl radical is found to predominantly undergo bimolecular reactions, and as a result sub-mechanisms for 5-methyl-2-formylfuran and 5-methyl-2-ethylfuran, and their derivatives, have also been developed with consumption pathways proposed. This study is the first to attempt to simulate the combustion of these species in any detail, although future refinements are likely necessary. The current study illustrates both quantitatively and qualitatively the complex chemical behavior of what is a high potential biofuel. Whilst the current work is the most comprehensive study on the oxidation of 25DMF in the literature to date, the mechanism cannot accurately reproduce laminar burning velocity measurements over a suitable range of unburnt gas temperatures, pressures and equivalence ratios, although discrepancies in the experimental literature data are highlighted. Resolving this issue should remain a focus of future work. PMID:24273333

Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition.

Science.gov (United States)

Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

2015-02-05

A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

International Nuclear Information System (INIS)

Doktorov, Alexander B.

2015-01-01

Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

Energy Technology Data Exchange (ETDEWEB)

Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

2015-08-21

Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

KAUST Repository

Kuti, Olawole

2014-04-01

Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68 species and 283 reactions) were implemented in the CONVERGE CFD to simulate the spray and combustion processes of the two fuels. Tetradecane (C14H30) and n- heptane (C7H 16) were used as surrogates for diesel. For the palm biodiesel, the mixture of methyl decanoate (C11H20O2), methyl-9-decenoate (C11H19O2) and n-heptane was used as surrogate. The palm biodiesel surrogates were combined in proportions based on the previous GC-MS results for the five major biodiesel components namely methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate. The Favre-Averaged Navier Stokes based simulation using the renormalization group (RNG) k-ε turbulent model was implemented in the numerical calculations of the spray formation processes while the SAGE chemical kinetic solver is used for the detailed kinetic modeling. The SAGE chemical kinetic solver is directly coupled with the gas phase calculations by renormalization group (RNG) k-ε turbulent model using a well-stirred reactor model. Validations of the spray liquid length, ignition delay and flame lift-off length data were performed against previous experimental results. The simulated liquid length, ignition delay and flame lift-off length were validated at an ambient density of 15kg/m3, and injection pressure conditions of 100, 200 and 300 MPa were utilized. The predicted liquid length, ignition delay and flame lift-off length agree with the trends obtained in the experimental data at all injection conditions. Copyright © 2014 SAE International.

Studies on the ruthenium complexes. IX. Kinetic studies on the deaquation-anation reaction of aquapentaammineruthenium(III) complexes

Energy Technology Data Exchange (ETDEWEB)

Ohyoshi, A; Hiraki, S I; Odate, T; Kohata, S; Oda, J [Kumamoto Univ. (Japan). Faculty of Engineering

1975-01-01

The deaquation-anation reaction of (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/-type complexes in the solid state, as shown by the (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/(s)..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/(s)+H/sub 2/O(g) equation, where X is Cl, Br, I, and NO/sub 3/ respectively, was kinetically studied by means of thermogravimetry (TG) along with differential thermal analysis (DTA). The activation energy and entropy in the reaction process (Esub(a) kcal/mol, ..delta..S c.u.) are, respectively, found by isothermal kinetic study to be (22.7, - 7.1) for the chloride, (23.4, - 5.2) for the bromide, (26.7, 5.8) for the iodide, and (19.3 - 15.9) for the nitrate. The reaction seems to proceed through the following two steps, except in the case of the iodide: (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/..-->..(RuX(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 2/..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/+H/sub 2/O. The first step is regarded as the rate-determining one.

Chemical kinetic functional sensitivity analysis: Elementary sensitivities

International Nuclear Information System (INIS)

Demiralp, M.; Rabitz, H.

1981-01-01

Sensitivity analysis is considered for kinetics problems defined in the space--time domain. This extends an earlier temporal Green's function method to handle calculations of elementary functional sensitivities deltau/sub i//deltaα/sub j/ where u/sub i/ is the ith species concentration and α/sub j/ is the jth system parameter. The system parameters include rate constants, diffusion coefficients, initial conditions, boundary conditions, or any other well-defined variables in the kinetic equations. These parameters are generally considered to be functions of position and/or time. Derivation of the governing equations for the sensitivities and the Green's funciton are presented. The physical interpretation of the Green's function and sensitivities is given along with a discussion of the relation of this work to earlier research

Multi-GPU unsteady 2D flow simulation coupled with a state-to-state chemical kinetics

Science.gov (United States)

Tuttafesta, Michele; Pascazio, Giuseppe; Colonna, Gianpiero

2016-10-01

In this work we are presenting a GPU version of a CFD code for high enthalpy reacting flow, using the state-to-state approach. In supersonic and hypersonic flows, thermal and chemical non-equilibrium is one of the fundamental aspects that must be taken into account for the accurate characterization of the plasma and state-to-state kinetics is the most accurate approach used for this kind of problems. This model consists in writing a continuity equation for the population of each vibrational level of the molecules in the mixture, determining at the same time the species densities and the distribution of the population in internal levels. An explicit scheme is employed here to integrate the governing equations, so as to exploit the GPU structure and obtain an efficient algorithm. The best performances are obtained for reacting flows in state-to-state approach, reaching speedups of the order of 100, thanks to the use of an operator splitting scheme for the kinetics equations.

Kinetics and mechanisms of the oxidation of alcohols and hydroxylamines by hydrogen peroxide, catalyzed by methyltrioxorhenium, MTO, and the oxygen binding properties of cobalt Schiff base complexes

Energy Technology Data Exchange (ETDEWEB)

Zauche, Timothy [Iowa State Univ., Ames, IA (United States)

1999-02-12

Catalysis is a very interesting area of chemistry, which is currently developing at a rapid pace. A great deal of effort is being put forth by both industry and academia to make reactions faster and more productive. One method of accomplishing this is by the development of catalysts. Enzymes are an example of catalysts that are able to perform reactions on a very rapid time scale and also very specifically; a goal for every man-made catalyst. A kinetic study can also be carried out for a reaction to gain a better understanding of its mechanism and to determine what type of catalyst would assist the reaction. Kinetic studies can also help determine other factors, such as the shelf life of a chemical, or the optimum temperature for an industrial scale reaction. An area of catalysis being studied at this time is that of oxygenations. Life on this earth depends on the kinetic barriers for oxygen in its various forms. If it were not for these barriers, molecular oxygen, water, and the oxygenated materials in the land would be in a constant equilibrium. These same barriers must be overcome when performing oxygenation reactions on the laboratory or industrial scale. By performing kinetic studies and developing catalysts for these reactions, a large number of reactions can be made more economical, while making less unwanted byproducts. For this dissertation the activation by transition metal complexes of hydrogen peroxide or molecular oxygen coordination will be discussed.

Dehydration kinetics of boehmite in the temperature range 723–873 K

International Nuclear Information System (INIS)

Xu, Bingan; Smith, Peter

2012-01-01

Highlights: ► The dehydration of boehmite is a complex topotactic process. ► The process is chemical control with a diffusion complication as the reaction progresses. ► Al cation diffusion is the rate-limiting step. ► The reaction rates predicted by the model-free method agree well with the measured values. - Abstract: The dehydration kinetics of boehmite prepared from the hydrothermal transformation of gibbsite has been comprehensively studied to clarify the mechanism of the dehydration process using a thermogravimetric technique under both isothermal and non-isothermal conditions. Selected residues were examined by XRD, SEM, TEM and selected area electron diffraction (SAED). Results indicate that the dehydration process is a topotactic reaction which brings about γ-Al 2 O 3 with porous microstructure and poor crystallinity. The kinetic data were analysed using the model-free (isoconversional) methods. The results indicate that the activation energy of the dehydration process depends on the reaction extent, signifying the dehydration process is chemical controlled with a diffusion complication as the reaction extent increases. Prediction of the dehydration extent was accomplished using the kinetic parameter of the non-isothermal process and the isoconversional method. The predicted rate is in a reasonably good agreement with the measured values. Finally the mechanism of the dehydration process is discussed based on the auxiliary results from the physical examination of the reacted residues and the kinetic behaviour.

Genetic and chemical diversity of high mucilaginous plants of Sida complex by ISSR markers and chemical fingerprinting.

Science.gov (United States)

Thul, Sanjog T; Srivastava, Ankit K; Singh, Subhash C; Shanker, Karuna

2011-09-01

A method was developed based on multiple approaches wherein DNA and chemical analysis was carried out toward differentiation of important species of Sida complex that is being used for commercial preparation. Isolated DNA samples were successfully performed through PCR amplification using ISSR markers and degree of genetic diversity among the different species of Sida is compared with that of chemical diversity. For genetic fingerprint investigation, selected 10 ISSR primers generating reproducible banding patterns were used. Among the total of 63 amplicons, 62 were recorded as polymorphic, genetic similarity index deduced from ISSR profiles ranged from 12 to 51%. Based on similarity index, S. acuta and S. rhombifolia found to be most similar (51%). High number of species-specific bands played pivotal role to delineate species at genetic level. Investigation based on HPTLC fingerprints analysis revealed 23 bands representing to characteristic chemicals and similarity index ranged from 73 to 91%. Prominent distinguishable bands were observed only in S. acuta, while S. cordifolia and S. rhombifolia shared most bands making them difficult to identify on chemical fingerprint basis. This report summarizes the genotypic and chemotypic diversity and the use of profiles for authentication of species of Sida complex.

A comparison of different methods for predicting coal devolatilisation kinetics

Energy Technology Data Exchange (ETDEWEB)

Arenillas, A.; Rubiera, F.; Pevida, C.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

2001-04-01

Knowledge of the coal devolatilisation rate is of great importance because it exerts a marked effect on the overall combustion behaviour. Different approaches can be used to obtain the kinetics of the complex devolatilisation process. The simplest are empirical and employ global kinetics, where the Arrhenius expression is used to correlate rates of mass loss with temperature. In this study a high volatile bituminous coal was devolatilised at four different heating rates in a thermogravimetric analyser (TG) linked to a mass spectrometer (MS). As a first approach, the Arrhenius kinetic parameters (k and A) were calculated from the experimental results, assuming a single step process. Another approach is the distributed-activation energy model, which is more complex due to the assumption that devolatilisation occurs through several first-order reactions, which occur simultaneously. Recent advances in the understanding of coal structure have led to more fundamental approaches for modelling devolatilisation behaviour, such as network models. These are based on a physico-chemical description of coal structure. In the present study the FG-DVC (Functional Group-Depolymerisation, Vaporisation and Crosslinking) computer code was used as the network model and the FG-DVC predicted evolution of volatile compounds was compared with the experimental results. In addition, the predicted rate of mass loss from the FG-DVC model was used to obtain a third devolatilisation kinetic approach. The three methods were compared and discussed, with the experimental results as a reference.

Computational Analyses of Complex Flows with Chemical Reactions

Science.gov (United States)

Bae, Kang-Sik

The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic

Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

OpenAIRE

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and concentration profiles for a wide range of processes and conditions, for both film and penetration model. With the aid of this mass transfer model it is demonstrated that the absorption rates in syst...

Quantum chemical prediction of antennae structures in lanthanide complexes

International Nuclear Information System (INIS)

Ottonelli, M.; Musso, G.F.; Rizzo, F.; Dellepiane, G.; Porzio, W.; Destri, S.

2008-01-01

In this paper the quantum chemical semiempirical procedure recently proposed by us to predict ground- and excited-state geometries of lanthanide complexes, the pseudo coordination centre method (PCC), is preliminarily compared with the semiempirical sparkle model for the calculation of lanthanide complexes (SMLC). Contrary to the SMLC method, where the rare-earth ion is replaced by a reparameterized sparkle atom, in our approach we replace it with a metal ion which is already present in the chosen semiempirical parameterization. This implies that in the optimization of the geometry of the complexes a different weight is implicitly given to the complex region including the rare-earth ion and its neighbour atoms with respect to the region of the ligands aggregate. As a consequence our approach is expected to reproduce better than the SMLC one the geometry of the ligands aggregate embedded in the complex, while the contrary happens for the coordination distances

Echinacea complex--chemical view and anti-asthmatic profile.

Science.gov (United States)

Šutovská, Martina; Capek, Peter; Kazimierová, Ivana; Pappová, Lenka; Jošková, Marta; Matulová, Mária; Fraňová, Soňa; Pawlaczyk, Izabela; Gancarz, Roman

2015-12-04

Echinacea purpurea (L.) Moench is one of the mostly used herbs in the traditional medicine for the treatment of respiratory diseases. Modern interest in Echinacea is directed to its immunomodulatory activity. Recent studies have shown that secretion of asthma-related cytokines in the bronchial epithelial cells can be reversed by Echinacea preparations. To examine the pharmacodynamics profile of Echinacea active principles, a complex has been isolated from its flowers by alkaline extraction and has been tested using an animal model of allergic asthma. The structural features of Echinacea purpurea complex was determined using chemical and spectroscopic methods. Allergic inflammation of the airways was induced by repetitive exposure of guinea pigs to ovalbumin. Echinacea complex was then administered 14 days in 50mg/kg b.w. daily dose perorally. Bronchodilatory effect was verified as decrease in the specific airway resistance (sRaw) in vivo and by reduced contraction amplitude (mN) of tracheal and pulmonary smooth muscle to cumulative concentrations of acetylcholine and histamine in vitro. The impact on mucociliary clearance evaluated measurement of ciliary beat frequency (CBF) in vitro using LabVIEW™ Software. Anti-inflammatory effect of Echinacea complex was verified by changes in exhaled NO levels and by Bio-Plex® assay of Th2 cytokine concentrations (IL-4, IL-5, IL-13 and TNF-alpha) in serum and bronchoalveolar lavage fluid (BALF). Chemical and spectroscopic studies confirmed the presence of carbohydrates, phenolic compounds and proteins, as well as the dominance of rhamnogalacturonan and arabinogalactan moieties in Echinacea complex. The significant decrease in sRaw values and suppressed histamine and acetylcholine-induced contractile amplitude of isolated airways smooth muscle that were similar to effects of control drug salbutamol confirmed Echinacea complex bronchodilatory activity. The anti-inflammatory effect was comparable with that of control agent

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

Directory of Open Access Journals (Sweden)

Jun-Xia Zhang

2016-03-01

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

Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition

Czech Academy of Sciences Publication Activity Database

Asadi, M.; Asadi, Z.; Savaripoor, N.; Dušek, Michal; Eigner, Václav; Shorkaei, M.R.; Sedaghat, M.

2015-01-01

Roč. 136, Feb (2015), 625-634 ISSN 1386-1425 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : Oxovanadium(IV) complexes * Schiff base * Kinetic s of thermal decomposition * Electrochemistry Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.653, year: 2015

Structure, Dynamics, and Kinetics of Weak Protein-Protein Complexes from NMR Spin Relaxation Measurements of Titrated Solutions

International Nuclear Information System (INIS)

Salmon, L.; Licinio, A.; Jensen, M.R.; Blackledge, M.; Ortega Roldan, J.L.; Van Nuland, N.; Lescop, E.

2011-01-01

We have recently presented a titration approach for the determination of residual dipolar couplings (RDCs) from experimentally inaccessible complexes. Here, we extend this approach to the measurement of 15 N spin relaxation rates and demonstrate that this can provide long-range structural, dynamic, and kinetic information about these elusive systems. (authors)

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

Science.gov (United States)

Castonguay, Thomas C; Wang, Feng

2008-03-28

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.

The kinetics of lanthanide complexation by EDTA and DTPA in lactate media.

