Analysis of kinetic reaction mechanisms

CERN Document Server

Turányi, Tamás

2014-01-01

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

Kinetics of subdiffusion-assisted reactions: non-Markovian stochastic Liouville equation approach

International Nuclear Information System (INIS)

Shushin, A I

2005-01-01

Anomalous specific features of the kinetics of subdiffusion-assisted bimolecular reactions (time-dependence, dependence on parameters of systems, etc) are analysed in detail with the use of the non-Markovian stochastic Liouville equation (SLE), which has been recently derived within the continuous-time random-walk (CTRW) approach. In the CTRW approach, subdiffusive motion of particles is modelled by jumps whose onset probability distribution function is of a long-tailed form. The non-Markovian SLE allows for rigorous describing of some peculiarities of these reactions; for example, very slow long-time behaviour of the kinetics, non-analytical dependence of the reaction rate on the reactivity of particles, strong manifestation of fluctuation kinetics showing itself in very slowly decreasing behaviour of the kinetics at very long times, etc

Kinetics of Bio-Reactions

DEFF Research Database (Denmark)

Villadsen, John

2015-01-01

his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

Reaction kinetics of bond rotations in graphene

KAUST Repository

Skowron, Stephen T.; Koroteev, Victor O.; Baldoni, Matteo; Lopatin, Sergei; Zurutuza, Amaia; Chuvilin, Andrey; Besley, Elena

2016-01-01

The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

Reaction kinetics of bond rotations in graphene

KAUST Repository

Skowron, Stephen T.

2016-04-12

The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

Modelling and simulation of a transketolase mediated reaction: Sensitivity analysis of kinetic parameters

DEFF Research Database (Denmark)

Sayar, N.A.; Chen, B.H.; Lye, G.J.

2009-01-01

In this paper we have used a proposed mathematical model, describing the carbon-carbon bond format ion reaction between beta-hydroxypyruvate and glycolaldehyde to synthesise L-erythrulose, catalysed by the enzyme transketolase, for the analysis of the sensitivity of the process to its kinetic...

Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions

Science.gov (United States)

Bui, T. T. T.; Sal'nikov, D. S.; Dereven'kov, I. A.; Makarov, S. V.

2017-04-01

The kinetics of aquacobalamin reaction with aspartic and glutamic acids, and with their amides in water solutions, is studied via spectrophotometry. The kinetic and activation parameters of the process are determined. It is shown that the reaction product is cobalamin-amino acid complex. The data are compared to results on the reaction between aquacobalamin and primary amines.

Kinetic studies of elementary chemical reactions

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

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.

An investigation of the general regularity of size dependence of reaction kinetics of nanoparticles

International Nuclear Information System (INIS)

Cui, Zixiang; Duan, Huijuan; Xue, Yongqiang; Li, Ping

2015-01-01

In the processes of preparation and application of nanomaterials, the chemical reactions of nanoparticles are often involved, and the size of nanoparticles has dramatic influence on the reaction kinetics. Nevertheless, there are many conflicts on regularities of size dependence of reaction kinetic parameters, and these conflicts have not been explained so far. In this paper, taking the reaction of nano-ZnO (average diameter is from 20.96 to 53.31 nm) with acrylic acid solution as a system, the influence regularities of the particle size on the kinetic parameters were researched. The regularities were consistent with that in most literatures, but inconsistent with that in a few of literatures, the reasons for the conflicts were interpreted. The reasons can be attributed to two factors: one is improper data processing for fewer data points, and the other is the difference between solid particles and porous particles. A general regularity of the size dependence of reaction kinetics for solid particles was obtained. The regularity shows that with the size of nanoparticles decreasing, the rate constant and the reaction order increase, while the apparent activation energy and the pre-exponential factor decrease; and the relationships of the logarithm of rate constant, the logarithm of pre-exponential factor, and the apparent activation energy to the reciprocal of the particle size are linear, respectively

Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

Science.gov (United States)

Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

2017-10-01

In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

Chemistry and reaction kinetics of biowaste torrefaction

NARCIS (Netherlands)

Stelt, van der M.J.C.

2011-01-01

This thesis addresses the question of how the chemistry and reaction kinetics of torrefaction are influenced by reaction conditions and the effects occuring during the reaction. This research question can be specified by questions such as, what controls their kinetics during torrefaction and what

Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde

International Nuclear Information System (INIS)

Agirre, I.; Garcia, I.; Requies, J.; Barrio, V.L.; Gueemez, M.B.; Cambra, J.F.; Arias, P.L.

2011-01-01

The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic ion exchange resin was studied. These acetals can be obtained from renewable sources (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for different applications such as oxygenated diesel additives. A preliminary kinetic study was performed in a batch stirred tank reactor studying the influence of different process parameters like temperature, feed composition and the stirring speed. A pseudo homogenous kinetic model able to explain the reaction mechanism was adjusted. Thus, the corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin showed a fairly good behavior allowing 100% of selectivity towards acetals formation. However, the studied acetalization reaction showed high thermodynamic limitations achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed. -- Highlights: → The reaction between glycerol and acetaldehyde shows thermodynamic limitations. → Amberlyst 47 ion exchange resins show 100% of selectivity. → A pseudo-homogeneous kinetic model is able to predict the reaction progress. → Isomerization reactions were observed from dioxalanes to dioxanes.

Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

International Nuclear Information System (INIS)

Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

2011-01-01

The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation

Science.gov (United States)

Zhdanov, Vladimir P.

2015-03-01

Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9

The reaction between iodine and organic coatings under severe PWR accident conditions. An experimental parameter study

Energy Technology Data Exchange (ETDEWEB)

Hellmann, S; Funke, F; Greger, G U; Bleier, A; Morell, W [Siemens AG, Power Generation Group, Erlangen (Germany)

1996-12-01

An extensive experimental parameter study was performed on the deposition and on the resuspension kinetics in the reaction system iodine/organically coated surfaces. Both reactions in the gas phase and in the liquid phase were investigated and kinetic rate constants suitable for modelling were derived. Previous experimental studies on the reaction of iodine with organic coated surfaces were mostly limited to temperatures below 100{sup o}C. Thus, this parameter study aims at filling a gap and providing kinetic data on heterogeneous reactions with organic surfaces in the accident-relevant temperature range of 100-160{sup o}C. Two types of laboratory experiments carried out at Siemens/KWU using coatings representative for German power plants (epoxy-tape paint), namely gas phase tests and liquid phase tests. (author) 6 figs., 6 tabs., 5 refs.

Maps of Fe-Al phases formation kinetics parameters during isothermal sintering

Energy Technology Data Exchange (ETDEWEB)

Pochec, Ewelina, E-mail: epochec@wat.edu.pl [Department of Advanced Materials and Technology, Military University of Technology (Poland); Jozwiak, Stanislaw; Karczewski, Krzysztof; Bojar, Zbigniew [Department of Advanced Materials and Technology, Military University of Technology (Poland)

2012-10-10

Highlights: Black-Right-Pointing-Pointer The sintering temperature and compaction pressure have a strong influence on the sinters structure. Black-Right-Pointing-Pointer The measurements confirmed the presence of the high-aluminium phases from Fe-Al equilibrium system in tested sinters. Black-Right-Pointing-Pointer The kinetics of Fe-Al phase formation can be described by Johnson-Mehl-Avrami modelling. - Abstract: The influence of technological parameters (compaction pressure and sintering temperature) on Fe-Al phase formation was investigated. The kinetics of phase transformation preceding and during an SHS reaction was studied in isothermal conditions by DSC using the JMA (Johnson-Mehl-Avrami) model. This model allowed us to determine basic kinetic parameters, including the Avrami exponent, which characterises the rate and manner of particular phase nucleation. The activation energy (E{sub a}) of particular phase formation was determined by the Kissinger method. XRD analysis and SEM observations of sintered material showed that not only Fe{sub 2}Al{sub 5} phase and low-aluminium solid solution in iron but also aluminium-rich FeAl{sub 2} and FeAl{sub 3} phases are formed during the sintering of an FeAl50 elementary powder mixture in isothermal conditions with an SHS reaction. The above conclusions were confirmed by iron-based solid solution lattice parameter studies and microhardness measurements.

Preventing Corrosion by Controlling Cathodic Reaction Kinetics

Science.gov (United States)

2016-03-25

3. DATES COVERED (From - To) 09/23/15 - 04/22/16 4. TITLE AND SUBTITLE Sa. CONTRACT NUMBER Preventing Corrosion by Controlling Cathodic Reaction...Preventing corrosion by controlling cathodic reaction kinetics Progress Report for Period: 1 SEP 2015-31 MAR 2016 John Keith Department of...25 March 2016 Preventing corrosion by controlling cathodic reaction kinetics Annual Summary Report: FY16 PI: John Keith, 412-624-7016,jakeith

Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

Science.gov (United States)

Tang, Shihua; Wang, Baiyang; Li, Youqun

2015-04-15

The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluation of the kinetic and thermodynamic parameters of oxidation reaction in biodiesel from a quaternary mixture of raw material

Directory of Open Access Journals (Sweden)

Karina Gomes Angilelli

2017-05-01

Full Text Available A mixture of vegetable oil and animal fat as raw materials was optimized by simplex-centroid mixture design to produce a type of biodiesel with good oxidative stability, flow properties and reaction yield. Further, kinetic and thermodynamic parameters of oxidation reaction were determined by the accelerated method at different temperatures. Biodiesel produced with sodium methoxide as catalyst presented 6.5°C of cloud point, 2.0°C of pour point, and oxidative stability at 110°C equal to 8.98h, with a reaction yield of 96.04%. Activation energy of the oxidation reaction was 81.03 kJ mol-1 for biodiesel produced with sodium hydroxide and 90.51 kJ mol-1 for sodium methoxide. The positive values for DH‡ and DG‡ indicate that the oxidation process is endothermic and endergonic. The less negative DS‡ for biodiesel produced with sodium methoxide (-28.87 JK-1 mol-1 showed that the process of degradation of this biofuel was slower than that produced with NaOH. The mixture of raw materials proposed, transesterified with the methoxide catalyst, resulted in a biofuel that resisted oxidation for longer periods, making unnecessary the addition of antioxidant

Combustion kinetics and reaction pathways

Energy Technology Data Exchange (ETDEWEB)

Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

1993-12-01

This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

Characterisation of sugar cane straw waste as pozzolanic material for construction: Calcining temperature and kinetic parameters

International Nuclear Information System (INIS)

Frias, Moises; Villar-Cocina, E.; Valencia-Morales, E.

2007-01-01

This paper reports on the influence of calcining temperature (800 and 1000 deg. C) on the pozzolanic activation of sugar cane straw (SCS). The reaction kinetics of SCS ash-lime mixtures were inferred from physicochemical characteristics (X-ray diffraction patterns and thermogravimetry analysis. The fitting of a kinetic-diffusive model to the experimental data (fixed lime versus time) allowed the computing of the kinetic parameters (reaction rate constant) of the pozzolanic reaction. Results obtained confirm that the sugar cane straw ash (SCSA) calcined at 800 and 1000 deg. C have properties indicative of very high pozzolanic activity. No influence of calcining temperature on the pozzolanic activity was observed. Also, no crystalline compounds during the pozzolanic reaction were identified up to 90 days of reaction. Environmental durability and strength of the consequential mortars remain to be assessed

Reaction kinetics of polybutylene terephthalate polycondensation reaction

NARCIS (Netherlands)

Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

2005-01-01

The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

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.

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

A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

Science.gov (United States)

Silvestri, Michael G.; Dills, Charles E.

1989-01-01

Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

Enzyme-catalyzed and binding reaction kinetics determined by titration calorimetry.

Science.gov (United States)

Hansen, Lee D; Transtrum, Mark K; Quinn, Colette; Demarse, Neil

2016-05-01

Isothermal calorimetry allows monitoring of reaction rates via direct measurement of the rate of heat produced by the reaction. Calorimetry is one of very few techniques that can be used to measure rates without taking a derivative of the primary data. Because heat is a universal indicator of chemical reactions, calorimetry can be used to measure kinetics in opaque solutions, suspensions, and multiple phase systems and does not require chemical labeling. The only significant limitation of calorimetry for kinetic measurements is that the time constant of the reaction must be greater than the time constant of the calorimeter which can range from a few seconds to a few minutes. Calorimetry has the unique ability to provide both kinetic and thermodynamic data. This article describes the calorimetric methodology for determining reaction kinetics and reviews examples from recent literature that demonstrate applications of titration calorimetry to determine kinetics of enzyme-catalyzed and ligand binding reactions. A complete model for the temperature dependence of enzyme activity is presented. A previous method commonly used for blank corrections in determinations of equilibrium constants and enthalpy changes for binding reactions is shown to be subject to significant systematic error. Methods for determination of the kinetics of enzyme-catalyzed reactions and for simultaneous determination of thermodynamics and kinetics of ligand binding reactions are reviewed. Copyright © 2015 Elsevier B.V. All rights reserved.

Energetics and kinetics of ferrocyanide and nitrate/nitrite reactions

International Nuclear Information System (INIS)

Scheele, R.D.; Burger, L.L.; Sell, R.L.

1994-01-01

During the 1950's, radiocesium scavenging at the Hanford site resulted in radioactive waste sludges containing ferrocyanide, nitrate, and nitrite. These waters are a concern since certain mixtures of ferrocyanide and nitrate and/or nitrite are known to explode when heated. The authors have used differential scanning calorimetry, thermogravimetric analysis, isothermal calorimetry and gravimetry, and accelerating rate calorimetry to measure the thermal behavior, the reaction enthalpies, and selected kinetic parameters for reactions between sodium nickel ferrocyanide, the suspected ferrocyanide form in Hanford wastes, and nitrate and/or nitrite. These studies indicate that the oxidation proceeds via multiple steps, the initial reaction begins near 200 degrees C, the initial step has a high activation energy (>200 kJ/mole-K), succeeding reaction steps have activation energies ranging from 90 to 160 kJ/mole-K, and that the oxidation yields about 50% of the theoretical heat of reaction for the most energetic reaction

Accurate label-free reaction kinetics determination using initial rate heat measurements

Science.gov (United States)

Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

2015-01-01

Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

Kinetic parameters for source driven systems

International Nuclear Information System (INIS)

Dulla, S.; Ravetto, P.; Carta, M.; D'Angelo, A.

2006-01-01

The definition of the characteristic kinetic parameters of a subcritical source-driven system constitutes an interesting problem in reactor physics with important consequences for practical applications. Consistent and physically meaningful values of the parameters allow to obtain accurate results from kinetic simulation tools and to correctly interpret kinetic experiments. For subcritical systems a preliminary problem arises for the adoption of a suitable weighting function to be used in the projection procedure to derive a point model. The present work illustrates a consistent factorization-projection procedure which leads to the definition of the kinetic parameters in a straightforward manner. The reactivity term is introduced coherently with the generalized perturbation theory applied to the source multiplication factor ks, which is thus given a physical role in the kinetic model. The effective prompt lifetime is introduced on the assumption that a neutron generation can be initiated by both the fission process and the source emission. Results are presented for simplified configurations to fully comprehend the physical features and for a more complicated highly decoupled system treated in transport theory. (authors)

Optimization and kinetic studies of sea mango (Cerbera odollam) oil for biodiesel production via supercritical reaction

International Nuclear Information System (INIS)

Ang, Gaik Tin; Ooi, San Nee; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

2015-01-01

Highlights: • Sea mango oil as feedstock for biodiesel via non-catalytic supercritical reaction. • Extracted sea mango oil with high FFA could produce high yield of FAME. • Employment of Response Surface Methodology for optimization of FAME. • Kinetic study for reversible transesterification and esterification reactions. - Abstract: Sea mango (Cerbera odollam) oil, which is rich in free fatty acids, was utilized to produce fatty acid methyl esters (FAME) via supercritical transesterification reaction. Sea mango oil was extracted from seeds and was subsequently reacted with methanol in a batch-type supercritical reactor. Response surface methodology (RSM) analysis was used to optimize important parameters, including reaction temperature, reaction time and the molar ratio of methanol to oil. The optimum conditions were found as 380 °C, 40 min and 45:1 mol/mol, respectively, to achieve 78% biodiesel content. The first kinetic modelling of FAME production from sea mango oil incorporating reversible transesterification and reversible esterification was verified simultaneously. The kinetic parameters, including reaction rate constants, k, the pre-exponential constant, A, and the activation energy, Ea, for transesterification and esterification were determined using an ordinary differential equation (ODE45) solver. The highest activation energy of 40 kJ/mol and the lowest reaction rate constant of 2.50 × 10 −5 dm 3 /mol s verified that the first stepwise reaction of TG to produce DG was the rate-limiting step

EQUILIBRIUM AND KINETIC PARAMETERS FOR THE SEDIMENTATION OF TARTARIC SALTS IN YOUNG WINES

Directory of Open Access Journals (Sweden)

Ecaterina Covaci

2015-06-01

Full Text Available In young wines potassium hydrogen tartrate is always present in supersaturating concentration and crystallizes spontaneously. The aim of this study is to obtain kinetic parameters, which explain the stability of young wines during the stabilization treatments. The kinetic and equilibrium parameters were evaluated and discussed. The heating factor has a decisive influence on the reaction rate of potassium hydrogen tartrate precipitation in young wines. An increase of temperature leads to a decrease in efficiency of stabilization process and to an enhancement of the activation energy of the system. According to the obtained experimental results, the optimal regime for production and stabilization of young wines has been established.

Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

Science.gov (United States)

Olanrewaju, Kazeem Bode

The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

Science.gov (United States)

Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

2018-05-01

The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

International Nuclear Information System (INIS)

Harikrishna, R.; Ponrathnam, S.; Tambe, S.S.

2014-01-01

Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction

Reactions of plutonium and uranium with water: Kinetics and potential hazards

International Nuclear Information System (INIS)

Haschke, J.M.

1995-12-01

The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

Calculation of statistic estimates of kinetic parameters from substrate uncompetitive inhibition equation using the median method

Directory of Open Access Journals (Sweden)

Pedro L. Valencia

2017-04-01

Full Text Available We provide initial rate data from enzymatic reaction experiments and tis processing to estimate the kinetic parameters from the substrate uncompetitive inhibition equation using the median method published by Eisenthal and Cornish-Bowden (Cornish-Bowden and Eisenthal, 1974; Eisenthal and Cornish-Bowden, 1974. The method was denominated the direct linear plot and consists in the calculation of the median from a dataset of kinetic parameters Vmax and Km from the Michaelis–Menten equation. In this opportunity we present the procedure to applicate the direct linear plot to the substrate uncompetitive inhibition equation; a three-parameter equation. The median method is characterized for its robustness and its insensibility to outlier. The calculations are presented in an Excel datasheet and a computational algorithm was developed in the free software Python. The kinetic parameters of the substrate uncompetitive inhibition equation Vmax, Km and Ks were calculated using three experimental points from the dataset formed by 13 experimental points. All the 286 combinations were calculated. The dataset of kinetic parameters resulting from this combinatorial was used to calculate the median which corresponds to the statistic estimator of the real kinetic parameters. A comparative statistical analyses between the median method and the least squares was published in Valencia et al. [3].

Kinetic study of the annealing reactions in Cu-Ni-Fe alloys

International Nuclear Information System (INIS)

Donoso, E.

2014-01-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi 3 phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi 3 phase. (Author)

Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

International Nuclear Information System (INIS)

Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

1993-01-01

Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

Kinetic concepts of thermally stimulated reactions in solids

Science.gov (United States)

Vyazovkin, Sergey

Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

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

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

Science.gov (United States)

Fedorenko, S. G.; Burshtein, A. I.

2014-09-01

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

Energy Technology Data Exchange (ETDEWEB)

Fedorenko, S. G. [Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk (Russian Federation); Burshtein, A. I. [Weizmann Institute of Science, 76100, Rehovot (Israel)

2014-09-21

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

International Nuclear Information System (INIS)

Fedorenko, S. G.; Burshtein, A. I.

2014-01-01

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics

Kinetics and Mechanisms of Calcite Reactions with Saline Waters

Energy Technology Data Exchange (ETDEWEB)

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

2015-09-02

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

Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

Energy Technology Data Exchange (ETDEWEB)

Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

2015-10-05

Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

Inverse modeling approach for evaluation of kinetic parameters of a biofilm reactor using tabu search.

Science.gov (United States)

Kumar, B Shiva; Venkateswarlu, Ch

2014-08-01

The complex nature of biological reactions in biofilm reactors often poses difficulties in analyzing such reactors experimentally. Mathematical models could be very useful for their design and analysis. However, application of biofilm reactor models to practical problems proves somewhat ineffective due to the lack of knowledge of accurate kinetic models and uncertainty in model parameters. In this work, we propose an inverse modeling approach based on tabu search (TS) to estimate the parameters of kinetic and film thickness models. TS is used to estimate these parameters as a consequence of the validation of the mathematical models of the process with the aid of measured data obtained from an experimental fixed-bed anaerobic biofilm reactor involving the treatment of pharmaceutical industry wastewater. The results evaluated for different modeling configurations of varying degrees of complexity illustrate the effectiveness of TS for accurate estimation of kinetic and film thickness model parameters of the biofilm process. The results show that the two-dimensional mathematical model with Edward kinetics (with its optimum parameters as mu(max)rho(s)/Y = 24.57, Ks = 1.352 and Ki = 102.36) and three-parameter film thickness expression (with its estimated parameters as a = 0.289 x 10(-5), b = 1.55 x 10(-4) and c = 15.2 x 10(-6)) better describes the biofilm reactor treating the industry wastewater.

The reaction between iodine and silver under severe PWR accident conditions. An experimental parameter study

Energy Technology Data Exchange (ETDEWEB)

Funke, F; Greger, G U; Bleier, A; Hellmann, S; Morell, W [Siemens AG, Power Generation Group, Erlangen (Germany)

1996-12-01

An extensive experimental parameter study was performed on the kinetics in the reaction system I{sub 2}/Ag and I{sup -}/Ag in a laboratory-scale apparatus.Starting with I{sub 2} or I{sup -} solutions and silver powder suspensions, the decrease of soluted I{sub 2} or I{sup -}, respectively, due to fixation on the silver particles, was monitored as function of time using the radioactive tracer I-131. The measured data were analyzed using a model of first order kinetics with respect to the iodine concentration. However, the analysis using first order kinetics had to be performed separately in an early, fast reaction phase and in a late, slow reaction phase. The reason for this unexpected behaviour was not identified. Thus, rate constant, two for each test, were deduced from 14 I{sub 2}/Ag main tests and from 36 I{sup -}/Ag tests. No dependencies of the rate constants were found on the parameters temperature, initial iodine concentration, presence of boric acid, type of silver educt, and pretreatment of the silver educt prior to the tests. However, the stirring of the reaction solution generally enhanced the kinetics highlighting the importance of mass transfer. The I{sup -}/Ag reaction proceeded only if there was no inertization of the reaction solution by sparging with nitrogen. The temperature-independent rate constant for the early, fast I{sub 2}/Ag reaction phase is 2E-5 m/s. However, a smaller rate constant of 6E-6 m/s is recommended for use in source term calculations with IMPAIR, which already contains a first order model. Analogously, the temperature-independent I{sup -}/Ag reaction rate constant is 8E-6 m/s in an early, fast reaction phase. For use in source term calculations, a smaller rate constant of 2E-6 m/s is recommended. The lower bound of the I{sup -}/Ag rate constant was 3E-8 m/s which could be used in very conservative source term calculations. (author) 20 figs., 6 tabs., 15 refs.

Kinetic modelling of the Maillard reaction between proteins and sugars

NARCIS (Netherlands)

Brands, C.M.J.

2002-01-01

Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses

The aim of this thesis was to determine the kinetics of the Maillard reaction between

Study of the kinetics parameters for subcritical media driven by source

International Nuclear Information System (INIS)

Lee, S.M.; Maiorino, J.R.

2009-01-01

This paper presents a theoretical study of reactor kinetics focusing on the methodology of calculation and the experimental measurements of the so-called kinetic parameters. A comparison between the methodology based on the Dulla's formalism and the classical method is made. The objective is to exhibit the dependence of the parameters on sub criticality level and perturbation. Two different slab type systems were considered: thermal one and fast one, both with homogeneous media. One group diffusion model was used for the fast reactor, and for the thermal system, two group diffusion model, considering, in both case only one precursor's family. For reason of simplicity, several additional assumptions were made for calculation of two group method: no up-scattering, fission reaction occurring only in thermal group, etc. The solutions for subcritical systems were obtained using the expansion method, and for critical systems, the methods presented in classical textbooks of reactor physics were applied. The numerical results presented their dependence on sub criticality level and perturbation. (author)

Spectroscopy and reaction kinetics of HCO

International Nuclear Information System (INIS)

Guo, Yili.

1989-01-01

The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs

Kinetic parameter estimation from attenuated SPECT projection measurements

International Nuclear Information System (INIS)

Reutter, B.W.; Gullberg, G.T.

1998-01-01

Conventional analysis of dynamically acquired nuclear medicine data involves fitting kinetic models to time-activity curves generated from regions of interest defined on a temporal sequence of reconstructed images. However, images reconstructed from the inconsistent projections of a time-varying distribution of radiopharmaceutical acquired by a rotating SPECT system can contain artifacts that lead to biases in the estimated kinetic parameters. To overcome this problem the authors investigated the estimation of kinetic parameters directly from projection data by modeling the data acquisition process. To accomplish this it was necessary to parametrize the spatial and temporal distribution of the radiopharmaceutical within the SPECT field of view. In a simulated transverse slice, kinetic parameters were estimated for simple one compartment models for three myocardial regions of interest, as well as for the liver. Myocardial uptake and washout parameters estimated by conventional analysis of noiseless simulated data had biases ranging between 1--63%. Parameters estimated directly from the noiseless projection data were unbiased as expected, since the model used for fitting was faithful to the simulation. Predicted uncertainties (standard deviations) of the parameters obtained for 500,000 detected events ranged between 2--31% for the myocardial uptake parameters and 2--23% for the myocardial washout parameters

Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

Science.gov (United States)

Carpinteiro, Inmaculada; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

2017-09-01

In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M -1  s -1 , 0.13-1.16 M -1  s -1 and 0.04-20.4 M -1  s -1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed

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

SABIO-RK: A data warehouse for biochemical reactions and their kinetics

Directory of Open Access Journals (Sweden)

Krebs Olga

2007-03-01

Full Text Available Systems biology is an emerging field that aims at obtaining a system-level understanding of biological processes. The modelling and simulation of networks of biochemical reactions have great and promising application potential but require reliable kinetic data. In order to support the systems biology community with such data we have developed SABIO-RK (System for the Analysis of Biochemical Pathways - Reaction Kinetics, a curated database with information about biochemical reactions and their kinetic properties, which allows researchers to obtain and compare kinetic data and to integrate them into models of biochemical networks. SABIO-RK is freely available for academic use at http://sabio.villa-bosch.de/SABIORK/.

