WorldWideScience

Sample records for pseudo-first-order reaction kinetics

  1. Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition

    Directory of Open Access Journals (Sweden)

    LJILJANA KOLAR-ANIC

    2000-10-01

    Full Text Available The kinetics of the Belousov-Zhabotinsky (BZ oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5×10-3 min-1, was found.

  2. Kinetic characteristics of gas-liquid ozone reactions

    Science.gov (United States)

    Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

    2017-10-01

    An experimental chemical method for determining the kinetic characteristics (volumetric mass transfer coefficient and rate constant of a second-order reaction) of gas-liquid ozone reactions in a bubble column reactor is described. The calculation formulas are substantiated, and the ranges of values of the experimental factors that determine the method's limits of applicability are found. The conditions under which the boundary-value problem of a gas-liquid ozone reaction of the second order can be reduced to a problem of a pseudo-first order reaction allowing an analytical solution are revealed.

  3. Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue ...

    African Journals Online (AJOL)

    , in aqueous solution by hypochlorite as a function of pH was investigated. While the degradation of dye obeyed pseudo-first-order kinetics, the oxidation of the dye occurred through two competitive reactions facilitated by [OCl–] and [HOCl].

  4. Pseudo first ordered adsorption of noxious textile dyes by low-temperature synthesized amorphous carbon nanotubes

    Science.gov (United States)

    Banerjee, D.; Bhowmick, P.; Pahari, D.; Santra, S.; Sarkar, S.; Das, B.; Chattopadhyay, K. K.

    2017-03-01

    Amorphous carbon nanotubes (a-CNTs) were synthesized by solid state reaction. The as prepared a-CNTs were characterized by X-ray diffraction, field emission scanning and high resolution transmission electron microscope and Raman spectroscopy. As-synthesized a-CNTs were used for, the first time, for removing different organic dyes from water. The dyes mainly include Rhodamine B and Methyl Orange and systematic batch mode studies of a-CNTs assisted adsorption have been executed in detail. The removing efficiency of a-CNTs has also been investigated for various sorption parameters like contact time, dosage, pH, initial dye concentration, contact time etc. It is seen that a-CNTs can be material of potential for removal of dyes. In case of Rhodamine B, the maximum time for removal was 45 min whereas for Methyl orange rapid removal was plausible in about 30 min even in ambient condition. The experimental data have been well correlated with classical Langmuir-Freundlich and Temkin adsorption models.

  5. Thermodynamic, kinetic and mechanistic investigations of ...

    Indian Academy of Sciences (India)

    standardized by iodometric titration and gravimetrically by the thiocyanate23 method. 2.3 Kinetic Measurements. Kinetics was followed under pseudo first order con- ditions where [PPZ] > [DPC] at 25 ± 0.1◦C, unless otherwise specified. The reaction was initiated by mix- ing the DPC to PPZ solution, which also contained.

  6. reactions of enolisable ketones with dichloroisocyanuric acid

    African Journals Online (AJOL)

    B. S. Chandravanshi

    ABSTRACT. Kinetics of reactions of enolisable ketones (S = acetone/2-butanone) with dichloroisocyanuric acid (DCICA) were studied in aqueous acetic acid and perchloric acid media in absence and presence of added chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in ...

  7. 1 H NMR-Based Kinetic-Mechanistic Study of the Intramolecular ...

    African Journals Online (AJOL)

    A 1H NMR study of the acid-catalyzed, intramolecular trans-esterification between isomeric 2-exo-3-exo-dihydroxybornane monoacrylate esters has afforded insights into the reaction mechanism and permitted the determination of kinetic and thermodynamic parameters for the pseudo-first-order processes. KEYWORDS ...

  8. An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

    Science.gov (United States)

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

    2011-01-01

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

  9. Reaction kinetics of resveratrol with tert-butoxyl radicals

    Science.gov (United States)

    Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

    2012-09-01

    The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

  10. Tebuconazole photocatalytic degradation kinetics

    OpenAIRE

    Prestes, Thiago de Hermann; Gibbon, Danielle de Oliveira; Lansarin, Marla Azário; Moro, Celso Camilo

    2010-01-01

    The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa) as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentr...

  11. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

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

  12. Photo-kinetics of photoinduced transformation reaction of methylene green with titanium trichloride in different solvents

    Science.gov (United States)

    Nadeem, Syed Muhammad Saqib; Saeed, Rehana

    2017-08-01

    The photo-kinetics of photoinduced transformation reaction of methylene green and titanium trichloride was investigated in water and different aqueous-alcoholic solvents. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at fixed concentration of methylene green. The effect of water and aqueous-alcoholic solvents was studied in the acidic range from 4 to 7. It was observed that the quantum yield (φ) of reaction increased with increase in polarity of the solvent. The quantum yield (φ) was high in acidic condition and decreased with further increase in acidity. The quantum yield (φ) increased sharply with increase in concentration of titanium trichloride while it almost remained unaffected by change in concentration of methylene green. The addition of ions increased the quantum yield (φ) of reaction. The increase in temperature decreased the rate and quantum yield (φ) of reaction. An electron transfer mechanism for the reaction has been proposed in accordance with the kinetics of reaction. The absence of any reaction intermediate was confirmed by spectroscopic investigations. Activation energy ( E a) was calculated by Arrhenius relation. Thermodynamic parameters such as activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G) and entropy change (Δ S) were also evaluated.

  13. Kinetics of nitrate adsorption and reduction by nano-scale zero valent iron (NZVI): Effect of ionic strength and initial pH

    DEFF Research Database (Denmark)

    Kim, Do-Gun; Hwang, Yuhoon; Shin, Hang-Sik

    2016-01-01

    Kinetic models for pollutants reduction by Nano-scale Zero Valent Iron (NZVI) were tested in this study to gain a better understanding and description of the reaction. Adsorption kinetic models and a heterogeneous catalytic reaction kinetic equation were proposed for nitrate removal and for ammonia...... generation, respectively. A widely used pseudo-first-order reaction model was a poor fit for nitrate removal in an iron-limiting condition and for ammonia generation in an excess iron condition. However, in this study, pseudo-first-order and pseudo-second-order adsorption kinetic equations were a good fit...... for nitrate removal; in addition, a Langmuir-Hinshelwood kinetic equation was able to successfully describe ammonia generation, regardless of the NZVI dose, the ionic strength, and the initial pH. These results strongly indicate that nitrate reduction by NZVI is a heterogeneous catalytic reaction...

  14. 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...

  15. Kinetics of the reduction of Rasaniline hydrochloride with sulphite ...

    African Journals Online (AJOL)

    The kinetics of the reduction of rosaniline hydrochloride (RH) in perchloric acid has been investigated under pseudo-first order condition of an excess [SO32-] at ionic strength of 1.0 mol dm-3 (CH3COONa), T = 30 0.1 oC and λmax = 540nm. The stoichiometry of the reaction was observed to be 1:1in terms of mole ratio of ...