Science.gov (United States)

Nash, K L; Brigham, D; Shehee, T C; Martin, A

2012-12-28

The interaction of trivalent lanthanide and actinide cations with polyaminopolycarboxylic acid complexing agents in lactic acid buffer systems is an important feature of the chemistry of the TALSPEAK process for the separation of trivalent actinides from lanthanides. To improve understanding of metal ion coordination chemistry in this process, the results of an investigation of the kinetics of lanthanide complexation by ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) and diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) in 0.3 M lactic acid/0.3 M ionic strength solution are reported. Progress of the reaction was monitored using the distinctive visible spectral changes attendant to lanthanide complexation by the colorimetric indicator ligand Arsenazo III, which enables the experiment but plays no mechanistic role. Under the conditions of these experiments, the reactions occur in a time regime suitable for study by stopped-flow spectrophotometric techniques. Experiments have been conducted as a function of EDTA/DTPA ligand concentration, total lactic acid concentration, and pH. The equilibrium perturbation reaction proceeds as a first order approach to equilibrium over a wide range of conditions, allowing the simultaneous determination of complex formation and dissociation rate constants. The rate of the complexation reaction has been determined for the entire lanthanide series (except Pm(3+)). The predominant pathway for lanthanide-EDTA and lanthanide-DTPA dissociation is inversely dependent on the total lactate concentration; the complex formation reaction demonstrates a direct dependence on [H(+)]. Unexpectedly, the rate of the complex formation reaction is seen in both ligand systems to be fastest for Gd(3+). Correlation of these results indicates that in 0.3 M lactate solutions the exchange of lanthanide ions between lactate complexes and the polyaminopolycarboxylate govern the process.

Ozone mass transfer and kinetics experiments

International Nuclear Information System (INIS)

Bollyky, L.J.; Beary, M.M.

1981-12-01

Experiments were conducted at the Hanford Site to determine the most efficient pH and temperature levels for the destruction of complexants in Hanford high-level defense waste. These complexants enhance migration of radionuclides in the soil and inhibit the growth of crystals in the evaporator-crystallizer. Ozone mass transfer and kinetics tests have been outlined for the determination of critical mass transfer and kinetics parameters of the ozone-complexant reaction

Parametric Investigation of the Isothermal Kinetics of Growth of Graphene on a Nickel Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

Science.gov (United States)

Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

2016-11-01

A kinetic model of isothermal synthesis of multilayer graphene on the surface of a nickel foil in the process of chemical vapor deposition, on it, of hydrocarbons supplied in the pulsed regime is considered. The dependences of the number of graphene layers formed and the time of their growth on the temperature of the process, the concentration of acetylene, and the thickness of the nickel foil were calculated. The regime parameters of the process of chemical vapor deposition, at which single-layer graphene and bi-layer graphene are formed, were determined. The dynamics of growth of graphene domains at chemical-vapor-deposition parameters changing in wide ranges was investigated. It is shown that the time dependences of the rates of growth of single-layer graphene and bi-layer graphene are nonlinear in character and that they are determined by the kinetics of nucleation and growth of graphene and the diffusion flow of carbon atoms in the nickel foil.

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

Science.gov (United States)

Curl, Robert F.; Glass, Graham P.

2004-11-01

This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

Chemical Kinetic Modeling of 2-Methylhexane Combustion

KAUST Repository

Mohamed, Samah Y.; Sarathy, Mani

2015-01-01

necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values

Formulation, radiopharmaceutical kinetics and dosimetry of the {sup 188}Re(V)-DMSA complex; Formulacion, radiofarmacocinetica y dosimetria del complejo {sup 188}Re(V)-DMSA

Energy Technology Data Exchange (ETDEWEB)

Garcia S, L; Ferro F, G [Departamento de Materiales Radiactivos. Instituto Nacional de Investigaciones Nucleares, C.P. 52045 Salazar, Estado de Mexico (Mexico); Murphy, C.A. de; Pedraza L, M [Departamento de Medicina Nuclear, Instituto Nacional de la Nutricion, Salvador Zubiran, Mexico D.F. (Mexico); Azorin N, J [Departamento de Fisica, Universidad Autonoma Metropolitana Iztapalapa, Mexico D.F. (Mexico)

1999-07-01

It was developed through experimental design (ANOVA), a formulation to prepare the {sup 188} Re(V)-Dmsa complex. Likewise, there were realized studies of radiopharmaceutical kinetics and internal dosimetry in animals, its normal and with induced tumors, considering an open bi compartmental model using the MIRD methodology. The {sup 188} Re(V)-Dmsa complex was obtained with a radiochemical purity greater than 95% incubating 30 min at 90 Centigrade under the following formulation: [SnCl{sub 2}] = 1.4 mg/ml, [ascorbic acid] = 0.5 mg/ml, p H = 2.0 - 3.0. The stability test of the formulation, shows that after 48 h of its preparation, does not produce radiolytic degradation neither chemical decomposition. The radiopharmaceutical kinetics data show an average residence time 7.2h, velocity constant {alpha} = 0.6508h{sup -1} and {beta} = 0.1046 h{sup -1} with an apparent distribution volume 6.9 l. The main elimination via was renal and it was observed osseous caption with an accumulated activity 522.049 {+-} 62 MBq h (residence time 14.1094 {+-} 1.69h). In according with the dosimetric calculations, by each 37 MBq injected, the equivalent dose at the tumor was 9.67{+-} 0.33 Sv/g, for an effective dose 0.292 {+-} 0.0017 mSv/MBq. The images obtained in the gamma camera of the mice with induced tumors, show that do not have significant accumulation in the metabolic organs. The caption in bone and in tumors induced of the {sup 188} Re(V)-Dmsa complex, show its potential for be used as a palliative agent for pain in patients with osseous metastasis and in the treatment of tumors of soft tissue. (Author)

Dehydration kinetics of boehmite in the temperature range 723-873 K

Energy Technology Data Exchange (ETDEWEB)

Xu, Bingan, E-mail: bingan.xu@csiro.au [A.J. Parker Cooperative Research Centre for Integrated Hydrometallurgy Solutions, CSIRO Light Metals Flagship (Division of Process Science and Engineering), PO Box 7229, Karawara, WA 6152 (Australia); Smith, Peter [A.J. Parker Cooperative Research Centre for Integrated Hydrometallurgy Solutions, CSIRO Light Metals Flagship (Division of Process Science and Engineering), PO Box 7229, Karawara, WA 6152 (Australia)

2012-03-10

Highlights: Black-Right-Pointing-Pointer The dehydration of boehmite is a complex topotactic process. Black-Right-Pointing-Pointer The process is chemical control with a diffusion complication as the reaction progresses. Black-Right-Pointing-Pointer Al cation diffusion is the rate-limiting step. Black-Right-Pointing-Pointer The reaction rates predicted by the model-free method agree well with the measured values. - Abstract: The dehydration kinetics of boehmite prepared from the hydrothermal transformation of gibbsite has been comprehensively studied to clarify the mechanism of the dehydration process using a thermogravimetric technique under both isothermal and non-isothermal conditions. Selected residues were examined by XRD, SEM, TEM and selected area electron diffraction (SAED). Results indicate that the dehydration process is a topotactic reaction which brings about {gamma}-Al{sub 2}O{sub 3} with porous microstructure and poor crystallinity. The kinetic data were analysed using the model-free (isoconversional) methods. The results indicate that the activation energy of the dehydration process depends on the reaction extent, signifying the dehydration process is chemical controlled with a diffusion complication as the reaction extent increases. Prediction of the dehydration extent was accomplished using the kinetic parameter of the non-isothermal process and the isoconversional method. The predicted rate is in a reasonably good agreement with the measured values. Finally the mechanism of the dehydration process is discussed based on the auxiliary results from the physical examination of the reacted residues and the kinetic behaviour.

High-Pressure Turbulent Flame Speeds and Chemical Kinetics of Syngas Blends with and without Impurities

Energy Technology Data Exchange (ETDEWEB)

Peterson, Eric; Mathieu, Olivier; Morones, Anibal; Ravi, Sankar; Keesee, Charles; Hargis, Joshua; Vivanco, Jose

2014-12-01

This Topical Report documents the first year of the project, from October 1, 2013 through September 30, 2014. Efforts for this project included experiments to characterize the atmospheric-pressure turbulent flame speed vessel over a range of operating conditions (fan speeds and turbulent length scales). To this end, a new LDV system was acquired and set up for the detailed characterization of the turbulence field. Much progress was made in the area of impurity kinetics, which included a numerical study of the effect of impurities such as NO2, NO, H2S, and NH3 on ignition delay times and laminar flame speeds of syngas blends at engine conditions. Experiments included a series of laminar flame speed measurements for syngas (CO/H2) blends with various levels of CH4 and C2H6 addition, and the results were compared to the chemical kinetics model of NUI Galway. Also, a final NOx kinetics mechanism including ammonia was assembled, and a journal paper was written and is now in press. Overall, three journal papers and six conference papers related to this project were published this year. Finally, much progress was made on the design of the new high-pressure turbulent flame speed facility. An overall design that includes a venting system was decided upon, and the detailed design is in progress.

A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction

Science.gov (United States)

Sattsangi, Prem D.

2011-01-01

A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

Behaviour of intrinsically disordered proteins in protein-protein complexes with an emphasis on fuzziness

DEFF Research Database (Denmark)

Olsen, Johan Gotthardt; Teilum, Kaare; Kragelund, Birthe Brandt

2017-01-01

in their malleability, which enables them to bind several different partners with high specificity. In addition, their interactions with other macromolecules can be regulated by a variable amount of chemically diverse post-translational modifications. Four kinetically and energetically different types of complexes...

Uranium (VI) complexing by macrocyclic or chelating ligands in aqueous solutions stability, formation kinetics, polarographic properties

International Nuclear Information System (INIS)

Brighli, M.

1984-07-01

Stability of chelates (with EDTA,N,N ethylenediamine diacetic acid EDDA nitrilotriacetic acid NTA and iminodiacetic acid) of UO 2 2+ and UO 4 species of uranium VI is studied in aqueous solution (NaClO 4 3M at 25 deg celcius). Structure in solution are proposed and discussed for mononuclear species. Only complexing kinetics (formation and acid hydrolysis) of UO 4 with EDDA and NTA are studied by spectrophotometry (other reactions are too fast). Besides UO 2 2+ complexes are formed with crown ethers I5C5 and I8C6 in aqueous solution (TEA ClO 4 M/10 at 25 deg celcius. Complexes are probably stabilized by solvation. Results are confirmed by voltametry and reduction mechanisms of UO 2 2+ and its complexes on mercury drop are proposed. 143 refs [fr

The science conceptions of chemical textbooks addressed to the high school, in treatment of chemical kinetics during the period from 1929 to 2004

Directory of Open Access Journals (Sweden)

Maria Eunice Ribeiro Marcondes

2009-12-01

Full Text Available This text is a part of the work that was developed based on the chemical kinetic theme and the target was how the scientific knowledge in this subject was used for high school textbooks, identifying the possible ideas about science related to these books. For that, based on the research developed by Níaz (1994 that used categories to represent the philosophical perspectives: the empirical/inductive and the rationalist, verifying which and how the concepts of science was inserted in the 20 Brazilians textbooks, edited in the period from 1929 to 2004.

An integrated fingerprinting and kinetic approach to accelerated shelf-life testing of chemical changes in thermally treated carrot puree.

Science.gov (United States)

Kebede, Biniam T; Grauwet, Tara; Magpusao, Johannes; Palmers, Stijn; Michiels, Chris; Hendrickx, Marc; Loey, Ann Van

2015-07-15

To have a better understanding of chemical reactions during shelf-life, an integrated analytical and engineering toolbox: "fingerprinting-kinetics" was used. As a case study, a thermally sterilised carrot puree was selected. Sterilised purees were stored at four storage temperatures as a function of time. Fingerprinting enabled selection of volatiles clearly changing during shelf-life. Only these volatiles were identified and studied further. Next, kinetic modelling was performed to investigate the suitability of these volatiles as quality indices (markers) for accelerated shelf-life testing (ASLT). Fingerprinting enabled selection of terpenoids, phenylpropanoids, fatty acid derivatives, Strecker aldehydes and sulphur compounds as volatiles clearly changing during shelf-life. The amount of Strecker aldehydes increased during storage, whereas the rest of the volatiles decreased. Out of the volatiles, based on the applied kinetic modelling, myristicin, α-terpinolene, β-pinene, α-terpineol and octanal were identified as potential markers for ASLT. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetics and mechanism of reduction of iron(iii) kojic acid complex by hydroquinone and l-cysteine

International Nuclear Information System (INIS)

Hussain, Z.; Perviaz, M.; Kazmi, S.A.; Johnson, A.S.; Offiong, O.E.

2014-01-01

The effect of pH on the kinetics of reduction of iron(III) kojic acid complex by hydroquinone (H/sub 2/Q) and L-cysteine (L-Cys) was studied in the pH range of 2.34 - 4.03 for H/sub 2/Q and 3.04 - 5.5 for L-cysteine at ionic strength of 0.5 M and at 35 degree C. The pseudo-first order rate constants for the reduction of Fe(KA)3 by L-cysteine and hydroquinone increase linearly with increasing reductant concentration, indicating first-order kinetics in reductant concentration. However, whereas the rate of reduction by H2Q increases with increasing pH, an opposite trend was observed in the case of reduction by L-cysteine. Plausible rate laws and mechanisms have been proposed in line with these observations. Activation parameters (delta H no and delta S no) were evaluated for the reduction of iron (III) kojic acid complex by cysteine and the values obtained are 35.25 kJmol-1, -141.4 JK-1mol-1 and 28.14 kJmol-1 , 161.2 JK-1mol-1 for pH 4.5 and 3.52 respectively. (author)

The Control Based on Internal Average Kinetic Energy in Complex Environment for Multi-robot System

Science.gov (United States)

Yang, Mao; Tian, Yantao; Yin, Xianghua

In this paper, reference trajectory is designed according to minimum energy consumed for multi-robot system, which nonlinear programming and cubic spline interpolation are adopted. The control strategy is composed of two levels, which lower-level is simple PD control and the upper-level is based on the internal average kinetic energy for multi-robot system in the complex environment with velocity damping. Simulation tests verify the effectiveness of this control strategy.

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

Science.gov (United States)

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.

Reduced Gasoline Surrogate (Toluene/n-Heptane/iso-Octane) Chemical Kinetic Model for Compression Ignition Simulations

KAUST Repository

Sarathy, Mani; Atef, Nour; Alfazazi, Adamu; Badra, Jihad; Zhang, Yu; Tzanetakis, Tom; Pei, Yuanjiang

2018-01-01

Toluene primary reference fuel (TPRF) (mixture of toluene, iso-octane and heptane) is a suitable surrogate to represent a wide spectrum of real fuels with varying octane sensitivity. Investigating different surrogates in engine simulations is a prerequisite to identify the best matching mixture. However, running 3D engine simulations using detailed models is currently impossible and reduction of detailed models is essential. This work presents an AramcoMech reduced kinetic model developed at King Abdullah University of Science and Technology (KAUST) for simulating complex TPRF surrogate blends. A semi-decoupling approach was used together with species and reaction lumping to obtain a reduced kinetic model. The model was widely validated against experimental data including shock tube ignition delay times and premixed laminar flame speeds. Finally, the model was utilized to simulate the combustion of a low reactivity gasoline fuel under partially premixed combustion conditions.