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.

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.

Kinetics of barium sulphate reaction crystallization in crystallizers with internal circulation

Directory of Open Access Journals (Sweden)

J. Koralewska

2008-06-01

Full Text Available Kinetic calculation results describing the observed nucleation and growth rates of barium sulphate crystals precipitated in an integrated reaction-crystallization process in a barium sulphate-ammonium chloride-water system are presented and analyzed. The scope of experiments included two continuous model DTM-type crystallizers (Draft Tube Magma with internal circulation of the suspension forced by a liquid jet-pump device responsible for stable and intensive enough ascending/descending flow of BaSO4 crystal magma in a mixing chamber. For comparison purposes the experimental data corresponding to a continuous DT (Draft Tube crystallizer with propeller agitator are presented and discussed. The various types of laboratory crystallizers used were fed with concentrated water solution of barium chloride (of 10 or 24 mass % and - in a stoichiometric proportion - crystalline ammonium sulphate, assuming isothermal (348 K and hydrodynamic (average residence time of suspension in a crystallizer: 900 s process conditions. The observed nucleation and growth rates of barium sulphate crystals were estimated on the basis of crystal size distributions (CSDs using convenient calculation scheme derived for an MSMPR (Mixed Suspension Mixed Product Removal model approach. Considering the experimental population density distribution courses, a size-dependent growth (SDG phenomenon was taken into account in the kinetic calculations. Five SDG kinetic models recommended in the accessible literature were used for kinetic parameter values estimation. It was proved statistically, that Rojkowski’s two SDG models (hyperbolic and exponential best suit for our own experimental data description. The experimental data presented can be practically applied for improving the constructions of liquid jet-pump DTM crystallizers recommended for reaction crystallization of sparingly soluble inorganic salts (especially for high concentrations of reaction substrates in the modern

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…

A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

Energy Technology Data Exchange (ETDEWEB)

Magnien, V

2005-12-15

The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (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

Lumping procedure for a kinetic model of catalytic naphtha reforming

Directory of Open Access Journals (Sweden)

H. M. Arani

2009-12-01

Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.

Reaction kinetics in open reactors and serial transfers between closed reactors

Science.gov (United States)

Blokhuis, Alex; Lacoste, David; Gaspard, Pierre

2018-04-01

Kinetic theory and thermodynamics of reaction networks are extended to the out-of-equilibrium dynamics of continuous-flow stirred tank reactors (CSTR) and serial transfers. On the basis of their stoichiometry matrix, the conservation laws and the cycles of the network are determined for both dynamics. It is shown that the CSTR and serial transfer dynamics are equivalent in the limit where the time interval between the transfers tends to zero proportionally to the ratio of the fractions of fresh to transferred solutions. These results are illustrated with a finite cross-catalytic reaction network and an infinite reaction network describing mass exchange between polymers. Serial transfer dynamics is typically used in molecular evolution experiments in the context of research on the origins of life. The present study is shedding a new light on the role played by serial transfer parameters in these experiments.

Reactivity and kinetic parameters determination in a multiplicative non-stationary system

International Nuclear Information System (INIS)

Minguez, E.

1982-01-01

A revision of several methods used for solving kinetic equations of a neutronic system is considered. Firstly, kinetic equations in general form are analized, before to revise more important aproximations: point-kinetic method; adiabatic; cuasistatic; eigenvalue equations; nodal, modal and systhesis methods; and variational principles for obtaining kinetic equations. Perturbation theory is used to obtain these parameters, with differents eigenvalue equations representatives of the parameter to be calculated. Also, experimental methods have been included in this work, because of importance the parameters can be measured, and related with those obtained by calculations. Finally, adjoint kinetic equations are resolved to obtain the importance function used in weighted reactivity and kinetic parameters determinations. (author)

Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

Science.gov (United States)

Yang, Mino

2007-06-07

Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

Science.gov (United States)

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

Science.gov (United States)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-03-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

Science.gov (United States)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-06-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Kinetic modeling of reactions in Foods

NARCIS (Netherlands)

Boekel, van M.A.J.S.

2008-01-01

The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to

Determination of kinetic parameters in the pyrolysis operation and thermal behavior of Prosopis juliflora using thermogravimetric analysis.

Science.gov (United States)

Chandrasekaran, Arunkumar; Ramachandran, Sethumadhavan; Subbiah, Senthilmurugan

2017-06-01

This paper deals with the pyrolysis of Prosopis juliflora fuelwood using thermogravimetric analysis to determine the kinetic parameters at six different heating rates of 2, 5, 10, 15, 20 and 25°C/min. The activation energy of pyrolysis was calculated using different methods, namely Kissinger, Kissinger-Akahira-Sunose, Ozawa-Flynn-Wall and Friedman model and corresponding calculated activation energy were found to be 164.6, 204, 203.2, and 219.3kJ/mol, respectively for each method. The three-pseudo component model was applied to calculate the following three kinetic parameters: activation energy, pre-exponential factor and order of reaction. The experimental results were validated with model prediction for all the six heating rates. The three-pseudo component model is able to predict experimental results much accurately while considering variable order reaction model (n≠1). Copyright © 2017 Elsevier Ltd. All rights reserved.

A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

Energy Technology Data Exchange (ETDEWEB)

Magnien, V

2005-12-15

The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

Pressure-dependent kinetics of initial reactions in iso-octane pyrolysis.

Science.gov (United States)

Ning, HongBo; Gong, ChunMing; Li, ZeRong; Li, XiangYuan

2015-05-07

This study focuses on the studies of the main pressure-dependent reaction types of iso-octane (iso-C8H18) pyrolysis, including initial C-C bond fission of iso-octane, isomerization, and β-scission reactions of the alkyl radicals produced by the C-C bond fission of iso-octane. For the C-C bond fission of iso-octane, the minimum energy potentials are calculated at the CASPT2(2e,2o)/6-31+G(d,p)//CAS(2e,2o)/6-31+G(d,p) level of theory. For the isomerization and the β-scission reactions of the alkyl radicals, the optimization of the geometries and the vibrational frequencies of the reactants, transition states, and products are performed at the B3LYP/CBSB7 level, and their single point energies are calculated by using the composite CBS-QB3 method. Variable reaction coordinate transition state theory (VRC-TST) is used for the high-pressure limit rate constant calculation and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is used to calculate the pressure-dependent rate constants of these channels with pressure varying from 0.01-100 atm. The rate constants obtained in this work are in good agreement with those available from literatures. We have updated the rate constants and thermodynamic parameters for species involved in these reactions into a current chemical kinetic mechanism and also have improved the concentration profiles of main products such as C3H6 and C4H6 in the shock tube pyrolysis of iso-octane. The results of this study provide insight into the pyrolysis of iso-octane and will be helpful in the future development of branched paraffin kinetic mechanisms.

Ametryn degradation by aqueous chlorine: Kinetics and reaction influences

International Nuclear Information System (INIS)

Xu Bin; Gao Naiyun; Cheng Hefa; Hu Chenyan; Xia Shengji; Sun Xiaofeng; Wang Xuejiao; Yang Shaogui

2009-01-01

The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 deg. C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10 2 M -1 s -1 under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10 2 and 1.58 x 10 3 M -1 s -1 , respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10 3 and 3.54 x 10 6 M -1 s -1 , respectively. These values are 10- to 10 3 -fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation.

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.

Internal Diffusion-Controlled Enzyme Reaction: The Acetylcholinesterase Kinetics.

Science.gov (United States)

Lee, Sangyun; Kim, Ji-Hyun; Lee, Sangyoub

2012-02-14

Acetylcholinesterase is an enzyme with a very high turnover rate; it quenches the neurotransmitter, acetylcholine, at the synapse. We have investigated the kinetics of the enzyme reaction by calculating the diffusion rate of the substrate molecule along an active site channel inside the enzyme from atomic-level molecular dynamics simulations. In contrast to the previous works, we have found that the internal substrate diffusion is the determinant of the acetylcholinesterase kinetics in the low substrate concentration limit. Our estimate of the overall bimolecular reaction rate constant for the enzyme is in good agreement with the experimental data. In addition, the present calculation provides a reasonable explanation for the effects of the ionic strength of solution and the mutation of surface residues of the enzyme. The study suggests that internal diffusion of the substrate could be a key factor in understanding the kinetics of enzymes of similar characteristics.

Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

Energy Technology Data Exchange (ETDEWEB)

Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

1978-09-01

The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

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.

Deuterium secondary isotope kinetic effects in imine formation reactions

International Nuclear Information System (INIS)

Amaral, L. do; Rossi, M.H.

1986-01-01

The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

Pre-steady-state kinetics of Escherichia coli aspartate aminotransferase catalyzed reactions and thermodynamic aspects of its substrate specificity

International Nuclear Information System (INIS)

Kuramitsu, Seiki; Hiromi, Keitaro; Hayashi, Hideyuki; Morino, Yoshimasa; Kagamiyama, Hiroyuki

1990-01-01

The four half-transamination reactions [the pyridoxal form of Escherichia coli aspartate aminotransferase (AspAT) with aspartate or glutamate and the pyridoxamine form of the enzyme with oxalacetate or 2-oxoglutarate] were followed in a stopped-flow spectrometer by monitoring the absorbance change at either 333 or 358 nm. The reaction progress curves in all cases gave fits to a monophasic exponential process. Kinetic analyses of these reactions showed that each half-reaction is composed of the following three processes: (1) the rapid binding of an amino acid substrate to the pyridoxal form of the enzyme; (2) the rapid binding of the corresponding keto acid to the pyridoxamine form of the enzyme; (3) the rate-determining interconversion between the two complexes. This mechanism was supported by the findings that the equilibrium constants for half- and overall-transamination reactions and the steady-state kinetic constants agreed well with the predicted values on the basis of the above mechanism using pre-steady-state kinetic parameters. The significant primary kinetic isotope effect observed in the reaction with deuterated amino acid suggests that the withdrawal of the α-proton of the substrates is rate determining. The pyridoxal form of E. coli AspAT reacted with a variety of amino acids as substrates. The substrate specificity of the E. coli enzyme was much broader than that of pig isoenzymes, reflecting some subtle but distinct difference in microenvironment accommodating the side chain of the substrate between e. coli and mammalian AspATs

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

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.

The kinetics of free radical metathetical and addition reactions in silane solutions

International Nuclear Information System (INIS)

Aloni, R.

1976-12-01

In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

Modified mean generation time parameter in the neutron point kinetics equations

Energy Technology Data Exchange (ETDEWEB)

Diniz, Rodrigo C.; Gonçalves, Alessandro C.; Rosa, Felipe S.S., E-mail: alessandro@nuclear.ufrj.br, E-mail: frosa@if.ufrj.br [Coordenacao de Pos-Graduacao e Pesquisa de Engenharia (PEN/COPPE/UFRJ), Rio de Janeiro, RJ (Brazil)

2017-07-01

This paper proposes an approximation for the modified point kinetics equations proposed by NUNES et. al, 2015, through the adjustment of a kinetic parameter. This approximation consists of analyzing the terms of the modified point kinetics equations in order to identify the least important ones for the solution, resulting in a modification of the mean generation time parameter that incorporates all influences of the additional terms of the modified kinetics. This approximation is applied on the inverse kinetics, to compare the results with the inverse kinetics from the modified kinetics in order to validate the proposed model. (author)

Modified mean generation time parameter in the neutron point kinetics equations

International Nuclear Information System (INIS)

Diniz, Rodrigo C.; Gonçalves, Alessandro C.; Rosa, Felipe S.S.

2017-01-01

This paper proposes an approximation for the modified point kinetics equations proposed by NUNES et. al, 2015, through the adjustment of a kinetic parameter. This approximation consists of analyzing the terms of the modified point kinetics equations in order to identify the least important ones for the solution, resulting in a modification of the mean generation time parameter that incorporates all influences of the additional terms of the modified kinetics. This approximation is applied on the inverse kinetics, to compare the results with the inverse kinetics from the modified kinetics in order to validate the proposed model. (author)

Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects.

Science.gov (United States)

Zaidi, A; Gainer, J L; Carta, G; Mrani, A; Kadiri, T; Belarbi, Y; Mir, A

2002-02-28

The esterification of long-chain fatty acids in n-hexane catalyzed by nylon-immobilized lipase from Candida rugosa has been investigated. Butyl oleate (22 carbon atoms), oleyl butyrate (22 carbon atoms) and oleyl oleate (36 carbon atoms) were produced at maximum reaction rates of approximately equal to 60 mmol h(-1) g(-1) immobilized enzyme when the substrates were present in equimolar proportions at an initial concentration of 0.6 mol l(-1). The observed kinetic behavior of all the esterification reactions is found to follow a ping-pong bi-bi mechanism with competitive inhibition by both substrates. The effect of the chain-length of the fatty acids and the alcohols could be correlated to some mechanistic models, in accordance with the calculated kinetic parameters.

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

Determination of kinetic parameters and Hammett ρ from the synthesis of triaryl phosphites using reaction calorimetry

International Nuclear Information System (INIS)

Seiceira, Rafael C.; Higa, Camila M.; Barreto, Amaro G.; Cajaiba da Silva, Joao F.

2005-01-01

Triaryl phosphites bearing electron donating and electron withdrawing substituents were prepared through the reaction of sodium phenoxides with phosphorus trichloride. The reactions were performed in a Mettler RC1 reaction calorimeter. The main purpose of this work was the determination of Hammett ρ from the synthesis of substituted triaryl phosphites through the interpretation of calorimetric data. The phenoxide bearing a methoxide group was the most reactive, and the one bearing the nitro group was the least reactive. It was demonstrated that the reaction rate depends mainly on the addition rate of phosphorus trichloride solution. A good correlation between the Hammet parameters (σ p + ) was obtained, indicating a reaction mechanism in which a decrease of the negative charge occurs in the transition state

Kinetics of two simultaneous second-order reactions occurring in different zones

International Nuclear Information System (INIS)

Dole, M.; Hsu, C.S.; Patel, V.M.; Patel, G.N.

1975-01-01

Equations have been derived for the case of free radicals recombining according to the second-order kinetics with or without diffusion control under the conditions that there are two simultaneous spatially separated recombination reactions but that only the overall free-radical concentration can be observed. The properties of these equations are discussed and methods for determining the three independent parameters in the first case and five in the second developed. The resulting equations have been applied to the interpretation of data obtained in studying the decay of allyl chain free radicals in irradiated extended chain crystalline polyethylene

Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

Energy Technology Data Exchange (ETDEWEB)

Gary Blythe; John Currie; David DeBerry

2008-03-31

This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling

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

Set-base dynamical parameter estimation and model invalidation for biochemical reaction networks.

Science.gov (United States)

Rumschinski, Philipp; Borchers, Steffen; Bosio, Sandro; Weismantel, Robert; Findeisen, Rolf

2010-05-25

Mathematical modeling and analysis have become, for the study of biological and cellular processes, an important complement to experimental research. However, the structural and quantitative knowledge available for such processes is frequently limited, and measurements are often subject to inherent and possibly large uncertainties. This results in competing model hypotheses, whose kinetic parameters may not be experimentally determinable. Discriminating among these alternatives and estimating their kinetic parameters is crucial to improve the understanding of the considered process, and to benefit from the analytical tools at hand. In this work we present a set-based framework that allows to discriminate between competing model hypotheses and to provide guaranteed outer estimates on the model parameters that are consistent with the (possibly sparse and uncertain) experimental measurements. This is obtained by means of exact proofs of model invalidity that exploit the polynomial/rational structure of biochemical reaction networks, and by making use of an efficient strategy to balance solution accuracy and computational effort. The practicability of our approach is illustrated with two case studies. The first study shows that our approach allows to conclusively rule out wrong model hypotheses. The second study focuses on parameter estimation, and shows that the proposed method allows to evaluate the global influence of measurement sparsity, uncertainty, and prior knowledge on the parameter estimates. This can help in designing further experiments leading to improved parameter estimates.

Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

Energy Technology Data Exchange (ETDEWEB)

Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

2015-03-01

Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

International Nuclear Information System (INIS)

Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; Titov, S. V.

2013-01-01

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ 0 =ℏω 0 /k B T where ω 0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ 0 0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the

Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction

Science.gov (United States)

Sobel, Sabrina G.; Cohen, Skyler

2010-01-01

Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

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.

Kinetic modeling and fitting software for interconnected reaction schemes: VisKin.

Science.gov (United States)

Zhang, Xuan; Andrews, Jared N; Pedersen, Steen E

2007-02-15

Reaction kinetics for complex, highly interconnected kinetic schemes are modeled using analytical solutions to a system of ordinary differential equations. The algorithm employs standard linear algebra methods that are implemented using MatLab functions in a Visual Basic interface. A graphical user interface for simple entry of reaction schemes facilitates comparison of a variety of reaction schemes. To ensure microscopic balance, graph theory algorithms are used to determine violations of thermodynamic cycle constraints. Analytical solutions based on linear differential equations result in fast comparisons of first order kinetic rates and amplitudes as a function of changing ligand concentrations. For analysis of higher order kinetics, we also implemented a solution using numerical integration. To determine rate constants from experimental data, fitting algorithms that adjust rate constants to fit the model to imported data were implemented using the Levenberg-Marquardt algorithm or using Broyden-Fletcher-Goldfarb-Shanno methods. We have included the ability to carry out global fitting of data sets obtained at varying ligand concentrations. These tools are combined in a single package, which we have dubbed VisKin, to guide and analyze kinetic experiments. The software is available online for use on PCs.

Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

International Nuclear Information System (INIS)

Yamada, Y.; Kawase, Y.

2006-01-01

In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%

Kinetics of ion/molecule reactions in Xe++acteone system

International Nuclear Information System (INIS)

Vinogradov, P.S.; Misharin, A.S.

2002-01-01

A reaction of Xe+ ion with acetone and subsequent transformations of the product ions at a buffer gas pressure (He) of 1.1 Torr were studied by the flow reactor technique mass spectrometry. A kinetic scheme describing the evolution of the ionic composition has been determined. The rate constants of the key reactions involved in the scheme have been evaluated. A channel of the production of acetone cation in A state in a charge transfer reaction was observed. A production of slowly reacting isomer of the acetone cation in secondary reactions was detected. Its product in the reaction with acetone is the 'nonprotonated dimer'. The kinetics of the production of ternary ions - ( CH 3 CO + CH 3 COCH 3 )(m/e=101), CH 3 COCH 3 H + (m/e=59) as well as the production of ions of the fourth generation ( CH 3 CO + (CH 3 COCH 3 ) 2 ) (m/e=159) and (CH 3 COCH 3 ) 2 H + was observed. CH 3 CO + ion (m/e=43) was found as the main reaction product. The main pathways scheme of ionic transformations is shown. (nevyjel)

Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

Energy Technology Data Exchange (ETDEWEB)

Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

2010-09-15

In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

A kinetic model for the glucose/glycine Maillard reaction pathways

NARCIS (Netherlands)

Martins, S.I.F.S.; Boekel, van M.A.J.S.

2005-01-01

A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

Kinetics of transuranium element oxidation-reduction reactions in solution

International Nuclear Information System (INIS)

Gourisse, D.

1966-09-01

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

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

Science.gov (United States)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced 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 extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Kinetics of elementary atom and radical reactions

International Nuclear Information System (INIS)

Gordon, R.J.

1990-06-01

During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

Kinetics of elementary atom and radical reactions: Progress report

International Nuclear Information System (INIS)

Gordon, R.J.

1986-01-01

Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

Kinetic study of the dehydration reaction of lithium sulfate monohydrate crystals using microscopy and modeling

Energy Technology Data Exchange (ETDEWEB)

Lan, Shuiquan [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Zondag, Herbert [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Energy research Center of the Netherlands – ECN, P.O. Box 1, 1755ZG Petten (Netherlands); Steenhoven, Anton van [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Rindt, Camilo, E-mail: c.c.m.rindt@tue.nl [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands)

2015-12-10

Highlights: • Kinetics of Li{sub 2}SO{sub 4}·H{sub 2}O single crystals were modeled based on elementary processes. • Kinetics of nucleation and nuclei growth were studied by using optical microscopy. • A novel experiment was designed to visualize the reaction front into crystal bulk. • Fractional conversion was calculated and compared with TGA-experiments. - Abstract: Simulation of gas–solid reactions occurring in industrial processes requires a robust kinetic model to be applicable in a wide range of complicated reaction conditions. However, in literature it is often seen that even the same reaction under specific controlled conditions is interpreted with different kinetic models. In the present work, a phenomenological model based on nucleation and nuclei growth processes is presented to study the kinetics of the dehydration reaction of lithium sulfate monohydrate single crystals. The two elementary processes of the reaction, nucleation and nuclei growth, are characterized and quantified as a function of temperature by using optical microscopy experiments. The in-situ measured characteristics of the dehydration reaction provided confirmatory evidence that the rate of nucleation obeys an exponential law and the rate of nuclei growth is approximately constant. With knowledge acquired from the optical observations as inputs of the kinetic model, the fractional conversion of the dehydration reaction was calculated and compared with experimental results from thermogravimetric analysis (TGA). A satisfactory comparison was found both in isothermal and non-isothermal conditions. It is demonstrated that this knowledge-based model has a great potential to represent the gas–solid reaction kinetics in a wide range of process conditions regarding temperature, pressure and particle geometry.

Reaction kinetics, reaction products and compressive strength of ternary activators activated slag designed by Taguchi method

NARCIS (Netherlands)

Yuan, B.; Yu, Q.L.; Brouwers, H.J.H.

2015-01-01

This study investigates the reaction kinetics, the reaction products and the compressive strength of slag activated by ternary activators, namely waterglass, sodium hydroxide and sodium carbonate. Nine mixtures are designed by the Taguchi method considering the factors of sodium carbonate content

Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

KAUST Repository

Hisatomi, Takashi

2014-10-16

Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

Energy Technology Data Exchange (ETDEWEB)

Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

2013-12-21

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the

Kinetics of heterogeneous catalytic reactions

CERN Document Server

Boudart, Michel

2014-01-01

This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

Directory of Open Access Journals (Sweden)

Cobbs Gary

2012-08-01

Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

Science.gov (United States)

Cobbs, Gary

2012-08-16

Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

Non-equilibrium reaction rates in chemical kinetic equations

Science.gov (United States)

Gorbachev, Yuriy

2018-05-01

Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

Energy Technology Data Exchange (ETDEWEB)

Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

2008-07-01

The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

Variational estimates of point-kinetics parameters

International Nuclear Information System (INIS)

Favorite, J.A.; Stacey, W.M. Jr.

1995-01-01

Variational estimates of the effect of flux shifts on the integral reactivity parameter of the point-kinetics equations and on regional power fractions were calculated for a variety of localized perturbations in two light water reactor (LWR) model problems representing a small, tightly coupled core and a large, loosely coupled core. For the small core, the flux shifts resulting from even relatively large localized reactivity changes (∼600 pcm) were small, and the standard point-kinetics approximation estimates of reactivity were in error by only ∼10% or less, while the variational estimates were accurate to within ∼1%. For the larger core, significant (>50%) flux shifts occurred in response to local perturbations, leading to errors of the same magnitude in the standard point-kinetics approximation of the reactivity worth. For positive reactivity, the error in the variational estimate of reactivity was only a few percent in the larger core, and the resulting transient power prediction was 1 to 2 orders of magnitude more accurate than with the standard point-kinetics approximation. For a large, local negative reactivity insertion resulting in a large flux shift, the accuracy of the variational estimate broke down. The variational estimate of the effect of flux shifts on reactivity in point-kinetics calculations of transients in LWR cores was found to generally result in greatly improved accuracy, relative to the standard point-kinetics approximation, the exception being for large negative reactivity insertions with large flux shifts in large, loosely coupled cores

Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

Directory of Open Access Journals (Sweden)

Hamadi Adel Sharif

2017-01-01

Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

Kinetics of the Reactions of IO Radicals with NO and NO2

Science.gov (United States)

Daykin, E. P.; Wine, P. H.

1997-01-01

A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

KAUST Repository

Mohamed, Samah; Cai, Liming; Khaled, Fathi; Banyon, Colin; Wang, Zhandong; Rachidi, Mariam El; Pitsch, Heinz; Curran, Henry J.; Farooq, Aamir; Sarathy, Mani

2016-01-01

Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

KAUST Repository

Mohamed, Samah

2016-03-21

Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

Kinetic parameter estimation from SPECT cone-beam projection measurements

International Nuclear Information System (INIS)

Huesman, Ronald H.; Reutter, Bryan W.; Zeng, G. Larry; Gullberg, Grant T.