  16. Reaction pathway and rate-determining step of the Schmidt rearrangement/fragmentation: a kinetic study.

    Science.gov (United States)

    Akimoto, Ryo; Tokugawa, Takehiro; Yamamoto, Yutaro; Yamataka, Hiroshi

    2012-04-20

    The Schmidt rearrangement of substituted 3-phenyl-2-butanone with trimethylsilyl azide in 90% (v/v) aqueous TFA gave two types of product, fragmentation and rearrangement, the ratio of which depends on the substituent: more fragmentation for a more electron-donating substituent. Rate measurements by azotometry indicated the presence of an induction period, and the pseudo-first-order rate constants showed saturation kinetics with respect to the azide concentration. It was indicated that the reaction proceeds through pre-equilibrium in the formation of iminodiazonium (ID) ion and that the N(2) liberation from the ID ion is rate-determining. Under high azide concentration conditions, where the effective reactant is the ID ion, the reaction gave a linear Hammett plot with a ρ value of -0.50. The observed substituent effects on the rate and the product selectivity imply that path bifurcation on the way from the rate-determining TS to the product states occurs, as suggested by previous molecular dynamics simulations, in a similar manner to the analogous Beckmann rearrangement/fragmentation reactions. © 2012 American Chemical Society

  17. Time-dependent kinetic complexities in cholinesterase-catalyzed reactions.

    Science.gov (United States)

    Masson, P

    2012-10-01

    Cholinesterases (ChEs) display a hysteretic behavior with certain substrates and inhibitors. Kinetic cooperativity in hysteresis of ChE-catalyzed reactions is characterized by a lag or burst phase in the approach to steady state. With some substrates damped oscillations are shown to superimpose on hysteretic lags. These time dependent peculiarities are observed for both butyrylcholinesterase and acetylcholinesterase from different sources. Hysteresis in ChE-catalyzed reactions can be interpreted in terms of slow transitions between two enzyme conformers E and E'. Substrate can bind to E and/or E', both Michaelian complexes ES and Ε'S can be catalytically competent, or only one of them can make products. The formal reaction pathway depends on both the chemical structure of the substrate and the type of enzyme. In particular, damped oscillations develop when substrate exists in different, slowly interconvertible, conformational, and/or micellar forms, of which only the minor form is capable of binding and reacting with the enzyme. Biphasic pseudo-first-order progressive inhibition of ChEs by certain carbamates and organophosphates also fits with a slow equilibrium between two reactive enzyme forms. Hysteresis can be modulated by medium parameters (pH, chaotropic and kosmotropic salts, organic solvents, temperature, osmotic pressure, and hydrostatic pressure). These studies showed that water structure plays a role in hysteretic behavior of ChEs. Attempts to provide a molecular mechanism for ChE hysteresis from mutagenesis studies or crystallographic studies failed so far. In fact, several lines of evidence suggest that hysteresis is controlled by the conformation of His438, a key residue in the catalytic triad of cholinesterases. Induction time may depend on the probability of His438 to adopt the operative conformation in the catalytic triad. The functional significance of ChE hysteresis is puzzling. However, the accepted view that proteins are in equilibrium between

  18. 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

  19. Kinetic Study of Free Radicals Scavenging by Saffron Petal Extracts

    Directory of Open Access Journals (Sweden)

    T. Ardalan

    2013-01-01

    Full Text Available Saffron petal is the main by-product of saffron processing which is produced in large amounts, annually. The objectives of this study were to study the antioxidant activity and free radical-scavenging effects of saffron petal extracts. The ability of saffron petal to act as an antioxidant using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH free-radical method was investigated by applying the Uv–Vis spectrometry. The Uv–Vis spectra of reaction mixtures in acetonitrile revealed that saffron petal has a considerable effect on scavenging free radical. Kinetic studies were conducted by measuring the disappearance of DPPH in acetonitrile over the wavelength range of 515-522 nm under pseudo-first-order conditions at 37oC. Furthermore, the pseudo first order rate constants were determined

  20. A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species.

    Science.gov (United States)

    Otamonga, Jean-Paul; Abdel-Mageed, Amal; Agater, Irena B; Jewsbury, Roger A

    2015-08-01

    In order to study the mechanism of the enhancement of solution chemiluminescence, the kinetics of the decay of the oxidant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn(3+) (aq) of glyoxylic acid, using stopped-flow spectrophotometry. Results are reported for the glyoxylic acid oxidized under pseudo first-order conditions and in an acidic medium at 25 °C. For permanganate under these conditions, the decay is sigmoidal, consistent with autocatalysis, and for manganese dioxide sol and Mn(3+) it is pseudo first order. The effects of the presence of aqueous formaldehyde and Mn(2+) were observed and a fit to a simple mechanism is discussed. It is concluded that chemiluminescent enhancement in these systems is best explained by reaction kinetics. Copyright © 2014 John Wiley & Sons, Ltd.

  1. Type-I pseudo-first-order phase transition induced electrocaloric effect in lead-free Bi0.5Na0.5TiO3-0.06BaTiO3 ceramics

    Science.gov (United States)

    Li, Feng; Chen, Guorui; Liu, Xing; Zhai, Jiwei; Shen, Bo; Li, Shandong; Li, Peng; Yang, Ke; Zeng, Huarong; Yan, Haixue

    2017-05-01

    In this study, the electrocaloric effect (ECE) of Bi0.5Na0.5TiO3-0.06BaTiO3 (BNT-0.06BT) ceramic has been directly measured using a home-made adiabatic calorimeter. The maximum adiabatic temperature change (ΔT) approaches 0.86 K under an electric field of 5 kV/mm at 110 °C, which provides experimental evidence for optimizing the ECE near the type-I pseudo-first-order phase transition (PFOPT). Most importantly, a considerable ΔT value can be maintained over a wide temperature range well above the temperature of the PFOPT under a high electric field. In addition, ΔT is closely related to the structural transition and electric field strength. This work provides a guideline to investigate the high ECE in BNT-based ferroelectric ceramics for applications in cooling technologies.

  2. Kinetics of heterogeneous reaction of ozone with linoleic acid and its dependence on temperature, physical state, RH, and ozone concentration.

    Science.gov (United States)

    Zeng, Guang; Holladay, Sara; Langlois, Danielle; Zhang, Yunhong; Liu, Yong

    2013-03-07

    Heterogeneous reaction between ozone and linoleic acid (LA) thin film was investigated by a flow reactor coupled to attenuated total reflection infrared spectroscopy (FR-ATR-IR) over wide ranges of temperature, relative humidity (RH), and ozone concentration under atmospheric pressure condition. Pseudo-first-order rate constants kapp and overall reactive uptake coefficients γ were acquired on the basis of changes in absorbance from peaks located near 1743, 1710, 1172, and 1110 cm(-1), which can be assigned to C═O in ester, C═O in acid, and C-C and C-O stretching modes, respectively. Results showed that the kapp and γ increased nearly by a factor of 6 with increasing temperatures from 258 to 314 K. It was noted the temperature effect on the reaction kinetics was much more pronounced at lower temperatures. Such behavior can be explained by a change in the physical state of LA at lower temperatures. In addition, kapp and γ were enhanced by 2-fold as the RH increased from 0 to 80%. Moreover, the effect of ozone concentration on the reaction kinetics was reported for the first time. kapp was found to display a Langmuir-Hinshelwood dependence on ozone concentration with KO3 = (1.146 ± 0.017) × 10(-15) molecules cm(-3) and k[S] = 0.0522 ± 0.0004 s(-1), where KO3 is a parameter that describes the partitioning of ozone to the thin film surface, and k[S] is the maximum pseudo-first-order coefficient at high ozone concentration. Furthermore, yields and hygroscopic properties of reaction products were also investigated by FTIR spectroscopy. The intensity ratio of two C═O stretching bands, A1743/A1710, which was utilized as an indicator of the product yields, increased sharply with increasing temperatures in the lower temperature region (258-284 K), and then remained nearly constant in the higher temperature region (284-314 K). The product yields showed no significant variation with RH, for the intensity ratio of A1743/A1710 barely changed in the wide RH range 0

  3. 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.

  4. 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.

  5. Discharge flow kinetic study of NO/sub 3/ reactions with free radicals: the reaction of NO/sub 3/ with Cl

    Energy Technology Data Exchange (ETDEWEB)

    Mellouki, A.; Le Bras, G.; Poulet, G.