Reduced Gasoline Surrogate (Toluene/n-Heptane/iso-Octane) Chemical Kinetic Model for Compression Ignition Simulations

KAUST Repository

Sarathy, Mani

2018-04-03

Toluene primary reference fuel (TPRF) (mixture of toluene, iso-octane and heptane) is a suitable surrogate to represent a wide spectrum of real fuels with varying octane sensitivity. Investigating different surrogates in engine simulations is a prerequisite to identify the best matching mixture. However, running 3D engine simulations using detailed models is currently impossible and reduction of detailed models is essential. This work presents an AramcoMech reduced kinetic model developed at King Abdullah University of Science and Technology (KAUST) for simulating complex TPRF surrogate blends. A semi-decoupling approach was used together with species and reaction lumping to obtain a reduced kinetic model. The model was widely validated against experimental data including shock tube ignition delay times and premixed laminar flame speeds. Finally, the model was utilized to simulate the combustion of a low reactivity gasoline fuel under partially premixed combustion conditions.

Complexity in Evolutionary Processes

International Nuclear Information System (INIS)

Schuster, P.

2010-01-01

Darwin's principle of evolution by natural selection is readily casted into a mathematical formalism. Molecular biology revealed the mechanism of mutation and provides the basis for a kinetic theory of evolution that models correct reproduction and mutation as parallel chemical reaction channels. A result of the kinetic theory is the existence of a phase transition in evolution occurring at a critical mutation rate, which represents a localization threshold for the population in sequence space. Occurrence and nature of such phase transitions depend critically on fitness landscapes. The fitness landscape being tantamount to a mapping from sequence or genotype space into phenotype space is identified as the true source of complexity in evolution. Modeling evolution as a stochastic process is discussed and neutrality with respect to selection is shown to provide a major challenge for understanding evolutionary processes (author)

The importance of variables and parameters in radiolytic chemical kinetics modeling

International Nuclear Information System (INIS)

Piepho, M.G.; Turner, P.J.; Reimus, P.W.

1989-01-01

Many of the pertinent radiochemical reactions are not completely understood, and most of the associated rate constants are poorly characterized. To help identify the important radiochemical reactions, rate constants, species, and environmental conditions, an importance theory code, SWATS (Sensitivitiy With Adjoint Theory-Sparse version)-LOOPCHEM, has been developed for the radiolytic chemical kinetics model in the radiolysis code LOOPCHEM. The LOOPCHEM code calculates the concentrations of various species in a radiolytic field over time. The SWATS-LOOPCHEM code efficiently calculates: the importance (relative to a defined response of interest) of each species concentration over time, the sensitivity of each parameter of interest, and the importance of each equation in the radiolysis model. The calculated results will be used to guide future experimental and modeling work for determining the importance of radiolysis on waste package performance. A demonstration (the importance of selected concentrations and the sensitivities of selected parameters) of the SWATS-LOOPCHEM code is provided for illustrative purposes

Measuring kinetics of complex single ion channel data using mean-variance histograms.

Science.gov (United States)

Patlak, J B

1993-07-01

The measurement of single ion channel kinetics is difficult when those channels exhibit subconductance events. When the kinetics are fast, and when the current magnitudes are small, as is the case for Na+, Ca2+, and some K+ channels, these difficulties can lead to serious errors in the estimation of channel kinetics. I present here a method, based on the construction and analysis of mean-variance histograms, that can overcome these problems. A mean-variance histogram is constructed by calculating the mean current and the current variance within a brief "window" (a set of N consecutive data samples) superimposed on the digitized raw channel data. Systematic movement of this window over the data produces large numbers of mean-variance pairs which can be assembled into a two-dimensional histogram. Defined current levels (open, closed, or sublevel) appear in such plots as low variance regions. The total number of events in such low variance regions is estimated by curve fitting and plotted as a function of window width. This function decreases with the same time constants as the original dwell time probability distribution for each of the regions. The method can therefore be used: 1) to present a qualitative summary of the single channel data from which the signal-to-noise ratio, open channel noise, steadiness of the baseline, and number of conductance levels can be quickly determined; 2) to quantify the dwell time distribution in each of the levels exhibited. In this paper I present the analysis of a Na+ channel recording that had a number of complexities. The signal-to-noise ratio was only about 8 for the main open state, open channel noise, and fast flickers to other states were present, as were a substantial number of subconductance states. "Standard" half-amplitude threshold analysis of these data produce open and closed time histograms that were well fitted by the sum of two exponentials, but with apparently erroneous time constants, whereas the mean

Chemical kinetics in the coma

International Nuclear Information System (INIS)

Huebner, W.F.

1980-01-01

Physical and chemical conditions in the coma of a bright new comet are related to the composition of the nucleus. Chemical and photolytic processes are described and related to distance in the coma above the nucleus and to heliocentric distance of the comet. Comparison of the model with coma observations leads to some restrictions about the nucleus composition. It is expected that these restrictions become more stringent as coma models are developed further and as observations become more detailed

Monte Carlo kinetics simulations of ice-mantle formation on interstellar grains

Science.gov (United States)

Garrod, Robin

2015-08-01

The majority of interstellar dust-grain chemical kinetics models use rate equations, or alternative population-based simulation methods, to trace the time-dependent formation of grain-surface molecules and ice mantles. Such methods are efficient, but are incapable of considering explicitly the morphologies of the dust grains, the structure of the ices formed thereon, or the influence of local surface composition on the chemistry.A new Monte Carlo chemical kinetics model, MIMICK, is presented here, whose prototype results were published recently (Garrod 2013, ApJ, 778, 158). The model calculates the strengths and positions of the potential mimima on the surface, on the fly, according to the individual pair-wise (van der Waals) bonds between surface species, allowing the structure of the ice to build up naturally as surface diffusion and chemistry occur. The prototype model considered contributions to a surface particle's potential only from contiguous (or "bonded") neighbors; the full model considers contributions from surface constituents from short to long range. Simulations are conducted on a fully 3-D user-generated dust-grain with amorphous surface characteristics. The chemical network has also been extended from the simple water system previously published, and now includes 33 chemical species and 55 reactions. This allows the major interstellar ice components to be simulated, such as water, methane, ammonia and methanol, as well as a small selection of more complex molecules, including methyl formate (HCOOCH3).The new model results indicate that the porosity of interstellar ices are dependent on multiple variables, including gas density, the dust temperature, and the relative accretion rates of key gas-phase species. The results presented also have implications for the formation of complex organic molecules on dust-grain surfaces at very low temperatures.

In vitro antioxidant activity, enzyme kinetics, biostability and cellular SOD mimicking ability of 1:1 curcumin-copper (II) complex

International Nuclear Information System (INIS)

Kunwar, A.; Mishra, B.; Barik, A.; Priyadarsini, K.I.; Narang, H.; Krishna, M.

2008-01-01

In vitro antioxidant activity of 1:1 curcumin copper (II) complex was evaluated by following the inhibition of γ-radiation induced lipid peroxidation and protein oxidation in model systems. The SOD enzyme kinetic parameters K m and V max values and the turn over number of the complex were determined. The complex is stable in bio-fluids and prevents oxidation of lipid and protein solution in presence of H 2 O 2 and showed reduction in MnSOD level in spleen cells without having any effect on cell viability. (author)

In vitro antioxidant activity, enzyme kinetics, biostability and cellular SOD mimicking ability of 1:1 curcumin-copper (II) complex

Energy Technology Data Exchange (ETDEWEB)

Kunwar, A; Mishra, B; Barik, A; Priyadarsini, K I [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India); Narang, H; Krishna, M [Radiation Biology and Health Sciences Div., Bhabha Atomic Research Centre, Mumbai (India)

2008-01-15

In vitro antioxidant activity of 1:1 curcumin copper (II) complex was evaluated by following the inhibition of {gamma}-radiation induced lipid peroxidation and protein oxidation in model systems. The SOD enzyme kinetic parameters K{sub m} and V{sub max} values and the turn over number of the complex were determined. The complex is stable in bio-fluids and prevents oxidation of lipid and protein solution in presence of H{sub 2}O{sub 2} and showed reduction in MnSOD level in spleen cells without having any effect on cell viability. (author)

The chemical fate of 212Bi-DOTA formed by β- decay of 212Pb(DOTA)2-

International Nuclear Information System (INIS)

Mirzadeh, S.; Kumar, K.; Gansow, O.A.

1993-01-01

The increasing use of inert metal complexes in radioimmunotherapy prompted us to explore the potential use of 212 Pb chelates. Herein, we report a study of the chemical fate of the 212 Bi-DOTA complex formed by β - decay of 212 Pb(DOTA) 2- (H 4 DOTA = 1,4,7,10-tetraazacyclododecanetetraacetic acid). To assure that both parent and daughter complexes were thermally stable, kinetic studies were performed with 203 Pb(II) and 206 Bi(III) which showed that both lead and bismuth complexes with DOTA undergo chemical exchange only very slowly in aqueous solution at pH 4-10. To investigate whether the complex ion which results from decay of 212 Pb(DOTA) 2- was intact and also stable, solutions initially containing only this ion were analyzed for amounts of DOTA-complexed and uncomplexed 212 Bi after attaining transient equilibrium with 212 Bi. The fraction of 212 Bi radioactivity not complexed to DOTA, vide infra, was found to be 36±2%. This value represents the fraction of breakup of 212 Bi(DOTA) - formed from β - decay of the parent complex. By considering the various extranuclear processes responsible for kinetic and electronic excitation of the 212 Bi daughter, break-up of the 212 Bi-DOTA complex is ascribed to the internal conversion of γ-rays emitted by the excited 212 Bi nuclide. (orig.)

A large scale analysis of information-theoretic network complexity measures using chemical structures.

Directory of Open Access Journals (Sweden)

Matthias Dehmer

Full Text Available This paper aims to investigate information-theoretic network complexity measures which have already been intensely used in mathematical- and medicinal chemistry including drug design. Numerous such measures have been developed so far but many of them lack a meaningful interpretation, e.g., we want to examine which kind of structural information they detect. Therefore, our main contribution is to shed light on the relatedness between some selected information measures for graphs by performing a large scale analysis using chemical networks. Starting from several sets containing real and synthetic chemical structures represented by graphs, we study the relatedness between a classical (partition-based complexity measure called the topological information content of a graph and some others inferred by a different paradigm leading to partition-independent measures. Moreover, we evaluate the uniqueness of network complexity measures numerically. Generally, a high uniqueness is an important and desirable property when designing novel topological descriptors having the potential to be applied to large chemical databases.

Stochastic lumping analysis for linear kinetics and its application to the fluctuation relations between hierarchical kinetic networks

Energy Technology Data Exchange (ETDEWEB)

Deng, De-Ming; Chang, Cheng-Hung [Institute of Physics, National Chiao Tung University, Hsinchu 300, Taiwan (China)

2015-05-14

Conventional studies of biomolecular behaviors rely largely on the construction of kinetic schemes. Since the selection of these networks is not unique, a concern is raised whether and under which conditions hierarchical schemes can reveal the same experimentally measured fluctuating behaviors and unique fluctuation related physical properties. To clarify these questions, we introduce stochasticity into the traditional lumping analysis, generalize it from rate equations to chemical master equations and stochastic differential equations, and extract the fluctuation relations between kinetically and thermodynamically equivalent networks under intrinsic and extrinsic noises. The results provide a theoretical basis for the legitimate use of low-dimensional models in the studies of macromolecular fluctuations and, more generally, for exploring stochastic features in different levels of contracted networks in chemical and biological kinetic systems.

Stochastic lumping analysis for linear kinetics and its application to the fluctuation relations between hierarchical kinetic networks.

Science.gov (United States)

Deng, De-Ming; Chang, Cheng-Hung

2015-05-14

Conventional studies of biomolecular behaviors rely largely on the construction of kinetic schemes. Since the selection of these networks is not unique, a concern is raised whether and under which conditions hierarchical schemes can reveal the same experimentally measured fluctuating behaviors and unique fluctuation related physical properties. To clarify these questions, we introduce stochasticity into the traditional lumping analysis, generalize it from rate equations to chemical master equations and stochastic differential equations, and extract the fluctuation relations between kinetically and thermodynamically equivalent networks under intrinsic and extrinsic noises. The results provide a theoretical basis for the legitimate use of low-dimensional models in the studies of macromolecular fluctuations and, more generally, for exploring stochastic features in different levels of contracted networks in chemical and biological kinetic systems.

Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

Science.gov (United States)

Adamovich, Igor V; Li, Ting; Lempert, Walter R

2015-08-13

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

A unified approach to model uptake kinetics of trace elements in complex aqueous – solid solution systems

International Nuclear Information System (INIS)

Thien, Bruno M.J.; Kulik, Dmitrii A.; Curti, Enzo

2014-01-01

Highlights: • There are several models able to describe trace element partitioning in growing minerals. • To describe complex systems, those models must be embedded in a geochemical code. • We merged two models into a unified one suitable for implementation in a geochemical code. • This unified model was tested against coprecipitation experimental data. • We explored how our model reacts to solution depletion effects. - Abstract: Thermodynamics alone is usually not sufficient to predict growth-rate dependencies of trace element partitioning into host mineral solid solutions. In this contribution, two uptake kinetic models were analyzed that are promising in terms of mechanistic understanding and potential for implementation in geochemical modelling codes. The growth Surface Entrapment Model (Watson, 2004) and the Surface Reaction Kinetic Model (DePaolo, 2011) were shown to be complementary, and under certain assumptions merged into a single analytical expression. This Unified Uptake Kinetics Model was implemented in GEMS3K and GEM-Selektor codes ( (http://gems.web.psi.ch)), a Gibbs energy minimization package for geochemical modelling. This implementation extends the applicability of the unified uptake kinetics model to accounting for non-trivial factors influencing the trace element partitioning into solid solutions, such as the changes in aqueous solution composition and speciation, or the depletion effects in closed geochemical systems

Reduced chemical kinetic model of detonation combustion of one- and multi-fuel gaseous mixtures with air

Science.gov (United States)

Fomin, P. A.

2018-03-01

Two-step approximate models of chemical kinetics of detonation combustion of (i) one hydrocarbon fuel CnHm (for example, methane, propane, cyclohexane etc.) and (ii) multi-fuel gaseous mixtures (∑aiCniHmi) (for example, mixture of methane and propane, synthesis gas, benzene and kerosene) are presented for the first time. The models can be used for any stoichiometry, including fuel/fuels-rich mixtures, when reaction products contain molecules of carbon. Owing to the simplicity and high accuracy, the models can be used in multi-dimensional numerical calculations of detonation waves in corresponding gaseous mixtures. The models are in consistent with the second law of thermodynamics and Le Chatelier's principle. Constants of the models have a clear physical meaning. The models can be used for calculation thermodynamic parameters of the mixture in a state of chemical equilibrium.