1998-01-01

Kinetic parameters are commonly estimated from dynamically acquired nuclear medicine data by first reconstructing a dynamic sequence of images and subsequently fitting the parameters to time-activity curves generated from regions of interest overlaid upon the image sequence. Biased estimates can result from images reconstructed using inconsistent projections of a time-varying distribution of radiopharmaceutical acquired by a rotating SPECT system. If the SPECT data are acquired using cone-beam collimators wherein the gantry rotates so that the focal point of the collimators always remains in a plane, additional biases can arise from images reconstructed using insufficient, as well as truncated, projection samples. To overcome these problems we have investigated the estimation of kinetic parameters directly from SPECT cone-beam projection data by modelling the data acquisition process. To accomplish this it was necessary to parametrize the spatial and temporal distribution of the radiopharmaceutical within the SPECT field of view. In a simulated chest image volume, kinetic parameters were estimated for simple one-compartment models for four myocardial regions of interest. Myocardial uptake and washout parameters estimated by conventional analysis of noiseless simulated cone-beam data had biases ranging between 3-26% and 0-28%, respectively. Parameters estimated directly from the noiseless projection data were unbiased as expected, since the model used for fitting was faithful to the simulation. Statistical uncertainties of parameter estimates for 10 000 000 events ranged between 0.2-9% for the uptake parameters and between 0.3-6% for the washout parameters. (author)

A kinetic study on non-catalytic reactions in hydroprocessing Boscan crude oil

Energy Technology Data Exchange (ETDEWEB)

A. Marafi; E. Kam; A. Stanislaus [Kuwait Institute for Scientific Research, Safat (Kuwait). Petroleum Refining Department, Petroleum Research and Studies Center

2008-08-15

Non-catalytic hydrothermal cracking reactions are known to associate with catalytic hydrocracking reactions. In a recent study on hydroprocessing of Boscan crude over a specific catalyst system containing three distinct catalysts, it was found that hydrodesulfurization (HDS) and hydrodemetallation (HDM) reactions continued even when the catalyst is severely deactivated. Since the reactor was packed with considerable amount of inert material besides the three catalysts, it will be advantage to determine if the inert materials can also facilitate hydroprocessing reactions. A series of kinetic experiments for the inert particles was undertaken under different space velocity and temperature conditions. The extent of catalytic and non-catalytic hydroprocessing reactions was assessed. Through statistical analysis, the initial reaction rate constant, reaction order and activation energy for various hydroprocessing reactions were then determined. The absolute average deviations (AAD) of the kinetics values obtained for inert materials are less than 10%. 25 refs., 7 figs., 4 tabs.

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.

Kinetics of catalytic reactions solutions manual

CERN Document Server

Vannice, M Albert

2005-01-01

Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.

Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction.

Science.gov (United States)

Mower, Matthew P; Blackmond, Donna G

2015-02-18

Unusual sigmoidal kinetic profiles in the Machetti-De Sarlo base-catalyzed 1,3-dipolar cycloaddition of acrylamide to N-methylnitroacetamide are rationalized by detailed in situ kinetic analysis. A dual role is uncovered in which a substrate acts as a precursor to catalyze its own reaction. Such kinetic studies provide a general protocol for distinguishing among different mechanistic origins of induction periods in complex organic reactions.

Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

International Nuclear Information System (INIS)

Akulov, G.P.; Korsakova, N.A.

1992-01-01

Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

Parameter Estimation

DEFF Research Database (Denmark)

Sales-Cruz, Mauricio; Heitzig, Martina; Cameron, Ian

2011-01-01

of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to generate a set......In this chapter the importance of parameter estimation in model development is illustrated through various applications related to reaction systems. In particular, rate constants in a reaction system are obtained through parameter estimation methods. These approaches often require the application...... of algebraic equations as the basis for parameter estimation.These approaches are illustrated using estimations of kinetic constants from reaction system models....

Adsorption kinetic parameters of Fe3+ and Ni2+ ions by gyrolite

Directory of Open Access Journals (Sweden)

Kestutis Baltakys

2015-03-01

Full Text Available In this work the adsorption kinetic parameters for Fe3+ and Ni2+ ions by gyrolite are presented. Additionally, the adsoption mechanism was described by using pseudo first order and pseudo second order  equations. It was determined that the adsorption capacity of gyrolite and intrusion of heavy metals ions in its structure depends on reaction time and the pH value of adsorptive. It was observed that the incorporation of Fe3+ ions occurs more intensive than Ni2+ ions. It was found that in the acidic solution the intrusion of Fe3+ ions into gyrolite structure proceeds by two types of chemical reaction mechanisms: substitution and addition. Meanwhile, nickel ions were participated only in substitution reaction: gyrolite-Ca0 + Mex+ ↔ gyrolite-Me0 + Ca2+. It was observed that the pseudo second order model fit well for iron and nickel ions adsorption mechanism. It was estimated that the adsorption reactions are not reversible process and the crystal structure of gyrolite is stable. Moreover, synthetic adsorbent and the products of sorption were characterized by XRD, STA and FT-IR methods.DOI: http://dx.doi.org/10.5755/j01.ms.21.1.5735

Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

Science.gov (United States)

Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

2013-12-21

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local

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.

Synchronous parallel kinetic Monte Carlo for continuum diffusion-reaction systems

International Nuclear Information System (INIS)

Martinez, E.; Marian, J.; Kalos, M.H.; Perlado, J.M.

2008-01-01

A novel parallel kinetic Monte Carlo (kMC) algorithm formulated on the basis of perfect time synchronicity is presented. The algorithm is intended as a generalization of the standard n-fold kMC method, and is trivially implemented in parallel architectures. In its present form, the algorithm is not rigorous in the sense that boundary conflicts are ignored. We demonstrate, however, that, in their absence, or if they were correctly accounted for, our algorithm solves the same master equation as the serial method. We test the validity and parallel performance of the method by solving several pure diffusion problems (i.e. with no particle interactions) with known analytical solution. We also study diffusion-reaction systems with known asymptotic behavior and find that, for large systems with interaction radii smaller than the typical diffusion length, boundary conflicts are negligible and do not affect the global kinetic evolution, which is seen to agree with the expected analytical behavior. Our method is a controlled approximation in the sense that the error incurred by ignoring boundary conflicts can be quantified intrinsically, during the course of a simulation, and decreased arbitrarily (controlled) by modifying a few problem-dependent simulation parameters

A methodology for modeling photocatalytic reactors for indoor pollution control using previously estimated kinetic parameters

Energy Technology Data Exchange (ETDEWEB)

Passalia, Claudio; Alfano, Orlando M. [INTEC - Instituto de Desarrollo Tecnologico para la Industria Quimica, CONICET - UNL, Gueemes 3450, 3000 Santa Fe (Argentina); FICH - Departamento de Medio Ambiente, Facultad de Ingenieria y Ciencias Hidricas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000 Santa Fe (Argentina); Brandi, Rodolfo J., E-mail: rbrandi@santafe-conicet.gov.ar [INTEC - Instituto de Desarrollo Tecnologico para la Industria Quimica, CONICET - UNL, Gueemes 3450, 3000 Santa Fe (Argentina); FICH - Departamento de Medio Ambiente, Facultad de Ingenieria y Ciencias Hidricas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000 Santa Fe (Argentina)

2012-04-15

Highlights: Black-Right-Pointing-Pointer Indoor pollution control via photocatalytic reactors. Black-Right-Pointing-Pointer Scaling-up methodology based on previously determined mechanistic kinetics. Black-Right-Pointing-Pointer Radiation interchange model between catalytic walls using configuration factors. Black-Right-Pointing-Pointer Modeling and experimental validation of a complex geometry photocatalytic reactor. - Abstract: A methodology for modeling photocatalytic reactors for their application in indoor air pollution control is carried out. The methodology implies, firstly, the determination of intrinsic reaction kinetics for the removal of formaldehyde. This is achieved by means of a simple geometry, continuous reactor operating under kinetic control regime and steady state. The kinetic parameters were estimated from experimental data by means of a nonlinear optimization algorithm. The second step was the application of the obtained kinetic parameters to a very different photoreactor configuration. In this case, the reactor is a corrugated wall type using nanosize TiO{sub 2} as catalyst irradiated by UV lamps that provided a spatially uniform radiation field. The radiative transfer within the reactor was modeled through a superficial emission model for the lamps, the ray tracing method and the computation of view factors. The velocity and concentration fields were evaluated by means of a commercial CFD tool (Fluent 12) where the radiation model was introduced externally. The results of the model were compared experimentally in a corrugated wall, bench scale reactor constructed in the laboratory. The overall pollutant conversion showed good agreement between model predictions and experiments, with a root mean square error less than 4%.

A Kinetic Study of the Gas-Phase Reaction of OH with Br2

Science.gov (United States)

Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

2011-01-01

An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

Kinetics Analysis of Synthesis Reaction of Struvite With Air-Flow Continous Vertical Reactors

Science.gov (United States)

Edahwati, L.; Sutiyono, S.; Muryanto, S.; Jamari, J.; Bayuseno, dan A. P.

2018-01-01

Kinetics reaction is a knowledge about a rate of chemical reaction. The differential of the reaction rate can be determined from the reactant material or the formed material. The reaction mechanism of a reactor may include a stage of reaction occurring sequentially during the process of converting the reactants into products. In the determination of reaction kinetics, the order of reaction and the rate constant reaction must be recognized. This study was carried out using air as a stirrer as a medium in the vertical reactor for crystallization of struvite. Stirring is one of the important aspects in struvite crystallization process. Struvite crystals or magnesium ammonium phosphate hexahydrates (MgNH4PO4·6H2O) is commonly formed in reversible reactions and can be generated as an orthorhombic crystal. Air is selected as a stirrer on the existing flow pattern in the reactor determining the reaction kinetics of the crystal from the solution. The experimental study was conducted by mixing an equimolar solution of 0.03 M NH4OH, MgCl2 and H3PO4 with a ratio of 1: 1: 1. The crystallization process of the mixed solution was observed in an inside reactor at the flow rate ranges of 16-38 ml/min and the temperature of 30°C was selected in the study. The air inlet rate was kept constant at 0.25 liters/min. The pH solution was adjusted to be 8, 9 and 10 by dropping wisely of 1 N KOH solution. The crystallization kinetics was examined until the steady state of the reaction was reached. The precipitates were filtered and dried at a temperature for subsequent material characterization, including Scanning Electron Microscope (SEM) and XRD (X-Ray diffraction) method. The results show that higher flow rate leads to less mass of struvite.

Kinetic Parameters of Thermal Degradation of Polymers

Institute of Scientific and Technical Information of China (English)

朱新生; 程嘉祺

2003-01-01

The derivative expressions between activation energy (E) and the temperature at the maximum mass loss rate(Tmax) and between activation energy (E) and exponent (N) were deduced in the light of Arrhenius theory. It was found that the increase of activation energy results in the decrease of exponent and the increase of Tmax. The kinetic parameters were involved in the analysis of the thermal degradation of several polymers. The degradation kinetics of these polymers well complied with the prediction of the derivative expressions for the polymer degradation with single mechanism dominated.

Kinetic modeling of hydrocracking reaction in a trickle-bed reactor with Pt/Y-zeolite catalysts

Energy Technology Data Exchange (ETDEWEB)

Lee, BalSang; Park, Myung-June; Kim, Young-A; Park, Eun Duck [Ajou University, Suwon (Korea, Republic of); Han, Jeongsik [Agency for Defense Development, Daejeon (Korea, Republic of); Jeong, Kwang-Eun; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology (KRICT), Daejeon (Korea, Republic of)

2014-03-15

A kinetic model is developed to predict the entire distribution of hydrocarbon products for the hydrocracking reaction with Pt/Y-zeolite catalysts in a trickle-bed reactor. Operating conditions, such as temperature, pressure, and wax and H{sub 2} flow rates were varied to evaluate their effects on conversion and distribution, and kinetic parameters were estimated using the experimental data that covers the window of operating conditions. The comparison between experimental data and simulated results corroborated the validity of the developed model, and the quantitative prediction of the reactor performance was clearly demonstrated. To make evident the usefulness of the model, an optimization method, genetic algorithm (GA), was applied, and the optimal condition for the maximum production of C{sub 10}-C{sub 17} was successfully calculated.

Kinetic modeling of hydrocracking reaction in a trickle-bed reactor with Pt/Y-zeolite catalysts

International Nuclear Information System (INIS)

Lee, BalSang; Park, Myung-June; Kim, Young-A; Park, Eun Duck; Han, Jeongsik; Jeong, Kwang-Eun; Kim, Chul-Ung; Jeong, Soon-Yong

2014-01-01

A kinetic model is developed to predict the entire distribution of hydrocarbon products for the hydrocracking reaction with Pt/Y-zeolite catalysts in a trickle-bed reactor. Operating conditions, such as temperature, pressure, and wax and H 2 flow rates were varied to evaluate their effects on conversion and distribution, and kinetic parameters were estimated using the experimental data that covers the window of operating conditions. The comparison between experimental data and simulated results corroborated the validity of the developed model, and the quantitative prediction of the reactor performance was clearly demonstrated. To make evident the usefulness of the model, an optimization method, genetic algorithm (GA), was applied, and the optimal condition for the maximum production of C 10 -C 17 was successfully calculated

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.

Multiresponse modelling of the caramelisation reaction

OpenAIRE

Quintas, Mafalda; Guimarães, Carla; Baylina, João; Brandão, Teresa R. S.; Silva, Cristina L.M.

2007-01-01

Multiresponse modelling is a powerful tool for studying complex kinetics of reactions occurring in food products. This modelling technique uses information of reactants and products involved, allowing insightful kinetic parameters estimation and helping in clarifying reaction mechanisms. One example of a complex reaction that occurs in food processing is the caramelisation reaction. Caramelisation is the common name for a group of reactions observed when carbohydrates are exposed to high temp...

Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

Science.gov (United States)

Asgharzadeh, Somaie; Vahedpour, Morteza

2018-06-01

Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

Reactions of sulfur atoms. XV. Absolute rate parameters for the S(3P210) + alkyne reactions

International Nuclear Information System (INIS)

van Roodselaar, A.; Safarik, I.; Strausz, O.P.; Gunning, H.E.

1978-01-01

Using flash photolysis with vacuum uv kinetic absorption spectroscopy, absolute rate constants and Arrhenius parameters have been measured for the addition of ground state S( 3 P 2 , 1 , 0 ) atoms to alkynes. The decay of sulfur atoms in COS, alkyne, and CO 2 -diluent mixtures is first order in sulfur atom concentration and the first-order decay rate constants are proportional to the alkyne concentration. The following rate constants were determined at room temperature: k(C 2 H 2 ) = k(C 2 D 2 ) + (2.3 +- 0.4) x 10 8 ; k(CHCCH 3 ) = (4.8 +- 0.2) x 10 9 ; k(CHCC 2 H 5 ) = (3.3 +- 0.2) x 10 9 ; k(CH 3 CCCH 3 ) = 1.6 +- 0.2) x 10 10 ; k(CH 3 CCC 2 C 5 ) = 1.8 +- 0.3) x 10 10 ; and k(CF 3 CCCF 3 ) = (2.1 +- 0.4) x 10 8 L mol -1 s -1 . The Arrhenius parameters determined are k(C 2 H 2 ) = (3.4 +- 1.9) x 10 10 exp[(-3000 +- 400)/RT] L mol -1 s -1 and k(CHCCH 3 ) = (2.0 +- 1.2) x 10 10 exp[(-900 +- 200)/RT] L mol -1 s -1 where error limits represent standard deviations. The rate parameters are compared to those obtained for the addition of other electrophilic reagents to alkynes and the results discussed in terms of structural and kinetic factors. Theoretical treatment of the secondary H/D isotope effect in the acetylene reaction satisfactorily reproduces the experimental value. 5 tables, 4 figures, 59 references

Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

Energy Technology Data Exchange (ETDEWEB)

Sailani, Riya; Bhasin, Meneka; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

2014-01-15

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be (61.67 ± 0.47) kJ mol{sup -1} and (-62.71 ± 2.48) JK{sup -1}mol{sup -1} respectively employing Eyring equation.

Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

Directory of Open Access Journals (Sweden)

Yongki Choi

2011-12-01

Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

A new general method for simultaneous fitting of temperature and concentration dependence of reaction rates yields kinetic and thermodynamic parameters for HIV reverse transcriptase specificity.

Science.gov (United States)

Li, An; Ziehr, Jessica L; Johnson, Kenneth A

2017-04-21

Recent studies have demonstrated the dominant role of induced fit in enzyme specificity of HIV reverse transcriptase and many other enzymes. However, relevant thermodynamic parameters are lacking, and equilibrium thermodynamic methods are of no avail because the key parameters can only be determined by kinetic measurement. By modifying KinTek Explorer software, we present a new general method for globally fitting data collected over a range of substrate concentrations and temperatures and apply it to HIV reverse transcriptase. Fluorescence stopped-flow methods were used to record the kinetics of enzyme conformational changes that monitor nucleotide binding and incorporation. The nucleotide concentration dependence was measured at temperatures ranging from 5 to 37 °C, and the raw data were fit globally to derive a single set of rate constants at 37 °C and a set of activation enthalpy terms to account for the kinetics at all other temperatures. This comprehensive analysis afforded thermodynamic parameters for nucleotide binding ( K d , Δ G , Δ H , and Δ S at 37 °C) and kinetic parameters for enzyme conformational changes and chemistry (rate constants and activation enthalpy). Comparisons between wild-type enzyme and a mutant resistant to nucleoside analogs used to treat HIV infections reveal that the ground state binding is weaker and the activation enthalpy for the conformational change step is significantly larger for the mutant. Further studies to explore the structural underpinnings of the observed thermodynamics and kinetics of the conformational change step may help to design better analogs to treat HIV infections and other diseases. Our new method is generally applicable to enzyme and chemical kinetics. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Ohsaka, Takeo

2009-01-01

In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

2009-10-01

In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

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

International Nuclear Information System (INIS)

Lalauze, Rene

1973-01-01

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

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.

Kinetic parameter estimation model for anaerobic co-digestion of waste activated sludge and microalgae.

Science.gov (United States)

Lee, Eunyoung; Cumberbatch, Jewel; Wang, Meng; Zhang, Qiong

2017-03-01

Anaerobic co-digestion has a potential to improve biogas production, but limited kinetic information is available for co-digestion. This study introduced regression-based models to estimate the kinetic parameters for the co-digestion of microalgae and Waste Activated Sludge (WAS). The models were developed using the ratios of co-substrates and the kinetic parameters for the single substrate as indicators. The models were applied to the modified first-order kinetics and Monod model to determine the rate of hydrolysis and methanogenesis for the co-digestion. The results showed that the model using a hyperbola function was better for the estimation of the first-order kinetic coefficients, while the model using inverse tangent function closely estimated the Monod kinetic parameters. The models can be used for estimating kinetic parameters for not only microalgae-WAS co-digestion but also other substrates' co-digestion such as microalgae-swine manure and WAS-aquatic plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Estimation of kinetic and thermodynamic ligand-binding parameters using computational strategies.

Science.gov (United States)

Deganutti, Giuseppe; Moro, Stefano

2017-04-01

Kinetic and thermodynamic ligand-protein binding parameters are gaining growing importance as key information to consider in drug discovery. The determination of the molecular structures, using particularly x-ray and NMR techniques, is crucial for understanding how a ligand recognizes its target in the final binding complex. However, for a better understanding of the recognition processes, experimental studies of ligand-protein interactions are needed. Even though several techniques can be used to investigate both thermodynamic and kinetic profiles for a ligand-protein complex, these procedures are very often laborious, time consuming and expensive. In the last 10 years, computational approaches have enormous potential in providing insights into each of the above effects and in parsing their contributions to the changes in both kinetic and thermodynamic binding parameters. The main purpose of this review is to summarize the state of the art of computational strategies for estimating the kinetic and thermodynamic parameters of a ligand-protein binding.

A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

International Nuclear Information System (INIS)

Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

2017-01-01

Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

1D to 3D diffusion-reaction kinetics of defects in crystals

DEFF Research Database (Denmark)

Trinkaus, H.; Heinisch, H.L.; Barashev, A.V.

2002-01-01

Microstructural features evolving in crystalline solids from diffusion-reaction kinetics of mobile components depend crucially on the dimension of the underlying diffusion process which is commonly assumed to be three-dimensional (3D). In metals, irradiation-induced displacement cascades produce...... clusters of self-interstitials performing 1D diffusion. Changes between equivalent 1D diffusion paths and transversal diffusion result in diffusion-reaction kinetics between one and three dimensions. An analytical approach suggests a single-variable function (master curve) interpolating between the 1D...

Modelling and determination of the kinetic parameters of the pyrolysis of Dichrostachys cinerea

International Nuclear Information System (INIS)

Abreu Naranjo, Reinier; Romero Romero, Osvaldo

2011-01-01

In the present study were analyzed biomass samples of Dichrostachys cinerea, commonly known in Cuba as marabou, by thermogravimetric method at various heating rates of devolatilization in nitrogen atmosphere at 5, 10 and 20 C min-1. On the kinetic analysis was used a mechanism of three independent reactions of order 1, generally attributed to three chief components of this kind of lignocellulose materials, hemicelluloses, cellulose and lignin. The values of activation energy, pre-exponential factor and contribution factor were similar to those reported in previous research for this type of biomass. The proposed model predicts with acceptable correlation the experimental and calculated curves of the decomposition of D. cinerea, with a deviation factor less than 5% for the temperature range studied. On the other hand, the kinetic parameters of the thermal decomposition coupled at equations of transport phenomena are essential to optimize the design and use of biomass thermochemical conversion processes, hence the importance of the research. (author)

Struvite Precipitation and Phosphorous Removal from Urine Synthetic Solution: Reaction Kinetic Study

Directory of Open Access Journals (Sweden)

Marwa Saied Shalaby

2015-03-01

Full Text Available Phosphorus, like oil, is a non-renewable resource that must be harvested from finite resources in the earth’s crust. An essential element for life, phosphorus is becoming increasingly scarce, contaminated, and difficult to extract. Struvite or magnesium ammonium phosphate (MgNH4PO4.6H2O is a white, crystalline phosphate mineral that can be used as a bio-available fertilizer. The main objective of this research is to indicate the most important operating parameters affecting struvite precipitation by means of chemical reaction kinetics. The present study explores struvite precipitation by chemical method under different starting molar ratios, pH and SSR. It is shown that an increase of starting Mg: PO4: NH4 with respect to magnesium (1.6:1:1 strongly influences the growth rate of struvite and so the efficiency of the phosphate removal. This was attributed to the effect of magnesium on the struvite solubility product and on the reached supersaturation Super Saturation Ratio at optimum starting molar ratio and pH. It was also shown, by using chemical precipitation method that the determined Super Saturation Ratio (SSR values of struvite, at 8, 8.5, 9, 9.5 and 10 are 1.314, 4.29, 8.89, 9.87 and 14.89 respectively are close to those presented in the literature for different origins of wastewater streams. The results show that SSR , pH, and starting molar ratio strongly influences the kinetics of precipitation and so phosphorous removal to reach 93% removal percent , 5.95 mg/lit as a minimum PO4 remained in solution, and 7.9 gm precipitated struvite from feed synthetic solution of 750 ml . The product was subjected to chemical analysis by means of EDIX-FTIR, SEM and XRD showing conformity with published literature. First-order kinetics was found to be sufficient to describe the rate data. The rates increased with increasing pH and so SSR and the apparent rate constants for the reaction were determined. © 2015 BCREC UNDIP. All rights reserved

Degradation of ibuprofen by hydrodynamic cavitation: Reaction pathways and effect of operational parameters.

Science.gov (United States)

Musmarra, Dino; Prisciandaro, Marina; Capocelli, Mauro; Karatza, Despina; Iovino, Pasquale; Canzano, Silvana; Lancia, Amedeo

2016-03-01

Ibuprofen (IBP) is an anti-inflammatory drug whose residues can be found worldwide in natural water bodies resulting in harmful effects to aquatic species even at low concentrations. This paper deals with the degradation of IBP in water by hydrodynamic cavitation in a convergent-divergent nozzle. Over 60% of ibuprofen was degraded in 60 min with an electrical energy per order (EEO) of 10.77 kWh m(-3) at an initial concentration of 200 μg L(-1) and a relative inlet pressure pin=0.35 MPa. Five intermediates generated from different hydroxylation reactions were identified; the potential mechanisms of degradation were sketched and discussed. The reaction pathways recognized are in line with the relevant literature, both experimental and theoretical. By varying the pressure upstream the constriction, different degradation rates were observed. This effect was discussed according to a numerical simulation of the hydroxyl radical production identifying a clear correspondence between the maximum kinetic constant kOH and the maximum calculated OH production. Furthermore, in the investigated experimental conditions, the pH parameter was found not to affect the extent of degradation; this peculiar feature agrees with a recently published kinetic insight and has been explained in the light of the intermediates of the different reaction pathways. Copyright © 2015 Elsevier B.V. All rights reserved.

Reaction kinetics of dolomite rim growth

Science.gov (United States)

Helpa, V.; Rybacki, E.; Abart, R.; Morales, L. F. G.; Rhede, D.; Jeřábek, P.; Dresen, G.

2014-04-01

Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750-850 °C temperature, and 3-146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5-71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12-80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.

Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

Science.gov (United States)

Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

2016-05-01

3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

International Nuclear Information System (INIS)

Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira; Abuin, Senen Paz; Soulé, Ezequiel R.; Williams, Roberto J.J.

2015-01-01

Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted

Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

Energy Technology Data Exchange (ETDEWEB)

Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Abuin, Senen Paz, E-mail: senen@gairesa.com [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Soulé, Ezequiel R. [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Williams, Roberto J.J., E-mail: williams@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

2015-09-20

Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.

Influence of external mass transfer limitation on apparent kinetic parameters of penicillin G acylase immobilized on nonporous ultrafine silica particles.

Science.gov (United States)

Kheirolomoom, Azadeh; Khorasheh, Farhad; Fazelinia, Hossein

2002-01-01

Immobilization of enzymes on nonporous supports provides a suitable model for investigating the effect of external mass transfer limitation on the reaction rate in the absence of internal diffusional resistance. In this study, deacylation of penicillin G was investigated using penicillin acylase immobilized on ultrafine silica particles. Kinetic studies were performed within the low-substrate-concentration region, where the external mass transfer limitation becomes significant. To predict the apparent kinetic parameters and the overall effectiveness factor, knowledge of the external mass transfer coefficient, k(L)a, is necessary. Although various correlations exist for estimation of k(L)a, in this study, an optimization scheme was utilized to obtain this coefficient. Using the optimum values of k(L)a, the initial reaction rates were predicted and found to be in good agreement with the experimental data.

Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

Energy Technology Data Exchange (ETDEWEB)

Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

2004-09-15

One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

Deviation from the kinetic law of mass action for reactions induced by binary encounters in liquid solutions

International Nuclear Information System (INIS)

Doktorov, Alexander B; Kipriyanov, Alexey A

2007-01-01

In considering the irreversible chemical reaction A+B→ C+B in liquid solutions two many-particle approaches to the derivation of binary non-Markovian kinetic equations are compared: simple superposition decoupling and a method of extracting 'pair' channels from three-particle correlation evolution. It is shown that both methods provide an almost identical description of this reaction. However, in studies of reversible reactions in liquid solutions only the channel extraction method gives a correct physically clear description of the reaction though it consists of a sequence of steps: the development of integral encounter theory (IET), effective pairs approximation (EPA), modified encounter theory (MET), and the final regular form (RF) of kinetic equations. It is shown that the rate equations often encountered in the literature correspond to the independence of transient channels of 'scattering' in the bimolecular reversible reaction (A+B -B), while the independent transient channel of 'decay' in the reversible reactionA+B -C is defined solely by time integral convolution. In the general case transient channels in non-Markovian theory are not independent, and their interference manifests itself as a non-Markovian inhomogeneous source in binary non-Markovian kinetic equations in regular form. Based on the derived equations new universal kinetics (independent of models) of chemical equilibrium attainment have been obtained. It is shown that these kinetics can differ essentially from the kinetics corresponding to the kinetic law of mass action of formal chemical kinetics

Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and ...

African Journals Online (AJOL)

The kinetic study of coupled gas-iron reactions at 15600 has been carried out for the system involving liquid iron containing carbon and silicon and a gas phase consisting carbon monoxide, silicon monoxide and carbon dioxide. The coupled reactions are: (1) 200(g) = CO2 + C. (2) SiO (g) + CO (g) = Si ¸ CO (g). (3) SiO (g) + ...

Kinetics of Slurry Phase Fischer-Tropsch Synthesis

Energy Technology Data Exchange (ETDEWEB)

Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski; Lech Nowicki; Madhav Nayapati

2006-12-31

The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. Three STSR tests of the Ruhrchemie LP 33/81 catalyst were conducted to collect data on catalyst activity and selectivity under 25 different sets of process conditions. The observed decrease in 1-olefin content and increase in 2-olefin and n-paraffin contents with the increase in conversion are consistent with a concept that 1-olefins participate in secondary reactions (e.g. 1-olefin hydrogenation, isomerization and readsorption), whereas 2-olefins and n-paraffins are formed in these reactions. Carbon number product distribution showed an increase in chain growth probability with increase in chain length. Vapor-liquid equilibrium calculations were made to check validity of the assumption that the gas and liquid phases are in equilibrium during FTS in the STSR. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Discrepancies between the calculated and experimental values for the liquid-phase composition (for some of the experimental data) are ascribed to experimental errors in the amount of wax collected from the reactor, and the relative amounts of hydrocarbon wax and Durasyn 164 oil (start-up fluid) in the liquid samples. Kinetic parameters of four kinetic models (Lox and Froment, 1993b; Yang et al., 2003; Van der Laan and Beenackers, 1998, 1999; and an extended kinetic model of Van der Laan and Beenackers) were estimated from experimental data in the STSR tests. Two of these kinetic models (Lox and Froment, 1993b; Yang et al., 2003) can predict a complete product distribution (inorganic species and hydrocarbons), whereas the kinetic model of Van der Laan and Beenackers (1998, 1999) can

Kinetics of Slurry Phase Fischer-Tropsch Synthesis

International Nuclear Information System (INIS)

Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski; Lech Nowicki; Madhav Nayapati

2006-01-01

The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. Three STSR tests of the Ruhrchemie LP 33/81 catalyst were conducted to collect data on catalyst activity and selectivity under 25 different sets of process conditions. The observed decrease in 1-olefin content and increase in 2-olefin and n-paraffin contents with the increase in conversion are consistent with a concept that 1-olefins participate in secondary reactions (e.g. 1-olefin hydrogenation, isomerization and readsorption), whereas 2-olefins and n-paraffins are formed in these reactions. Carbon number product distribution showed an increase in chain growth probability with increase in chain length. Vapor-liquid equilibrium calculations were made to check validity of the assumption that the gas and liquid phases are in equilibrium during FTS in the STSR. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Discrepancies between the calculated and experimental values for the liquid-phase composition (for some of the experimental data) are ascribed to experimental errors in the amount of wax collected from the reactor, and the relative amounts of hydrocarbon wax and Durasyn 164 oil (start-up fluid) in the liquid samples. Kinetic parameters of four kinetic models (Lox and Froment, 1993b; Yang et al., 2003; Van der Laan and Beenackers, 1998, 1999; and an extended kinetic model of Van der Laan and Beenackers) were estimated from experimental data in the STSR tests. Two of these kinetic models (Lox and Froment, 1993b; Yang et al., 2003) can predict a complete product distribution (inorganic species and hydrocarbons), whereas the kinetic model of Van der Laan and Beenackers (1998, 1999) can

CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

International Nuclear Information System (INIS)

Hsiang, Hsing-I; Lu, Li-Hsin; Chang, Yu-Lun; Ray, Dahtong; Yen, Fu-Su

2011-01-01

Highlights: → CuInSe 2 phase increased gradually accompanied with a decrease in γ-In 2 Se 3 and no intermediate phase during calcination. → CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a one-dimensional diffusion-controlled reaction with apparent activation energy of about 122.5 kJ/mol. → The solid reaction kinetics may be dominated by the diffusion of In 3+ ions. - Abstract: The reaction mechanism and CuInSe 2 formation kinetics using a solid state reaction from Cu 2 Se and In 2 Se 3 powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe 2 phase increased gradually, accompanied with a decrease in γ-In 2 Se 3 with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu 2 Se and In 2 Se 3 phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe 2 crystallites was close to that of the Cu 2 Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In 3+ ions.

The effects of one-dimensional glide on the reaction kinetics of interstitial clusters

DEFF Research Database (Denmark)

Heinisch, H.L.; Singh, B.N.; Golubov, S.I.

2000-01-01

is therefore 'mixed 1D/3D migration' along a 3D path consisting of 1D segments, The defect reaction kinetics under mixed 1D/3D diffusion are different from pure 1D diffusion and pure 3D diffusion, both of which can be formulated within analytical rate theory models of microstructure evolution under irradiation....... Atomic-scale kinetic Monte Carlo (kMC) defect migration simulations are used to investigate the effects of mixed 1D/3D migration on defect reaction kinetics as a guide for implementing mixed 1D/3D migration into the analytical rate theory. The functional dependence of the sink strength on the size...

Kinetics and

Directory of Open Access Journals (Sweden)

Mojtaba Ahmadi

2016-11-01

Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

Isothermal reaction calorimetry as a tool for kinetic analysis

International Nuclear Information System (INIS)

Zogg, Andreas; Stoessel, Francis; Fischer, Ulrich; Hungerbuehler, Konrad

2004-01-01

Reaction calorimetry has found widespread application for thermal and kinetic analysis of chemical reactions in the context of thermal process safety as well as process development. This paper reviews the most important reaction calorimetric principles (heat-flow, heat-balance, power-compensation, and Peltier principle) and their applications in commercial or scientific devices. The discussion focuses on the different dynamic behavior of the main calorimetric principles during an isothermal reaction measurement. Examples of available reaction calorimeters are further compared considering their detection limit, time constant as well as temperature range. In a second part, different evaluation methods for the isothermally measured calorimetric data are reviewed and discussed. The methods will be compared, focusing especially on the fact that reaction calorimetric data always contains additional informations not directly related to the actual chemical reaction such as heat of mixing, heat of phase-transfer/change processes or simple measurement errors. Depending on the evaluation method applied such disturbances have a significant influence on the calculated reaction enthalpies or rate constants

Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

Science.gov (United States)

Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

Using linear time-invariant system theory to estimate kinetic parameters directly from projection measurements

International Nuclear Information System (INIS)

Zeng, G.L.; Gullberg, G.T.

1995-01-01

It is common practice to estimate kinetic parameters from dynamically acquired tomographic data by first reconstructing a dynamic sequence of three-dimensional reconstructions and then fitting the parameters to time activity curves generated from the time-varying reconstructed images. However, in SPECT, the pharmaceutical distribution can change during the acquisition of a complete tomographic data set, which can bias the estimated kinetic parameters. It is hypothesized that more accurate estimates of the kinetic parameters can be obtained by fitting to the projection measurements instead of the reconstructed time sequence. Estimation from projections requires the knowledge of their relationship between the tissue regions of interest or voxels with particular kinetic parameters and the project measurements, which results in a complicated nonlinear estimation problem with a series of exponential factors with multiplicative coefficients. A technique is presented in this paper where the exponential decay parameters are estimated separately using linear time-invariant system theory. Once the exponential factors are known, the coefficients of the exponentials can be estimated using linear estimation techniques. Computer simulations demonstrate that estimation of the kinetic parameters directly from the projections is more accurate than the estimation from the reconstructed images

Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

International Nuclear Information System (INIS)

Dzeba, I.; Mihaljevic, B.

2011-01-01

Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

Generation of a library of two-group diffusion and kinetics parameters for DYN3D

International Nuclear Information System (INIS)

Petkov, P.T.; Christoskov, I.D.; Kamenov, K.; Antov, A.

2002-01-01

A library of two-group diffusion and kinetics parameters has been generated for the neutron kinetics code DYN3D for analysis of reactivity initiated accidents for the WWER-440 reactors, based on the MAGRU approximation methodology for the diffusion and kinetics parameters. The accuracy of this methodology has been tested and the conclusion is that it is not adequate. A new approximation methodology, based on interpolation for the most widely varying parameters, i.e. the moderator temperature and density, and on approximation for all other independent parameters, is presented. The methodology of calculation of the kinetics parameters using primary data from ENDF-B/VI is described in detail (Authors)

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

2010-12-15

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

2010-01-01

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

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.

Evaluation of rate law approximations in bottom-up kinetic models of metabolism

DEFF Research Database (Denmark)

Du, Bin; Zielinski, Daniel C.; Kavvas, Erol S.

2016-01-01

mass action rate law that removes the role of the enzyme from the reaction kinetics. We utilized in vivo data for the human red blood cell to compare the effect of rate law choices against the backdrop of physiological flux and concentration differences. We found that the Michaelis-Menten rate law......Background: The mechanistic description of enzyme kinetics in a dynamic model of metabolism requires specifying the numerical values of a large number of kinetic parameters. The parameterization challenge is often addressed through the use of simplifying approximations to form reaction rate laws....... These approximate rate laws were: 1) a Michaelis-Menten rate law with measured enzyme parameters, 2) a Michaelis-Menten rate law with approximated parameters, using the convenience kinetics convention, 3) a thermodynamic rate law resulting from a metabolite saturation assumption, and 4) a pure chemical reaction...

Ethanol Production from Whey by Kluyveromyces marxianus in Batch Fermentation System: Kinetics Parameters Estimation

Directory of Open Access Journals (Sweden)

Dessy Ariyanti

2013-03-01

Full Text Available Whey is the liquid remaining after milk has been curdled and strained. It is a by-product of the manufacture of cheese or casein and has several commercial uses. In environmental point of view, whey is kind of waste which has high pollution level due to it’s contain high organic compound with BOD and COD value 50 and 80 g/L respectively. On the other side, whey also contain an amount of lactose (4.5%-5%; lactose can be used as carbon source and raw material for producing ethanol via fermentation using yeast strain Kluyveromyces marxianus. The objective of this research is to investigate the ethanol production kinetics from crude whey through fermentation using Kluyveromyces marxianus and to predict the model kinetics parameter. The yeast was able to metabolize most of the lactose within 16 h to give 8.64 g/L ethanol, 4.43 g/L biomass, and remain the 3.122 g/L residual lactose. From the results presented it also can be concluded that common kinetic model for microbial growth, substrate consumption, and product formation is a good alternative to describe an experimental batch fermentation of Kluyveromyces marxianus grown on a medium composed of whey. The model was found to be capable of reflecting all batch culture phases to a certain degree of accuracy, giving the parameter value: μmax, Ks, YX/S, α, β : 0.32, 10.52, 0.095, 1.52, and 0.11 respectively. © 2013 BCREC UNDIP. All rights reserved(Selected Paper from International Conference on Chemical and Material Engineering (ICCME 2012Received: 27th September 2012; Revised: 29th November 2012; Accepted: 7th December 2012[How to Cite: D. Ariyanti, H. Hadiyanto, (2013. Ethanol Production from Whey by Kluyveromyces marxianus in Batch Fermentation System: Kinetics Parameters Estimation. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 179-184. (doi:10.9767/bcrec.7.3.4044.179-184][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4044.179-184 ] View in  |

Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

Directory of Open Access Journals (Sweden)

Kelath Murali Manoj

Full Text Available Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP, uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes.

Kinetic study of the reaction of chlorine atoms with hydroxyacetone in gas-phase

Science.gov (United States)

Stoeffler, Clara; Joly, Lilian; Durry, Georges; Cousin, Julien; Dumelié, Nicolas; Bruyant, Aurélien; Roth, Estelle; Chakir, Abdelkhaleq

2013-12-01

In this letter the kinetics of the reaction of hydroxyacetone CH3C(O)CH2OH with Cl atoms is investigated using the relative rate technique. Experiments are carried out in a 65 L multipass photoreactor in the temperature range of 281-350 K. A mid-infrared spectrometer based on a quantum cascade laser in external cavity emitting at 9.5 μm is used to analyze the reactants. The determined rate coefficient for the investigated reaction is (1.7 ± 0.3) × 10-11exp(381.5 ± 57.3/T). The results are presented and discussed in terms of precision and compared with those obtained previously. The impact of Cl atoms on the atmospheric life time of hydroxyacetone is also discussed. Developing analytical techniques to quantify this compound in the atmosphere. Several methods of measurement have been used including the technique of proton transfer mass spectrometry (PTR-MS) [2] and derivatization with a chemical agent such as dinitrophenylhydrazine (DNPH) [3,4] followed by GC/MS or HPLC analyses. The HA amount in the troposphere was found to be in the order of a few hundred parts per trillion by volume [4], Performing laboratory experiments in order to study the HA reactivity with atmospheric oxidants. The first study on the kinetic of the reaction between OH radicals and HA was made by Dagault et al. [5] whose work was performed at room temperature by flash photolysis-resonance fluorescence. The determined rate constant implies a lifetime of a few days for HA relative to oxidation by OH radicals. Orlando et al. performed mechanistic and kinetics studies of the reaction of HA with OH radicals and Cl atoms at room temperature using a relative method [6]. Products detection was performed using FTIR spectroscopy. Moreover, these authors studied the photolysis of HA to determine its quantum yield and UV absorption spectrum. These studies showed that HA is principally removed from the atmosphere by reaction with OH radicals. Kinetic studies of the reaction of OH radicals with HA as a

Kinetics of the Reaction of CO2 with Aqueous Potassium Salt of Taurine and Glycine

NARCIS (Netherlands)

Kumar, P.S.; Hogendoorn, J.A.; Versteeg, G.F.; Feron, P.H.M.

2003-01-01

The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas–liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

Kinetics of the reaction of CO2 with aqueous potassium salt of taurine and glycine

NARCIS (Netherlands)

Kumar Paramasivam Senthil, P.S.; Hogendoorn, Kees; Versteeg, Geert; Feron, P.H.M.

2003-01-01

The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas-liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

The kinetics of the reduction reaction of plutonium(IV) with N,N-dimethylhydroxylamine

International Nuclear Information System (INIS)

Yanxin Chen; Honbing Tang; Jinping Liu; Hui He

2011-01-01

The kinetics of reduction reactions between N,N-dimethylhydroxylamine (DMHAN) and plutonium(IV) in nitric acid solution have been studied spectrophotometrically. The kinetic equation of the reaction is determined to be -d[Pu(IV)]/dt = k 0 [Pu(IV)][DMHAN] 1.18 /[H + ] 2.22 at the beginning, where, the rate constant of the reaction (k 0 ) is 10.5 ± 1.8(mol/L) 1.04 s -1 at 14.5 deg C. By regressing of the time-concentration curve of the reaction, The complete rate equation is calculated as -d[Pu(IV)] / dt = k[Pu(IV)] 2 [DMHAN] 1.18 /[H + ] 2.22 / 8.12[Pu(III)]+95.9[Pu(IV)] with the reaction constant k about 1,000(mol/L) 1.04 s -1 at 14.5 deg C and an ionic strength (μ) of 4.0 mol/L. (author)

Reaction kinetics for preparation of silica film with Stoeber method

International Nuclear Information System (INIS)

Shang Mengying; Jiang Xiaodong; Liu Miao; Luo Xuan; Tang Yongjian; Cao Linhong

2013-01-01

A new formula was proposed to investigate the relationship between reaction time and tetraethylorthosilicate (TEOS) conversion rate for preparation of silica sol with Stöber method, by studying the reaction kinetics of TEOS hydrolytic process. An appropriate conversion rate was then determined and used to calculate the theoretical optimal reaction time. Meanwhile, silica sols were prepared by sol-gel process using TEOS as precursor and ammonia as catalyst. It was found that the reaction time decreases with an increasing amount of ammonia and water. The values of experimental optimal reaction time were obtained, and agree with the theoretical results (the errors are within 5%), which shows good applicability of our formula. (authors)

Conductometric Studies Of Kinetics Of Ionic Reaction Between Ag And Cl- In Aqueous Solution

Directory of Open Access Journals (Sweden)

Md. Rezwan Miah

2017-01-01

Full Text Available In the present report conductometric studies on the kinetic of formation of AgCl by ionic reaction between Ag and Clamp61485 in aqueous solution have been presented. The order of the mentioned reaction was determined by a new conductometric approach using half-life method. The obtained result showed that the reaction follows a second-order kinetics. The second-order rate constant of the reaction was obtained conductometrically using different initial concentrations of the reactants in the range of 2.5-5.0 mM. The average value of the rate constant was obtained as 20.648 L molamp614851 samp614851 at 25 amp61616C.

Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

Directory of Open Access Journals (Sweden)

Masood Ahmad Rizvi

2015-03-01

Full Text Available Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III redox reaction using spectrophotometric and potentiometric methods. The results were corroborated with the complexation effect on redox potential of iron(III-iron(II redox couple. The selected ligands were found to increase the rate of cysteine iron (III redox reaction in proportion to their stability of iron (II complex (EDTA < terpy < bipy < phen. A kinetic profile and the catalytic role of copper (II ions by means of redox shuttle mechanism for the cysteine iron (III redox reaction in presence of 1,10-phenanthroline (phen ligand is also reported.

Kinetics and optimization on discoloration of dyeing wastewater by schorl-catalyzed fenton-like reaction

Directory of Open Access Journals (Sweden)

Xu Huan-Yan

2014-01-01

Full Text Available Kinetics and optimization on the discoloration of an active commercial dye, Argazol Blue BFBR (ABB by heterogeneous Fenton-like reaction catalyzed by natural schorl were investigated in this study. Kinetic investigations revealed that the first-order kinetic model was more favorable to describe the discoloration of ABB at different reaction conditions than the second-order and Behnajady-Modirshahla-Ghanbery models. The relationship between the reaction rate constant k and reaction temperature T followed the Arrhenius equation, with the apparent activation energy Ea of 51.31kJ•mol-1. The central composite design under the response surface methodology was employed for the experimental design and optimization of the ABB discoloration process. The significance of a second order polynomial model for predicting the optimal values of ABB discoloration was evaluated by the analysis of variance and 3D response surface plots for the interactions between two variables were constructed. Then, the optimum conditions were determined.

Kinetic parameters and TL mechanism in cadmium tetra borate phosphor

International Nuclear Information System (INIS)

Annalakshmi, O.; Jose, M.T.; Sridevi, J.; Venkatraman, B.; Amarendra, G.; Mandal, A.B.

2014-01-01

Polycrystalline powder samples of cadmium tetra borate were synthesized by a simple solid state sintering technique and gamma irradiated sample showed a simple Thermoluminescence (TL) glow peak around 460 K. The TL kinetic parameters of gamma irradiated phosphor were determined by initial rise (IR), isothermal decay (ID), peak shape (PS), variable heating rate (VHR) and glow curve de-convolution method. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated by IR, ID, PS and VHR methods are in the order of ∼1.05 eV, 10 9 –10 12 s −1 and 1.58, respectively. From the results of TL and PL emission studies carried out on the phosphor revealed that the defect centers related to TL is different from that for PL. EPR measurements were carried out to identify the defect centers formed in cadmium tetra borate phosphor on gamma irradiation. Based on EPR studies the mechanism for TL process in cadmium tetra borate is proposed in this paper -- Highlights: • Polycrystalline powder samples of undoped cadmium tetra borate synthesized. • Cadmium tetra borate phosphor exhibits a dosimetric peak at 458 K. • Kinetic parameters of the trap responsible for TL evaluated. • TL mechanism is proposed from TL to EPR correlation studies

Kinetic parameters and TL mechanism in cadmium tetra borate phosphor

Energy Technology Data Exchange (ETDEWEB)

Annalakshmi, O. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Jose, M.T., E-mail: mtj@igcar.gov.in [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Sridevi, J. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India); Venkatraman, B. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Amarendra, G. [Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Mandal, A.B. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India)

2014-03-15

Polycrystalline powder samples of cadmium tetra borate were synthesized by a simple solid state sintering technique and gamma irradiated sample showed a simple Thermoluminescence (TL) glow peak around 460 K. The TL kinetic parameters of gamma irradiated phosphor were determined by initial rise (IR), isothermal decay (ID), peak shape (PS), variable heating rate (VHR) and glow curve de-convolution method. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated by IR, ID, PS and VHR methods are in the order of ∼1.05 eV, 10{sup 9}–10{sup 12} s{sup −1} and 1.58, respectively. From the results of TL and PL emission studies carried out on the phosphor revealed that the defect centers related to TL is different from that for PL. EPR measurements were carried out to identify the defect centers formed in cadmium tetra borate phosphor on gamma irradiation. Based on EPR studies the mechanism for TL process in cadmium tetra borate is proposed in this paper -- Highlights: • Polycrystalline powder samples of undoped cadmium tetra borate synthesized. • Cadmium tetra borate phosphor exhibits a dosimetric peak at 458 K. • Kinetic parameters of the trap responsible for TL evaluated. • TL mechanism is proposed from TL to EPR correlation studies.

SABIO-RK: an updated resource for manually curated biochemical reaction kinetics

Science.gov (United States)

Rey, Maja; Weidemann, Andreas; Kania, Renate; Müller, Wolfgang

2018-01-01

Abstract SABIO-RK (http://sabiork.h-its.org/) is a manually curated database containing data about biochemical reactions and their reaction kinetics. The data are primarily extracted from scientific literature and stored in a relational database. The content comprises both naturally occurring and alternatively measured biochemical reactions and is not restricted to any organism class. The data are made available to the public by a web-based search interface and by web services for programmatic access. In this update we describe major improvements and extensions of SABIO-RK since our last publication in the database issue of Nucleic Acid Research (2012). (i) The website has been completely revised and (ii) allows now also free text search for kinetics data. (iii) Additional interlinkages with other databases in our field have been established; this enables users to gain directly comprehensive knowledge about the properties of enzymes and kinetics beyond SABIO-RK. (iv) Vice versa, direct access to SABIO-RK data has been implemented in several systems biology tools and workflows. (v) On request of our experimental users, the data can be exported now additionally in spreadsheet formats. (vi) The newly established SABIO-RK Curation Service allows to respond to specific data requirements. PMID:29092055

KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS. FOURTH ANNUAL TECHNICAL PROGRESS REPORT

International Nuclear Information System (INIS)

Bukur, Dragomir B.; Froment, Gilbert F.; Olewski, Tomasz

2006-01-01

This report covers the fourth year of a research project conducted under the University Coal Research Program. The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (water, carbon dioxide, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the fourth year of the project, an analysis of experimental data collected during the second year of this project was performed. Kinetic parameters were estimated utilizing product distributions from 27 mass balances. During the reporting period two kinetic models were employed: a comprehensive kinetic model of Dr. Li and co-workers (Yang et al., 2003) and a hydrocarbon selectivity model of Van der Laan and Beenackers (1998, 1999) The kinetic model of Yang et al. (2003) has 24 parameters (20 parameters for hydrocarbon formation, and 4 parameters for the water-gas-shift (WGS) reaction). Kinetic parameters for the WGS reaction and FTS synthesis were estimated first separately, and then simultaneously. The estimation of these kinetic parameters employed the Levenberg-Marquardt (LM) method and the trust-region reflective Newton large-scale (LS) method. A genetic algorithm (GA) was incorporated into estimation of parameters for FTS reaction to provide initial estimates of model parameters. All reaction rate constants and activation energies were found to be positive, but at the 95% confidence level the intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons are predicted fairly accurately, whereas the model underpredicts values of higher molecular weight

Computer controlled automated assay for comprehensive studies of enzyme kinetic parameters.

Directory of Open Access Journals (Sweden)

Felix Bonowski

Full Text Available Stability and biological activity of proteins is highly dependent on their physicochemical environment. The development of realistic models of biological systems necessitates quantitative information on the response to changes of external conditions like pH, salinity and concentrations of substrates and allosteric modulators. Changes in just a few variable parameters rapidly lead to large numbers of experimental conditions, which go beyond the experimental capacity of most research groups. We implemented a computer-aided experimenting framework ("robot lab assistant" that allows us to parameterize abstract, human-readable descriptions of micro-plate based experiments with variable parameters and execute them on a conventional 8 channel liquid handling robot fitted with a sensitive plate reader. A set of newly developed R-packages translates the instructions into machine commands, executes them, collects the data and processes it without user-interaction. By combining script-driven experimental planning, execution and data-analysis, our system can react to experimental outcomes autonomously, allowing outcome-based iterative experimental strategies. The framework was applied in a response-surface model based iterative optimization of buffer conditions and investigation of substrate, allosteric effector, pH and salt dependent activity profiles of pyruvate kinase (PYK. A diprotic model of enzyme kinetics was used to model the combined effects of changing pH and substrate concentrations. The 8 parameters of the model could be estimated from a single two-hour experiment using nonlinear least-squares regression. The model with the estimated parameters successfully predicted pH and PEP dependence of initial reaction rates, while the PEP concentration dependent shift of optimal pH could only be reproduced with a set of manually tweaked parameters. Differences between model-predictions and experimental observations at low pH suggest additional protonation

On enzyme kinetic parameters modification of gamma irradiation

International Nuclear Information System (INIS)

Ferdes, O.S.; Ferdes, M.; Turcu, G.R.