    1987-10-22

    The discharge flow technique was used to perform a direct measurement of the rate constant for the reaction NO/sub 3/ + Cl ..-->.. ClO + NO/sub 2/ (1) under pseudo-first-order conditions with NO/sub 3/ in excess. NO/sub 3/ was produced via the reaction F + HNO/sub 3/ ..-->.. HF + NO/sub 3/ (2) for which the rate constant was also determined: k/sub 2/ = (2.7 +/- 0.5) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K. Absolute titration of NO/sub 3/ was done using NO and 2,3-dimethyl-2-butene as the titrants. The titration experiments with NO were simulated, and the analysis of potential errors resulting from the secondary chemistry indicated that NO is a precise titrant of NO/sub 3/ in discharge flow studies. In the kinetic investigation of reaction 1, the obtained value of k/sub 1/ at 298 K was k/sub 1/ = (2.6 +/- 0.5) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/.

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

    Science.gov (United States)

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

    2015-08-01

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

  7. Reactions of enolisable ketones with dichloroisocyanuric acid in absence and presence of added chloride ions – a kinetic study

    Directory of Open Access Journals (Sweden)

    Y. L. Kumar

    2015-01-01

    Full Text Available Kinetics of reactions of enolisable ketones (S = acetone/2-butanone with dichloroisocyanuric acid (DCICA were studied in aqueous acetic acid and perchloric acid media in absence and presence of added chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in absence and presence of chloride ions respectively. Both in presence and absence of chloride ions, first order and fractional order in substrate and perchloric acid were observed respectively. An increase in the rate of reaction was observed with an increase in chloride ion concentration as well as acetic acid composition. The results were interpreted in terms of probable mechanisms involving (i rate-determining enol formation from the conjugate acid of the ketone (SH+ in the absence of added chloride ions and (ii rate-determining interaction of SH+ with the most effective molecular chlorine species produced by the hydrolysis of DCICA (rather than a rate-determining interaction of enol with chlorine in the presence of added chloride ions, prior to the rapid steps of product formation. DOI: http://dx.doi.org/10.4314/bcse.v29i1.12

  8. 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

  9. [Determination of trace amounts of nitrite and its chemical reaction kinetics].

    Science.gov (United States)

    Luo, Zhi-yong; Zheng, Huai-li

    2014-06-01

    A catalytic kinetic spectrophotometric method for the determination of nitrite, NO2(-)-S2O8(2-)-MR, was developed. It is based on the fading reaction of methyl red (MR) oxidized by potassium persulfate which can be catalyzed by NO2- in the medium of dilute HCl. The optimum experimental conditions were gained by combining single factor experiments with orthogonal experiments. Calibration curve, detection limit, precision, and anti-interference under the optimum experimental conditions were researched. Its kinetics principles and parameters were discussed. Its quantitative principle was investigated. The results show that the optimum experimental conditions of this method should be as follows: 1.0 mL 0.3 mol x L(-1) HCl, 1.0 mL 0.01 mol x L(-1) K2S2O8, 0.6 mL 0.2 g x L(-1) MR, reaction temperature 80 degrees C and reaction time 9 min. The principles for the quantitative determination of trace nitrite is that variation of MR concentration at the maximum absorption wavelength of 518 nm, ln(A0/A), shows a good linear relationship with the concentration of NO2- under the optimum experimental conditions. Its determination range is 0.01-0.80 mg x L(-1) and its detection limit is 0.007 mg x L(-1). The kinetic characteristics are that the reaction order in NO2- is 1 and the fading reaction is a pseudo first order reaction. Its apparent activation energy is 85.04 kJ x mol(-1). Its apparent rate constant is 0.021 4 min(-1), and the half-life is 32.39 min at 80 degrees C. The kinetic principle is that the variation of MR concentration is directly proportional to the concentration of NO2-, ln(A0/A) = kc(NO2-). This new method for the determination of trace nitrite has never previously been reported in the published literature so far. It is highly sensitive and selective. Most of the common ions don't interfere with the determination of nitrite. This method has the advantages of convenient operation and the regents used are cheap and nontoxic. It was applied to the determination

  10. Polyoxometalate oxidation of non-phenolic lignin subunits in water : effect of substrate structure on reaction kinetics

    Science.gov (United States)

    Tomoya Yokoyama; Hou-min Chang; Richard S. Reiner; Raja H. Atalla; Ira A. Weinstock; John F. Kadla

    2004-01-01

    The effect of lignin-biopolymer structure on the mechanism of its oxidative depolymerization by polyoxometalates (POMs) was investigated by reacting an equilibrated POM ensemble with a series of ring-substituted benzyl alcohols. Under anaerobic conditions in mixed water/methanol, observed pseudo-first order reaction rates (150°C) of 8.96 x 10–3 and 4.89 x 10–3 sec–1...

  11. Preventing Corrosion by Controlling Cathodic Reaction Kinetics

    Science.gov (United States)

    2016-03-25

    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...elements on the kinetics of oxygen reduction reaction catalyzed on titanium oxide in order to develop new approaches for controlling galvanic corrosion

  12. Kinetic study on aminolysis of 4-pyridyl benzoate and o-4-pyridyl thionobenzoate in acetonitrile: Factors influencing reactivity and reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Um, Ik Hwan; Kim, Min Young [Dept. of Chemistry, and Nano Science, Ewha Womans University, Seoul (Korea, Republic of); Lee, Jae In [Dept. of Chemistry, and Plant Resources Research Institute, Duksung Women' s University, Seoul (Korea, Republic of)

    2016-10-15

    A kinetic study on nucleophilic substitution reactions of 4-pyridyl benzoate (2a) and O-4-pyridyl thionobenzoate (2b) with a series of cyclic secondary amines in acetonitrile at 25.0°C is reported. Plots of pseudo-first-order rate constant (k{sub obsd}) vs. [amine] are linear and pass through the origin for the reactions of 2a but curve upward for those of 2b. The upward curvature observed for the reactions of 2b is typical for reactions that proceed through a stepwise mechanism with a zwitterionic intermediate T{sup ±}, which decomposes to the products via uncatalyzed and catalyzed routes competitively. The reaction of 2a has been suggested to proceed through a stepwise mechanism with T±, in which expulsion of the leaving group occurs in the rate-determining step on the basis of a linear Broensted-type plot with β{sub nuc} = 0.77. The catalyzed reaction of 2b from T{sup ±} has been proposed to proceed through a concerted mechanism with a six-membered cyclic transition state rather than via a stepwise pathway with an anionic intermediate T{sup −}. Factors influencing reactivity and reaction mechanism are discussed in detail.

  13. Degradação fotocatalítica do fungicida tebuconazole em solução aquosa Tebuconazole photocatalytic degradation kinetics

    Directory of Open Access Journals (Sweden)

    Thiago de Hermann Prestes

    2010-01-01

    Full Text Available The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentration and pH 7.7.

  14. 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.

  15. Ladle Metallurgy Kinetics: Inclusion-Inclusion Reactions

    Science.gov (United States)

    Pistorius, P. Chris

    An example is presented to illustrate the joint effect of local reaction equilibria and mass transfer limitations, for reactions during ladle refining of steel. The example relies on some of the kinetic principles that David Robertson has employed to quantify many metallurgical processes. In calcium treatment of alumina inclusions in aluminum-killed steels, solid CaS forms as an intermediate reaction product. During subsequent reaction, CaS disappears and calcium aluminate forms; at the same time, aluminum and sulfur dissolve in the steel. Kinetic analysis shows that the rate of this reaction is not limited by mass transfer of dissolved aluminum and sulfur away from the reacting inclusions. The reaction rate is likely limited by transport of dissolved calcium. This example also illustrates the use of FactSage macros for kinetic modeling.