Complex biological and bio-inspired systems

Energy Technology Data Exchange (ETDEWEB)

Ecke, Robert E [Los Alamos National Laboratory

2009-01-01

The understanding and characterization ofthe fundamental processes of the function of biological systems underpins many of the important challenges facing American society, from the pathology of infectious disease and the efficacy ofvaccines, to the development of materials that mimic biological functionality and deliver exceptional and novel structural and dynamic properties. These problems are fundamentally complex, involving many interacting components and poorly understood bio-chemical kinetics. We use the basic science of statistical physics, kinetic theory, cellular bio-chemistry, soft-matter physics, and information science to develop cell level models and explore the use ofbiomimetic materials. This project seeks to determine how cell level processes, such as response to mechanical stresses, chemical constituents and related gradients, and other cell signaling mechanisms, integrate and combine to create a functioning organism. The research focuses on the basic physical processes that take place at different levels ofthe biological organism: the basic role of molecular and chemical interactions are investigated, the dynamics of the DNA-molecule and its phylogenetic role are examined and the regulatory networks of complex biochemical processes are modeled. These efforts may lead to early warning algorithms ofpathogen outbreaks, new bio-sensors to detect hazards from pathomic viruses to chemical contaminants. Other potential applications include the development of efficient bio-fuel alternative-energy processes and the exploration ofnovel materials for energy usages. Finally, we use the notion of 'coarse-graining,' which is a method for averaging over less important degrees of freedom to develop computational models to predict cell function and systems-level response to disease, chemical stress, or biological pathomic agents. This project supports Energy Security, Threat Reduction, and the missions of the DOE Office of Science through its efforts to

Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

International Nuclear Information System (INIS)

Roh, Heui-Seol

2015-01-01

Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

Uranium complexes with macrosyclic polyethers. Synthesis and structural chemical analysis

International Nuclear Information System (INIS)

Elbasyouny, A.

1983-01-01

This dissertation reports about studies on the chemical coordination behaviour of uranium of oxidation stages IV and VI with regard to twelve different macrocyclic ligands. For the preparation of the complexes, for every system a different method has been developed. The elementary analysis of the various complexes including the uranium had been done by X-ray fluorescence analysis, and the structural characterization proceeded via vibrational, uv-vis and emission spectroscopy as well as 1 H-NMR and 13 C-spin-lattice relaxation time studies. Conformational analysis of the polyethers used allowed the structural changes in the complexes to be observed. The structural analysis of the hydrous uranium VI crown ether complexes yielded information of characteristic features of these types of complexes. The first coordination sphere of the uranyl ion with covalently bonded anion remains unchanged. As to the water content, there is a certain range. Depending upon the solvent used, the complexes have two or four H 2 O molecules per formula unit. (orig./EF) [de

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions. Polyarograficheskoe issledovanie kinetiki kompleksoobrazovaniya poliakrilat-anionov s ionami kadmiya

Energy Technology Data Exchange (ETDEWEB)

Avlyanov, Zh K; Kabanov, N M; Zezin, A B; Askarov, M A

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions.

Thorium oxide dissolution kinetics for hydroxide and carbonate complexation

International Nuclear Information System (INIS)

Jardin, R.; Curran, V.; Czerwinski, K.R.

2002-01-01

The purpose of this project was to determine the kinetics and thermodynamics of thorium oxide dissolution in the environment. Solubility is important because it establishes an upper concentration limit on the concentration of a dissolved radionuclide in solution L1. While understanding the behavior of thorium fuels in the proposed repository at Yucca Mountain is most applicable, a more rigorous study of thorium solubility over a wide pH range was performed so that the data could also be used to model the behavior of thorium fuels in any environmental system. To achieve this, the kinetics and thermodynamics of thorium oxide dissolution under both pure argon and argon with P CO2 of 0. 1 were studied under the full pH range available in each atmosphere. In addition, thorium oxide powder remnants were studied after each experiment to examine structural changes that may affect kinetics

Stochastic mechano-chemical kinetics of molecular motors: A multidisciplinary enterprise from a physicist’s perspective

Energy Technology Data Exchange (ETDEWEB)

Chowdhury, Debashish, E-mail: debchg@gmail.com

2013-08-01

A molecular motor is made of either a single macromolecule or a macromolecular complex. Just like their macroscopic counterparts, molecular motors “transduce” input energy into mechanical work. All the nano-motors considered here operate under isothermal conditions far from equilibrium. Moreover, one of the possible mechanisms of energy transduction, called Brownian ratchet, does not even have any macroscopic counterpart. But, molecular motor is not synonymous with Brownian ratchet; a large number of molecular motors execute a noisy power stroke, rather than operating as Brownian ratchet. We review not only the structural design and stochastic kinetics of individual single motors, but also their coordination, cooperation and competition as well as the assembly of multi-module motors in various intracellular kinetic processes. Although all the motors considered here execute mechanical movements, efficiency and power output are not necessarily good measures of performance of some motors. Among the intracellular nano-motors, we consider the porters, sliders and rowers, pistons and hooks, exporters, importers, packers and movers as well as those that also synthesize, manipulate and degrade “macromolecules of life”. We review mostly the quantitative models for the kinetics of these motors. We also describe several of those motor-driven intracellular stochastic processes for which quantitative models are yet to be developed. In part I, we discuss mainly the methodology and the generic models of various important classes of molecular motors. In part II, we review many specific examples emphasizing the unity of the basic mechanisms as well as diversity of operations arising from the differences in their detailed structure and kinetics. Multi-disciplinary research is presented here from the perspective of physicists.

Kinetic models of partially ionized complex plasmas in the low frequency regime

International Nuclear Information System (INIS)

Tolias, P.; Ratynskaia, S.; Angelis, U. de

2011-01-01

The results from three kinetic models of complex plasmas taking into account collisions with neutrals are compared in the low-frequency regime: The ''full'' model which considers the absorption of plasma fluxes on dust particles and dust charge fluctuations, the ''multi-component'' model where both these effects are neglected, and the ''standard'' model which takes into account the dust charge perturbations but not the absorption of fluxes. We derive and numerically evaluate expressions of the low frequency responses of these models, also taking into account the modification of the capture cross-sections due to the effect of neutrals. The role of plasma sources and collisions with neutrals is assessed by computing the plasma permittivities and static permittivities for all the three models.

Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

Science.gov (United States)

Lee, Seung-Mahn

2003-10-01

Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP

Kinetics of the tungsten hexafluoride-silane reaction for the chemical vapor deposition of tungsten

International Nuclear Information System (INIS)

Gokce, Huseyin.

1991-01-01

In this study, the kinetics of the low-pressure chemical vapor deposition (LPCVD) of tungsten by silane reduction of tungsten hexafluoride on Si(100) surfaces was studied. A single-wafer, cold-wall reactor was sued for the experiments. The SiH 4 /WF 6 ratio was 1.0. The pressure and temperature range were 1-10 torr and 137-385 degree C, respectively. Kinetic data were obtained in the absence of mass-transfer effects. The film thicknesses were measured by gravimetry. Scanning electron microscopy (SEM), Auger electron spectroscopy (AES), x-ray diffraction (XRD), and resistivity measurements were used to analyze the W films. For the horizontal substrate position and 4-minute reaction times, the apparent activation energies were determined to be 0.35 eV/atom for 10 torr, 0.17 eV/atom for 3 torr, and 0.08 eV/atom for 1 torr. Lower temperatures and higher pressures produced porous films, while higher temperatures and lower pressures resulted in continuous films with smoother surfaces. As the Si-W interface, a W(110) preferential orientation was observed. As the W films grew thicker, W orientation switched from (110) to (100). Apparent activation energy seems to change with thickness

MAKSIMA-CHEMIST: a program for Mass Action Kinetics Simulation by Automatic Chemical Equation Manipulation and Integration using Stiff Techniques

International Nuclear Information System (INIS)

Carver, M.B.; Hanley, D.V.; Chaplin, K.R.

1979-02-01

MAKSIMA-CHEMIST was written to compute the kinetics of simultaneous chemical reactions. The ordinary differential equations, which are automatically derived from the stated chemical equations, are difficult to integrate, as they are coupled in a highly nonlinear manner and frequently involve a large range in the magnitude of the reaction rates. They form a classic 'stiff' differential equaton set which can be integrated efficiently only by recently developed advanced techniques. The new program also contains provision for higher order chemical reactions, and has a dynamic storage and decision feature. This permits it to accept any number of chemical reactions and species, and choose an integraton scheme which will perform most efficiently within the available memory. Sparse matrix techniques are used when the size and structure of the equation set is suitable. Finally, a number of post-analysis options are available, including printer and Calcomp plots of transient response of selected species, and graphical representation of the reaction matrix. (auth)

Drug Release Kinetics and Front Movement in Matrix Tablets Containing Diltiazem or Metoprolol/λ-Carrageenan Complexes

Directory of Open Access Journals (Sweden)

Ruggero Bettini

2014-01-01

Full Text Available In this work we investigated the moving boundaries and the associated drug release kinetics in matrix tablets prepared with two complexes between λ-carrageenan and two soluble model drugs, namely, diltiazem HCl and metoprolol tartrate aiming at clarifying the role played by drug/polymer interaction on the water uptake, swelling, drug dissolution, and drug release performance of the matrix. The two studied complexes released the drug with different mechanism indicating two different drug/polymer interaction strengths. The comparison between the drug release behaviour of the complexes and the relevant physical mixtures indicates that diltiazem gave rise to a less soluble and more stable complex with carrageenan than metoprolol. The less stable metoprolol complex afforded an erodible matrix, whereas the stronger interaction between diltiazem and carrageenan resulted in a poorly soluble, slowly dissolving matrix. It was concluded that the different stability of the studied complexes affords two distinct drug delivery systems: in the case of MTP, the dissociation of the complex, as a consequence of the interaction with water, affords a classical soluble matrix type delivery system; in the case of DTZ, the dissolving/diffusing species is the complex itself because of the very strong interaction between the drug and the polymer.

Probabilistic parameter estimation in a 2-step chemical kinetics model for n-dodecane jet autoignition

Science.gov (United States)

Hakim, Layal; Lacaze, Guilhem; Khalil, Mohammad; Sargsyan, Khachik; Najm, Habib; Oefelein, Joseph

2018-05-01

This paper demonstrates the development of a simple chemical kinetics model designed for autoignition of n-dodecane in air using Bayesian inference with a model-error representation. The model error, i.e. intrinsic discrepancy from a high-fidelity benchmark model, is represented by allowing additional variability in selected parameters. Subsequently, we quantify predictive uncertainties in the results of autoignition simulations of homogeneous reactors at realistic diesel engine conditions. We demonstrate that these predictive error bars capture model error as well. The uncertainty propagation is performed using non-intrusive spectral projection that can also be used in principle with larger scale computations, such as large eddy simulation. While the present calibration is performed to match a skeletal mechanism, it can be done with equal success using experimental data only (e.g. shock-tube measurements). Since our method captures the error associated with structural model simplifications, we believe that the optimised model could then lead to better qualified predictions of autoignition delay time in high-fidelity large eddy simulations than the existing detailed mechanisms. This methodology provides a way to reduce the cost of reaction kinetics in simulations systematically, while quantifying the accuracy of predictions of important target quantities.

A new mathematical model for coal flotation kinetics

OpenAIRE

Guerrero-Pérez, Juan Sebastián; Barraza-Burgos, Juan Manuel

2017-01-01

Abstract This study describes the development and formulation of a novel mathematical model for coal flotation kinetic. The flotation rate was considered as a function of chemical, operating and petrographic parameters for a global flotation order n. The equation for flotation rate was obtained by dimensional analysis using the Rayleigh method. It shows the dependency of flotation kinetic on operating parameters, such as air velocity and particle size; chemical parameters, such as reagents do...

The redox reaction kinetics of Sinai ore for chemical looping combustion applications

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

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

Science.gov (United States)

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

Gas-solids kinetics of CuO/Al2O3 as an oxygen carrier for high-pressure chemical looping processes : the influence of the total pressure

NARCIS (Netherlands)

San Pio Bordeje, M.A.; Gallucci, F.; Roghair, I.; van Sint Annaland, M.

2017-01-01

Copper oxide on alumina is often used as oxygen carrier for chemical looping combustion owing to its very high reduction rates at lower temperatures and its very good mechanical and chemical stability at not too high temperatures. In this work, the redox kinetics of CuO/Al2O3 have been studied at

Biosorption of Cu (II onto chemically modified waste mycelium of Aspergillus awamori: Equilibrium, kinetics and modeling studies

Directory of Open Access Journals (Sweden)

ZDRAVKA VELKOVA

2012-01-01

Full Text Available The biosorption potential of chemically modified waste mycelium of industrial xylanase-producing strain Aspergillus awamori for Cu (II removal from aqueous solutions was evaluated. The influence of pH, contact time and initial Cu (II concentration on the removal efficiency was evaluated. Maximum biosorption capacity was reached by sodium hydroxide treated waste fungal mycelium at pH 5.0. The Langmuir adsorption equation matched very well the adsorption equilibrium data in the studied conditions. The process kinetic followed the pseudo-firs order model.

Probing Interactions in Complex Molecular Systems through Ordered Assembly

International Nuclear Information System (INIS)

De Yoreo, J.J.; Bartelt, M.C.; Orme, C.A.; Villacampa, A.; Weeks, B.L.; Miller, A.E.

2002-01-01

Emerging from the machinery of epitaxial science and chemical synthesis, is a growing emphasis on development of self-organized systems of complex molecular species. The nature of self-organization in these systems spans the continuum from simple crystallization of large molecules such as dendrimers and proteins, to assembly into large organized networks of nanometer-scale structures such as quantum dots or nanoparticles. In truth, self-organization in complex molecular systems has always been a central feature of many scientific disciplines including fields as diverse as structural biology, polymer science and geochemistry. But over the past decade, changes in those fields have often been marked by the degree to which researchers are using molecular-scale approaches to understand the hierarchy of structures and processes driven by this ordered assembly. At the same time, physical scientists have begun to use their knowledge of simple atomic and molecular systems to fabricate synthetic self-organized systems. This increasing activity in the field of self-organization is testament to the success of the physical and chemical sciences in building a detailed understanding of crystallization and epitaxy in simple atomic and molecular systems, one that is soundly rooted in thermodynamics and chemical kinetics. One of the fundamental challenges of chemistry and materials science in the coming decades is to develop a similarly well-founded physical understanding of assembly processes in complex molecular systems. Over the past five years, we have successfully used in situ atomic force microscopy (AFM) to investigate the physical controls on single crystal epitaxy from solutions for a wide range of molecular species. More recently, we have combined this method with grazing incidence X-ray diffraction and kinetic Monte Carlo modeling in order to relate morphology to surface atomic structure and processes. The purpose of this proposal was to extend this approach to assemblies

Gas-Phase Molecular Dynamics: Theoretical Studies in Spectroscopy and Chemical Dynamics

Energy Technology Data Exchange (ETDEWEB)

Yu, H.G.; Muckerman, J.T.

2010-06-01

The goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods.

Modeling of kinetics of the inducible protein complexes of the SOS system in bacteria E. coli which realize TLS process

International Nuclear Information System (INIS)

Belov, O.V.

2008-01-01

The mathematical model describing kinetics of the inducible genes of the protein complexes, formed during SOS response in bacteria Escherichia coli is developed. Within the bounds of developed approaches the auxiliary mathematical model describing changes in concentrations of the dimers, which are the components of final protein complexes, is developed. The solutions of both models are based on the experimental data concerning expression of the basic genes of the SOS system in bacteria Escherichia coli

Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

Science.gov (United States)

Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

2011-01-28

Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF) of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM) or fluorescence-correlation spectroscopy (FCS) to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

Lateral interactions and non-equilibrium in surface kinetics

Science.gov (United States)

Menzel, Dietrich

2016-08-01

Work modelling reactions between surface species frequently use Langmuir kinetics, assuming that the layer is in internal equilibrium, and that the chemical potential of adsorbates corresponds to that of an ideal gas. Coverage dependences of reacting species and of site blocking are usually treated with simple power law coverage dependences (linear in the simplest case), neglecting that lateral interactions are strong in adsorbate and co-adsorbate layers which may influence kinetics considerably. My research group has in the past investigated many co-adsorbate systems and simple reactions in them. We have collected a number of examples where strong deviations from simple coverage dependences exist, in blocking, promoting, and selecting reactions. Interactions can range from those between next neighbors to larger distances, and can be quite complex. In addition, internal equilibrium in the layer as well as equilibrium distributions over product degrees of freedom can be violated. The latter effect leads to non-equipartition of energy over molecular degrees of freedom (for products) or non-equal response to those of reactants. While such behavior can usually be described by dynamic or kinetic models, the deeper reasons require detailed theoretical analysis. Here, a selection of such cases is reviewed to exemplify these points.