1993-01-01

To elucidate the molecular mechanisms of gamma-ray action on biomolecules there were investigated the modifications in activity and other kinetic parameters for some enzymes irradiated in pure dry state at relative high doses. There were considered bacterial and fungal α-amylases, glucoamylase and Mucor sp. protease irradiated by a 60 Co gamma-ray source in the dose range 1.0-30.0 kGy, at different dose-rates between 0.5-2.0 kGy/h, at room temperature. Considering the enzyme inactivation in this dose range, the dose-effect relationships have an expected form and depend on the irradiation conditions but not significantly on the dose rate. The catalytic properties of enzymes were modified by irradiation. By usual methods it is evidenced a direct correlation between the enzymatic activities, Michaelis-Menten constant, K m , reaction velocities, v, and the irradiation dose. These experimental findings can support a self-consistent theoretical approach on biophysical radiation action on biological active molecules like enzymes. At the same time, some enzyme behaviour to irradiation could be considered like a good biological indicator of radiation response. (Author) 4 Figs., 19 Refs

Kinetics parameter measurements on RSG-GAS, a low-enriched fuel reactor

International Nuclear Information System (INIS)

Jujuratisbela, U; Arbie, B; Pinem, S.; Tukiran; Suparlina, L.; Singh, O.P.

1995-01-01

Kinetics parameter measurements, such as reactivity worths of control rods and fuel elements, beam tube void reactivity, power reactivity coefficient and xenon poisoning reactivity have been performed on different cores of Reaktor Serba Guna G.A. Siwabessy (RSG-GAS). In parallel, a programme was also initiated to measure the other kinetics parameters like effective delayed neutron life time, prompt neutron decay constant, validation of period reactivity relationship and zero power frequency response function. The paper provides the results of these measurements. (author)

Estimating kinetic mechanisms with prior knowledge I: Linear parameter constraints.

Science.gov (United States)

Salari, Autoosa; Navarro, Marco A; Milescu, Mirela; Milescu, Lorin S

2018-02-05

To understand how ion channels and other proteins function at the molecular and cellular levels, one must decrypt their kinetic mechanisms. Sophisticated algorithms have been developed that can be used to extract kinetic parameters from a variety of experimental data types. However, formulating models that not only explain new data, but are also consistent with existing knowledge, remains a challenge. Here, we present a two-part study describing a mathematical and computational formalism that can be used to enforce prior knowledge into the model using constraints. In this first part, we focus on constraints that enforce explicit linear relationships involving rate constants or other model parameters. We develop a simple, linear algebra-based transformation that can be applied to enforce many types of model properties and assumptions, such as microscopic reversibility, allosteric gating, and equality and inequality parameter relationships. This transformation converts the set of linearly interdependent model parameters into a reduced set of independent parameters, which can be passed to an automated search engine for model optimization. In the companion article, we introduce a complementary method that can be used to enforce arbitrary parameter relationships and any constraints that quantify the behavior of the model under certain conditions. The procedures described in this study can, in principle, be coupled to any of the existing methods for solving molecular kinetics for ion channels or other proteins. These concepts can be used not only to enforce existing knowledge but also to formulate and test new hypotheses. © 2018 Salari et al.

Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

Energy Technology Data Exchange (ETDEWEB)

Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

2015-12-31

A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

Nonequilibrium transition and pattern formation in a linear reaction-diffusion system with self-regulated kinetics

Science.gov (United States)

Paul, Shibashis; Ghosh, Shyamolina; Ray, Deb Shankar

2018-02-01

We consider a reaction-diffusion system with linear, stochastic activator-inhibitor kinetics where the time evolution of concentration of a species at any spatial location depends on the relative average concentration of its neighbors. This self-regulating nature of kinetics brings in spatial correlation between the activator and the inhibitor. An interplay of this correlation in kinetics and disparity of diffusivities of the two species leads to symmetry breaking non-equilibrium transition resulting in stationary pattern formation. The role of initial noise strength and the linear reaction terms has been analyzed for pattern selection.

Kinetics on the reaction of 6-chloroquinoline and p-substituted benzoylchlorides under high pressures

International Nuclear Information System (INIS)

Kim, Eung Ryul; Lim, Jong Wan; Kim, Se Kyong; Ko, Young Shin

2002-01-01

The reactions rates of substituted 6-chloroquinoline, with p-substituted benzoyichlorides (p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15,20,25 .deg. C) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ΔV ≠ , ΔH ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substituents in substrate (p-NO 2 ) with 6-chloroquinoline. When, the activation volume and the activation entropy are all negative. And the Hammett ρ values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in bond formation favored with increasing pressures

Kinetics and mechanisms of thiol-disulfide exchange covering direct substitution and thiol oxidation-mediated pathways.

Science.gov (United States)

Nagy, Péter

2013-05-01

Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol-disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. This review is focused on the kinetics and mechanisms of thiol-disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery.

Estimation of parameter sensitivities for stochastic reaction networks

KAUST Repository

Gupta, Ankit

2016-01-07

Quantification of the effects of parameter uncertainty is an important and challenging problem in Systems Biology. We consider this problem in the context of stochastic models of biochemical reaction networks where the dynamics is described as a continuous-time Markov chain whose states represent the molecular counts of various species. For such models, effects of parameter uncertainty are often quantified by estimating the infinitesimal sensitivities of some observables with respect to model parameters. The aim of this talk is to present a holistic approach towards this problem of estimating parameter sensitivities for stochastic reaction networks. Our approach is based on a generic formula which allows us to construct efficient estimators for parameter sensitivity using simulations of the underlying model. We will discuss how novel simulation techniques, such as tau-leaping approximations, multi-level methods etc. can be easily integrated with our approach and how one can deal with stiff reaction networks where reactions span multiple time-scales. We will demonstrate the efficiency and applicability of our approach using many examples from the biological literature.

Correlating thermodynamic and kinetic parameters with amorphous stability

DEFF Research Database (Denmark)

Graeser, Kirsten A; Patterson, James E; Zeitler, J Axel

2009-01-01

Poor physical stability is one of the single most important factors limiting the widespread use of the amorphous state in pharmaceutics. The purpose of this study is to move away from the case study approach by investigating thermodynamic and kinetic parameters as potential predictors of physical...

Kinetics parameters of a slurry remediation process in rotating drum bioreactors

International Nuclear Information System (INIS)

Esquivel-Rios, I.; Rodriguez-Meza, M. A.; Barrera-Cortes, J.

2009-01-01

The knowledge of biotransformation pollution dynamics in any systems is important for design and optimization purposes of biochemical processes involved. this is focus to the determination of kinetics parameters such as the maximum specific growth rate (μMAX), saturation constant (Ks), biomass yield (YX/S; X: biomass, S: substrate) and oxygen consumption (YO 2 /S; O 2 : oxygen). Several approximations, based on Monod equation, have been developed for estimating kinetics parameters in terms of concentration and type of substrate, bioprocess type and microflora available. (Author)

Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

Science.gov (United States)

Rangel, Cipriano; Espinosa-Garcia, Joaquin

2018-02-07

Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

On the analysis of glow curves with the general order kinetics: Reliability of the computed trap parameters

Energy Technology Data Exchange (ETDEWEB)

Ortega, F. [Facultad de Ingeniería (UNCPBA) and CIFICEN (UNCPBA – CICPBA – CONICET), Av. del Valle 5737, 7400 Olavarría (Argentina); Santiago, M.; Martinez, N.; Marcazzó, J.; Molina, P.; Caselli, E. [Instituto de Física Arroyo Seco (UNCPBA) and CIFICEN (UNCPBA – CICPBA – CONICET), Pinto 399, 7000 Tandil (Argentina)

2017-04-15

Nowadays the most employed kinetics for analyzing glow curves is the general order kinetics (GO) proposed by C. E. May and J. A. Partridge. As shown in many articles this kinetics might yield wrong parameters characterizing trap and recombination centers. In this article this kinetics is compared with the modified general order kinetics put forward by M. S. Rasheedy by analyzing synthetic glow curves. The results show that the modified kinetics gives parameters, which are more accurate than that yield by the original general order kinetics. A criterion is reported to evaluate the accuracy of the trap parameters found by deconvolving glow curves. This criterion was employed to assess the reliability of the trap parameters of the YVO{sub 4}: Eu{sup 3+} compounds.

Kinetics of the gas-phase tritium oxidation reaction

International Nuclear Information System (INIS)

Failor, R.A.

1989-01-01

Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

International Nuclear Information System (INIS)

Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

2006-01-01

Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

The binding of quinone to the photosynthetic reaction centers: kinetics and thermodynamics of reactions occurring at the QB-site in zwitterionic and anionic liposomes.

Science.gov (United States)

Mavelli, Fabio; Trotta, Massimo; Ciriaco, Fulvio; Agostiano, Angela; Giotta, Livia; Italiano, Francesca; Milano, Francesco

2014-07-01

Liposomes represent a versatile biomimetic environment for studying the interaction between integral membrane proteins and hydrophobic ligands. In this paper, the quinone binding to the QB-site of the photosynthetic reaction centers (RC) from Rhodobacter sphaeroides has been investigated in liposomes prepared with either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG) to highlight the role of the different phospholipid polar heads. Quinone binding (K Q) and interquinone electron transfer (L AB) equilibrium constants in the two type of liposomes were obtained by charge recombination reaction of QB-depleted RC in the presence of increasing amounts of ubiquinone-10 over the temperature interval 6-35 °C. The kinetic of the charge recombination reactions has been fitted by numerically solving the ordinary differential equations set associated with a detailed kinetic scheme involving electron transfer reactions coupled with quinone release and uptake. The entire set of traces at each temperature was accurately fitted using the sole quinone release constants (both in a neutral and a charge separated state) as adjustable parameters. The temperature dependence of the quinone exchange rate at the QB-site was, hence, obtained. It was found that the quinone exchange regime was always fast for PC while it switched from slow to fast in PG as the temperature rose above 20 °C. A new method was introduced in this paper for the evaluation of constant K Q using the area underneath the charge recombination traces as the indicator of the amount of quinone bound to the QB-site.

Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Kinetic parameters of hydroprocessing reactions in a flow reactor

Energy Technology Data Exchange (ETDEWEB)

Raychaudhuri, U.; Banerjee, T.S.; Ghar, R.N. (Indian Institute of Technology, Kharagpur (India))

1994-01-01

The change in distillation properties of a blend of light and heavy distillates over a commercial hydrotreating catalyst was studied using a small packed bed reactor. The results were interpreted assuming a pseudo-component model that took into account the physical and chemical complexity of the system. A first order series-parallel reaction mechanism was found to be valid for the operating conditions involved. Pore diffusion effects were also taken into consideration. 8 refs., 7 figs., 1 tab.

Theoretical Study of the Kinetics of the Pyrolytic Elimination Reaction of Ethyl Chloride

Directory of Open Access Journals (Sweden)

Isaiah Ajibade Adejoro

2010-01-01

Full Text Available The products of the gas-phase elimination of ethyl chloride are hydrogen chloride and ethane. Using AM1, MNDO and PM3 Hamiltonians of quantum mechanical computer code called MOPAC, a procedure for the kinetics and computation of the Arrhenius parameters for the pyrolytic elimination reaction of ethyl chloride was devised in order to evaluate the predictive ability of the three Hamiltonians used. The first-order rate coefficient for the three Hamiltonians are 1.15x10-8s-1, 4.55x10-15s-1 and 5.36x10-4s-1 for AM1, MNDO and PM3 respectively. The results obtained showed that the rate constant for the computed Arrhenius parameters compare well with the experimental values in the literature, thus showing that the computational procedure adequately simulates experimental results; also the semi-empirical AMI calculation has the best predictive ability with experiment followed by PM3 while MNDO has the least.

Determination of thermoluminescence kinetic parameters of thulium doped lithium calcium borate

International Nuclear Information System (INIS)

Jose, M.T.; Anishia, S.R.; Annalakshmi, O.; Ramasamy, V.

2011-01-01

For the first time kinetic parameters of thulium doped Lithium calcium borate (LCB) Thermoluminescence (TL) material are reported here. Irradiated LCB:Tm 3+ powder has revealed two intense TL glow peaks one at 510 (peak 1) and the other at 660 K (peak 2). Activation energy (E), frequency factor (s) and order of kinetics (b) of these peaks were determined by various heating rate (VHR), initial rise (IR), and peak shape (PS) methods. The trap depth and frequency factor determined for peaks 1 and 2 of LCB:Tm phosphor using VHR and IR methods are in good agreement. The average activation energy of peaks 1 and 2 obtained by these methods is 1.62 and 1.91 eV respectively. The frequency factors of peaks 1 and 2 are in the range of 10 13-16 and 10 12-14 sec -1 respectively. The E and s values estimated using the glow peak shape dependent parameters are relatively less compared to the values obtained from other methods. The large difference in these values is due to the complex nature of the glow curves. The order of the kinetics process for complex glow curve peaks could not be assigned on the basis of shape parameters alone but T m response on absorbed dose is to be considered for final confirmation. Glow peaks 1 and 2 of LCB:Tm 3+ obey first and general order kinetics respectively. - Highlights: → Trap depth and frequency factor are determined for the peaks at 510 and 660 K of LCB:Tm. → Parameters obtained by various heating rate and initial rise methods are in good agreement. → Trap depth of peak 1 and peak 2 is 1.61 eV and 1.91 eV respectively. → T m response to absorbed dose is used to distinguish a first order or non-first order kinetics.

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

Determination of kinetic parameters during the thermal decomposition of epoxy/carbon fiber composite material

International Nuclear Information System (INIS)

Lee, Jae Hun; Kim, Kwang Seok; Kim, Hyo

2013-01-01

An in-depth study to determine the thermal decomposition kinetics parameters such as the activation energy E_a, the reaction order n, and the pre-exponential factor A of epoxy/carbon fiber composite material has been conducted. We employ not only the modified peak property method that is proposed here, but also the conventional method in analyzing the experimental data, and compare the results to show the performance of the proposed model. The pyrolysis tests for the epoxy/carbon fiber composite materials are conducted by using thermogravimetric analyser at various heating rates. As a result, the best prediction to the experimental data can be obtained by the modified peak property method. Besides, among the methods applied here, the modified peak property method provides most convenient way to recover the parameters: it does not require a curve fitting of the data nor a long iterative computation

Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

Science.gov (United States)

Chambon, J.; Lemming, G.; Manoli, G.; Broholm, M. M.; Bjerg, P.; Binning, P. J.

2011-12-01

Enhanced Reductive Dechlorination (ERD) has been successfully used in high permeability media, such as sand aquifers, and is considered to be a promising technology for low permeability settings. Pilot and full-scale applications of ERD at several sites in Denmark have shown that the main challenge is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion transport processes, and this affects the timeframes for the remediation. Due to the limited ERD applications and the complex transport and reactive processes occurring in low-permeability media, design guidelines are currently not available for ERD in such settings, and remediation performance assessments are limited. The objective of this study is to combine existing knowledge from several sites with numerical modeling to assess the effect of the injection interval, development of bioactive zones and reaction kinetics on the remediation efficiency for ERD in diffusion-dominated media. A numerical model is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities and hydraulic parameters, which are relevant for clay till sites in general. The numerical model couples flow and transport in the fracture network and low-permeability matrix. Sequential degradation of TCE to ethene is modeled using Monod kinetics, and the kinetic parameters are obtained from laboratory experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected

An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

Science.gov (United States)

Grima, R

2010-07-21

Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

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

Mixtures of rubber tyre and plastic wastes pyrolysis: A kinetic study

International Nuclear Information System (INIS)

Miranda, Miguel; Cabrita, I.; Pinto, Filomena; Gulyurtlu, I.

2013-01-01

The study performed aimed at analysing possible routes for pyrolysis reaction mechanisms of polymeric materials namely RT (rubber tyre) and plastic wastes (PE (polyethylene), PP (polypropylene) and PS (polystyrene)). Consequently, and seeking sustainable transformation of waste streams into valuable chemicals and renewable liquid fuels, mixture of 30% RT, 20% PE, 30% PP and 20% PS was subjected to pyrolysis. Different kinetic models were studied using experimental data. None of the mechanisms found in literature led to a numerical adjustment and different pathways were investigated. Kinetic studies were performed aiming to evaluate direct conversions into new solid, liquid and gaseous products and if parallel reactions and/or reversible elementary steps should be included. Experiments were performed in batch system at different temperatures and reaction times. Kinetic models were evaluated and reaction pathways were proposed. Models reasonably fit experimental data, allow explaining wastes thermal degradation. Kinetic parameters were estimated for all temperatures and dependence of Ea and pre-exponential factor on temperature was evaluated. The rate constant of some reactions exhibited nonlinear temperature dependence on the logarithmic form of Arrhenius law. This fact strongly suggests that temperature has a significant effect on reaction mechanism of pyrolysis of mixtures of rubber tyre and plastic wastes. - Highlights: • Kinetic study of rubber tyre (RT) and different plastic wastes (PE, PP and PS) was performed in batch reactor. • Definition of possible pathways taken into account for the formation of final products. • Kinetic parameters were estimated. • The effect of reaction temperature and reaction time on liquid composition was performed

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...

Determination of the kinetic parameters of BeO thermoluminescent samples using different methods

Energy Technology Data Exchange (ETDEWEB)

Algarve, Fábio J.; Caldas, Linda V.E., E-mail: fjalgarve@ipen.br, E-mail: lcaldas@ipen.br [Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil)

2017-07-01

The objective of this work was to determine the kinetic parameters of BeO thermoluminescent (TL) samples. The knowledge of the kinetic parameters is important for the general description of the physical characteristics of a thermoluminescent material. Using a linear heating rate of 5K/s{sup -1}, the BeO peak temperatures obtained were (474.7 ± 1.2) K and (620.5 ± 1.2) K, respectively, for the first and second TL peaks. The peak shape and the glow curve area measurement methods and the Urbach formula have been used for the trap parameter determination. A kinetic order of about two was determined for the first peak, whereas the second peak followed the first-order kinetics according to the geometrical factor. The energy activation values obtained using different kinds of measurements are in good agreement, including the Kitis method for deconvolution of the glow curve. Furthermore the results agree with those presented by other authors. (author)

Kinetics based reaction optimization of enzyme catalysed reduction of formaldehyde to methanol with synchronous cofactor regeneration

DEFF Research Database (Denmark)

Marpani, Fauziah Binti; Sárossy, Zsuzsa; Pinelo, Manuel

2017-01-01

regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor...... regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization...... experiments were conducted to verify the kinetically modelled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes...

Estimation of Adjoint-Weighted Kinetics Parameters in Monte Carlo Wieland Calculations

International Nuclear Information System (INIS)

Choi, Sung Hoon; Shim, Hyung Jin

2013-01-01

The effective delayed neutron fraction, β eff , and the prompt neutron generation time, Λ, in the point kinetics equation are weighted by the adjoint flux to improve the accuracy of the reactivity estimate. Recently the Monte Carlo (MC) kinetics parameter estimation methods by using the self-consistent adjoint flux calculated in the MC forward simulations have been developed and successfully applied for the research reactor analyses. However these adjoint estimation methods based on the cycle-by-cycle genealogical table require a huge memory size to store the pedigree hierarchy. In this paper, we present a new adjoint estimation in which the pedigree of a single history is utilized by applying the MC Wielandt method. The effectiveness of the new method is demonstrated in the kinetics parameter estimations for infinite homogeneous two-group problems and the Godiva critical facility

Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

Science.gov (United States)

McCarrick, Thomas A.; McLafferty, Fred W.

1984-01-01

Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

Kinetic and thermodynamic analysis of the polymerization of polyurethanes by a rheological method

International Nuclear Information System (INIS)

Lucio, Beatriz; Fuente, José Luis de la

2016-01-01

Graphical abstract: - Highlights: • Kinetic and thermodynamic analysis for the formation of a functional polyurethane (PU) has been carried out. • Rheological parameters were used to obtain the profile of the resin's curing degree. • Kamal-Sourour autocatalytic kinetic model describes well this polyaddition reaction. • A deeper understanding of the mechanism of PU systems has been achieved. • This metallo-PU finds its application in the chemistry of advanced energetic materials. - Abstract: As part of an investigation into the mechanism and chemorheology of linear segmented polyurethane (PU) systems, this paper presents the kinetic and thermodynamic characterization of the reaction between an advanced functional metallo-polyol derivative of hydroxyl-terminated polybutadiene (HTPB), (ferrocenylbutyl)dimethylsilane grafted HTPB, and isophorone diisocyanate (IPDI). The evolution of viscoelastic properties, such as the storage modulus (G′), was recorded in bulk under isothermal conditions at four different temperatures between 50 and 80 °C, and a resin curing degree profile was obtained for this elastic modulus. The use of the Kamal-Sourour autocatalytic kinetic model was proposed, describing the overall curing process perfectly. All the kinetic and thermodynamic parameters, including reaction orders, kinetic constants and activation energy, were determined for the polyaddition reaction under study. A relevant autocatalysis effect, promoted by the urethane group, has been found. The isoconversion method was also used to analyze the variation of the global activation energy with conversion. The global activation energy increases slightly as the curing reaction proceeds with a maximum value reached at approximately 30% conversion. In addition, the Eyring parameters were calculated from the obtained kinetic data.

Kinetic and thermodynamic analysis of the polymerization of polyurethanes by a rheological method

Energy Technology Data Exchange (ETDEWEB)

Lucio, Beatriz; Fuente, José Luis de la, E-mail: fuentegj@inta.es

2016-02-10

Graphical abstract: - Highlights: • Kinetic and thermodynamic analysis for the formation of a functional polyurethane (PU) has been carried out. • Rheological parameters were used to obtain the profile of the resin's curing degree. • Kamal-Sourour autocatalytic kinetic model describes well this polyaddition reaction. • A deeper understanding of the mechanism of PU systems has been achieved. • This metallo-PU finds its application in the chemistry of advanced energetic materials. - Abstract: As part of an investigation into the mechanism and chemorheology of linear segmented polyurethane (PU) systems, this paper presents the kinetic and thermodynamic characterization of the reaction between an advanced functional metallo-polyol derivative of hydroxyl-terminated polybutadiene (HTPB), (ferrocenylbutyl)dimethylsilane grafted HTPB, and isophorone diisocyanate (IPDI). The evolution of viscoelastic properties, such as the storage modulus (G′), was recorded in bulk under isothermal conditions at four different temperatures between 50 and 80 °C, and a resin curing degree profile was obtained for this elastic modulus. The use of the Kamal-Sourour autocatalytic kinetic model was proposed, describing the overall curing process perfectly. All the kinetic and thermodynamic parameters, including reaction orders, kinetic constants and activation energy, were determined for the polyaddition reaction under study. A relevant autocatalysis effect, promoted by the urethane group, has been found. The isoconversion method was also used to analyze the variation of the global activation energy with conversion. The global activation energy increases slightly as the curing reaction proceeds with a maximum value reached at approximately 30% conversion. In addition, the Eyring parameters were calculated from the obtained kinetic data.

A general framework for thermodynamically consistent parameterization and efficient sampling of enzymatic reactions.

Directory of Open Access Journals (Sweden)

Pedro Saa

2015-04-01

Full Text Available Kinetic models provide the means to understand and predict the dynamic behaviour of enzymes upon different perturbations. Despite their obvious advantages, classical parameterizations require large amounts of data to fit their parameters. Particularly, enzymes displaying complex reaction and regulatory (allosteric mechanisms require a great number of parameters and are therefore often represented by approximate formulae, thereby facilitating the fitting but ignoring many real kinetic behaviours. Here, we show that full exploration of the plausible kinetic space for any enzyme can be achieved using sampling strategies provided a thermodynamically feasible parameterization is used. To this end, we developed a General Reaction Assembly and Sampling Platform (GRASP capable of consistently parameterizing and sampling accurate kinetic models using minimal reference data. The former integrates the generalized MWC model and the elementary reaction formalism. By formulating the appropriate thermodynamic constraints, our framework enables parameterization of any oligomeric enzyme kinetics without sacrificing complexity or using simplifying assumptions. This thermodynamically safe parameterization relies on the definition of a reference state upon which feasible parameter sets can be efficiently sampled. Uniform sampling of the kinetics space enabled dissecting enzyme catalysis and revealing the impact of thermodynamics on reaction kinetics. Our analysis distinguished three reaction elasticity regions for common biochemical reactions: a steep linear region (0> ΔGr >-2 kJ/mol, a transition region (-2> ΔGr >-20 kJ/mol and a constant elasticity region (ΔGr <-20 kJ/mol. We also applied this framework to model more complex kinetic behaviours such as the monomeric cooperativity of the mammalian glucokinase and the ultrasensitive response of the phosphoenolpyruvate carboxylase of Escherichia coli. In both cases, our approach described appropriately not only

The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions

Science.gov (United States)

Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.

2013-12-01

During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, σ, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (≈ 2 -5 μm grain size) form next to calcite and elongated palisade-shaped grains (1-6 μm diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 μm thick granular dolomite layer

Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

Energy Technology Data Exchange (ETDEWEB)

Creighton, J.R.; Coltrin, M.E.

1994-03-01

This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

Science.gov (United States)

Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

2018-02-01

The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

Kinetics of enzymatic trans-esterification of glycerides for biodiesel production.