  16. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

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

  17. Kinetics of the reaction of iodine atoms with HO sub 2 radicals

    Energy Technology Data Exchange (ETDEWEB)

    Jenkin, M.E.; Cox, R.A. (Harwell Laboratory, Oxfordshire (England)); Mellouki, A.; Le Bras, G.; Poulet, G. (CNRS, Orleans (France))

    1990-04-05

    The rate coefficient (k{sub 7}) for the reaction of iodine atoms with HO{sub 2} radicals, I + HO{sub 2} {yields} HI + O{sub 2}, has been measured directly with use of the discharge-flow/EPR technique, and the molecular-modulation/UV-absorption spectroscopy technique. Discharge-flow measurements were made under pseudo-first-order conditions with iodine atoms in large excess over HO{sub 2}. Molecular-modulation measurements were made with iodine atoms in excess over HO{sub 2}, but the I + HO{sub 2} reaction was occurring in competition with the self-reaction of HO{sub 2}. The potential significance of this reaction as a sink for iodine in the troposphere and other aspects of tropospheric iodine chemistry are considered with a simple model of the atmospheric boundary layer.

  18. Evaluation of the kinetic oxidation of aqueous volatile organic compounds by permanganate.

    Science.gov (United States)

    Mahmoodlu, Mojtaba G; Hassanizadeh, S Majid; Hartog, Niels

    2014-07-01

    The use of permanganate solutions for in-situ chemical oxidation (ISCO) is a well-established groundwater remediation technology, particularly for targeting chlorinated ethenes. The kinetics of oxidation reactions is an important ISCO remediation design aspect that affects the efficiency and oxidant persistence. The overall rate of the ISCO reaction between oxidant and contaminant is typically described using a second-order kinetic model while the second-order rate constant is determined experimentally by means of a pseudo first order approach. However, earlier studies of chlorinated hydrocarbons have yielded a wide range of values for the second-order rate constants. Also, there is limited insight in the kinetics of permanganate reactions with fuel-derived groundwater contaminants such as toluene and ethanol. In this study, batch experiments were carried out to investigate and compare the oxidation kinetics of aqueous trichloroethylene (TCE), ethanol, and toluene in an aqueous potassium permanganate solution. The overall second-order rate constants were determined directly by fitting a second-order model to the data, instead of typically using the pseudo-first-order approach. The second-order reaction rate constants (M(-1) s(-1)) for TCE, toluene, and ethanol were 8.0×10(-1), 2.5×10(-4), and 6.5×10(-4), respectively. Results showed that the inappropriate use of the pseudo-first-order approach in several previous studies produced biased estimates of the second-order rate constants. In our study, this error was expressed as a function of the extent (P/N) in which the reactant concentrations deviated from the stoichiometric ratio of each oxidation reaction. The error associated with the inappropriate use of the pseudo-first-order approach is negatively correlated with the P/N ratio and reached up to 25% of the estimated second-order rate constant in some previous studies of TCE oxidation. Based on our results, a similar relation is valid for the other volatile

  19. Reaction networks and kinetics of biochemical systems.

    Science.gov (United States)

    Arceo, Carlene Perpetua P; Jose, Editha C; Lao, Angelyn R; Mendoza, Eduardo R

    2017-01-01

    This paper further develops the connection between Chemical Reaction Network Theory (CRNT) and Biochemical Systems Theory (BST) that we recently introduced [1]. We first use algebraic properties of kinetic sets to study the set of complex factorizable kinetics CFK(N) on a CRN, which shares many characteristics with its subset of mass action kinetics. In particular, we extend the Theorem of Feinberg-Horn [9] on the coincidence of the kinetic and stoichiometric subsets of a mass action system to CF kinetics, using the concept of span surjectivity. We also introduce the branching type of a network, which determines the availability of kinetics on it and allows us to characterize the networks for which all kinetics are complex factorizable: A "Kinetics Landscape" provides an overview of kinetics sets, their algebraic properties and containment relationships. We then apply our results and those (of other CRNT researchers) reviewed in [1] to fifteen BST models of complex biological systems and discover novel network and kinetic properties that so far have not been widely studied in CRNT. In our view, these findings show an important benefit of connecting CRNT and BST modeling efforts. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Reactions of sulfur-nitrosyl iron complexes of "g=2.03" family with hemoglobin (Hb): kinetics of Hb-NO formation in aqueous solutions.

    Science.gov (United States)

    Sanina, N A; Syrtsova, L A; Shkondina, N I; Rudneva, T N; Malkova, E S; Bazanov, T A; Kotel'nikov, A I; Aldoshin, S M

    2007-03-01

    NO-donating ability of nitrosyl [Fe-S] complexes, namely, mononuclear dinitrosyl complexes of anionic type [Fe(S2O3)2(NO)2]-(I) and neutral [Fe2(SL1)2(NO)2] with L1=1H-1,2,4-triazole-3-yl (II); tetranitrosyl binuclear neutral complexes [Fe2(SL2)2(NO)4] with L2=5-amino-1,2,4-triazole-3-yl (III); 1-methyl-1H-tetrazole-5-yl (IV); imidazole-2-yl (V) and 1-methyl-imidazole-2-yl (VI) has been studied. In addition, Roussin's "red salt" Na2[Fe2S2(NO)4] x 8H2O (VII) and Na2[Fe(CN)5NO] x H2O (VIII) have been investigated. The method for research has been based on the formation of Hb-NO adduct upon the interaction of hemoglobin with NO generated by complexes I-VIII in aqueous solutions. Kinetics of NO formation was studied by registration of absorption spectra of the reaction systems containing Hb and the complex under study. For determination of HbNO concentration, the experimental absorption spectra were processed during the reaction using standard program MATHCAD to determine the contribution of individual Hb and HbNO spectra in each spectrum. The reaction rate constants were obtained by analyzing kinetic dependence of Hb interaction with NO donors under study. All kinetic dependences for complexes I-VI were shown to be described well in the frame of formalism of pseudo first-order reactions. The effective first-order rate constants for the studied reactions have been determined. As follows from the values of rate constants, the rate of interaction of sulfur-nitrosyl iron complexes (I-VI) with Hb is limited by the stage of NO release in the solution.

  1. Chemistry and kinetics of I2 loss in urine distillate and humidity condensate

    Science.gov (United States)

    Atwater, James E.; Wheeler, Richard R., Jr.; Olivadoti, J. T.; Sauer, Richard L.

    1992-01-01

    Time-resolved molecular absorption spectrophotometry of iodinated ersatz humidity condensates and iodinated ersatz urine distillates across the UV and visible spectral regions are used to investigate the chemistry and kinetics of I2 loss in urine distillate and humidity condensate. Single contaminant systems at equivalent concentrations are also employed to study rates of iodine. Pseudo-first order rate constants are identified for ersatz contaminant model mixtures and for individual reactive constituents. The second order bimolecular reaction of elemental iodine with formic acid, producing carbon dioxide and iodine anion, is identified as the primary mechanism underlying the decay of residual I2 in ersatz humidity concentrate.

  2. Modeling the enzyme kinetic reaction.

    Science.gov (United States)

    Atangana, Abdon

    2015-09-01

    The Enzymatic control reactions model was presented within the scope of fractional calculus. In order to accommodate the usual initial conditions, the fractional derivative used is in Caputo sense. The methodologies of the three analytical methods were used to derive approximate solution of the fractional nonlinear system of differential equations. Two methods use integral operator and the other one uses just an integral. Numerical results obtained exhibit biological behavior of real world problem.