Evaluation of the catalytic mechanism of AICAR transformylase by pH-dependent kinetics, mutagenesis, and quantum chemical calculations.

Science.gov (United States)

Shim, J H; Wall, M; Benkovic, S J; Díaz, N; Suárez, D; Merz, K M

2001-05-23

The catalytic mechanism of 5-aminoimidazole-4-carboxamide ribonucleotide transformylase (AICAR Tfase) is evaluated with pH dependent kinetics, site-directed mutagenesis, and quantum chemical calculations. The chemistry step, represented by the burst rates, was not pH-dependent, which is consistent with our proposed mechanism that the 4-carboxamide of AICAR assists proton shuttling. Quantum chemical calculations on a model system of 5-amino-4-carboxamide imidazole (AICA) and formamide using the B3LYP/6-31G level of theory confirmed that the 4-carboxamide participated in the proton-shuttling mechanism. The result also indicated that the amide-assisted mechanism is concerted such that the proton transfers from the 5-amino group to the formamide are simultaneous with nucleophilic attack by the 5-amino group. Because the process does not lead to a kinetically stable intermediate, the intramolecular proton transfer from the 5-amino group through the 4-carboxamide to the formamide proceeds in the same transition state. Interestingly, the calculations predicted that protonation of the N3 of the imidazole of AICA would reduce the energy barrier significantly. However, the pK(a) of the imidazole of AICAR was determined to be 3.23 +/- 0.01 by NMR titration, and AICAR is likely to bind to the enzyme with its imidazole in the free base form. An alternative pathway was suggested by modeling Lys266 to have a hydrogen-bonding interaction with the N3 of the imidazole of AICAR. Lys266 has been implicated in catalysis based on mutagenesis studies and the recent X-ray structure of AICAR Tfase. The quantum chemical calculations on a model system that contains AICA complexed with CH3NH3+ as a mimic of the Lys residue confirmed that such an interaction lowered the activation energy of the reaction and likewise implicated the 4-carboxamide. To experimentally verify this hypothesis, we prepared the K266R mutant and found that its kcat is reduced by 150-fold from that of the wild type

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

DEFF Research Database (Denmark)

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

2014-01-01

This work is an extension to a previously reported work on chemical kinetic mechanism reduction scheme for large-scale mechanisms. Here, Perfectly Stirred Reactor (PSR) was added as a criterion of data source for mechanism reduction instead of using only auto-ignition condition. As a result......) simulations were performed to study the spray combustion phenomena within a constant volume bomb. Both non-reacting and reacting conditions were applied in this study. Liquid and vapor penetration lengths were replicated for non-reacting diesel spray. For reacting diesel spray, both ignition delay and lift......-off length were simulated. The simulation results were then compared to the experimental data of Sandia National Laboratories and No. 2 Diesel Fuel (D2) was designated as the reference fuel. Both liquid and vapor penetrations for non-reacting condition were well-matched, while ignition delay was advanced...

Numerical Modeling of Lead Oxidation in Controlled Lead Bismuth Eutectic Systems: Chemical Kinetics and Hydrodynamic Effects

International Nuclear Information System (INIS)

Wu, Chao; Kanthi Kiran Dasika; Chen, Yitung; Moujaes, Samir

2002-01-01

Using liquid Lead-Bismuth Eutectic (LBE) as coolant in nuclear systems has been studied for more than 50 years. And LBE has many unique nuclear, thermo physical and chemical attributes which are attractive for practical application. But, corrosion is one of the greatest concerns in using liquid Lead-Bismuth Eutectic (LBE) as spallation target in the Accelerator-driven Transmutation of Waste (ATW) program. Los Alamos National Laboratory has designed and built the Liquid Lead-Bismuth Materials Test Loop (MTL) to study the materials behavior in a flow of molten LBE. A difference of 100 deg. C was designed between the coldest and the hottest parts at a nominal flow rate of 8.84 GPM. Liquid LBE flow was activated by a mechanical sump pump or by natural convection. In order to maintain a self-healing protective film on the surface of the stainless steel pipe, a certain concentration of oxygen has to be maintained in the liquid metal. Therefore, it is of importance to understand what the oxygen concentrations are in the LBE loop related to the corrosion effects on the metal surface, the temperature profiles, the flow rates, and diffusion rates through the metal surface. The chemical kinetics also needs to be fully understood in the corrosion processes coupled with the hydrodynamics. The numerical simulation will be developed and used to analyze the system corrosion effects with different kind of oxygen concentrations, flow rates, chemical kinetics, and geometries. The hydrodynamics modeling of using computational fluid dynamics will provide the necessary the levels of oxygen and corrosion products close to the boundary or surface. This paper presents an approach towards the above explained tasks by analyzing the reactions between the Lead and oxygen at a couple of sections in the MTL. Attempt is also made to understand the surface chemistry by choosing an example model and estimating the near wall surface concentration values for propane and oxygen. (authors)

Brain alpha-ketoglutarate dehydrogenase complex: kinetic properties, regional distribution, and effects of inhibitors.

Science.gov (United States)

Lai, J C; Cooper, A J

1986-11-01

The substrate and cofactor requirements and some kinetic properties of the alpha-ketoglutarate dehydrogenase complex (KGDHC; EC 1.2.4.2, EC 2.3.1.61, and EC 1.6.4.3) in purified rat brain mitochondria were studied. Brain mitochondrial KGDHC showed absolute requirement for alpha-ketoglutarate, CoA and NAD, and only partial requirement for added thiamine pyrophosphate, but no requirement for Mg2+ under the assay conditions employed in this study. The pH optimum was between 7.2 and 7.4, but, at pH values below 7.0 or above 7.8, KGDHC activity decreased markedly. KGDHC activity in various brain regions followed the rank order: cerebral cortex greater than cerebellum greater than or equal to midbrain greater than striatum = hippocampus greater than hypothalamus greater than pons and medulla greater than olfactory bulb. Significant inhibition of brain mitochondrial KGDHC was noted at pathological concentrations of ammonia (0.2-2 mM). However, the purified bovine heart KGDHC and KGDHC activity in isolated rat heart mitochondria were much less sensitive to inhibition. At 5 mM both beta-methylene-D,L-aspartate and D,L-vinylglycine (inhibitors of cerebral glucose oxidation) inhibited the purified heart but not the brain mitochondrial enzyme complex. At approximately 10 microM, calcium slightly stimulated (by 10-15%) the brain mitochondrial KGDHC. At concentrations above 100 microM, calcium (IC50 = 1 mM) inhibited both brain mitochondrial and purified heart KGDHC. The present results suggest that some of the kinetic properties of the rat brain mitochondrial KGDHC differ from those of the purified bovine heart and rat heart mitochondrial enzyme complexes. They also suggest that the inhibition of KGDHC by ammonia and the consequent effect on the citric acid cycle fluxes may be of pathophysiological and/or pathogenetic importance in hyperammonemia and in diseases (e.g., hepatic encephalopathy, inborn errors of urea metabolism, Reye's syndrome) where hyperammonemia is a

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

Science.gov (United States)

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.

Chemical Equilibrium Models for the S3 State of the Oxygen-Evolving Complex of Photosystem II.

Science.gov (United States)

Isobe, Hiroshi; Shoji, Mitsuo; Shen, Jian-Ren; Yamaguchi, Kizashi

2016-01-19

We have performed hybrid density functional theory (DFT) calculations to investigate how chemical equilibria can be described in the S3 state of the oxygen-evolving complex in photosystem II. For a chosen 340-atom model, 1 stable and 11 metastable intermediates have been identified within the range of 13 kcal mol(-1) that differ in protonation, charge, spin, and conformational states. The results imply that reversible interconversion of these intermediates gives rise to dynamic equilibria that involve processes with relocations of protons and electrons residing in the Mn4CaO5 cluster, as well as bound water ligands, with concomitant large changes in the cluster geometry. Such proton tautomerism and redox isomerism are responsible for reversible activation/deactivation processes of substrate oxygen species, through which Mn-O and O-O bonds are transiently ruptured and formed. These results may allow for a tentative interpretation of kinetic data on substrate water exchange on the order of seconds at room temperature, as measured by time-resolved mass spectrometry. The reliability of the hybrid DFT method for the multielectron redox reaction in such an intricate system is also addressed.

The role of metal complexes in nuclear reactor decontamination

Energy Technology Data Exchange (ETDEWEB)

Prince, A.A.M.; Raghavan, P.S.; Gopalan, R. [Madras Christian College, Tambaram, Chennai (India); Velmurugan, S.; Narasimhan, S.V. [Bhabha Atomic Research Center (BARC) (IN). Water and Steam Chemistry Lab. (WSCL)

2006-07-15

Chemical decontamination is the process of removal of radioactivity from corrosion products formed on structural materials in the nuclear reactors. These corrosion products cause problems for the operation and maintenance of the plants. Removal of the radioactive contaminants can be achieved by dissolving the oxide from the system surface using organic complexing agents in low concentrations known as dilute chemical decontamination (DCD) formulations. These organic complexing agents attack the oxide surface and form metal complexes, which further accelerate the dissolution process. The stability of the complexes plays an important role in dissolving the radioactive contaminated oxides. In addition, the DCD process is operated through ion exchange resins for the removal of the dissolved metal ions and radioactive nuclides. In the present study, the kinetics of dissolution of various model corrosion products such as magnetite (Fe{sub 3}O{sub 4}), hematite ({alpha}-Fe{sub 2}O{sub 3}) and maghemite ({gamma}-Fe{sub 2}O{sub 3}) have been studied in the presence of complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylethylenediaminepentaacetic acid (HEEDTA), and 2,6 pyridinedicarboxylic acid (PDCA). The reductive roles of metal complexes and organic reducing agents are discussed. (orig.)

PumpKin: A tool to find principal pathways in plasma chemical models

Science.gov (United States)

Markosyan, A. H.; Luque, A.; Gordillo-Vázquez, F. J.; Ebert, U.

2014-10-01

PumpKin is a software package to find all principal pathways, i.e. the dominant reaction sequences, in chemical reaction systems. Although many tools are available to integrate numerically arbitrarily complex chemical reaction systems, few tools exist in order to analyze the results and interpret them in relatively simple terms. In particular, due to the large disparity in the lifetimes of the interacting components, it is often useful to group reactions into pathways that recycle the fastest species. This allows a researcher to focus on the slow chemical dynamics, eliminating the shortest timescales. Based on the algorithm described by Lehmann (2004), PumpKin automates the process of finding such pathways, allowing the user to analyze complex kinetics and to understand the consumption and production of a certain species of interest. We designed PumpKin with an emphasis on plasma chemical systems but it can also be applied to atmospheric modeling and to industrial applications such as plasma medicine and plasma-assisted combustion.

Coupling between solute transport and chemical reactions models

International Nuclear Information System (INIS)

Samper, J.; Ajora, C.

1993-01-01

During subsurface transport, reactive solutes are subject to a variety of hydrodynamic and chemical processes. The major hydrodynamic processes include advection and convection, dispersion and diffusion. The key chemical processes are complexation including hydrolysis and acid-base reactions, dissolution-precipitation, reduction-oxidation, adsorption and ion exchange. The combined effects of all these processes on solute transport must satisfy the principle of conservation of mass. The statement of conservation of mass for N mobile species leads to N partial differential equations. Traditional solute transport models often incorporate the effects of hydrodynamic processes rigorously but oversimplify chemical interactions among aqueous species. Sophisticated chemical equilibrium models, on the other hand, incorporate a variety of chemical processes but generally assume no-flow systems. In the past decade, coupled models accounting for complex hydrological and chemical processes, with varying degrees of sophistication, have been developed. The existing models of reactive transport employ two basic sets of equations. The transport of solutes is described by a set of partial differential equations, and the chemical processes, under the assumption of equilibrium, are described by a set of nonlinear algebraic equations. An important consideration in any approach is the choice of primary dependent variables. Most existing models cannot account for the complete set of chemical processes, cannot be easily extended to include mixed chemical equilibria and kinetics, and cannot handle practical two and three dimensional problems. The difficulties arise mainly from improper selection of the primary variables in the transport equations. (Author) 38 refs

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

Directory of Open Access Journals (Sweden)

Stuart Bartlett

2017-08-01

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

Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

Directory of Open Access Journals (Sweden)

Tales Tiecher

2014-10-01

Full Text Available Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure. All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

Kinetic mechanism for modeling of electrochemical reactions.

Science.gov (United States)

Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

2012-04-01

We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

Science.gov (United States)

Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-01-01

Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

The chemical kinetics of the reactions of lithium with steam-air mixtures

International Nuclear Information System (INIS)

Barnett, D.S.; Kazimi, M.S.

1989-04-01

This work involved the experimental and analytical determination of the consequences of lithium fires in the presence of steam. Experiments were performed to characterize the chemical reactions of lithium with steam-nitrogen and steam-air mixtures. Models were introduced in the LITFIRE code to describe lithium fires in the presence of steam inside the containment building and plasma chamber of a hypothetical fusion reactor. The code was also equipped with the capability to determine the effects of decay heat and lithium fire on the temperature response of the reactor first wall in the event of a coolant disturbance. Forty-two kinetics experiments were performed in which a stream of steam-nitrogen or steam-air was passed over and reacted with approximately three grams of lithium heated to a predetermined temperature. The lithium reaction rates with the constituent gases were measured and characterized for a wide range of lithium temperatures and gas compositions. Experiments were performed with steam molar concentrations of 5, 15 and 30% and lithium temperatures ranging from 400 to 1100 degree C, inclusive. The LITFIRE code was modified to enable it to model the interactions of lithium with steam-air atmospheres. Results of the reaction kinetics experiments were used in the reaction model, and the heat transfer model was expanded to allow it to handle condensible atmospheres. Three groups of accidents were investigated: a spill on the containment building floor, a spill inside the reactor plasma chamber, and a spill inside the plasma chamber with steam injection to the containment building simulating a steam line break. The results were compared to dry air cases under the same conditions. 23 refs., 66 figs., 18 tabs

Low Temperature Synthesis of CdSe Quantum Dots with Amine Derivative and Their Chemical Kinetics

Science.gov (United States)

Seongmi Hwang,; Youngmin Choi,; Sunho Jeong,; Hakyun Jung,; Chang Gyoun Kim,; Teak-Mo Chung,; Beyong-Hwan Ryu,

2010-05-01

The chemical kinetics of growing CdSe nanocrystals was studied in order to investigate the effects of amine capping agents on the size of resulting quantum dots (QDs). CdSe QDs were prepared in phenyl ether, and the amine ligand dependence of QD size was determined. The results show that the size of CdSe nanocrystals can be regulated by controlling reaction rate, with smaller QDs being formed in slower processes. The results of photoluminescence (PL) studies show that the emission wavelengths of the QDs well correlate with particle size. This simple process for forming different-sized QDs, which uses a cheap solvent and various capping agents, has the potential for preparing CdSe nanocrystals more economically.