Science.gov (United States)

Calabrò, Vincenza; Ricca, Emanuele; De Paola, Maria Gabriela; Curcio, Stefano; Iorio, Gabriele

2010-08-01

In this paper, the reaction of enzymatic trans-esterification of glycerides with ethanol in a reaction medium containing hexane at a temperature of 37 degrees C has been studied. The enzyme was Lipase from Mucor miehei, immobilized on ionic exchange resin, aimed at achieving high catalytic specific surface and recovering, regenerating and reusing the biocatalyst. A kinetic analysis has been carried out to identify the reaction path; the rate equation and kinetic parameters have been also calculated. The kinetic model has been validated by comparison between predicted and experimental results. Mass transport resistances estimation was undertaken in order to verify that the kinetics found was intrinsic. Model potentialities in terms of reactors design and optimization are also shown.

Study of kinetics of reaction of lithium deuteride powder with O2, CO2 and water vapor

International Nuclear Information System (INIS)

Li Gan; Lu Guangda; Jing Wenyong; Qin Cheng

2004-01-01

The kinetics of reaction of lithium deuteride powder with O 2 , CO 2 and water vapor is studied. The experimental results show that lithium deuteride reacts with O 2 and CO 2 at very small reaction rate but with water vapor at comparatively larger rate at room temperature (≅28 degree C). The reaction process with water vapor could be described using the unreacted shrinking core model. The second-order kinetics is appropriate for the chemical reaction on the surface of lithium deuteride and reaction rate constant is 0.281 kPa -1 ·min -1

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…

Studies of ruthenium complexes, 8. Kinetic studies of the thermal substitution reaction of hexaammine and cis--dihalogenotetraammineruthenium(III) complexes in the solid state

Energy Technology Data Exchange (ETDEWEB)

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

1975-01-01

The kinetics of the thermal substitution reaction of hexaamineruthenium (III) halides and cis-dihalogenotetraamineruthenium (III) halides have been studied in the solid state. The reaction rates and kinetic parameters were determined for these two reactions; (Ru(NH/sub 3/)/sub 6/)X/sub 3/..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/+NH/sub 3/, (X=Br, I) and cis - (RuX/sub 2/(NH/sub 3/)/sub 4/)X..-->..(RuX/sub 3/(NH/sub 3/)/sub 3/)+NH/sub 3/, (X=Cl, Br). The values of the rate constant, the activation energy, and the activation entropy were 2.10x10/sup -5/ s/sup -1/ (at 161/sup 0/C), 23.2 kcal mol/sup -1/, and -29.3 e.u. for the hexaamine bromide, and 2.92x10/sup -5/ s/sup -1/ (at 162/sup 0/C), 31.3 kcal mol/sup -1/, and -10.1 e.u. for the cis-dibromotetraamine bromide. The Ssub(N)2 mechanism is more probable for the former reaction, while the Ssub(N)1 mechanism is more probable for the latter reaction.

Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

International Nuclear Information System (INIS)

Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

1987-01-01

The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

Directory of Open Access Journals (Sweden)

AbdulMunem A. Karim

2013-05-01

Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

Kinetics on the reaction of substituted quinolines and p-substituted benzoylchlorides under various pressures

International Nuclear Information System (INIS)

Kim, Young Cheul; Lim, Jong Wan; Choi, Sung Yong; Kim, Se Kyong

1999-01-01

The reaction rates of substituted quinolines(6-CH 3 C 9 H 7 N, C 9 H 7 N) with p-substituted benzoylchlorides(p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15, 20, 25 .deg. C) and pressures(1, 200, 500, 1000bar). From the values of rate constants, the activation parameters(Ea, ΔV ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increase as a function of temperatures and pressures, and are further increase by introduction the electron donor substituents in nucleophile(p-CH 3 ) or electron acceptor(p-NO 2 ) substituents in substrate. The activation volume, and the activation entropy are all negative. Hammett ρ values are also negative for nucleophile (ρ X ) and positive for the substrate (ρ Y ) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in which bond formation favored with increasing pressures

Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

Science.gov (United States)

Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

2011-11-01

An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

KAUST Repository

Khan, Abdulaziz M.

2016-01-01

the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized

Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

International Nuclear Information System (INIS)

Zamfirescu, C.; Naterer, G.F.; Dincer, I.

2009-01-01

The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

Effect of long-term physical aging on the kinetic parameters in a common pharmaceutical drug: Flutab

International Nuclear Information System (INIS)

Abu-Sehly, A.A.; Elabbar, A.A.

2011-01-01

Differential scanning calorimetry (DSC) measurements were performed to investigate the effects of long-term physical aging on kinetic parameters of the pharmaceutical drug (Flutab). Kinetics parameters such as activation energy (E) and fragility parameter (m) of the glass transition for aged and rejuvenated glasses were determined using different kinetic models. Evidence of variation of E with temperature is presented. It is shown in this work that natural storage of the drug introduced significant physical aging as indicated by changes in the glass transition temperature, activation energy and fragility parameter.

Measurements for kinetic parameters estimation in the RA-0 research reactor

International Nuclear Information System (INIS)

Gomez, A; Bellino, P A

2012-01-01

In the present work, measurements based on the neutron noise technique and the inverse kinetic method were performed to estimate the different kinetic parameters of the reactor in its critical state. By means of the neutron noise technique, we obtained the current calibration factor of the ionization chamber M6 belonging to the power range channels of the reactor instrumentation. The maximum current allowed compatible with the maximum power authorized by the operation license was also obtained. Using the neutron noise technique, the reduced mean reproduction time (Λ*) was estimated. This parameter plays a fundamental role in the deterministic analysis of criticality accidents. Comparison with previous values justified performing new measurements to study systematic trends in the value of Λ*. Using the inverse kinetics method, the reactivity worth of the control rods was estimated, confirming the existence of spatial effects and trends previously observed (author)

Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

International Nuclear Information System (INIS)

Fagerstroem, K.

1993-01-01

The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

Reaction kinetic analysis of reactor surveillance data

Energy Technology Data Exchange (ETDEWEB)

Yoshiie, T., E-mail: yoshiie@rri.kyoto-u.ac.jp [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Kinomura, A. [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Nagai, Y. [The Oarai Center, Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan)

2017-02-15

In the reactor pressure vessel surveillance data of a European-type pressurized water reactor (low-Cu steel), it was found that the concentration of matrix defects was very high, and a large number of precipitates existed. In this study, defect structure evolution obtained from surveillance data was simulated by reaction kinetic analysis using 15 rate equations. The saturation of precipitation and the growth of loops were simulated, but it was not possible to explain the increase in DBTT on the basis of the defect structures. The sub-grain boundary segregation of solutes was discussed for the origin of the DBTT increase.

Kinetics of the thermal decomposition of pine needles

Directory of Open Access Journals (Sweden)

Dhaundiyal Alok

2015-12-01

Full Text Available A kinetic study of the pyrolysis process of pine needles was examined using a thermogravimetric analyser. The weight loss was measured in nitrogen atmosphere at a purge flow rate of 100 ml/min. The samples were heated over a range of temperature of 19°C–600°C with a heating rate of 10°C/min. The results obtained from the thermal decomposition process indicate that there are three main stages: dehydration, active and passive pyrolysis. The kinetic parameters for the different samples, such as activation energy and pre-exponential factor, are obtained by the shrinking core model (reaction-controlled regime, the model-free, and the first-order model. Experimental results showed that the shrinking model is in good agreement and can be successfully used to understand degradation mechanism of loose biomass. The result obtained from the reaction-controlled regime represented actual values of kinetic parameters which are the same for the whole pyrolysis process; whereas the model-free method presented apparent values of kinetic parameters, as they are dependent on the unknown function ϕ(C, on the sum of the parameters of the physical processes, and on the chemical reactions that happen simultaneously during pyrolysis. Experimental results showed that values of kinetic constant from the first-order model and the SCM are in good agreement and can be successfully used to understand the behaviour of loose biomass (pine needles in the presence of inert atmosphere. Using TGA results, the simulating pyrolysis can be done, with the help of computer software, to achieve a comprehensive detail of the devolatilization process of different types of biomasses.

Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols

NARCIS (Netherlands)

Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

2007-01-01

This paper reports on determination of the intrinsic reaction kinetics in reactive extraction of chiral compounds. It is important to know the mass transfer rates and reaction kinetics separately for a reliable scale-up. A kinetic model is developed to interpret the experimental data from the

Kinetics and Mechanisms of Thiol–Disulfide Exchange Covering Direct Substitution and Thiol Oxidation-Mediated Pathways

Science.gov (United States)

2013-01-01

Abstract Significance: Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol–disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. Critical Issues: This review is focused on the kinetics and mechanisms of thiol–disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Recent Advances and Future Directions: Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery. Antioxid. Redox Signal. 18, 1623–1641. PMID:23075118

Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly

Science.gov (United States)

Lundberg, Dan; Stjerndahl, Maria

2011-01-01

The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

Science.gov (United States)

Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

2018-04-01

A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography–mass spectrometry

Directory of Open Access Journals (Sweden)

JUN WANG

2010-01-01

Full Text Available As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3--dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography–mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems.

Kinetic modelling of hydrocracking catalytic reactions by the single events theory; Modelisation cinetique des reactions catalytiques d`hydrocraquage par la theorie des evenements constitutifs

Energy Technology Data Exchange (ETDEWEB)

Schweitzer, J.M.

1998-11-23

Kinetic modelling of petroleum hydrocracking is particularly difficult given the complexity of the feedstocks. There are two distinct classes of kinetics models: lumped empirical models and detailed molecular models. The productivity of lumped empirical models is generally not very accurate, and the number of kinetic parameters increases rapidly with the number of lumps. A promising new methodology is the use of kinetic modelling based on the single events theory. Due to the molecular approach, a finite and limited number of kinetic parameters can describe the kinetic behaviour of the hydrocracking of heavy feedstock. The parameters are independent of the feedstock. However, the available analytical methods are not able to identify the products on the molecular level. This can be accounted for by means of an posteriori lamping technique, which incorporates the detailed knowledge of the elementary step network. Thus, the lumped kinetic parameters are directly calculated from the fundamental kinetic coefficients and the single event model is reduced to a re-lumped molecular model. Until now, the ability of the method to extrapolate to higher carbon numbers had not been demonstrated. In addition, no study had been published for three phase (gas-liquid-solid) systems and a complex feedstock. The objective of this work is to validate the `single events` method using a paraffinic feedstock. First of all, a series of experiments was conducted on a model compound (hexadecane) in order to estimate the fundamental kinetic parameters for acyclic molecules. To validate the single event approach, these estimated kinetic coefficients were used to simulate hydrocracking of a paraffinic mixture ranging from C11 to C18. The simulation results were then compared to the results obtained from the hydrocracking experiments. The comparison allowed to validate the model for acyclic molecules and to demonstrate that the model is applicable to compounds with higher carbon numbers. (author

Kinetics of in situ combustion. SUPRI TR 91

Energy Technology Data Exchange (ETDEWEB)

Mamora, D.D.; Ramey, H.J. Jr.; Brigham, W.E.; Castanier, L.M.

1993-07-01

Oxidation kinetic experiments with various crude oil types show two reaction peaks at about 250{degree}C (482{degree}F) and 400{degree}C (725{degree}F). These experiments lead to the conclusion that the fuel during high temperature oxidation is an oxygenated hydrocarbon. A new oxidation reaction model has been developed which includes two partially-overlapping reactions: namely, low-temperature oxidation followed by high-temperature oxidation. For the fuel oxidation reaction, the new model includes the effects of sand grain size and the atomic hydrogen-carbon (H/C) and oxygen-carbon (O/C) ratios of the fuel. Results based on the new model are in good agreement with the experimental data. Methods have been developed to calculate the atomic H/C and O/C ratios. These methods consider the oxygen in the oxygenated fuel, and enable a direct comparison of the atomic H/C ratios obtained from kinetic and combustion tube experiments. The finding that the fuel in kinetic tube experiments is an oxygenated hydrocarbon indicates that oxidation reactions are different in kinetic and combustion tube experiments. A new experimental technique or method of analysis will be required to obtain kinetic parameters for oxidation reactions encountered in combustion tube experiments and field operations.

SurfKin: an ab initio kinetic code for modeling surface reactions.

Science.gov (United States)

Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

2014-10-05

In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

Characterization of excited-state reactions with instant spectra of fluorescence kinetics

International Nuclear Information System (INIS)

Tomin, Vladimir I.; Ushakou, Dzmitryi V.

2015-01-01

Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

Characterization of excited-state reactions with instant spectra of fluorescence kinetics

Energy Technology Data Exchange (ETDEWEB)

Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

2015-10-15

Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

OpenAIRE

Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

2015-01-01

Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III) redox reaction using spectrophotometric and potentiometric methods. The results were corroborated...

A Study on the Pyrolysis of Peanut Shells at Different Isothermal Conditions and Determination of the Kinetic Parameters

Directory of Open Access Journals (Sweden)

Şeyda Taşar

2015-12-01

Full Text Available The pyrolysis process, which is applied for the aim of producing energy and raw materials which are implemented for the chemical industry from biomass sources, is a thermal conversion process. Determination of the pyrolysis kinetic parameters are important In order to suitable equipment and process design. In this target, in the study the pyrolysis of peanut shells was conducted in a muffle furnace at static atmosphere with temperatures ranging from 300-700 °C. The effects of various parameters on the rate of thermal decomposition rate and the solid yield were determined. The parameters of interest were temperature 300-700 °C, particle size 4-50 mesh, pelletizing, and pelletizing pressure 1.103-5.103 kgf/cm2. Regression coefficients for the total decomposition step were obtained using the thermographs were obtained as a result of the pyrolysis of the peanut shells, and 20 different theoretical model equations that represented the degradation by the Coast-Redfern method. According to regression coefficients of the theoretical model equations, we determined the kinetic model that best represented the degradation. Using this model to represent the degradation, the activation energy (Ea and Arhenius frequency factor ln(A for the total reaction were calculated to be 38.245 kJ/mol and 8.124, respectively.

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

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

Kinetic aspects of the embedded clusters: Reaction - Rate Theory

International Nuclear Information System (INIS)

Despa, F.; Apostol, M.

1995-07-01

The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs

Heterogeneous photocatalysis of real textile wastewater: evaluation of reaction kinetics and characterization.

Science.gov (United States)

Sahoo, Chittaranjan; Gupta, Ashok K; Pillai, Indu M Sasidharan

2012-01-01

Real textile wastewater collected from the cotton dyeing bath of a fabric dyeing and finishing plant was subjected to heterogeneous photocatalysis using Ag(+) doped TiO(2) under UV irradiation in a batch reactor. The photocatalysts were characterized by FESEM, XRD, EDS, FTIR, DRS and BET analyses. The kinetics of the reaction was also evaluated. Colour removal was more than 88%, 94% and 99%, respectively for undiluted, 2 times diluted and 5 times diluted wastewater with Ag(+) doped TiO(2) (2.5 g/L) after UV irradiation for 360 minutes. The COD removal for undiluted, 2 times diluted and 5 times diluted wastewater was 47%, 70% and 92%, respectively under similar conditions. The reaction followed Langmuir-Hinshelwood pseudo first order kinetic model and the data fitted well to polynomial regression analysis.

Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

Science.gov (United States)

Kocadağlı, Tolgahan; Gökmen, Vural

2016-11-15

The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic study of enzymatic hydrolysis of potato starch

Directory of Open Access Journals (Sweden)

Óscar Fernando Castellanos Domínguez

2004-01-01

Full Text Available This article describes the kinetic study of potato starch enzymatic hydrolysis using soluble enzymes (Novo Nordisk. Different assays divided into four groups were used: reaction time (with which it was possible to reduce the 48-72 hour duration reported in the literature to 16 hours with comparable productivity levels; selecting the set of enzymes to be used (different types were evaluated - BAN and Termamyl as alfa-amylases during dextrinisation stage, and AMG, Promozyme and Fungamyl for sacarification reaction- identifying those presenting the best performance during hydrolysis.Reaction conditions were optimised for the process's two stages (destrinisation and sacarification. Enzyme dose, calcium cofactor concentration, pH, temperature and agitation speed were studied for the first stage. Enzyme ratio, pH and agitation speed were studied for sacarification; the latter parameter reported values having no antecedents in the literature (60 rpm and 30 rpm for first and second reactions, respectively. Michaelis Menten kinetics were calculated once conditions had been optimised, varying substrate from 10-50% P/V, obtaining km and Vmax kinetic parameters for each reaction. A kinetic model was found according to local working conditions which was able to explain potato starch conversion to glucose syrup, achieving 96 dextrose equivalents by the end of the reaction, being well within the maximum range reported in the literature (94-98.Laboratory equipment was constructed prior to carrying out assays which was able to reproduce and improve the conditions reported in the literature, making it a useful, reliable tool for use in assays returning good results.

A study of butyl acetate synthesis. 4-reaction kinetics

Directory of Open Access Journals (Sweden)

Álvaro Orjuela Londoño

2006-05-01

Full Text Available This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (P atm =0.76 Bar,using an ion exchange resin (Lewatit K-2431 as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w temperature (73°C, 80°C, 87°C and molar ratio (1:2, 1:1, 2:1 acid/alcohol on reaction rate was carried out and both LHHW and pseudo-homogeneous kinetic expressions were obtained, these being in good agreement with the experimental data.

Thermogravimetric analysis and kinetic study of formation of lithium titanate by solid state route

International Nuclear Information System (INIS)

Sonak, Sagar; Jain, Uttam; Sahu, Ashok Kumar; Kumar, Sanjay; Krishnamurthy, Nagaiyar

2015-01-01

The kinetics of formation of lithium titanate from the solid state reaction of lithium carbonate and titanium oxide was studied using non-isothermal thermogravimetric technique. Thermogravimetric data for the reaction of lithium carbonate and titanium oxide was obtained at various heating rates. The methods such as Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose were used to estimate the kinetic parameters from the obtained thermogravimetric data. The average activation energy for the formation of lithium titanate by solid state route was found to be 243 kJ/mol K. The reaction mechanism was determined by the method given by Malek. It was found that the three dimensional diffusion model best describes the reaction kinetics. A kinetic equation describing the reaction is proposed and reaction mechanism is discussed

Diagnostic Appraisal of Grade 12 Students' Understanding of Reaction Kinetics

Science.gov (United States)

Yan, Yaw Kai; Subramaniam, R.

2016-01-01

The study explored grade 12 students' understanding of reaction kinetics, a topic which has not been extensively explored in the chemistry education literature at this level. A 3-tier diagnostic instrument with 11 questions was developed--this format is of very recent origin and has been the subject of only a handful of studies. The findings…

Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

International Nuclear Information System (INIS)

Thomassen, M.; Karlsen, C.; Borresen, B.; Tunold, R.

2006-01-01

The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm -3 and varying H + concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H + concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO 2 and RTO. The expression of the kinetic current as a function of chlorine and H + concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential

Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions

Energy Technology Data Exchange (ETDEWEB)

Ntampegliotis, K. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Riga, A. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Karayannis, V. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Bontozoglou, V. [Department of Mechanical and Industrial Engineering, University of Thessaly, Pedion Areos, T.K 383 34 Volos (Greece); Papapolymerou, G. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece)]. E-mail: papapoly@teilar.gr

2006-08-10

The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H{sub 2}O{sub 2} and Fe{sup 3+} and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl{sup -}, CO{sub 3} {sup 2-} or HCO{sub 3} {sup -} on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe{sup 3+} and H{sub 2}O{sub 2} at molar ratios of H{sub 2}O{sub 2}/Fe{sup 3+} from about 100 to 10. The addition of CO{sub 3} {sup 2-} and HCO{sub 3} {sup -} substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl{sup -}. At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.

Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions.

Science.gov (United States)

Ntampegliotis, K; Riga, A; Karayannis, V; Bontozoglou, V; Papapolymerou, G

2006-08-10

The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H(2)O(2) and Fe(3+) and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl(-), CO(3)(2-) or HCO(3)(-) on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe(3+) and H(2)O(2) at molar ratios of H(2)O(2)/Fe(3+) from about 100 to 10. The addition of CO(3)(2-) and HCO(3)(-) substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl(-). At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.

Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate.

Science.gov (United States)

Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D

2008-11-25

o-Succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered bi uni uni bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first half-reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the "F" form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered bi uni uni bi iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogues with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogues tested as none were active except 4-[2-(trifluoromethyl)phenyl]-4-oxobutyric acid which exhibited a 100-fold decrease in k(cat)/K(m). On the basis of an understanding of OSB-CoA synthetase's kinetic mechanism and substrate specificity, a reaction intermediate analogue of OSB-AMP, 5'-O-{N-[2-(trifluoromethyl)phenyl]-4-oxobutyl}adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

Science.gov (United States)

Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

2013-12-01

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the

Spectroscopy and kinetics of combustion gases at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Hanson, R.K.; Bowman, C.T. [Stanford Univ., CA (United States)

1993-12-01

This program involves two complementary activities: (1) development and application of cw ring dye laser absorption methods for sensitive detection of radical species and measurement of fundamental spectroscopic parameters at high temperatures; and (2) shock tube studies of reaction kinetics relevant to combustion. Species currently under investigation in the spectroscopic portion of the research include NO and CH{sub 3}; this has necessitated the continued operated at wavelengths in the range 210-230 nm. Shock tube studies of reaction kinetics currently are focussed on reactions involving CH{sub 3} radicals.

Kinetics of reactions of chromium, molybdenum and tungsten hexacarbonyls with hydroxylamine and trimethylamine oxide

International Nuclear Information System (INIS)

Maksakov, V.A.; Ershova, V.A.

1994-01-01

Mechanism of M(CO) 6 (M = Cr, Mo, W) reaction with hydroxylamine was studied. On the basis of kinetic data it was ascertained that as a result of the reaction CO oxidation to CO 2 and intramolecular transfer of amine formed to the central atom of metal occur. Mechanisms of M(CO) 6 reactions with hydroxylamine and trimethylamine oxide are compared

Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

KAUST Repository

Hanson, Ronald K.; Pang, Genny A.; Chakraborty, Sreyashi; Ren, Wei; Wang, Shengkai; Davidson, David Frank

2013-01-01

We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we

The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics

Science.gov (United States)

Zhao, Haoyu; Simon, Sindee

The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.

Improving fuel quality by whole crude oil hydrotreating: A kinetic model for hydrodeasphaltenization in a trickle bed reactor

International Nuclear Information System (INIS)

Jarullah, A.T.; Mujtaba, I.M.; Wood, A.S.

2012-01-01

Highlights: ► Asphaltene contaminant must be removed to a large extent from the fuel to meet the regulatory demand. ► Kinetics for hydrodeasphaltenization are estimated via experimentation and modeling. ► Using the kinetic parameters, a full process model for the trickle bed reactor (TBR) is developed. ► The model is used for simulating the behavior of the TBR to get further insight of the process. ► The influences of operating conditions in the hydrodeasphaltenization process are reported. -- Abstract: Fossil fuel is still a predominant source of the global energy requirement. Hydrotreating of whole crude oil has the ability to increase the productivity of middle distillate fractions and improve the fuel quality by simultaneously reducing contaminants such as sulfur, nitrogen, vanadium, nickel and asphaltene to the levels required by the regulatory bodies. Hydrotreating is usually carried out in a trickle bed reactor (TBR) where hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and hydrodeasphaltenization (HDAs) reactions take place simultaneously. To develop a detailed and a validated TBR process model which can be used for design and optimization of the hydrotreating process, it is essential to develop kinetic models for each of these reactions. Most recently, the authors have developed kinetic models for all of these chemical reactions except that of HDAs. In this work, a kinetic model (in terms of kinetic parameters) for the HDAs reaction in the TBR is developed. A three phase TBR process model incorporating the HDAs reactions with unknown kinetic parameters is developed. Also, a series of experiments has been conducted in an isothermal TBR under different operating conditions affecting the removal of asphaltene. The unknown kinetic parameters are then obtained by applying a parameter estimation technique based on minimization of the sum of square errors (SSEs) between the experimental and predicted concentrations of

Kinetic parameters evaluation of PWRs using static cell and core calculation codes

International Nuclear Information System (INIS)

Jahanbin, Ali; Malmir, Hessam

2012-01-01

Highlights: ► In this study, we have calculated effective delayed neutron fraction and prompt neutron lifetime in PWRs. ► New software has been developed to link the WIMS, BORGES and CITATION codes in Visual C computer programming language. ► This software is used for calculation of the kinetic parameters in a typical VVER-1000 and NOK Beznau reactor. ► The ratios ((β eff ) i )/((β eff ) core ) , which are the important input data for the reactivity accident analysis, are also calculated. - Abstract: In this paper, evaluation of the kinetic parameters (effective delayed neutron fraction and prompt neutron lifetime) in PWRs, using static cell and core calculation codes, is reported. A new software has been developed to link the WIMS, BORGES and CITATION codes in Visual C computer programming language. Using the WIMS cell calculation code, multigroup microscopic cross-sections and number densities of different materials can be generated in a binary file. By the use of BORGES code, these binary-form cross-sections and number densities are converted to a format readable by the CITATION core calculation code, by which the kinetic parameters can be finally obtained. This software is used for calculation of the kinetic parameters in a typical VVER-1000 and NOK Beznau reactor. The ratios ((β eff ) i )/((β eff ) core ) , which are the important input data for the reactivity accident analysis, are also calculated. Benchmarking of the results against the final safety analysis report (FSAR) of the aforementioned reactors shows very good agreements with these published documents.

Antioxidant pool in beer and kinetics of EPR spin-trapping.