  3. Rapid biocatalytic polytransesterification: reaction kinetics in an exothermic reaction

    Science.gov (United States)

    Chaudhary; Beckman; Russell

    1998-08-20

    Biocatalytic polytransesterification at high concentrations of monomers proceeds rapidly and is accompanied by an increase in the temperature of the reaction mixture due to liberation of heat of reaction during the initial phase. We have used principles of reaction calorimetry to monitor the kinetics of polymerization during this initial phase, thus relating the temperature to the extent of polymerization. Rate of polymerization increases with the concentration of monomers. This is also reflected by the increase in the temperature of the reaction mixture. Using time-temperature-conversion contours, a differential method of kinetic analysis was used to calculate the energy of activation ( approximately 15.1 Kcal/mol). Copyright 1998 John Wiley & Sons, Inc.

  4. Kinetics of the O + ICN reaction.

    Science.gov (United States)

    Feng, Wenhui; Hershberger, John F

    2012-05-24

    The kinetics of the O + ICN reaction was studied using a relative rate method, with O + C(2)H(2) as the competing reaction. Carbon monoxide products formed in the competing reaction and subsequent secondary chemistry were detected as a function of reagent ICN pressure to obtain total rate constants for the O + ICN reaction. Analysis of the experimental data yields rate constants of k(1) = (3.7 ± 1.0 to 26.2 ± 4.0) × 10(-14) cm(3) molecule(-1) s(-1) over the total pressure range 1.5-9.5 Torr. Product channel NCO + I, the only bimolecular exothermic channel of the reaction, was investigated by detection of N(2)O in the presence of NO and found to be insignificant. An ab initio calculation of the potential energy surface (PES) of the reaction at the CCSD(T)/CEP-31G//DFT-B3LYP/CEP-31G level of theory was also performed. The pathways leading to bimolecular product channels are kinetically unfavorable. Formation and subsequent stabilization of an ICNO adduct species appears to dominate the reaction, in agreement with the experimentally observed pressure dependent rate constants.

  5. Changes in the Kinetics of Uranium(VI) Sorption Reactions to Mineral Surfaces in the Presence of Fulvic Acid

    Science.gov (United States)

    Honeyman, B. D.; Tinnacher, R. M.

    2010-12-01

    In this study, we investigate changes in the kinetics of uranium(VI) sorption reactions to silica sand due to the presence of fulvic acid, a recalcitrant natural organic matter fraction. On the field scale, local contact times between metal contaminants and bulk mineral phases may often be too short to attain full sorption equilibria. Hence, kinetic limitations for surface reactions need to be included in predictive transport models. Natural organic matter is ubiquitous in the environment and can substantially influence metal sorption and transport behavior in saturated porous media. However, at this point little is known about potential effects of organic matter on metal sorption kinetics. Therefore, we investigated the kinetics of uranium(VI) (U(VI)) sorption onto a pretreated silica sand in the absence and presence of fulvic acid in lab-scale experiments. Furthermore, experimental data were simulated in pseudo-first order kinetic models in order to determine the characteristic times for U(VI) sorption reactions under various chemical conditions. Last, speciation modeling allowed for a qualitative assessment of dominant U(VI) solution species as a function of organic ligand concentrations and pH. Results indicate that U(VI) surface reactions are slowed down in the presence of low concentrations of fulvic acid (0.4 and 4.3 mg/l TOC), at conditions where U(VI)-fulvic acid solution complexes can be neglected. This kinetic behavior can be attributed to the competition of U(VI) and fulvic acid for a limited number of fast-sorbing surface sites. In contrast, metal sorption reactions seem to be faster relative to the binary metal-mineral system at a high FA concentration (26 mg/l TOC) and pH conditions where a substantial fraction of U(VI)-FA solution complexes is expected. In this case, U(VI) and fulvic acid sorption kinetics appear to be very similar, which suggests the formation of ternary U(VI)-FA-surface complexes. Hence, kinetic sorption data indicate a change in

  6. Kinetics and Mechanistic Studies on the Reaction between Cytochrome c and Tea Catechins

    Directory of Open Access Journals (Sweden)

    Lihua Wang

    2014-08-01

    Full Text Available Green tea is characterized by the presence of an abundance of polyphenolic compounds, also known as catechins, including epicatechin (EC, epigallocatechin (EGC, epicatechin gallate (EGC and epigallocatechin gallate (EGCG. In addition to being a popular beverage, tea consumption has been suggested as a mean of chemoprevention. However, its mode of action is unclear. It was discovered that tea catechins can react with cytochrome c. When oxidized cytochrome c was mixed with catechins commonly found in green tea under non-steady-state conditions, a reduction of cytochrome c was observed. The reaction rate of the catechins was dependent on the pH and the nature of the catechin. The pseudo-first order rate constant obtained increased in the order of EC < ECG < EGC < EGCG, which is consistent with previously reported superoxide reduction activities and Cu2+ reduction activities of tea catechins.

  7. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); Stolte, Stefan [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); UFT-Centre of Environmental Research and Sustainable Technology, University of Bremen, Leobener Straße UFT, D-28359 Bremen (Germany); Siedlecka, Ewa Maria, E-mail: ewa.siedlecka@ug.edu.pl [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland)

    2014-09-15

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.

  8. 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.

  9. Experimental studies of the kinetics of small polyatomic free radicals in combustion reactions; Moniatomisten radikaalien kinetiikka palamisreaktioissa, kokeellinen tutkimus

    Energy Technology Data Exchange (ETDEWEB)

    Seetula, J. [Helsinki Univ. (Finland). Lab. of Physical Chemistry

    1996-12-01

    The kinetics of the reactions of CH{sub 2}Cl, CHClBr, CH{sub 3}CCl{sub 2} and CCl{sub 3}, with Cl{sub 2} has been investigated in a tubular reactor coupled to a photoionization mass spectrometer. The radicals of interest, R, were generated homogeneously in the reactor by pulse 248 nm exciplex laser photolysis. The decay of R was monitored as a function of Cl{sub 2} concentration under pseudo-first-order condition to determine the rate constant as a function of temperature pressure. The reactions were studied separately over a temperature range up to a temperature of 873 K. The rate constants of CH{sub 2}Cl, CHClBr and CH{sub 3}CCl{sub 2} radicals determined were fitted to three-parameter Arrhenius-type expression (with units of cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 2}Cl) = 1.05x10{sup -16} x (T){sup 1.4} x exp(-357 J mol{sup -1} / RT), k(CHClBr) = 5.83x10{sup -20} x (T){sup 2.3} x exp(-300 J mol{sup -1}/ RT) and k(CH{sub 3}CCl{sub 2}) 1.10x10{sup -}2{sup 6} x (T){sup 4.3} x exp(15000 J mol{sup -1}/ RT). The rate constants CCl{sub 3} radical were fitted to a two-parameter Arrhenius expression (units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CCl{sub 3}) = (8.1 +- 6.7)10{sup -l3} exp[-(25.0 +- 8.7) kJ mol{sup -1}/ RT]. An Arrhenius expression for the reaction of Cl+CCl{sub 4} -> <- CCl{sub 3}+Cl{sub 2} is also obtained from the kinetics of the reaction of CCl{sub 3} radical with Cl{sub 2} combined with the known heat of formation and entropy values of CCl{sub 3} free radical to be as follows (in units cm{sup 3} molecule{sup -1-}5 s{sup -1}): k(Cl+CCl{sub 4}) = (3.9 + 3.2)10{sup -10} exp[-(71 + 9) kJ mol{sup -1}/ RT]. The error limits stated are l{sigma}+Student`s t and base on statistical uncertainties only. (author)

  10. Kinetics of rouleau formation. II. Reversible reactions

    OpenAIRE

    Samsel, R.W.; Perelson, A S

    1984-01-01

    Red blood cells aggregate face-to-face to form long, cylindrical, straight chains and sometimes branched structures called rouleaux. Here we extend a kinetic model developed by R. W. Samsel and A. S. Perelson (1982, Biophys. J. 37:493-514) to include both the formation and dissociation of rouleaux. We examine thermodynamic constraints on the rate constants of the model imposed by the principle of detailed balance. Incorporation of reverse reactions allows us to compute mean sizes of rouleaux ...