[Physico-chemical features of dinitrosyl iron complexes with natural thiol-containing ligands underlying biological activities of these complexes].

Science.gov (United States)

Vanin, A F; Borodulin, R R; Kubrina, L N; Mikoian, V D; Burbaev, D Sh

2013-01-01

Current notions and new experimental data of the authors on physico-chemical features of dinitrosyl iron complexes with natural thiol-containing ligands (glutathione or cysteine), underlying the ability of the complexes to act as NO molecule and nitrosonium ion donors, are considered. This ability determines various biological activities of dinitrosyl iron complexes--inducing long-lasting vasodilation and thereby long-lasting hypotension in human and animals, inhibiting pellet aggregation, increasing red blood cell elasticity, thereby stimulating microcirculation, and reducing necrotic zone in animals with myocardial infarction. Moreover, dinitrosyl iron complexes are capable of accelerating skin wound healing, improving the function of penile cavernous tissue, blocking apoptosis development in cell cultures. When decomposed dinitrosyl iron complexes can exert cytotoxic effect that can be used for curing infectious and carcinogenic pathologies.

Unquenched Complex Dirac Spectra at Nonzero Chemical Potential: Two-Color QCD Lattice Data versus Matrix Model

International Nuclear Information System (INIS)

Akemann, Gernot; Bittner, Elmar

2006-01-01

We compare analytic predictions of non-Hermitian chiral random matrix theory with the complex Dirac operator eigenvalue spectrum of two-color lattice gauge theory with dynamical fermions at nonzero chemical potential. The Dirac eigenvalues come in complex conjugate pairs, making the action of this theory real and positive for our choice of two staggered flavors. This enables us to use standard Monte Carlo simulations in testing the influence of the chemical potential and quark mass on complex eigenvalues close to the origin. We find excellent agreement between the analytic predictions and our data for two different volumes over a range of chemical potentials below the chiral phase transition. In particular, we detect the effect of unquenching when going to very small quark masses

Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

International Nuclear Information System (INIS)

Maulois, Melissa; Ribière, Maxime; Eichwald, Olivier; Yousfi, Mohammed; Azaïs, Bruno

2016-01-01

The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N_2 and 20% O_2) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 10"1"3" cm"−"3 is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the

Towards Free-Form Kinetic Structures

DEFF Research Database (Denmark)

Parigi, Dario; Kirkegaard, Poul Henning

2012-01-01

of pin-slot paths starting from the local displacements of element [2] [3]. In the design of kinetic structures, in particular when complex three dimensional and non regular configurations are involved, the functionality is frequently related to a global displacement capability of the assembly rather...... for the generation of free-form kinetic structures....

Kinetics and thermodynamics of small molecule binding to pincer-PCP rhodium(I) complexes

KAUST Repository

Doherty, Mark D.

2013-04-15

The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H 4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH 2PtBu2] (1) and Rh[tBu 2P(CH2)2(CH)(CH2)2P tBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C 2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10 5 M-1 s-1 for L = C2H4; 4.0 × 106 M-1 s-1 for L = N2; 5.5 × 108 M-1 s-1 for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a

Kinetics and thermodynamics of small molecule binding to pincer-PCP rhodium(I) complexes

KAUST Repository

Doherty, Mark D.; Grills, David C.; Huang, Kuo-Wei; Muckerman, James T.; Polyansky, Dmitry E.; Van Eldik, Rudi V.; Fujita, Etsuko

2013-01-01

The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H 4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH 2PtBu2] (1) and Rh[tBu 2P(CH2)2(CH)(CH2)2P tBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C 2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10 5 M-1 s-1 for L = C2H4; 4.0 × 106 M-1 s-1 for L = N2; 5.5 × 108 M-1 s-1 for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a

Recent results in muonium solution kinetics

International Nuclear Information System (INIS)

Jean, Y.C.; Ito, Y.; Stadlbauer, J.M.; Ng, B.W.; Walker, D.C.

1983-06-01

Using muonium spin rotation (MSR) techniques the aqueous solution kinetics of several muonium addition reactions and spin conversion interactions have been studied. The addition reactions show both diffusion and activation-controlled reaction rates with isotope effects between 1 and 3 for diffusion-control and between 7 and 31 for activation-control reactions. Barrier energies are typically approximately 15 kJ/mole and approximately 30 kJ/mole, respectively, for these processes in water. Spin-conversion interactions involving Ni +2 (aq) and Ni(cyclam) +2 complexes showed that spin-conversion of 'triplet' Mu by a paramagnetic solute occurs at or near the diffusion-controlled limit while the chemical reaction with the diamagnetic configuration of Ni(cyclam) +2 occurred some 100 times slower at ksub(M) 18 M -1 s -1

Three-dimensional laser-induced fluorescence measurements of turbulent chemical plumes

Science.gov (United States)

True, Aaron; Crimaldi, John

2017-11-01

In order to find prey, mates, and suitable habitat, many organisms must navigate through complex chemical plume structures in turbulent flow environments. In this context, we investigate the spatial and temporal structure of chemical plumes released isokinetically into fractal-grid-generated turbulence in an open channel flow. We first utilized particle image velocimetry (PIV) to characterize flow conditions (mean free stream velocities, turbulence intensities, turbulent kinetic energy dissipation rates, Taylor Reynolds numbers). We then implemented a newly developed high-resolution, high-speed, volumetric scanning laser-induced fluorescence (LIF) system for near time-resolved measurements of three-dimensional chemical plume structures. We investigated cases with and without a cylinder wake, and compare statistical (mean, variance, intermittency, probability density functions) and spectral (power spectrum of concentration fluctuations) characteristics of the chemical plume structure. Stretching and folding of complex three-dimensional filament structures during chaotic turbulent mixing is greatly enhanced in the cylinder wake case. In future experiments, we will implement simultaneous PIV and LIF, enabling computation of the covariance of the velocity and chemical concentration fluctuations and thus estimation of turbulent eddy diffusivities. NSF PHY 1555862.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-02-25

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

Rapid kinetics of iron responsive element (IRE) RNA/iron regulatory protein 1 and IRE-RNA/eIF4F complexes respond differently to metal ions.

Science.gov (United States)

Khan, Mateen A; Ma, Jia; Walden, William E; Merrick, William C; Theil, Elizabeth C; Goss, Dixie J

2014-06-01

Metal ion binding was previously shown to destabilize IRE-RNA/IRP1 equilibria and enhanced IRE-RNA/eIF4F equilibria. In order to understand the relative importance of kinetics and stability, we now report rapid rates of protein/RNA complex assembly and dissociation for two IRE-RNAs with IRP1, and quantitatively different metal ion response kinetics that coincide with the different iron responses in vivo. kon, for FRT IRE-RNA binding to IRP1 was eight times faster than ACO2 IRE-RNA. Mn(2+) decreased kon and increased koff for IRP1 binding to both FRT and ACO2 IRE-RNA, with a larger effect for FRT IRE-RNA. In order to further understand IRE-mRNA regulation in terms of kinetics and stability, eIF4F kinetics with FRT IRE-RNA were determined. kon for eIF4F binding to FRT IRE-RNA in the absence of metal ions was 5-times slower than the IRP1 binding to FRT IRE-RNA. Mn(2+) increased the association rate for eIF4F binding to FRT IRE-RNA, so that at 50 µM Mn(2+) eIF4F bound more than 3-times faster than IRP1. IRP1/IRE-RNA complex has a much shorter life-time than the eIF4F/IRE-RNA complex, which suggests that both rate of assembly and stability of the complexes are important, and that allows this regulatory system to respond rapidly to change in cellular iron. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

Mechanisms and Kinetics of Organic Aging in High-Level Nuclear Wastes

International Nuclear Information System (INIS)

Camaioni, Donald M.; Autrey, S. Thomas; Linehan, John L.

1999-01-01

The goal of this project is to develop a fundamental understanding of organic aging and to assemble a model that describes and predicts the thermal and radiolytic aging of organic compounds in high-level wastes (HLW). To reach this goal, we will measure kinetics and elucidate products and mechanisms of organic reactions occurring under conditions of waste storage, retrieval, and processing. Initial emphasis will be placed on studying thermal effects, because organic reaction mechanisms and effects of varying conditions are uncertain, and because we benefit from collaborations with earlier Environmental Management Science Program (EMSP) projects that have worked on radiation effects. Organic complexants are of greatest concern regarding both safety and pretreatment because they have been found to degrade to gases, combust in dry wastes, and interfere with radionuclide separations. Therefore, efforts will focus on studying the reactions of these organic chemicals and associated degradation products. In preliminary work, the authors have used mechanistic kinetic modeling techniques to successfully model the radiolytic degradation of formate to carbonate in HLW simulants. The research will continue development of the model using an iterative process that measures degradation products and kinetics of increasingly complex molecules while adapting the model to reproduce the results each step of the way. Several mechanistic probe experiments have been designed to learn the fundamental mechanisms that operate during thermal degradations so that thermal and radiolytic processes may be integrated within the model. Key kinetic data and thermodynamic properties relating to thermal reactivity will also be acquired so that rate-controlling and product-forming reactions can be predicted. Thermochemical properties of key intermediates will be experimentally and/or theoretically determined to facilitate mechanism verification, structure/reactivity correlation, and prediction of

Numerical Modeling of Mixing of Chemically Reacting, Non-Newtonian Slurry for Tank Waste Retrieval

International Nuclear Information System (INIS)

Yuen, D.A.; Onishi, Y.

2001-01-01

In the U.S. Department of Energy (DOE) complex, 100 million gallons of radioactive and chemical wastes from plutonium production are stored in 281 underground storage tanks. Retrieval of the wastes from the tanks is the first step in its ultimate treatment and disposal. Because billions of dollars are being spent on this effort, waste retrieval demands a strong scientific basis for its successful completion. As will be discussed in Section 4.2, complex interactions among waste chemical reactions, rheology, and mixing of solid and liquid tank waste (and possibly with a solvent) will occur in DSTs during the waste retrieval (mixer pump) operations. The ultimate goal of this study was to develop the ability to simulate the complex chemical and rheological changes that occur in the waste during processing for retrieval. This capability would serve as a scientific assessment tool allowing a priori evaluation of the consequences of proposed waste retrieval operations. Hanford tan k waste is a multiphase, multicomponent, high-ionic strength, and highly basic mixture of liquids and solids. Wastes stored in the 4,000-m3 DSTs will be mixed by 300-hp mixer pumps that inject high-speed (18.3 m/s) jets to stir up the sludge and supernatant liquid for retrieval. During waste retrieval operations, complex interactions occur among waste mixing, chemical reactions, and associated rheology. Thus, to determine safe and cost-effective operational parameters for waste retrieval, decisions must rely on new scientific knowledge to account for physical mixing of multiphase flows, chemical reactions, and waste rheology. To satisfy this need, we integrated a computational fluid dynamics code with state-of-the-art equilibrium and kinetic chemical models and non-Newtonian rheology (Onishi (and others) 1999). This development is unique and holds great promise for addressing the complex phenomena of tank waste retrieval. The current model is, however, applicable only to idealized tank waste

Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

Directory of Open Access Journals (Sweden)

Rajesh Ramaswamy

2011-01-01

Full Text Available Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM or fluorescence-correlation spectroscopy (FCS to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

New Procedure to Develop Lumped Kinetic Models for Heavy Fuel Oil Combustion

KAUST Repository

Han, Yunqing

2016-09-20

A new procedure to develop accurate lumped kinetic models for complex fuels is proposed, and applied to the experimental data of the heavy fuel oil measured by thermogravimetry. The new procedure is based on the pseudocomponents representing different reaction stages, which are determined by a systematic optimization process to ensure that the separation of different reaction stages with highest accuracy. The procedure is implemented and the model prediction was compared against that from a conventional method, yielding a significantly improved agreement with the experimental data. © 2016 American Chemical Society.

Characterization of the functional epitope on the urokinase receptor. Complete alanine scanning mutagenesis supplemented by chemical cross-linking

DEFF Research Database (Denmark)

Gårdsvoll, Henrik; Gilquin, Bernard; Le Du, Marie Hélène

2006-01-01

a comprehensive alanine scanning mutagenesis of uPAR combined with low resolution distance constraints defined within the complex using chemical cross-linkers as molecular rulers. The kinetic rate constants for the interaction between pro-uPA and 244 purified uPAR mutants with single-site replacements were...

Pyrolysis of Waste Castor Seed Cake: A Thermo-Kinetics Study

Directory of Open Access Journals (Sweden)

Abdullahi Muhammad Sokoto

2018-03-01

Full Text Available Biomass pyrolysis is a thermo-chemical conversion process that is of both industrial and ecological importance. The efficient chemical transformation of waste biomass to numerous products via pyrolysis reactions depends on process kinetic rates; hence the need for kinetic models to best design and operate the pyrolysis. Also, for an efficient design of an environmentally sustainable pyrolysis process of a specific lignocellulosic waste, a proper understanding of its thermo-kinetic behavior is imperative. Thus, pyrolysis kinetics of castor seed de-oiled cake (Ricinus communis using thermogravimetric technique was studied. The decomposition of the cake was carried out in a nitrogen atmosphere with a flow rate of 100mL min-1 from ambient temperature to 900 °C. The results of the thermal profile showed moisture removal and devolatilization stages, and maximum decomposition of the cake occurred at a temperature of 200-400 °C. The kinetic parameters such as apparent activation energy, pre-exponential factor, and order of reaction were determined using Friedman (FD, Kissinger-Akahira-Sunose (KAS, and Flynn-Wall-Ozawa (FWO kinetic models. The average apparent activation energy values of 124.61, 126.95 and 129.80 kJmol-1 were calculated from the slopes of the respective models. The apparent activation energy values obtained depends on conversion, which is an evidence of multi-step kinetic process during the pyrolytic decomposition of the cake. The kinetic data would be of immense benefit to model, design and develop a suitable thermo-chemical system for the conversion of waste de-oil cake to energy carrier.

Half-sandwich cobalt complexes in the metal-organic chemical vapor deposition process

Energy Technology Data Exchange (ETDEWEB)

Georgi, Colin [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Hapke, Marko; Thiel, Indre [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), Albert-Einstein-Straße 29a, Rostock 18059 (Germany); Hildebrandt, Alexander [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Waechtler, Thomas; Schulz, Stefan E. [Fraunhofer Institute of Electronic Nano Systems (ENAS), Technologie-Campus 3, Chemnitz 09126 (Germany); Technische Universität Chemnitz, Center for Microtechnologies (ZfM), Chemnitz 09107 (Germany); Lang, Heinrich, E-mail: heinrich.lang@chemie.tu-chemnitz.de [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany)

2015-03-02

A series of cobalt half-sandwich complexes of type [Co(η{sup 5}-C{sub 5}H{sub 5})(L)(L′)] (1: L, L′ = 1,5-hexadiene; 2: L = P(OEt){sub 3}, L′ = H{sub 2}C=CHSiMe{sub 3}; 3: L = L′ = P(OEt){sub 3}) has been studied regarding their physical properties such as the vapor pressure, decomposition temperature and applicability within the metal-organic chemical vapor deposition (MOCVD) process, with a focus of the influence of the phosphite ligands. It could be shown that an increasing number of P(OEt){sub 3} ligands increases the vapor pressure and thermal stability of the respective organometallic compound. Complex 3 appeared to be a promising MOCVD precursor with a high vapor pressure and hence was deposited onto Si/SiO{sub 2} (100 nm) substrates. The resulting reflective layer is closed, dense and homogeneous, with a slightly granulated surface morphology. X-ray photoelectron spectroscopy (XPS) studies demonstrated the formation of metallic cobalt, cobalt phosphate, cobalt oxide and cobalt carbide. - Highlights: • Thermal studies and vapor pressure measurements of cobalt half-sandwich complexes was carried out. • Chemical vapor deposition with cobalt half-sandwich complexes is reported. • The use of Co-phosphites results in significant phosphorous-doped metallic layers.