Science.gov (United States)

Kocherginsky, Nikolai M; Kostetski, Yuri Yu; Smirnov, Alex I

2005-08-24

The kinetics of spin-trap adduct formation in beer oxidation exhibits an induction period if the reaction is carried out at elevated temperatures and in the presence of air. This lag period lasts until the endogenous antioxidants are almost completely depleted, and its duration is used as an indicator of the flavor stability and shelf life of beer. This paper demonstrates that the total kinetics of the process can be characterized by three parameters-the lag period, the rate of spin-trap adduct formation, and, finally, the steady-state spin-adduct concentration. A steady-state chain reaction mechanism is described, and quantitative estimates of the main kinetic parameters such as the initiation rate, antioxidant pool, effective content of organic molecules participating in the chain reactions, and the rate constant of the 1-hydroxyethyl radical EtOH(*) spin-adduct disappearance are given. An additional new dimensionless parameter is suggested to characterize the antioxidant pool-the product of the lag time and the rate of spin-trap radical formation immediately after the lag time, normalized by the steady-state concentration of the adducts. The results of spin-tapping EPR experiments are compared with the nitroxide reduction kinetics measured in the same beer samples. It is shown that although the kinetics of nitroxide reduction in beer can be used to evaluate the reducing power of beer, the latter parameter does not correlate with the antioxidant pool. The relationship of free radical processes, antioxidant pool, reducing power, and beer staling is discussed.

Reactor thermal behaviors under kinetics parameters variations in fast reactivity insertion

Energy Technology Data Exchange (ETDEWEB)

Abou-El-Maaty, Talal [Reactors Department, Atomic Energy Authority, Cairo 13759 (Egypt)], E-mail: talal22969@yahoo.com; Abdelhady, Amr [Reactors Department, Atomic Energy Authority, Cairo 13759 (Egypt)

2009-03-15

The influences of variations in some of the kinetics parameters affecting the reactivity insertion are considered in this study, it has been accomplished in order to acquire knowledge about the role that kinetic parameters play in prompt critical transients from the safety point of view. The kinetics parameters variations are limited to the effective delayed neutron fraction ({beta}{sub eff}) and the prompt neutron generation time ({lambda}). The reactor thermal behaviors under the variations in effective delayed neutron fraction and prompt neutron generation time included, the reactor power, maximum fuel temperature, maximum clad temperature, maximum coolant temperature and the mass flux variations at the hot channel. The analysis is done for a typical swimming pool, plate type research reactor with low enriched uranium. The scram system is disabled during the accidents simulations. Calculations were done using PARET code. As a result of simulations, it is concluded that, the reactor (ETRR2) thermal behavior is considerably more sensitive to the variation in the effective delayed neutron fraction than to the variation in prompt neutron generation time and the fast reactivity insertion in both cases causes a flow expansion and contraction at the hot channel exit. The amplitude of the oscillated flow is a qualitatively increases with the decrease in both {beta}{sub eff} and {lambda}.

A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

Energy Technology Data Exchange (ETDEWEB)

Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

2013-03-01

Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

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

Kinetic parameter estimation and fluctuation analysis of CO at SnO 2 single nanowires

KAUST Repository

Tulzer, Gerhard

2013-07-12

In this work, we present calculated numerical values for the kinetic parameters governing adsorption/desorption processes of carbon monoxide at tin dioxide single-nanowire gas sensors. The response of such sensors to pulses of 50 ppm carbon monoxide in nitrogen is investigated at different temperatures to extract the desired information. A rate-equation approach is used to model the reaction kinetics, which results in the problem of determining coefficients in a coupled system of nonlinear ordinary differential equations. The numerical values are computed by inverse-modeling techniques and are then used to simulate the sensor response. With our model, the dynamic response of the sensor due to the gas-surface interaction can be studied in order to find the optimal setup for detection, which is an important step towards selectivity of these devices. We additionally investigate the noise in the current through the nanowire and its changes due to the presence of carbon monoxide in the sensor environment. Here, we propose the use of a wavelet transform to decompose the signal and analyze the noise in the experimental data. This method indicates that some fluctuations are specific for the gas species investigated here. © 2013 IOP Publishing Ltd.

Kinetic parameter estimation and fluctuation analysis of CO at SnO 2 single nanowires

KAUST Repository

Tulzer, Gerhard; Baumgartner, Stefan; Brunet, Elise; Mutinati, Giorgio C; Steinhauer, Stephan; Kö ck, Anton; Barbano, Paolo E; Heitzinger, Clemens

2013-01-01

In this work, we present calculated numerical values for the kinetic parameters governing adsorption/desorption processes of carbon monoxide at tin dioxide single-nanowire gas sensors. The response of such sensors to pulses of 50 ppm carbon monoxide in nitrogen is investigated at different temperatures to extract the desired information. A rate-equation approach is used to model the reaction kinetics, which results in the problem of determining coefficients in a coupled system of nonlinear ordinary differential equations. The numerical values are computed by inverse-modeling techniques and are then used to simulate the sensor response. With our model, the dynamic response of the sensor due to the gas-surface interaction can be studied in order to find the optimal setup for detection, which is an important step towards selectivity of these devices. We additionally investigate the noise in the current through the nanowire and its changes due to the presence of carbon monoxide in the sensor environment. Here, we propose the use of a wavelet transform to decompose the signal and analyze the noise in the experimental data. This method indicates that some fluctuations are specific for the gas species investigated here. © 2013 IOP Publishing Ltd.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

International Nuclear Information System (INIS)

Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

1982-01-01

The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

Kinetic Monte Carlo studies of the reaction kinetics of crystal defects that diffuse one-dimensionally with occasional transverse migration

DEFF Research Database (Denmark)

Heinisch, H.L.; Trinkaus, H.; Singh, Bachu Narain

2007-01-01

The reaction kinetics of the various species of mobile defects in irradiated materials are crucially dependent on the dimensionality of their migration. Sink strengths for one-dimensionally (1D) gliding interstitial loops undergoing occasional direction changes have been described analytically...

Mathematical Modeling of Conversion Kinetics during Vitrification of Nuclear Waste

International Nuclear Information System (INIS)

Pokorny, Richard; Pierce, David A.; Chun, Jae Hun; Hrma, Pavel

2012-01-01

crystalline forms release chemically bonded water, and reactions of nitrates with organics and molten salts with solid silica release copious amounts of NO x , CO x , and O 2 . Because it is formidable to identify the chemistry of reactions associated with individual peaks, we focused on obtaining the kinetic parameters needed for cold cap modeling. The number of kinetic parameters in Equation (1) is rather large. Therefore, in our recent study, we fitted TGA data using solely a first-order reaction kinetics, i.e., n i = 1, for each reaction peak. In this study, we present an improved model in which the reaction order is a variable parameter

Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

NARCIS (Netherlands)

Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

2001-01-01

Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

KAUST Repository

Hanson, Ronald K.

2013-09-01

We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we demonstrate that this strategy eliminates the possibility of non-localized (remote) ignition in shock tubes. Furthermore, we show that this same strategy can also effectively eliminate or minimize pressure changes due to combustion heat release, thereby enabling quantitative modeling of the kinetics throughout the combustion event using a simple assumption of specified pressure and enthalpy. We measure temperature and OH radical time-histories during ethylene-oxygen combustion behind reflected shock waves in a constrained reaction volume and verify that the results can be accurately modeled using a detailed mechanism and a specified pressure and enthalpy constraint. © 2013 The Combustion Institute.

Using a Multi-Tier Diagnostic Test to Explore the Nature of Students' Alternative Conceptions on Reaction Kinetics

Science.gov (United States)

Yan, Yaw Kai; Subramaniam, R.

2018-01-01

This study focused on grade 12 students' understanding of reaction kinetics. A 4-tier diagnostic instrument was developed for this purpose and administered to 137 students in the main study. Findings showed that reaction kinetics is a difficult topic for these students, with a total of 25 alternative conceptions (ACs) being uncovered. Except for…

Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

International Nuclear Information System (INIS)

Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.

2014-01-01

Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

Kinetics and Mechanism of Oxidation of Benzyl Alcohol by Benzimidazolium Fluorochromate

Directory of Open Access Journals (Sweden)

J. Dharmaraja

2008-01-01

Full Text Available The kinetics of oxidation of benzyl alcohol (BzOH by benzimidazolium fluorochromate (BIFC has been studied in 50% aqueous acetic acid medium at 308 K. The reaction is first order with respect to [oxidant] and [benzyl alcohol]. The reaction is catalysed by hydrogen ions. The decrease in dielectric constant of the medium increases the rate of the reaction. Addition of sodium perchlorate increases the rate of the reaction appreciably. No polymerization with acrylonitrile. The reaction has been conducted at four different temperature and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed.

Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration.

Science.gov (United States)

Marpani, Fauziah; Sárossy, Zsuzsa; Pinelo, Manuel; Meyer, Anne S

2017-12-01

Enzymatic reduction of carbon dioxide (CO 2 ) to methanol (CH 3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH 3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO 2 to CH 3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH 3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH 3 OH, a TTN of 160 and BPR of 24 μmol CH 3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH 3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

Science.gov (United States)

Jin, Qusheng; Kirk, Matthew F

2016-01-01

Geological carbon sequestration captures CO 2 from industrial sources and stores the CO 2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO 2 concentration. This study uses biogeochemical modeling to explore the influence of CO 2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO 2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO 2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO 2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO 2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

Thermodynamic and kinetic response of microbial reactions to high CO2

Directory of Open Access Journals (Sweden)

Qusheng Jin

2016-11-01

Full Text Available Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

Energy dissipation in the process of ternary fission in heavy nuclear reaction

International Nuclear Information System (INIS)

Li Xian; Wang Chengqian; Yan Shiwei

2015-01-01

We studied the evolution of the collective motion, interaction potential, the total kinetic and excitation energies in ternary fissions of 197 Au + 197 Au system at 15 MeV/u, and discussed energy dissipation of this reaction. Through the comparison with energy-angle correlation data in binary fissions, we preliminarily concluded that the rst fission of ternary fission was an extreme deep-inelastic process. We further analyzed the correlation of the total kinetic energy with impact parameters in both binary and ternary reactions, and found that the total energy of binary reactions systems was lost about 150 MeV more than ternary fission with small impact parameters, and with larger impact parameters the total energy of ternary reactions were lost 300 MeV more than binary reactions. (authors)

Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

Directory of Open Access Journals (Sweden)

Dhaundiyal Alok

2018-02-01

Full Text Available A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO, Kissinger-Akahira-Sonuse (KAS and Kissinger, and model-fitting (Coats Redfern. The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

Analysis of lipid peroxidation kinetics. I

DEFF Research Database (Denmark)

Doktorov, Alexander B.; Lukzen, Nikita N.; Pedersen, Jørgen Boiden

2008-01-01

concentrations of reactants or different ways of initiating the re-  action. Nor has it been possible to predict the time dependence of the  products. The reason for these problems is the complicated structure  of the kinetic scheme, which includes a chain reaction. In this work  we perform an in depth analysis......  The kinetics of the lipid peroxidation reaction is only partly under-  stood. Although the set of reactions constituting the overall reaction  is believed to be known, it has not been possible to predict how the  reaction will respond to a change of one or more of the parameters, e.g.  initial...... of the importance of the individual  reaction steps and we introduce a new quasi-stationary concentration  method based on the assumption that one or more concentrations vary  much slower than the others. We show that it is justified to use a  quasi-stationary concentration approximation for the alkyl radical L...

An Inverse Michaelis–Menten Approach for Interfacial Enzyme Kinetics

DEFF Research Database (Denmark)

Kari, Jeppe; Andersen, Morten; Borch, Kim

2017-01-01

Interfacial enzyme reactions are ubiquitous both in vivo and in technical applications, but analysis of their kinetics remains controversial. In particular, it is unclear whether conventional Michaelis–Menten theory, which requires a large excess of substrate, can be applied. Here, an extensive...... experimental study of the enzymatic hydrolysis of insoluble cellulose indeed showed that the conventional approach had a limited applicability. Instead we argue that, unlike bulk reactions, interfacial enzyme catalysis may reach a steady-state condition in the opposite experimental limit, where...... for kinetic analyses of interfacial enzyme reactions and that its analogy to established theory provides a bridge to the accumulated understanding of steady-state enzyme kinetics. Finally, we show that the ratio of parameters from conventional and inverted Michaelis–Menten analysis reveals the density...

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

A Capacity Fading Model of Lithium-Ion Battery Cycle Life Based on the Kinetics of Side Reactions for Electric Vehicle Applications

International Nuclear Information System (INIS)

Gu, Weijun; Sun, Zechang; Wei, Xuezhe; Dai, Haifeng

2014-01-01

Highlights: • Describe the aging mechanism of lithium-ion battery with electrochemical kinetics. • Establish the fading rate equation based on Eyring Equation. • The established equation is applicable to any reaction order. • Integrate the internal kinetics with external degradation characteristics. - Abstract: Battery life prediction is one of the critical issues that restrict the development of electric vehicles. Among the typical battery life models, the mechanism model focusing on the internal physical or electrochemical processes has a stronger theoretical foundation and greater accuracy. The empirical formula, which relies on the simplified mechanism, has a concise model structure and more flexibility in vehicle applications. However, the internal aging mechanism rarely correlates with the external operating characteristics. Based on the summary of the capacity fading mechanism and the reasoning of the internal kinetics of side reactions during the aging process, a lifetime model of the lithium-ion battery is established in this paper. The solutions to the vital parameters based on the external accelerated life testing results are also presented. The testing sample is a manganese oxide lithium-ion battery of 8 Ah. The validation results indicated that the life model established in this paper can describe the capacity fading law of the lithium-ion battery and the operability and accuracy for vehicle applications

Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

Science.gov (United States)

Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

2016-11-01

Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Kinetics of the reaction between H· and superheated water probed with muonium

International Nuclear Information System (INIS)

Alcorn, C.; Brodovitch, J.-C.; Ghandi, K.; Kennedy, A.; Percival, P.W.; Smith, M.

2011-01-01

Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650"oC. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H_2 gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H_2O and D_2O at temperatures up to 450"oC.

Cell kinetic parameters of a solid mammary adenocarcinoma

International Nuclear Information System (INIS)

Porschen, R.; Feinendegen, L.E.

1978-01-01

Several cell kinetic parameters of the mammary adenocarcinoma EO 771 were evaluated by means of tumor volume measurements and of 125 I-UdR. The in-situ measured activity loss rate is disturbed by a slow elimination of labelled necrotic cells and by reutilization of 125 I-UdR. The restrictions of the I-UdR method are mentioned and the measured activity loss rates are compared with calculated volume loss rates. (orig./MG) [de

Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate †

Science.gov (United States)

Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D.

2009-01-01

O-succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered Bi Uni Uni Bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct-binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first-half reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the ‘F’ form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered Bi Uni Uni Bi Iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogs with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogs tested as none were active except 4-(2-trifluoromethylphenyl)-4-oxobutyric acid which exhibited a 100-fold decrease in kcat/Km. Based on an understanding of OSB-CoA synthetase’s kinetic mechanism and substrate specificity, a reaction intermediate analog of OSB-AMP, 5’-O-(N-(2-trifluoromethylphenyl)-4-oxobutyl) adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase class of

Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

OpenAIRE

Krivtsova, Nadezhda Igorevna; Tataurshikov, A.; Kotkova, Elena

2016-01-01

Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

2001-01-01

Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

Kinetics of the water formation in the propene epoxidation over gold-titania catalysts

NARCIS (Netherlands)

Nijhuis, T.A.; Weckhuysen, B.M.

2007-01-01

The kinetics of the hydrogen oxidation were determined for a number of different gold catalysts supported on titania, silica, and silicalite-1. A dual site Langmuir-Hinshelwood kinetic model was able to describe the reaction well. The kinetic parameters are independent of the support. Water was

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).

Comparison Of A Neutron Kinetics Parameter For A Polyethylene Moderated Highly Enriched Uranium System

Energy Technology Data Exchange (ETDEWEB)

McKenzie, IV, George Espy [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Goda, Joetta Marie [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Grove, Travis Justin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Sanchez, Rene Gerardo [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-04-17

This paper examines the comparison of MCNP® code’s capability to calculate kinetics parameters effectively for a thermal system containing highly enriched uranium (HEU). The Rossi-α parameter was chosen for this examination because it is relatively easy to measure as well as easy to calculate using MCNP®’s kopts card. The Rossi-α also incorporates many other parameters of interest in nuclear kinetics most of which are more difficult to precisely measure. The comparison looks at two different nuclear data libraries for comparison to the experimental data. These libraries are ENDF/BVI (.66c) and ENDF/BVII (.80c).

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

Determination of kinetic parameters for 123-I thyroid uptake in healthy Japanese

Science.gov (United States)

Kusuhara, Hiroyuki; Maeda, Kazuya

2017-09-01

The purpose of this study was to compare the kinetic parameters for iodide thyroid accumulation in Japanese today with previously reported values. We determined the thyroid uptake of 123-I at 24 hours after the oral administration in healthy male Japanese without any diet restriction. The mean value was 16.1±5.4%, which was similar or rather lower than those previously reported in Japan (1958-1972). Kinetic model analysis was conducted to obtain the clearance for thyroid uptake from the blood circulation. The thyroid uptake clearance of 123-I was 0.540±0.073 ml/min, which was almost similar to those reported previously. There is no obvious difference in the thyroid uptake for 24 hours, and kinetic parameters in healthy Japanese for these 50 years. The fraction of distributed to the thyroid gland is lower than the ICRP reference man, and such difference must be taken into consideration to estimate the radiation exposure upon Fukushima accident in Japan.

Kinetic study of ozonation of molasses fermentation wastewater

International Nuclear Information System (INIS)

Coca, M.; Pena, M.; Gonzalez, G.

2007-01-01

A kinetic study of molasses wastewater ozonation was carried out in a stirred tank reactor to obtain the rate constants for the decolorization reaction and the regime through which ozone is absorbed. First, fundamental mass transfer parameters such as ozone solubility, volumetric mass transfer coefficients and ozone decomposition kinetics were determined from semi-batch experiments in organic-free solutions with an ionic composition similar that of industrial wastewater. The influence of operating variables such as the stirring rate and gas flow rate on the kinetic and mass transfer parameters was also studied. The application of film theory allows to establish that the reactions between ozone and colored compounds in wastewater take place in the fast and pseudo-first-order regime, within the liquid film. The decolorization rate constants were evaluated at pH 8.7 and 25 deg. C, varying from 0.6 x 10 7 to 3.8 x 10 7 L mol -1 s -1 , depending on the stirring rate and the inlet gas flow

Determination of the kinetic parameters of BeO using isothermal decay method

International Nuclear Information System (INIS)

Nieto, Juan Azorin; Vega, Claudia Azorin; Montalvo, Teodoro Rivera; Cabrera, Eugenio Torijano

2016-01-01

Most of the existing methods for obtaining the frequency factors make use of the trap depth (activation energy) making some assumptions about the order of the kinetics. This causes inconsistencies in the reported values of trapping parameters due that the values of the activation energy obtained by different methods differ appreciably among them. Then, it is necessary to use a method independent of the trap depth making use of the isothermal luminescence decay (ILD) method. The trapping parameters associated with the prominent glow peak of BeO (280 °C) are reported using ILD method. As a check, the trap parameters are also calculated by glow curve shape (Chen's) method after isolating the prominent glow peak by thermal cleaning technique. Our results show a very good agreement between the trapping parameters calculated by the two methods. ILD method was used for determining the trapping parameters of BeO. Results obtained applying this method are in good agreement with those obtained using other methods, except in the value of the frequency factor. - Highlights: • Kinetic parameters of BeO were determined. • Isothermal decay method was used. • Frecuency factor not agree with those obtained by other methods.

Sequence-dependent theory of oligonucleotide hybridization kinetics

International Nuclear Information System (INIS)

Marimuthu, Karthikeyan; Chakrabarti, Raj

2014-01-01

A theoretical approach to the prediction of the sequence and temperature-dependent rate constants for oligonucleotide hybridization reactions has been developed based on the theory of relaxation kinetics. One-sided and two-sided melting reaction mechanisms for oligonucleotide hybridization reactions have been considered, analyzed, modified, and compared to select a physically consistent as well as robust model for prediction of the relaxation times of DNA hybridization reactions that agrees with the experimental evidence. The temperature- and sequence-dependent parameters of the proposed model have been estimated using available experimental data. The relaxation time model that we developed has been combined with the nearest neighbor model of hybridization thermodynamics to estimate the temperature- and sequence-dependent rate constants of an oligonucleotide hybridization reaction. The model-predicted rate constants are compared to experimentally determined rate constants for the same oligonucleotide hybridization reactions. Finally, we consider a few important applications of kinetically controlled DNA hybridization reactions

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 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

Kinetics of Oxidation of Metochlopramide withChloramine-T in HClO4 Medium

Directory of Open Access Journals (Sweden)

K. M. Meenakshi

2009-01-01

Full Text Available The kinetics of oxidation of metochlopramide hydrochloride (MCP with sodium N-chloro p-toluenesulfonamide (CAT in perchloric acid solution has been studied at 313K. The reaction rate shows a first order dependence on [CAT], fractional order on [MCP] and inverse fractional order on [H+]. There is a negative effect of dielectric constant of the solvent. The addition of the reduction product of CAT has no significant effect on the rate. The rate remained unchanged with the variation in the ionic strength of the medium. The reaction fails to induce the polymerization of acrylonitrile. Thermodynamic parameters have been computed by Arrhenius plot. The stoichiometry of the reaction was found to be 1:2 and oxidation products were identified. The Michaelis-Menten type of kinetics has been proposed. CH3C6H4SO2NHCl have been assumed to be the reactive oxidizing species. Thermodynamic parameters were computed by studying reactions at different temperatures. A mechanism consistent with observed kinetics is proposed.

Kinetic and thermodynamic studies of reactional system (X-I-O-H) by high temperature mass spectrometry

International Nuclear Information System (INIS)

Roki, F.Z.

2009-01-01

High temperature mass spectrometry is used for analysis of vapors coming from iodine reaction with fission products in case of a severe nuclear accident in a pressurized water reactor. Two main ways are used, - (i) thermodynamic analysis of vaporization processes of CsOH, CsI and mixtures CsI-CsOH. - (ii) building a dedicated reactor for kinetic analysis of the recombination of atoms into these stables molecular species. The present study confirms the existence of Cs 2 IOH(g) molecule. Vapor pressures of gaseous molecules CsOH(g), Cs 2 O 2 H 2 (g) and Cs 2 IOH(g) have been determined. Molecular parameters of the mixed molecule have been estimated on the basis of the pure dimmers Cs 2 O 2 H 2 (g) and Cs 2 I 2 (g) and its enthalpy of formation are established. The acquisition of kinetic data needs a new reactor, the conception of which is presented in this work as well as qualification tests: thermal, flow regimes and pressure calibration tests. (author)

KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYSTHESIS

International Nuclear Information System (INIS)

Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

2005-01-01

This report covers the third year of this research grant under the University Coal Research program. The overall objective of this project is to develop a comprehensive kinetic model for slurry phase Fischer-Tropsch synthesis (FTS) on iron catalysts. This model will be validated with experimental data obtained in a stirred tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (H 2 O, CO 2 , linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the reporting period we utilized experimental data from the STSR, that were obtained during the first two years of the project, to perform vapor-liquid equilibrium (VLE) calculations and estimate kinetic parameters. We used a modified Peng-Robinson (PR) equation of state (EOS) with estimated values of binary interaction coefficients for the VLE calculations. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Occasional discrepancies (for some of the experimental data) between calculated and experimental values of the liquid phase composition were ascribed to experimental errors. The VLE calculations show that the vapor and the liquid are in thermodynamic equilibrium under reaction conditions. Also, we have successfully applied the Levenberg-Marquardt method (Marquardt, 1963) to estimate parameters of a kinetic model proposed earlier by Lox and Froment (1993b) for FTS on an iron catalyst. This kinetic model is well suited for initial studies where the main goal is to learn techniques for parameter estimation and statistical analysis of estimated values of model parameters. It predicts that the chain growth parameter (α) and olefin to paraffin ratio are independent of carbon number, whereas our experimental data show that they vary with the carbon number. Predicted molar flow

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.

Comparative study on ion-isotopic exchange reaction kinetics by application of tracer technique

International Nuclear Information System (INIS)

Lokhande, R.S.; Singare, P.U.

2007-01-01

The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reactions using industrial grade ion exchange resins Amberlite IRA-400. The experiments were performed to understand the effect of temperature and concentration of ionic solution on kinetics of exchange reactions. Both the exchange reactions were greatly influenced by rise in temperature, which result in higher percentage of ions exchanged. For bromide ion-isotopic exchange reactions, the calculated values of specific reaction rate/min -1 , and amount of ions exchanged/mmol were obtained higher than that for iodide ion-isotopic exchange reactions under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (orig.)

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.

Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

Science.gov (United States)

Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

2015-12-01

Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

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.

Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

Directory of Open Access Journals (Sweden)

Krivtcova Nadezhda

2016-01-01

Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

Determination of the temperature coefficients and the kinetic parameters for the HTTR safety analysis

International Nuclear Information System (INIS)

Tokuhara, K.; Nakata, T.; Murata, I.; Yamashita, K.; Shindo, R.