  11. 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.

  12. 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

  13. Spectroscopy and reaction kinetics of HCO

    Energy Technology Data Exchange (ETDEWEB)

    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 ..nu../sub 1/ band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ..nu../sub 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/sub 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/sup 3/ molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF/sub 6/ buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO/sub 2/. The product channel, H + CO/sub 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.

  14. Kinetics of rouleau formation. II. Reversible reactions.

    Science.gov (United States)

    Samsel, R W; Perelson, A S

    1984-01-01

    Red blood cells aggregate face-to-face to form long, cylindrical, straight chains and sometimes branched structures called rouleaux. Here we extend a kinetic model developed by R. W. Samsel and A. S. Perelson (1982, Biophys. J. 37:493-514) to include both the formation and dissociation of rouleaux. We examine thermodynamic constraints on the rate constants of the model imposed by the principle of detailed balance. Incorporation of reverse reactions allows us to compute mean sizes of rouleaux and straight chain segments within rouleaux, as functions of time and at equilibrium. Using the Flory - Stockmayer method from polymer chemistry, we obtain a closed-form solution for the size distribution of straight chain segments within rouleaux at any point in the evolution of the reaction. The predictions of our theory compare favorably with data collected by D. Kernick , A.W.L. Jay , S. Rowlands , and L. Skibo (1973, Can. J. Physiol. Pharmacol. 51:690-699) on the kinetics of rouleau formation. When rouleaux grow large, they may contain rings or loops and take on the appearance of a network. We demonstrate the importance of including the kinetics of ring closure in the development of realistic models of rouleaux formation. Images FIGURE 1 FIGURE 13 PMID:6426540

  15. Adsorption kinetics for the removal of chromium (VI) from aqueous ...

    African Journals Online (AJOL)

    A comparison of kinetic models applied to the adsorption of Cr(VI) ions on the adsorbents was evaluated for the pseudo first-order, the pseudo second-order, Elovich and intraparticle diffusion kinetic models, respectively. Results show that the pseudo second-order kinetic model was found to correlate the experimental data ...

  16. Reaction rates for mesoscopic reaction-diffusion kinetics.

    Science.gov (United States)

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-01

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.

  17. 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.

  18. The Reaction of Allyl Isothiocyanate with Hydroxyl/Water and β-Cyclodextrin Using Ultraviolet Spectrometry

    Directory of Open Access Journals (Sweden)

    Zi-Tao Jiang

    2006-01-01

    Full Text Available The reaction of allyl isothiocyanate (AITC with hydroxyl/water and β-cyclodextrin (β-CD in different acidic-alkaline media has been investigated by ultraviolet spectrometry. The kinetic parameters of the reaction were measured. It was found that after AITC translating into thiourea, the absorption peak shifted from 240 to 226 nm and the molar absorptivity increased about 16 times. The reaction can be seen as a pseudo first order reaction because the concentration of hydroxyl was constant. β-CD can inhibit the reaction of AITC with hydroxyl/water, i.e. the hydrolysis of AITC. The formation constant (Ka and thermodynamic parameters of the complex reaction were calculated. Ka decreased with the increase of temperature. The experimental results indicated that the inclusive process was an exothermic and enthalpy-driven process accompanied with a negative entropic contribution.

  19. Kinetic study of microwave-assisted alkaline hydrolysis of Jatropha curcas oil

    Science.gov (United States)

    Yusuf, Nur'aini Raman; Kamil, Ruzaimah Nik Mohamad; Yusup, Suzana

    2016-11-01

    The kinetics of hydrolysis of Jatropha curcas oil under microwave irradation in the presence of alkaline solution was studied. The temperature of 50°C, 65°C and 80°C were studied in the range of optimum condition of 1.75 M catalyst, solvent/oil ratio of (1: 68) and 15 minutes reaction time. The rate constants of oil hydrolysis are corresponding to triglyceride disappearance concentration. The rates of reaction for fatty acids production was determined by pseudo first order. The activation energy (Ea) achieved at 30.61 kJ/mol is lower using conventional method. This conclude that the rate of reaction via microwave heating is less temperature sensitive therefore reaction can be obtained at lower temperature.

  20. 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…

  1. SABIO-RK: Curated Kinetic Data of Biochemical Reactions

    OpenAIRE

    Ulrike Wittig

    2009-01-01

    SABIO-RK ("http://sabio.villa-bosch.de/SABIORK/":http://sabio.villa-bosch.de/SABIORK/) is a curated, web-accessible database for modellers and wet-lab scientists to get comprehensive information about biochemical reactions and their kinetic properties. It integrates data from different origin in order to facilitate the access to reaction kinetics data and corresponding information. Since most of the kinetic data is exclusively found in the literature SABIO-RK offers data manually ex...

  2. Hydrodechlorination of dichlorobenzenes and their derivatives over Ni-Mo/C catalyst: kinetic analysis and effect of molecular structure of reactant.

    Science.gov (United States)

    Gryglewicz, Stanisław; Piechocki, Wojciech

    2011-04-01

    The kinetics of the catalytic hydrodechlorination (HDC) process of selected dichlorobenzenes (DCBs), dichlorotoluenes (DCTs) and dichlorodiphenyls (DCDs) was studied in the presence of a sulphided carbon-supported Ni-Mo catalyst. The HDC runs were performed in a magnetic stirred batch reactor in the range of 210-230°C under the hydrogen pressure of 3MPa. The kinetic constants were evaluated and the reaction network was proposed assuming the pseudo-first order kinetics of dechlorination process. The HDC of aromatic dichloroderivatives proceeded via a network of sequential-parallel reactions. At 210°C DCBs, DCTs and DCDs followed mainly the pathway of direct transformation to respective aromatic hydrocarbon. At 230°C, the contribution of sequential dechlorination to monochloroderivative became more predominant. Copyright © 2010 Elsevier Ltd. All rights reserved.

  3. Removal of COD from olive mill wastewater by Fenton's reagent: Kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, Marco S. [Centro de Quimica, Universidade de Tras-os-Montes e Alto Douro (UTAD), Apartado 1013, 5001-801 Vila Real (Portugal); Peres, Jose A., E-mail: jperes@utad.pt [Centro de Quimica, Universidade de Tras-os-Montes e Alto Douro (UTAD), Apartado 1013, 5001-801 Vila Real (Portugal)

    2009-09-15

    This work describes the application of Fenton's reagent (H{sub 2}O{sub 2}/Fe{sup 2+}) to the removal of chemical oxygen demand (COD) from olive mill wastewater (OMW) in a laboratory-scale batch reactor. The effect of different operational conditions, namely, hydrogen peroxide and ferrous ion concentrations, temperature and initial pH were evaluated. ORP, pH and dissolved oxygen were on-line monitored. Working with an initial pH equal to 3.5, a temperature of 30 deg. C, a molar ratio H{sub 2}O{sub 2}/Fe{sup 2+} = 15 and a weight ratio R = H{sub 2}O{sub 2}/COD = 1.75 makes possible a COD conversion of 70%. A kinetic study was carried out using a modified pseudo-first-order model. The experiments performed at different temperatures allowed the calculation of the Arrhenius equation parameters and the global activation energy for the pseudo-first-order reaction (28.2 kJ/mol).