A new improvement on a chemical kinetic model of primary reference fuel for multi-dimensional CFD simulation

International Nuclear Information System (INIS)

Zhen, Xudong; Wang, Yang; Liu, Daming

2016-01-01

Highlights: • A new optimized chemical kinetic mechanism for PRF is developed. • New mechanism optimization is performed based on the CHEMKIN simulations. • More reactions of C_0–C_1 oxidation are added in the present mechanism. • Good performance is achieved of mechanism by validating various reactors and operating conditions. - Abstract: In the present study, for the multi-dimensional CFD (computational fluid dynamics) combustion simulations of internal combustion engines, a new optimized chemical kinetic reaction mechanism for the oxidation of PRF (primary reference fuel) instead of gasoline has been developed. In order to carry out the in-depth research for combustion phenomenon of internal combustion engines, an optimized reduced PRF mechanism including more intermediate species and radicals was developed. The developed mechanism contains of iso-octane (C_8H_1_8) and n-heptane (C_7H_1_6) surrogates, which contains of 51-species and 193 reactions. Compared with many other mechanisms of PRF, more reactions of C_0–C_1 oxidation (100 reactions) are added in the present mechanism. In order to improve the performances of the model, the developed mechanism focused on the improvement through the prediction of the ignition delay time. The developed mechanism has been validated against various experimental and simulation data including shock tube data, laminar flame speed data and HCCI (homogeneous charge compression ignition) engine data. The results showed that the developed PRF mechanism was agreements with the experimental data and other approved reduced mechanisms, and it could be applied to the multi-dimensional CFD simulations for internal combustion engines.

Collective behaviours: from biochemical kinetics to electronic circuits

Science.gov (United States)

Agliari, Elena; Barra, Adriano; Burioni, Raffaella; di Biasio, Aldo; Uguzzoni, Guido

2013-12-01

In this work we aim to highlight a close analogy between cooperative behaviors in chemical kinetics and cybernetics; this is realized by using a common language for their description, that is mean-field statistical mechanics. First, we perform a one-to-one mapping between paradigmatic behaviors in chemical kinetics (i.e., non-cooperative, cooperative, ultra-sensitive, anti-cooperative) and in mean-field statistical mechanics (i.e., paramagnetic, high and low temperature ferromagnetic, anti-ferromagnetic). Interestingly, the statistical mechanics approach allows a unified, broad theory for all scenarios and, in particular, Michaelis-Menten, Hill and Adair equations are consistently recovered. This framework is then tested against experimental biological data with an overall excellent agreement. One step forward, we consistently read the whole mapping from a cybernetic perspective, highlighting deep structural analogies between the above-mentioned kinetics and fundamental bricks in electronics (i.e. operational amplifiers, flashes, flip-flops), so to build a clear bridge linking biochemical kinetics and cybernetics.

Mapping of Drug-like Chemical Universe with Reduced Complexity Molecular Frameworks.

Science.gov (United States)

Kontijevskis, Aleksejs

2017-04-24

The emergence of the DNA-encoded chemical libraries (DEL) field in the past decade has attracted the attention of the pharmaceutical industry as a powerful mechanism for the discovery of novel drug-like hits for various biological targets. Nuevolution Chemetics technology enables DNA-encoded synthesis of billions of chemically diverse drug-like small molecule compounds, and the efficient screening and optimization of these, facilitating effective identification of drug candidates at an unprecedented speed and scale. Although many approaches have been developed by the cheminformatics community for the analysis and visualization of drug-like chemical space, most of them are restricted to the analysis of a maximum of a few millions of compounds and cannot handle collections of 10 8 -10 12 compounds typical for DELs. To address this big chemical data challenge, we developed the Reduced Complexity Molecular Frameworks (RCMF) methodology as an abstract and very general way of representing chemical structures. By further introducing RCMF descriptors, we constructed a global framework map of drug-like chemical space and demonstrated how chemical space occupied by multi-million-member drug-like Chemetics DNA-encoded libraries and virtual combinatorial libraries with >10 12 members could be analyzed and mapped without a need for library enumeration. We further validate the approach by performing RCMF-based searches in a drug-like chemical universe and mapping Chemetics library selection outputs for LSD1 targets on a global framework chemical space map.

Unique effects of microwave heating on polymerization kinetics of poly(methyl methacrylate) composites

Energy Technology Data Exchange (ETDEWEB)

Spasojević, Pavle [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Jovanović, Jelena, E-mail: jelenaj@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia); Adnadjevic, Borivoj [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia)

2013-09-16

The effects of heating mode (conventional and microwave) on the kinetics of isothermal polymerization of MMA composite materials were investigated. Isothermal kinetics curves at temperature range from 343 K to 363 K for both conventional (CH) and microwave heating (MWH) were determined. It was found that the polymerization of MMA composite materials was kinetically elementary reaction for both CH and MWH. The kinetics of CH polymerization can be described by the model of phase-boundary controlled process (contracting volume), whereas the kinetics of MWH polymerization can be described by the model of first-order chemical reaction. The kinetics parameters (E{sub a} and ln A) of the polymerization under microwave heating are lower than for conventional heating. The established decreases in the activation energy and pre-exponential factor under the MWH compared to the CH is explained with the increase in the energy of ground vibrational level of the C–O valence vibrations (ν = 987 cm{sup −1}) in methyl methacrylate molecule and with the decrease in its anharmonicity factor which is caused with the selective resonant transfer of energy from the energetic reservoir to the oscillators in methyl methacrylate molecules. - Graphical abstract: Display Omitted - Highlights: • The MWH speeds the MMA material polymerization and changes the kinetics model. • A novel concept of MWH action based on activation complexes formation is presented. • The Selective Energy Transfer model is used to explain the effects of MWH. • The kinetics parameters under MWH are lower than for CH. • The activation energy for both MWH and CH polymerization is quantized.

Alkylation of Chlorobenzene. An Experiment Illustrating Kinetic versus Thermodynamic Control.

Science.gov (United States)

Kolb, Kenneth; And Others

1988-01-01

Describes an experiment which illustrates the kinetic versus thermodynamic control of chemical reactions for organic chemistry students. Considers the laboratory procedures including the isolation of both the kinetic and thermodynamic products. (CW)

Optimal Bayesian Experimental Design for Combustion Kinetics

KAUST Repository

Huan, Xun

2011-01-04

Experimental diagnostics play an essential role in the development and refinement of chemical kinetic models, whether for the combustion of common complex hydrocarbons or of emerging alternative fuels. Questions of experimental design—e.g., which variables or species to interrogate, at what resolution and under what conditions—are extremely important in this context, particularly when experimental resources are limited. This paper attempts to answer such questions in a rigorous and systematic way. We propose a Bayesian framework for optimal experimental design with nonlinear simulation-based models. While the framework is broadly applicable, we use it to infer rate parameters in a combustion system with detailed kinetics. The framework introduces a utility function that reflects the expected information gain from a particular experiment. Straightforward evaluation (and maximization) of this utility function requires Monte Carlo sampling, which is infeasible with computationally intensive models. Instead, we construct a polynomial surrogate for the dependence of experimental observables on model parameters and design conditions, with the help of dimension-adaptive sparse quadrature. Results demonstrate the efficiency and accuracy of the surrogate, as well as the considerable effectiveness of the experimental design framework in choosing informative experimental conditions.

untangling chemical kinetics through tangible and visual

African Journals Online (AJOL)

Temechegn

elementary chemical reactions as part of the learning process. Despite employing ... relation between reaction rates of reactants and their products involves the use .... Experiment Journal of Chemical Education, 77, 1013– 1014. 19. Niaz, M. A ...

Evaluation and Development of Chemical Kinetic Mechanism Reduction Scheme for Biodiesel and Diesel Fuel Surrogates

DEFF Research Database (Denmark)

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

2013-01-01

The aim of this study is to evaluate the existing chemical kinetic mechanism reduction techniques. From here, an appropriate reduction scheme was developed to create compact yet comprehensive surrogate models for both diesel and biodiesel fuels for diesel engine applications. The reduction...... techniques applied here were Directed Relation Graph (DRG), DRG with Error Propagation, DRG-aided Sensitivity Analysis, and DRG with Error Propagation and Sensitivity Analysis. Nonetheless, the reduced mechanisms generated via these techniques were not sufficiently small for application in multi......-dimensional computational fluid dynamics (CFD) study. A new reduction scheme was therefore formulated. A 68-species mechanism for biodiesel surrogate and a 49-species mechanism for diesel surrogate were successfully derived from the respective detailed mechanisms. An overall 97% reduction in species number...

Radiological and chemical source terms for Solid Waste Operations Complex

International Nuclear Information System (INIS)

Boothe, G.F.

1994-01-01

The purpose of this document is to describe the radiological and chemical source terms for the major projects of the Solid Waste Operations Complex (SWOC), including Project W-112, Project W-133 and Project W-100 (WRAP 2A). For purposes of this document, the term ''source term'' means the design basis inventory. All of the SWOC source terms involve the estimation of the radiological and chemical contents of various waste packages from different waste streams, and the inventories of these packages within facilities or within a scope of operations. The composition of some of the waste is not known precisely; consequently, conservative assumptions were made to ensure that the source term represents a bounding case (i.e., it is expected that the source term would not be exceeded). As better information is obtained on the radiological and chemical contents of waste packages and more accurate facility specific models are developed, this document should be revised as appropriate. Radiological source terms are needed to perform shielding and external dose calculations, to estimate routine airborne releases, to perform release calculations and dose estimates for safety documentation, to calculate the maximum possible fire loss and specific source terms for individual fire areas, etc. Chemical source terms (i.e., inventories of combustible, flammable, explosive or hazardous chemicals) are used to determine combustible loading, fire protection requirements, personnel exposures to hazardous chemicals from routine and accident conditions, and a wide variety of other safety and environmental requirements

Interdependent effect of chemical composition and thermal history on artificial aging of AA6061

International Nuclear Information System (INIS)

Pogatscher, S.; Antrekowitsch, H.; Uggowitzer, P.J.

2012-01-01

In this study, the interdependent effect of chemical composition and thermal history on artificial aging was investigated for the aluminum alloy AA6061. Based on thermodynamic calculations, including Al, Fe, Cr, Zn, Ti, Mg, Si and Cu, model alloys exhibiting a maximum variation of the reachable solute super-saturation of elements relevant for precipitation hardening within the compositional limits of AA6061 were produced. The artificial aging behavior of these alloys at 175 °C was studied by tensile testing for two thermal histories, including very short- and long-term room temperature storage after quenching. Precipitation during artificial aging was investigated by an analysis of yield strength data. As generally expected, precipitation kinetics was found to depend strongly on the solute super-saturation in the case of very short room temperature storage. For artificial aging after long-term room temperature storage the kinetics showed almost no dependence on the chemical composition. This seems to be an exception from simple precipitation kinetics and can be explained based on the complex role of quenched-in vacancies in artificial aging of AA6061.

Empirical, thermodynamic and quantum-chemical investigations of inclusion complexation between flavanones and (2-hydroxypropyl)-cyclodextrins.

Science.gov (United States)

Liu, Benguo; Li, Wei; Nguyen, Tien An; Zhao, Jian

2012-09-15

The inclusion complexation of (2-hydroxypropyl)-cyclodextrins with flavanones was investigated by phase solubility measurements, as well as thermodynamic and quantum chemical methods. Inclusion complexes were formed between (2-hydroxypropyl)-α-cyclodextrin (HP-α-CD), (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD), (2-hydroxypropyl)-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD) and four flavanones (naringenin, naringin, hesperetin and dihydromyricetin) in aqueous solutions and their phase solubility was determined. For all the flavanones, the stability constants of their complexes formed with different CDs followed the rank order: HP-β-CD (MW 1540)>HP-β-CD (MW 1460)>HP-β-CD (MW 1380)>β-CD>HP-γ-CD>HP-α-CD. Experimental results and quantum chemical calculations showed that the ability of flavanones to form inclusion complex with (2-hydroxypropyl)-cyclodextrins was determined by both the steric effect and hydrophobicity of the flavanones. For flavanones that have similar molecular volumes, the hydrophobicity of the molecule was the main determining factor of its ability to form inclusion complexes with HP-β-CD, and the hydrophobicity parameter Log P is highly correlated with the stability constant of the complexes. Results of thermodynamic study demonstrated that hydrophobic interaction is the main driving force for the formation process of the flavanone-CD inclusion complexes. Quantum chemical analysis of the most active hydroxyl groups and HOMO (the highest occupied molecular orbital) showed that the B ring of the flavanones was most likely involved in hydrogen bonding with the side groups in the cavity of the CDs, through which the inclusion complex was stabilised. Copyright © 2012 Elsevier Ltd. All rights reserved.

From Molecules to Life: Quantifying the Complexity of Chemical and Biological Systems in the Universe.

Science.gov (United States)

Böttcher, Thomas

2018-01-01

Life is a complex phenomenon and much research has been devoted to both understanding its origins from prebiotic chemistry and discovering life beyond Earth. Yet, it has remained elusive how to quantify this complexity and how to compare chemical and biological units on one common scale. Here, a mathematical description of molecular complexity was applied allowing to quantitatively assess complexity of chemical structures. This in combination with the orthogonal measure of information complexity resulted in a two-dimensional complexity space ranging over the entire spectrum from molecules to organisms. Entities with a certain level of information complexity directly require a functionally complex mechanism for their production or replication and are hence indicative for life-like systems. In order to describe entities combining molecular and information complexity, the term biogenic unit was introduced. Exemplified biogenic unit complexities were calculated for ribozymes, protein enzymes, multimeric protein complexes, and even an entire virus particle. Complexities of prokaryotic and eukaryotic cells, as well as multicellular organisms, were estimated. Thereby distinct evolutionary stages in complexity space were identified. The here developed approach to compare the complexity of biogenic units allows for the first time to address the gradual characteristics of prebiotic and life-like systems without the need for a definition of life. This operational concept may guide our search for life in the Universe, and it may direct the investigations of prebiotic trajectories that lead towards the evolution of complexity at the origins of life.

Predicting oil and gas compositional yields via chemical structure-chemical yield modeling (CS-CYM): Part 1 - Concepts and implementation

Energy Technology Data Exchange (ETDEWEB)

Freund, H.; Walters, C.C.; Kelemen, S.R.; Siskin, M.; Gorbaty, M.L.; Curry, D.J.; Bence, A.E. [ExxonMobil Research & Engineering Co., Annandale, NJ (United States)

2007-07-01

We have developed a method to calculate the amounts and composition of products resulting from the thermal decomposition of a solid complex carbonaceous material. This procedure provides a means of using laboratory measurements of complex carbonaceous solids to construct a representative model of its chemical structure (CS) that is then coupled with elementary reaction pathways to predict the chemical yield (CY) upon thermal decomposition. Data from elemental analysis, H, N, O, S, solid state {sup 13}C NMR, X-ray photoelectron spectroscopy (XPS), sulfur X-ray absorption structure spectroscopy (XANES), and pyrolysis-gas chromatography (GC) are used to constrain the construction of core molecular structures representative of the complex carbonaceous material. These core structures are expanded stochastically to describe large macromolecules ({gt} 10{sup 6} cores with similar to 10{sup 6} atoms) with bulk properties that match the experimental results. Gas, liquid and solid product yields, resulting from thermal decomposition, are calculated by identifying reactive functional groups within the CS stochastic ensemble and imposing a reaction network constrained by fundamental thermodynamics and kinetics. An expulsion model is added to the decomposition model to calculate the chemical products in open and closed systems. Product yields may then be predicted under a wide range of time-temperature conditions used in rapid laboratory pyrolysis experiments, refinery processes, or geologic maturation.