1991-01-01

This report describes the calculational methods which were employed to determine the temperature coefficients and the kinetic parameters for the safety analysis in the HTTR (High Temperature Engineering Test Reactor). The temperature coefficients (doppler, moderator temperature) and the kinetic parameters (prompt neutron life time; l, effective delayed neutron fraction; β eff) are important for the point model core dynamic analysis and should be evaluated properly. The temperature coefficients were calculated by the whole core model. Doppler coefficient was evaluated under the conditions of all control rods withdrawn and the uniform change of fuel temperature. The minimum and the maximum value of the evaluated doppler coefficients in a burnup cycle are -4.6x10 -5 and -1.5x10 -5 ΔK/K/deg. C respectively. The moderator temperature coefficient was evaluated under the conditions of all control rods withdrawn and the uniform change of moderator temperature. The minimum and the maximum value of the evaluated moderator temperature coefficients in a burnup cycle are -17.1x10 -5 and 0.99x10 -5 ΔK/K/deg. C respectively. In spite of positive moderator temperature coefficient, the power coefficient is always negative. Therefore the HTTR possesses inherent power-suppressing feed back characteristic in all operating condition. We surveyed the effects of the Xe existence, the control rods existence, the fuel temperature and the region in which the temperature was changed on the moderator temperature coefficients. The kinetic parameters were calculated by the perturbation method with the whole core model. The minimum and the maximum value of the evaluated effective delayed neutron fraction (β eff) are 0.0047 and 0.0065 respectively. These of the evaluated prompt neutron life time (l) are 0.67 and 0.78 ms respectively. We have surveyed the effects of the fuel depletion and the core power level on these parameters, and considered these effects on the kinetic parameters. From

Kinetics of the reaction between H· and superheated water probed with muonium

Energy Technology Data Exchange (ETDEWEB)

Alcorn, C. [Mount Allison Univ., Sackville, NB (Canada); Brodovitch, J.-C. [Simon Fraser Univ., Burnaby, BC (Canada); Ghandi, K.; Kennedy, A. [Mount Allison Univ., Sackville, NB (Canada); Percival, P.W. [Simon Fraser Univ., Burnaby, BC (Canada); TRIUMF, Vancouver, BC (Canada); Smith, M. [Mount Allison Univ., Sackville, NB (Canada)

2011-07-01

Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650{sup o}C. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H{sub 2} gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H{sub 2}O and D{sub 2}O at temperatures up to 450{sup o}C.

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.

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

Assessing the impact of azadirachtin application to soil on ureaseactivity and its kinetic parameters

OpenAIRE

KIZILKAYA, RIDVAN; SAMOFALOVA, IRAIDA; MUDRYKH, NATALYA; MİKAİLSOY, FARİZ; AKÇA, İZZET; SUSHKOVA, SVETLANA; MINKINA, TATIANA

2015-01-01

Abstract: The kinetic parameters of soil urease have attracted considerable attention; however, little information is available on its kinetic parameters and behaviors in response to azadirachtin application to the soil. A short (14-day) field experiment was conducted using Albic Luvisol soil (loam texture; pH 6.70; electrical conductivity 0.81 dS m-1; CaCO3 content 0.04%; total organic carbon 0.99%) as the experimental soil in the Perm region of the Russian Federation to investigate the effe...

Reaction parameters for controlled sonosynthesis of gold nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Gonzalez M, A. L. [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Paseo Colon esq. Paseo Tollocan s/n, 50120 Toluca, Estado de Mexico (Mexico); Cabrera L, L. I. [UNAM-UAEM, Centro Conjunto de Investigacion en Quimica Sustentable, Km 14.5 Carretera Toluca-Atlacomulco, 50200 San Cayetano-Toluca, Estado de Mexico (Mexico)

2015-07-01

The synthesis of gold nanoparticles by sonochemical technique has been previously performed with excellent results. The synthesis has been carried out in the presence of citric acid, a strong reducing agent, which allows the nucleation and growth of gold nanoparticles, at the same time that controls particle size. In this work we report the use of sodium tartrate as a mild reducing agent that allows a better understanding of the effect of the reaction parameters during gold nanoparticle synthesis. A conventional sonication bath (37 k Hz) was used for the sonochemical synthesis. This work focuses on the reaction temperature effect and the effect of sodium tartrate concentration. It was confirmed that particle size, and particle morphology is dependent of these two reaction parameters. Equally, colloidal stabilization was related to reaction temperature and sodium tartrate concentration. It was also determined that Ostwald ripening takes place during sonochemical reaction under our conditions, allowing to understand the mechanism that takes place during synthesis. Gold nanoparticles with main particle size of 17 nm were achieved by this method. Characterization techniques used: Fourier transform infrared spectra (Ftir), X-ray diffraction and Atomic Force Microscope was used in order to determine particle size of the synthetic product of reaction M10c by tapping mode. (Author)

Reaction parameters for controlled sonosynthesis of gold nanoparticles

International Nuclear Information System (INIS)

Gonzalez M, A. L.; Cabrera L, L. I.

2015-01-01

The synthesis of gold nanoparticles by sonochemical technique has been previously performed with excellent results. The synthesis has been carried out in the presence of citric acid, a strong reducing agent, which allows the nucleation and growth of gold nanoparticles, at the same time that controls particle size. In this work we report the use of sodium tartrate as a mild reducing agent that allows a better understanding of the effect of the reaction parameters during gold nanoparticle synthesis. A conventional sonication bath (37 k Hz) was used for the sonochemical synthesis. This work focuses on the reaction temperature effect and the effect of sodium tartrate concentration. It was confirmed that particle size, and particle morphology is dependent of these two reaction parameters. Equally, colloidal stabilization was related to reaction temperature and sodium tartrate concentration. It was also determined that Ostwald ripening takes place during sonochemical reaction under our conditions, allowing to understand the mechanism that takes place during synthesis. Gold nanoparticles with main particle size of 17 nm were achieved by this method. Characterization techniques used: Fourier transform infrared spectra (Ftir), X-ray diffraction and Atomic Force Microscope was used in order to determine particle size of the synthetic product of reaction M10c by tapping mode. (Author)

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 ...

Mechanistic and kinetic aspects of microbial inactivation in food irradiation processes

International Nuclear Information System (INIS)

Tukenmez, I.

2004-01-01

Full text: A proper reaction mechanism was searched by analyzing the inactivation processes of microorganisms during food irradiation by ionizing radiation. By employing transition-state theory, it was assumed that the overall inactivation process involves a reversible sub-lethal stress and repair reactions to form reversibly injured cell or sensitized cell, which then undergoes irreversible injury leading to dead cell. A shoulder in low dose range in survival kinetics was associated with the repair process. Depending on the postulated mechanism, kinetic model equations were derived. The kinetics of cell inactivation by irradiation was expressed as depending on irradiation dose. By using experimental data in the developed model the inactivation parameters including threshold dose, radiation yield, decimal reduction dose and minimum sterilization dose were evaluated and microbial inactivation by irradiation was simulated by using the numerical values of the parameters. Developed model and model parameters may be used for the process control and the assessment of product quality in radiation preservation of food

Modeling of uncertainties in biochemical reactions.

Science.gov (United States)

Mišković, Ljubiša; Hatzimanikatis, Vassily

2011-02-01

Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

International Nuclear Information System (INIS)

Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

1986-01-01

The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

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.

Activity, stability and kinetic parameters for α-chymotrypsin catalysed ...

Indian Academy of Sciences (India)

Three typical surfactants were selected based on their head group charges: a non-ionic surfactant Triton-X 100 and two zwitterionic sulphobetaine surfactants of the type CH2+1N+Me2 (CH2)3 SO 3 − (n = 10; SB3-10, n = 16; SB3-16). The kinetic parameters (such as cat and M) of the -CT at 27°C were determined ...

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...

Photocatalytic mineralization of commercial herbicides in a pilot-scale solar CPC reactor: photoreactor modeling and reaction kinetics constants independent of radiation field.

Science.gov (United States)

Colina-Márquez, Jose; Machuca-Martínez, Fiderman; Li Puma, Gianluca

2009-12-01

The six-flux absorption-scattering model (SFM) of the radiation field in the photoreactor, combined with reaction kinetics and fluid-dynamic models, has proved to be suitable to describe the degradation of water pollutants in heterogeneous photocatalytic reactors, combining simplicity and accuracy. In this study, the above approach was extended to model the photocatalytic mineralization of a commercial herbicides mixture (2,4-D, diuron, and ametryne used in Colombian sugar cane crops) in a solar, pilot-scale, compound parabolic collector (CPC) photoreactor using a slurry suspension of TiO(2). The ray-tracing technique was used jointly with the SFM to determine the direction of both the direct and diffuse solar photon fluxes and the spatial profile of the local volumetric rate of photon absorption (LVRPA) in the CPC reactor. Herbicides mineralization kinetics with explicit photon absorption effects were utilized to remove the dependence of the observed rate constants from the reactor geometry and radiation field in the photoreactor. The results showed that the overall model fitted the experimental data of herbicides mineralization in the solar CPC reactor satisfactorily for both cloudy and sunny days. Using the above approach kinetic parameters independent of the radiation field in the reactor can be estimated directly from the results of experiments carried out in a solar CPC reactor. The SFM combined with reaction kinetics and fluid-dynamic models proved to be a simple, but reliable model, for solar photocatalytic applications.

Using ground reaction force to predict knee kinetic asymmetry following anterior cruciate ligament reconstruction.

Science.gov (United States)

Dai, B; Butler, R J; Garrett, W E; Queen, R M

2014-12-01

Asymmetries in sagittal plane knee kinetics have been identified as a risk factor for anterior cruciate ligament (ACL) re-injury. Clinical tools are needed to identify the asymmetries. This study examined the relationships between knee kinetic asymmetries and ground reaction force (GRF) asymmetries during athletic tasks in adolescent patients following ACL reconstruction (ACL-R). Kinematic and GRF data were collected during a stop-jump task and a side-cutting task for 23 patients. Asymmetry indices between the surgical and non-surgical limbs were calculated for GRF and knee kinetic variables. For the stop-jump task, knee kinetics asymmetry indices were correlated with all GRF asymmetry indices (P kinetic asymmetry indices were correlated with the peak propulsion vertical GRF and vertical GRF impulse asymmetry indices (P kinetic asymmetries and therefore may assist in optimizing rehabilitation outcomes and minimizing re-injury rates. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Kinetics of liquid lithium reaction with oxygen-nitrogen mixtures

International Nuclear Information System (INIS)

Gil, T.K.; Kazimi, M.S.

1986-01-01

A series of experiments have been conducted in order to characterize the kinetics of lithium chemical reaction with a mixture of oxygen and nitrogen. Three mixed gas compositions were used; 80% N 2 and 20% O 2 , 90% N 2 and 10% O 2 , and 95% N 2 and 5% O 2 . The reaction rate was obtained as a function of lithium temperature and the oxygen fraction. Liquid lithium temperature varied from 400 to 1100 0 C. By varying the composition, the degree of inhibition of the lithium-nitrogen reaction rate due to the presence of oxygen was observed. The results indicate that the lithium-nitrogen reaction rate depended on both the fraction of oxygen present and lithium temperature. The lithium nitride layer formed from the reaction also had a significant inhibition effect on the lithium-nitrogen reaction rate while the lithium-oxygen reaction rate was not as greatly hindered. LITFIRE, a computer code which simulates temperature and pressure history in a containment building following lithium spills, was modified by including (1) an improved model for the lithium-nitrogen reaction rate and (2) a model for the lithium-CO 2 reaction. LITFIRE was used to simulate HEDL's LC-2 and LA-5 experiments, and the predicted temperatures and pressures were in a reasonable agreement. Furthermore, LITFIRE was applied to a prototypical fusion reactor containment in order to simulate the consequences of a lithium spill accident. The result indicated that if nitrogen was used as containment building gas during the accident, the consequences of the accident would be less severe than those with air. The pressure rise in the building was found to be reduced by 50% and the maximum temperature of the combustion zone was limited to 900 0 C instead of 1200 0 C in the case of air

Constraining statistical-model parameters using fusion and spallation reactions

Directory of Open Access Journals (Sweden)

Charity Robert J.

2011-10-01

Full Text Available The de-excitation of compound nuclei has been successfully described for several decades by means of statistical models. However, such models involve a large number of free parameters and ingredients that are often underconstrained by experimental data. We show how the degeneracy of the model ingredients can be partially lifted by studying different entrance channels for de-excitation, which populate different regions of the parameter space of the compound nucleus. Fusion reactions, in particular, play an important role in this strategy because they fix three out of four of the compound-nucleus parameters (mass, charge and total excitation energy. The present work focuses on fission and intermediate-mass-fragment emission cross sections. We prove how equivalent parameter sets for fusion-fission reactions can be resolved using another entrance channel, namely spallation reactions. Intermediate-mass-fragment emission can be constrained in a similar way. An interpretation of the best-fit IMF barriers in terms of the Wigner energies of the nascent fragments is discussed.

Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

Science.gov (United States)

Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

2017-01-25

This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

Kinetic parameters of silicon uptake by rice cultivars

Directory of Open Access Journals (Sweden)

Priscila Oliveira Martins

2012-02-01

Full Text Available Silicon is considered an important chemical element for rice, because it can improve tolerance to biotic and abiotic stress. However, in many situations no positive effect of silicon was observed, probably due to genetic factors. The objective of this research was to monitor Si uptake kinetics and identify responses of rice cultivars in terms of Si uptake capacity and use. The experiment was carried out in a greenhouse of the São Paulo State University (UNESP, Brazil. The experiment was arranged in a completely randomized, factorial design with three replications. that consisted of two rice cultivars and two Si levels. Kinetic parameters (Vmax, Km, and Cmin, root morphology variables, dry matter yield, Si accumulation and levels in shoots and roots, uptake efficiency, utilization efficiency, and root/shoot ratio were evaluated. Higher Si concentrations in the nutrient solution did not increase rice dry matter. The development of the low-affinity silicon uptake system of the rice cultivar 'Caiapó' was better than of 'Maravilha'.

Two-detector cross-correlation noise technique and its application in measuring reactor kinetic parameters

International Nuclear Information System (INIS)

Lu Guiping; Peng Feng; Yi Jieyi

1988-01-01

The two-detector cross-correlation noise technique is a new method of measuring reactor kinetic parameters developed in the sixties. It has the advantages of non-perturbation in core, high signal to noise ratio, low space dependent effect, and simple and reliable in measurement. A special set of cross-correlation analyzer has been prepared for measuring kinetic parameters of several reactor assemblies, such as the High Flux Engineering Test Reactor, its zero power mock up facility and a low enriched uranium light water lattice zero power facility

Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

Science.gov (United States)

Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

2012-01-01

Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

Directory of Open Access Journals (Sweden)

Ziya Kalay

Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

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.

New types of experimental data shape the use of enzyme kinetics for dynamic network modeling.

Science.gov (United States)

Tummler, Katja; Lubitz, Timo; Schelker, Max; Klipp, Edda

2014-01-01

Since the publication of Leonor Michaelis and Maude Menten's paper on the reaction kinetics of the enzyme invertase in 1913, molecular biology has evolved tremendously. New measurement techniques allow in vivo characterization of the whole genome, proteome or transcriptome of cells, whereas the classical enzyme essay only allows determination of the two Michaelis-Menten parameters V and K(m). Nevertheless, Michaelis-Menten kinetics are still commonly used, not only in the in vitro context of enzyme characterization but also as a rate law for enzymatic reactions in larger biochemical reaction networks. In this review, we give an overview of the historical development of kinetic rate laws originating from Michaelis-Menten kinetics over the past 100 years. Furthermore, we briefly summarize the experimental techniques used for the characterization of enzymes, and discuss web resources that systematically store kinetic parameters and related information. Finally, describe the novel opportunities that arise from using these data in dynamic mathematical modeling. In this framework, traditional in vitro approaches may be combined with modern genome-scale measurements to foster thorough understanding of the underlying complex mechanisms. © 2013 FEBS.

Kinetics with deactivation of methylcyclohexane dehydrogenation for hydrogen energy storage

Energy Technology Data Exchange (ETDEWEB)

Maria, G; Marin, A; Wyss, C; Mueller, S; Newson, E [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

The methylcyclohexane dehydrogenation step to recycle toluene and release hydrogen is being studied as part of a hydrogen energy storage project. The reaction is performed catalytically in a fixed bed reactor, and the efficiency of this step significantly determines overall system economics. The fresh catalyst kinetics and the deactivation of the catalyst by coke play an important role in the process analysis. The main reaction kinetics were determined from isothermal experiments using a parameter sensitivity analysis for model discrimination. An activation energy for the main reaction of 220{+-}11 kJ/mol was obtained from a two-parameter model. From non-isothermal deactivation in PC-controlled integral reactors, an activation energy for deactivation of 160 kJ/mol was estimated. A model for catalyst coke content of 3-17 weight% was compared with experimental data. (author) 3 figs., 6 refs.

Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

International Nuclear Information System (INIS)

Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

2015-01-01

Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

Three Rate-Constant Kinetic Model for Permanganate Reactions Autocatalyzed by Colloidal Manganese Dioxide: The Oxidation of L-Phenylalanine.

Science.gov (United States)

Perez-Benito, Joaquin F; Ferrando, Jordi

2014-12-26

The reduction of permanganate ion to MnO(2)-Mn(2)O(3) soluble colloidal mixed oxide by l-phenylalanine in aqueous phosphate-buffered neutral solutions has been followed by a spectrophotometric method, monitoring the decay of permanganate ion at 525 nm and the formation of the colloidal oxide at 420 nm. The reaction is autocatalyzed by the manganese product, and three rate constants have been required to fit the experimental absorbance-time kinetic data. The reaction shows base catalysis, and the values of the activation parameters at different pHs have been determined. A mechanism including both the nonautocatalytic and the autocatalytic reaction pathways, and in agreement with the available experimental data, has been proposed. Some key features of this mechanism are the following: (i) of the two predominant forms of the amino acid, the anionic form exhibits a stronger reducing power than the zwitterionic form; (ii) the nonautocatalytic reaction pathway starts with the transfer of the hydrogen atom in the α position of the amino acid to permanganate ion; and (iii) the autocatalytic reaction pathway involves the reduction of Mn(IV) to Mn(II) by the amino acid and the posterior reoxidation of Mn(II) to Mn(IV) by permanganate ion.

Kinetic parameters of nitridation of molybdenum and niobium alloys with various structure states

International Nuclear Information System (INIS)

Solodkin, G.A.; Bulgach, A.A.; Likhacheva, T.E.

1985-01-01

Effect of preliminary plastic strain under rolling on kinetic parameters of nitridation of VN-2AEh, VN-3 niobium alloys and molybdenum alloy with hafnium is investigated. Extreme character of dependence of kinetic parameters of nitridation on the degree of reduction under rolling is determined. Preliminary plastic strain at negligible reduction is shown to accelerate growth of the zone of internal nitridation and decelerates growth of the nitride zone. Nitrogen atom removal from the surface to the centre is retarded at the increase of the degree of reduction up to 50% and higher. The degree of deformations is the higher the lower nitridation temperature is

Quantitative modeling of the reaction/diffusion kinetics of two-chemistry photopolymers

Science.gov (United States)

Kowalski, Benjamin Andrew

Optically driven diffusion in photopolymers is an appealing material platform for a broad range of applications, in which the recorded refractive index patterns serve either as images (e.g. data storage, display holography) or as optical elements (e.g. custom GRIN components, integrated optical devices). A quantitative understanding of the reaction/diffusion kinetics is difficult to obtain directly, but is nevertheless necessary in order to fully exploit the wide array of design freedoms in these materials. A general strategy for characterizing these kinetics is proposed, in which key processes are decoupled and independently measured. This strategy enables prediction of a material's potential refractive index change, solely on the basis of its chemical components. The degree to which a material does not reach this potential reveals the fraction of monomer that has participated in unwanted reactions, reducing spatial resolution and dynamic range. This approach is demonstrated for a model material similar to commercial media, achieving quantitative predictions of index response over three orders of exposure dose (~1 to ~103 mJ cm-2) and three orders of feature size (0.35 to 500 microns). The resulting insights enable guided, rational design of new material formulations with demonstrated performance improvement.

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

Science.gov (United States)

Hynes, A. J.; Wine, P. H.

1997-01-01

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

alfa-Deuterium kinetic isotope effects in reactions of methyllithium. Is better aggregation the cause of lower reactivity?

DEFF Research Database (Denmark)

Holm, Torkil

1996-01-01

The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium......The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium...

Thermoluminescence kinetic parameters of different amount La-doped ZnB2O4

International Nuclear Information System (INIS)

Kucuk, Nil; Gozel, Aziz Halit; Yüksel, Mehmet; Dogan, Tamer; Topaksu, Mustafa

2015-01-01

The kinetic parameters of 1%, 2%, 3% and 4% La-doped ZnB 2 O 4 phosphors (i.e. ZnB 2 O 4 :0.01La, ZnB 2 O 4 :0.02La, ZnB 2 O 4 :0.03La and ZnB 2 O 4 :0.04La) synthesized by nitric acid method have been calculated. Thermoluminescence (TL) glow curves of ZnB 2 O 4 :La phosphors after beta-irradiation showed a very well defined main peak having the maximum temperature at around 200 °C and a shoulder peak at around 315 °C with a constant heating rate of 5 °C/s. The kinetic parameters of ZnB 2 O 4 :La phosphors TL glow peaks (i.e. order of kinetics (b), activation energies (E a ) and frequency factors (s)) have been determined and evaluated by Computerized Glow Curve Deconvolution (CGCD), and Peak Shape (PS) methods using the glow curve data. From the results, it can conclude that the values of E a obtained with these methods for ZnB 2 O 4 :La phosphors are consistent with each other, but the s values differ considerably. - Highlights: • Calculation of TL kinetic parameters for La-doped ZnB 2 O 4 . • La-doped ZnB 2 O 4 was synthesized by nitric acid method. • Well defined main peak at about 200 °C

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.

Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

Science.gov (United States)

Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

2018-03-20

Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

Science.gov (United States)

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

2016-05-01

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

Energy transfer and kinetics in mechanochemistry.

Science.gov (United States)

Chen, Zhiliang; Lu, Shengyong; Mao, Qiongjing; Buekens, Alfons; Wang, Yuting; Yan, Jianhua

2017-11-01

Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor-total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.

Thermoluminescent kinetic parameters of the perovskite, KMgF3, activated with lanthanum

International Nuclear Information System (INIS)

Sepulveda M, F.; Azorin N, J.; Rivera M, T.; Furetta, C.; Sanipoli, C.

2004-01-01

The thermoluminescent curves induced by the beta radiation in the perovskite KMgF 3 were investigated activated with lanthanum. The classic methods were used to determine the kinetic parameters (the kinetic order b, the activation energy E and the frequency of escape intent s) associated with the peaks of the thermoluminescent curve (Tl) in the KMgF 3 activated with lanthanum after the irradiation with beta rays. The method is based on the position of the thermoluminescent peaks, obtained of the temperature change of the peak in the maximum emission caused by the change in the heating rapidity to which the samples were measured. In this work, the samples in form of pellets were re cooked previously at 400 C during one hour before irradiating them with beta particles. The Tl measures were made with a Tl reader system using three different heating rapidities and storing the glow curves. To calculate the depth of the E traps and the frequency factor s, the parameters of the glow curve were determined experimentally of the shame of the glow curve by means of the mensuration of the shame of the maximum temperature of the peak, T M like a function of the heating rapidity. The results indicate that the values of the kinetic parameters are very near among if when they are obtained indistinctly of anyone of the different methods. (Author)

Parameter Estimates in Differential Equation Models for Chemical Kinetics

Science.gov (United States)

Winkel, Brian

2011-01-01

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

Thermodynamic Activity-Based Progress Curve Analysis in Enzyme Kinetics.

Science.gov (United States)

Pleiss, Jürgen

2018-03-01

Macrokinetic Michaelis-Menten models based on thermodynamic activity provide insights into enzyme kinetics because they separate substrate-enzyme from substrate-solvent interactions. Kinetic parameters are estimated from experimental progress curves of enzyme-catalyzed reactions. Three pitfalls are discussed: deviations between thermodynamic and concentration-based models, product effects on the substrate activity coefficient, and product inhibition. Copyright © 2017 Elsevier Ltd. All rights reserved.

A study of redox kinetic in silicate melt

International Nuclear Information System (INIS)

Magnien, V.

2005-12-01

The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

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

International Nuclear Information System (INIS)

Adda, Y.

1955-06-01

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

On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

Energy Technology Data Exchange (ETDEWEB)

Slavov, Chavdar Lyubomirov

2009-07-09

The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

Kinetic study of the annealing reactions in Cu-Ni-Fe alloys; Estudio cinetico de las reacciones de recocido en aleaciones de Cu-Ni-Fe

Energy Technology Data Exchange (ETDEWEB)

Donoso, E.

2014-07-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi{sub 3} phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi{sub 3} phase. (Author)

Kinetics of Heterogeneous Reaction of Sulfur Dioxide on Authentic Mineral Dust: Effects of Relative Humidity and Hydrogen Peroxide.

Science.gov (United States)

Huang, Liubin; Zhao, Yue; Li, Huan; Chen, Zhongming

2015-09-15

Heterogeneous reaction of SO2 on mineral dust seems to be an important sink for SO2. However, kinetic data about this reaction on authentic mineral dust are scarce and are mainly limited to low relative humidity (RH) conditions. In addition, little is known about the role of hydrogen peroxide (H2O2) in this reaction. Here, we investigated the uptake kinetics of SO2 on three authentic mineral dusts (i.e., Asian mineral dust (AMD), Tengger desert dust (TDD), and Arizona test dust (ATD)) in the absence and presence of H2O2 at different RHs using a filter-based flow reactor, and applied a parameter (effectiveness factor) to the estimation of the effective surface area of particles for the calculation of the corrected uptake coefficient (γc). We found that with increasing RH, the γc decreases on AMD particles, but increases on ATD and TDD particles. This discrepancy is probably due to the different mineralogy compositions and aging extents of these dust samples. Furthermore, the presence of H2O2 can promote the uptake of SO2 on mineral dust at different RHs. The probable explanations are that H2O2 rapidly reacts with SO2 on mineral dust in the presence of adsorbed water, and OH radicals, which can be produced from the heterogeneous decomposition of H2O2 on the mineral dust, immediately react with adsorbed SO2 as well. Our results suggest that the removal of SO2 via the heterogeneous reaction on mineral dust is an important sink for SO2 and has the potential to alter the physicochemical properties (e.g., ice nucleation ability) of mineral dust particles in the atmosphere.

Kinetic isotope effect in the reaction of dehydration of fructose into 5-hydroxymethylfurfural

International Nuclear Information System (INIS)

Grin', S.A.; Tsimbaliev, S.R.; Gel'fand, S.Yu.

1993-01-01

Kinetic isotopic effect in the reaction of fructose dehydration into 5- hydroxymethylfurfural was determined. The results suggest hydrogen participation in the limiting stage of the process. The assumption that proton addition to 4, 5, 6 -trihydroxy - 2- on - hexal is the limiting stage is made