  4. Kinetics of Oxidation of Aliphatic Alcohols by Potassium Dichromate ...

    African Journals Online (AJOL)

    The pseudo-first-order rate constants were found to be independent of concentration of the oxidant. The presence of TX-100 enhanced the rate of the reaction for all alcohols. Negative salt effects were observed with addition of KCl to the reaction mixture. A suitable mechanism for the reaction was suggested which agrees ...

  5. KINETICS AND MECHANISM OF REACTION OF ACIDIC ...

    African Journals Online (AJOL)

    For both Nile blue and Meldola\\'s blue reactions the rates have first-order dependence on each substrate, chlorite and acid. Both reactions showed negative salt effect indicating the reaction is between the oppositely charged species, likely the substrate cation and chlorite anion. The acidic chlorite reaction with MB+ was ...

  6. Kinetics of tetrabromobisphenol A (TBBPA) reactions with H{sub 2}SO{sub 4}, HNO{sub 3} and HCl: Implication for hydrometallurgy of electronic wastes

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Yin [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640 (China); Li, Dan; Mao, Zhe [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Huang, Weilin [Department of Environmental Sciences, Rutgers, The State University of New Jersey, 14 College Farm Road, New Brunswick 08901, NJ (United States); Peng, Ping’an, E-mail: pinganp@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640 (China); Chen, Pei [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Mei, Jun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640 (China); Department of Chemistry, Guangdong Medical College, Dongguan 523808 (China)

    2014-04-01

    Highlights: • Effect of hydrometallurgical processes on the fate of TBBPA was evaluated. • TBBPA could react rapidly with HNO{sub 3} and concentrated H{sub 2}SO{sub 4}. • TBBPA did not show measurable reactivity in HCl and the dilute H{sub 2}SO{sub 4} (≤24 wt%). • The reaction kinetics of TBBPA with HNO{sub 3} differed from that with concentrated H{sub 2}SO{sub 4}. • The transformation pathways of TBBPA in different acids were different. - Abstract: Hydrometallurgy is an acid leaching based process widely used for recovering precious metals from electronic wastes (e-wastes). The effects of acid leaching on the fate of brominated flame retardants (BFRs) in typical hydrometallurgical processes remain largely unknown. This study was aimed at evaluating the fate of tetrabromobisphenol A (TBBPA), a commonly used BFR, in three acid leaching reagents (i.e. H{sub 2}SO{sub 4}, HNO{sub 3}, and HCl) commonly used in hydrometallurgy. It was found that the reactions of TBBPA with concentrated H{sub 2}SO{sub 4} followed a pseudo-zero-order rate and the reaction rates declined rapidly as the concentrations of H{sub 2}SO{sub 4} decreased. In contrast, TBBPA could be easily transformed in less concentrated HNO{sub 3} solutions (<21.7 wt%) and the reactions followed a pseudo-first-order rate. The reaction products identified by GC–MS indicated different transformation pathways of TBBPA in H{sub 2}SO{sub 4} and HNO{sub 3}. HCl or HCl/H{sub 2}SO{sub 4} mixtures (3:1, v/v) did not appear to react with TBBPA, while aqua regia (3:1 HCl/HNO{sub 3}, v/v) reacted violently with TBBPA and led to almost complete disappearance of TBBPA within a minute. It suggested that HNO{sub 3} significantly affected the fate of TBBPA and the use of HNO{sub 3} as leaching reagents in hydrometallurgy of e-wastes should be carefully evaluated. Collectively, our findings of distinct fate of TBBPA in different acid leaching reagents provided fundamental information for design of hydrometallurgical

  7. Chemistry of N,N'-dimethylformamidine. II. Hydrolysis: kinetically controlled formation of cis-N-methylformamide

    Energy Technology Data Exchange (ETDEWEB)

    Halliday, J.D.; Symons, E.A.

    1978-06-01

    The hydrolysis of N,N'-dimethylformamidine (DMFA) has been investigated in acid and alkaline aqueous media by /sup 1/H nmr; only a narrow basic pH range could be extensively studied kinetically. The pseudo-first-order k/sub obs/, rose steadily from pH 11.5 to 13.0 (reaction approximately first order in OH/sup -/), then became independent of pH above 13.5 (9.3 x 10/sup -4/ s/sup -1/ at 10/sup 0/C). In contrast to many amidines, DMFA is quite stable in acid solution (estimated value of the pseudo-first-order hydrolysis rate constant is 1.4 x 10/sup -11/ s/sup -1/ at 10/sup 0/C, pH 0.05, from measurements at 100 and 140/sup 0/C). This stability is ascribed to the difficulty of eliminating the fairly stron base methylamine from the tetrahedral intermediate in acid solution. N-Methylformamide (NMF), one of the products, is formed initially as the cis isomer. A somewhat slower conversion then occurs to the thermodynamically more stable trans isomer. This unusual result is explained in terms of Deslongchamps and co-workers' theory of stereo-electronic control for the orbital-assisted breakdown of tetrahedral intermediates. 4 figures, 1 table.

  8. The thermodynamic natural path in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    Moishe garfinkle

    2000-01-01

    Full Text Available The Natural Path approach to chemical reaction kinetics was developed to bridge the considerable gap between the Mass Action mechanistic approach and the non-mechanistic irreversible thermodynamic approach. The Natural Path approach can correlate empirical kinetic data with a high degree precision, as least equal to that achievable by the Mass-Action rate equations, but without recourse mechanistic considerations. The reaction velocities arising from the particular rate equation chosen by kineticists to best represent the kinetic behavior of a chemical reaction are the natural outcome of the Natural Path approach. Moreover, by virtue of its thermodynamic roots, equilibrium thermodynamic functions can be extracted from reaction kinetic data with considerable accuracy. These results support the intrinsic validity of the Natural Path approach.

  9. Reaction of a hydrated electron with gentamycin and collagen—A pulse radiolysis study

    Science.gov (United States)

    Pietrucha, K.; Góra, L.; Doillon, C. J.

    1996-01-01

    The reactions of a hydrated electron (e aq-) with aminoglycoside anbiotic gentamycin and collagen in aqueous medium at different pH have been investigated employing a pulse radiolysis technique. The pseudo-first order equation of reaction kinetics was used to give an accurate description of the decay of e aq- in gentamycin solutions. The rate constant of the e aq- decay in collagen solution was high and reached 3.2 × 10 10 M -1 s -1. The rate constants for the reaction of the e aq- with gentamycin were found to be influenced by pH, decreasing with the deprotonation of the -NH 3 groups, while for pH > pK a which for gentamycin is equal to 7.8, the rate constant was unchanged. These observations suggest that when the amino groups are protonated, reductive deamination occurs, but for unprotonated non-reactive amino groups, a radical anion is formed on the glycoside moiety.

  10. Kinetics of Model Reactions for Interfacial Polymerization

    Directory of Open Access Journals (Sweden)

    Henry Hall

    2012-02-01

    Full Text Available To model the rates of interfacial polycondensations, the rates of reaction of benzoyl chloride and methyl chloroformate with various aliphatic monoamines in acetonitrile were determined at 25 °C. Buffering with picric acid slowed these extremely fast reactions so the rate constants could be determined from the rate of disappearance of picrate ion. The rates of the amine reactions correlated linearly with their Swain-Scott nucleophilicities.