Kinetic Isotope Effect Determination Probes the Spin of the Transition State, Its Stereochemistry, and Its Ligand Sphere in Hydrogen Abstraction Reactions of Oxoiron(IV) Complexes.

Science.gov (United States)

Mandal, Debasish; Mallick, Dibyendu; Shaik, Sason

2018-01-16

This Account outlines interplay of theory and experiment in the quest to identify the reactive-spin-state in chemical reactions that possess a few spin-dependent routes. Metalloenzymes and synthetic models have forged in recent decades an area of increasing appeal, in which oxometal species bring about functionalization of hydrocarbons under mild conditions and via intriguing mechanisms that provide a glimpse of Nature's designs to harness these reactions. Prominent among these are oxoiron(IV) complexes, which are potent H-abstractors. One of the key properties of oxoirons is the presence of close-lying spin-states, which can mediate H-abstractions. As such, these complexes form a fascinating chapter of spin-state chemistry, in which chemical reactivity involves spin-state interchange, so-called two-state reactivity (TSR) and multistate reactivity (MSR). TSR and MSR pose mechanistic challenges. How can one determine the structure of the reactive transition state (TS) and its spin state for these mechanisms? Calculations can do it for us, but the challenge is to find experimental probes. There are, however, no clear kinetic signatures for the reactive-spin-state in such reactions. This is the paucity that our group has been trying to fill for sometime. Hence, it is timely to demonstrate how theory joins experiment in realizing this quest. This Account uses a set of the H-abstraction reactions of 24 synthetic oxoiron(IV) complexes and 11 hydrocarbons, together undergoing H-abstraction reactions with TSR/MSR options, which provide experimentally determined kinetic isotope effect (KIE exp ) data. For this set, we demonstrate that comparing KIE exp results with calculated tunneling-augmented KIE (KIE TC ) data leads to a clear identification of the reactive spin-state during H-abstraction reactions. In addition, generating KIE exp data for a reaction of interest, and comparing these to KIE TC values, provides the mechanistic chemist with a powerful capability to

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate

Energy Technology Data Exchange (ETDEWEB)

Forsey, S.P.; Thomson, N.R.; Barker, J.F. [University of Waterloo, Waterloo, ON (Canada). Dept. of Civil & Environmental Engineering

2010-04-15

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalene < phenanthrene < pyrene. The rate of side chain reactivity is controlled by the C-H bond strength. For the alkyl substituted benzenes an excellent correlation was observed between the reaction rate coefficients and bond dissociation energies, but for the substituted PAHs the relationship was poor. A trend was found between the reaction rate coefficients and the calculated heats of complexation indicating that significant ring oxidation occurred in addition to side chain oxidation. Clar's aromatic sextet theory was used to predict the relative stability of arenes towards ring oxidation by permanganate.

Kinetics of molybdenum(6) complexation with o,o'-dihydroxyazo compounds or heterocyclic azo compounds in the presence of hydroxylamine

International Nuclear Information System (INIS)

Kochelaeva, G.A.; Degtyarev, M.Yu.; Ivanov, V.M.; Prokhorova, G.V.; Figurovskaya, V.N.

1999-01-01

The kinetics of complexation in the system molybdenum(6)-azo compound-hydroxylamine was studied. Azo compounds of the types o,o'-dihydroxyazo compounds, such as Lyumogallion IREA and Magneson IREA, and heterocyclic azo compounds, such as 4-(2-pyridylazo)resorcinol and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol, were studied. The formation of mixed-ligand complexes with the ratio of component 1 : 1 : 1 was detected. Rate constants, activation energies, and stability constants of the forming compounds were evaluated. It was concluded that the reagents under study are promising for the analytical chemistry of molybdenum [ru

Isoconversional kinetics of thermally stimulated processes

CERN Document Server

Vyazovkin, Sergey

2015-01-01

The use of isoconversional kinetic methods for analysis of thermogravimetric and calorimetric data on thermally stimulated processes is quickly growing in popularity. The purpose of this book is to create the first comprehensive resource on the theory and applications of isoconversional methodology. The book introduces the reader to the kinetics of physical and chemical condensed phase processes that occur as a result of changing temperature and discusses how isoconversional analysis can provide important kinetic insights into them. The book will help the readers to develop a better understanding of the methodology, and promote its efficient usage and successful development.

Recruitment kinetics of DNA repair proteins Mdc1 and Rad52 but not 53BP1 depend on damage complexity.

Directory of Open Access Journals (Sweden)

Volker Hable

Full Text Available The recruitment kinetics of double-strand break (DSB signaling and repair proteins Mdc1, 53BP1 and Rad52 into radiation-induced foci was studied by live-cell fluorescence microscopy after ion microirradiation. To investigate the influence of damage density and complexity on recruitment kinetics, which cannot be done by UV laser irradiation used in former studies, we utilized 43 MeV carbon ions with high linear energy transfer per ion (LET = 370 keV/µm to create a large fraction of clustered DSBs, thus forming complex DNA damage, and 20 MeV protons with low LET (LET = 2.6 keV/µm to create mainly isolated DSBs. Kinetics for all three proteins was characterized by a time lag period T(0 after irradiation, during which no foci are formed. Subsequently, the proteins accumulate into foci with characteristic mean recruitment times τ(1. Mdc1 accumulates faster (T(0 = 17 ± 2 s, τ(1 = 98 ± 11 s than 53BP1 (T(0 = 77 ± 7 s, τ(1 = 310 ± 60 s after high LET irradiation. However, recruitment of Mdc1 slows down (T(0 = 73 ± 16 s, τ(1 = 1050 ± 270 s after low LET irradiation. The recruitment kinetics of Rad52 is slower than that of Mdc1, but exhibits the same dependence on LET. In contrast, the mean recruitment time τ(1 of 53BP1 remains almost constant when varying LET. Comparison to literature data on Mdc1 recruitment after UV laser irradiation shows that this rather resembles recruitment after high than low LET ionizing radiation. So this work shows that damage quality has a large influence on repair processes and has to be considered when comparing different studies.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-10-01

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

Inactivation kinetics of various chemical disinfectants on Aeromonas hydrophila planktonic cells and biofilms.

Science.gov (United States)

Jahid, Iqbal Kabir; Ha, Sang-Do

2014-05-01

The present article focuses on the inactivation kinetics of various disinfectants including ethanol, sodium hypochlorite, hydrogen peroxide, peracetic acid, and benzalkonium chloride against Aeromonas hydrophila biofilms and planktonic cells. Efficacy was determined by viable plate count and compared using a modified Weibull model. The removal of the biofilms matrix was determined by the crystal violet assay and was confirmed by field-emission scanning electron microscope. The results revealed that all the experimental data and calculated Weibull α (scale) and β (shape) parameters had a good fit, as the R(2) values were between 0.88 and 0.99. Biofilms are more resistant to disinfectants than planktonic cells. Ethanol (70%) was the most effective in killing cells in the biofilms and significantly reduced (preduction as well as the effectiveness of chemical disinfectants on biofilms. The study showed that the Weibull model could successfully be used on food and food contact surfaces to determine the exact contact time for killing biofilms-forming foodborne pathogens.

Design of a high-pressure single pulse shock tube for chemical kinetic investigations

International Nuclear Information System (INIS)

Tranter, R. S.; Brezinsky, K.; Fulle, D.

2001-01-01

A single pulse shock tube has been designed and constructed in order to achieve extremely high pressures and temperatures to facilitate gas-phase chemical kinetic experiments. Postshock pressures of greater than 1000 atmospheres have been obtained. Temperatures greater than 1400 K have been achieved and, in principle, temperatures greater than 2000 K are easily attainable. These high temperatures and pressures permit the investigation of hydrocarbon species pyrolysis and oxidation reactions. Since these reactions occur on the time scale of 0.5--2 ms the shock tube has been constructed with an adjustable length driven section that permits variation of reaction viewing times. For any given reaction viewing time, samples can be withdrawn through a specially constructed automated sampling apparatus for subsequent species analysis with gas chromatography and mass spectrometry. The details of the design and construction that have permitted the successful generation of very high-pressure shocks in this unique apparatus are described. Additional information is provided concerning the diaphragms used in the high-pressure shock tube

Thermodynamics of axial substitution and kinetics of reactions with amino acids for the paddlewheel complex tetrakis(acetato)chloridodiruthenium(II,III).

Science.gov (United States)

Santos, Rodrigo L S R; van Eldik, Rudi; de Oliveira Silva, Denise

2012-06-18

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

Chemical kinetics, thermodynamics and the interpretation of in vivo processes - Part I

International Nuclear Information System (INIS)

Ferreira, R.

1976-01-01

A brief review of thermodynamic and kinetic concepts, the relationships between thermodynamic and kinetic information and the limitations of these concepts when confronted with the problems of biochemical processes and biological evaluation at the molecular level are presented [pt

Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

KAUST Repository

El-Sepelgy, Osama

2016-09-29

A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

KAUST Repository

El-Sepelgy, Osama; Alandini, Nurtalya; Rueping, Magnus

2016-01-01

A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Kinetic aspects of the Maillard reaction: a critical review

NARCIS (Netherlands)

Boekel, van M.A.J.S.

2001-01-01

The literature concerning the kinetics of the Maillard reaction was critically discussed according to the initial, intermediate and advanced stages, as this is the way the Maillard reaction is traditionally analysed. For each stage, a division is made between simple kinetics and complex kinetics.

Chemical Kinetics in Support of Syngas Turbine Combustion

Energy Technology Data Exchange (ETDEWEB)

Dryer, Frederick

2007-07-31

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

Moessbauer spectroscopy-nuclear hyperfine technique for studying dynamic chemical states of iron complexes

International Nuclear Information System (INIS)

Maeda, Y.

2005-01-01

A brief introduction of Moessbauer spectroscopy will be presented, followed by a discussion of the Moessbauer parameters, isomer shifts, quadrupole splittings, and spectral shapes of complexes in the presence of relaxation of the electronic states of the iron atoms. The usefulness of Moessbauer spectroscopy to demonstrate the dynamic phenomena of electronic states will be discussed in this lecture. (1) The Moessbauer spectra of mixed valence dinuclear and trinuclear iron complexes will be discussed in connection with the chemical structure of the complexes: The values of the quadrupole splittings and isomer shifts of [Fe II Fe III (bpmp) (ppa) 2 ](BF 4 ) 2 increase on raising the temperature, where Hbpmp represents 2,6-bis[bis(2- pyridylmethyl)aminoethyl]-4-methylphenol and ppa is 3-n-phenylpropionic acid. The spectra can be accounted for by postulating intramolecular electron exchange between two energetically inequivalent vibronic states Fe A 2+ Fe B 3+ and Fe A 3+ Fe B 2+ : The apparent time averaged valence states of the iron atoms are 2.2 and 2.8 on the Moessbauer time scale at 293 K. (2) The Moessbauer spectra of iron(III) spin-crossover complexes will be discussed in connection with the spin-transition rate and chemical structure of the complexes. The Moessbauer spectra of spin-crossover iron(III) complexes with LIESST (Light Induced Electronic Spin-State Transition) and of metallomesogens will be discussed to illustrate the extension of this research area by the use of Moessbauer spectroscopy.

Stability of HAMLET--a kinetically trapped alpha-lactalbumin oleic acid complex.

Science.gov (United States)

Fast, Jonas; Mossberg, Ann-Kristin; Svanborg, Catharina; Linse, Sara

2005-02-01

The stability toward thermal and urea denaturation was measured for HAMLET (human alpha-lactalbumin made lethal to tumor cells) and alpha-lactalbumin, using circular dichroism and fluorescence spectroscopy as well as differential scanning calorimetry. Under all conditions examined, HAMLET appears to have the same or lower stability than alpha-lactalbumin. The largest difference is seen for thermal denaturation of the calcium free (apo) forms, where the temperature at the transition midpoint is 15 degrees C lower for apo HAMLET than for apo alpha-lactalbumin. The difference becomes progressively smaller as the calcium concentration increases. Denaturation of HAMLET was found to be irreversible. Samples of HAMLET that have been renatured after denaturation have lost the specific biological activity toward tumor cells. Three lines of evidence indicate that HAMLET is a kinetic trap: (1) It has lower stability than alpha-lactalbumin, although it is a complex of alpha-lactalbumin and oleic acid; (2) its denaturation is irreversible and HAMLET is lost after denaturation; (3) formation of HAMLET requires a specific conversion protocol.

Physico-Chemical and In-vitro Microbial Studies of Newly Synthesis Organometallic Complexes

Directory of Open Access Journals (Sweden)

Isam Hussain Al-Karkhi

2014-05-01

Full Text Available Drugs normally synthesized to use as medication to treat diseases like cancer and microbial infections, these synthesized drugs were interested more than naturally-derived drugs which have been shows low activity or not as efficient against diseases. A new ligand 3-methylbenzyl (2Z-2-[1-(pyridin-4-ylethylidene]hydrazine carbodithioate (PE3MBC and its Cd(II, Cu(II, Co(II and Zn(II metal complexes. The new ligand and metal complexes were characterized via various physico-chemical and spectroscopic techniques. Cd(II complex show more activity against microbes and against cancer cell line MCF-7, while other complexes does not shows activity like cadmium complex, all the complexes does not shows any activity against MDAMB-231 cell line. The fatal of the cancer and the microbes cell was due to inhibition of DNA synthesis which was probably due to chelating with metals complexes, or could be referred to lipophilicity, presence of hydrophobic moiety in the complex molecule, also could be due to steric effects and electronic effects.

Kinetics of Oxidation of Cobalt(III Complexes of a Acids by Hydrogen Peroxide in the Presence of Surfactants

Directory of Open Access Journals (Sweden)

Mansur Ahmed

2008-01-01

Full Text Available Hydrogen peroxide oxidation of pentaamminecobalt(III complexes of α-hydroxy acids at 35°C in micellar medium has been attempted. In this reaction the rate of oxidation shows first order kinetics each in [cobalt(III] and [H2O2]. Hydrogen peroxide induced electron transfer in [(NH35 CoIII-L]2+ complexes of α-hydroxy acids readily yields 100% of cobalt(II with nearly 100% of C-C bond cleavage products suggesting that it behaves mainly as one equivalent oxidant in micellar medium. With unbound ligand also it behaves only as C-C cleavage agent rather than C-H cleavage agent. With increasing micellar concentration an increase in the rate is observed.

A kinetics database and scripts for PHREEQC

Science.gov (United States)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

Energy Technology Data Exchange (ETDEWEB)

Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

2010-10-01

Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

Exploring the science of thinking independently together: Faraday Discussion Volume 204 - Complex Molecular Surfaces and Interfaces, Sheffield, UK, July 2017.