  11. Kinetics of Model Reactions for Interfacial Polymerization

    OpenAIRE

    Henry Hall; Robert Bates (Harvard University); Jeffrey Robertson; Anne Padias; Trevor Centeno-Hall

    2012-01-01

    To model the rates of interfacial polycondensations, the rates of reaction of benzoyl chloride and methyl chloroformate with various aliphatic monoamines in acetonitrile were determined at 25 °C. Buffering with picric acid slowed these extremely fast reactions so the rate constants could be determined from the rate of disappearance of picrate ion. The rates of the amine reactions correlated linearly with their Swain-Scott nucleophilicities.

  12. A study of the Sabatier-methanation reaction kinetics

    Science.gov (United States)

    Verostko, C. E.; Forsythe, R. K.

    1974-01-01

    The kinetics of the Sabatier methanation reaction, the reduction of carbon dioxide with hydrogen to methane and water, was investigated for 58 percent nickel on kieselguhr catalyst and 20 percent ruthenium on alumina catalyst. Differential rate data from an experimental program were correlated with a power function rate equation both for forward and reverse reactions. The kinetic parameters of activation energy, frequency rate constant and reaction order were determined for the rate equation. The values of these parameters were obtained from an Arrhenius plot of the experimental differential rate data. Also the carbon monoxide side reaction effect was measured and included in the correlation of parameters. The reaction was found to fit the rate equation experimentally within the temperature range 421 K, where the reaction effectively begins, the 800 K where the reaction rate drops and departs from the rate equation form.

  13. Degradation of 2,4-dihydroxibenzoic acid by vacuum UV process in aqueous solution: Kinetic, identification of intermediates and reaction pathway

    Energy Technology Data Exchange (ETDEWEB)

    Azrague, Kamal [Laboratoire IMRCP, CNRS UMR 5623, University of Toulouse, 118 route de Narbonne, 31062 Toulouse (France); Department for Water and Environment, SINTEF, Klaebuveien 153, Trondheim 7465 (Norway); Pradines, Vincent; Bonnefille, Eric [Laboratoire IMRCP, CNRS UMR 5623, University of Toulouse, 118 route de Narbonne, 31062 Toulouse (France); Laboratoire LCC, CNRS, 205 route de Narbonne, F31077 Toulouse Cedex 4 (France); Claparols, Catherine [Laboratoire LCC, CNRS, 205 route de Narbonne, F31077 Toulouse Cedex 4 (France); Universite de Toulouse, UPS, Service Commun de Spectrometrie de Masse, 118 route de Narbonne, F31062 Toulouse Cedex 9 (France); Maurette, Marie-Therese [Laboratoire IMRCP, CNRS UMR 5623, University of Toulouse, 118 route de Narbonne, 31062 Toulouse (France); Benoit-Marquie, Florence, E-mail: florence@chimie.ups-tlse.fr [Laboratoire IMRCP, CNRS UMR 5623, University of Toulouse, 118 route de Narbonne, 31062 Toulouse (France)

    2012-10-30

    Highlights: Black-Right-Pointing-Pointer Degradation of 2,4-dihydroxybenzoic acid (DHBA) by vacuum UV photolysis of water. Black-Right-Pointing-Pointer V-UV Xe-excimer lamps produced essentially hydroxyl radicals (HO Degree-Sign ). Black-Right-Pointing-Pointer Identification of all intermediates formed allowed us to propose a reaction pathway. Black-Right-Pointing-Pointer This reaction pathway showed that DHBA reacts differently with HO Degree-Sign and h+. Black-Right-Pointing-Pointer DHBA would be used as a probe to determine which of these entities were involved. - Abstract: 2,4-Dihydroxybenzoic acid (2,4-DHBA) is found frequently as a pollutant in natural waters and represents a threat to water quality because it is a precursor to the formation of quinones which are highly toxic. The degradation of 2,4-DHBA using the vacuum UV photolysis of water has been investigated. Irradiation was carried out in an annular photoreactor equipped with a Xe-excimer lamp situated in the centre and emitting at 172 nm. The degradation kinetic followed a pseudo first order and the reaction has been found to be very heterogeneous, especially at low concentration. Impacts of oxygen or temperature have also been investigated but no effect has been shown. LC-MS and HPLC-UV combined with other analytical techniques allowed the identification of the formation of trihydroxybenzoiec acids and trihydroxybenzenes which underwent a ring opening, conducting to the formation of aliphatic products named {alpha}, {beta}, {delta} and {gamma}. These products were in turn degraded successively into maleiec acid, malic and succinic acid, malonic acid, glyoxalic acid and oxalic acid before reaching the complete mineralization in about 180 min. The proposed reaction pathway has shown to be very different from the one observed for the TiO{sub 2} photocatalysis which involves only holes (h{sup +}) without any formation of aromatic intermediates. The different behaviours of 2,4-DHBA towards the h

  14. Use of Competition Kinetics with Fast Reactions of Grignard Reagents

    DEFF Research Database (Denmark)

    Holm, Torkil

    2000-01-01

    Competition kinetics are useful for estimation of the reactivities of Grignard reagents if the reaction rates do not differ widely and if exact rates are not needed. If the rate of mixing is slower than the rate of reaction the ratios between the rates of fast and slow reagents are found to be too...... small.This is concluded from experiments in which results obtained by competition kinetics are compared with results obtained directly by flow stream procedures. A clearer picture of the reactivity ratios is obtained when the highly reactive reagent is highly diluted with its competitor. A fast reagent...... found for the four substrates do not differ significantly and it seems possible that there is a ceiling over the rate of reaction of this reagent, for example caused by diffusion control. This may explain that competition kinetics using allylmagnesium bromide have failed to show kinetic isotope effects...

  15. Unravelling the Maillard reaction network by multiresponse kinetic modelling

    NARCIS (Netherlands)

    Martins, S.I.F.S.

    2003-01-01

    The Maillard reaction is an important reaction in food industry. It is responsible for the formation of colour and aroma, as well as toxic compounds as the recent discovered acrylamide. The knowledge of kinetic parameters, such as rate constants and activation energy, is necessary to predict its

  16. 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.

  17. Reaction Kinetics Model of Polymerization in the Absence of ...

    African Journals Online (AJOL)

    This paper is on reaction kinetics models for approximating diffuse propagation reaction fronts in one-dimensional gasless combustion type models. This study is carried out in the context of free-radical frontal polymerization (FP) via a propagating, self sustaining reacting front in the absence of material diffusion. The model ...

  18. Kinetics of enzymatic reactions in lipid membranes containing domains.

    Science.gov (United States)

    Zhdanov, Vladimir P; Höök, Fredrik

    2015-03-06

    An appreciable part of enzymes operating in vivo is associated with lipid membranes. The function of such enzymes can be influenced by the presence of domains containing proteins and/or composed of different lipids. The corresponding experimental model-system studies can be performed under well controlled conditions, e.g., on a planar supported lipid bilayer or surface-immobilized vesicles. To clarify what may happen in such systems, we propose general kinetic equations describing the enzyme-catalyzed substrate conversion occurring via the Michaelis-Menten (MM) mechanism on a membrane with domains which do not directly participate in reaction. For two generic situations when a relatively slow reaction takes place primarily in or outside domains, we take substrate saturation and lateral substrate-substrate interactions at domains into account and scrutinize the dependence of the reaction rate on the average substrate coverage. With increasing coverage, depending on the details, the reaction rate reaches saturation via an inflection point or monotonously as in the conventional MM case. In addition, we show analytically the types of reaction kinetics occurring primarily at domain boundaries. In the physically interesting situation when the domain growth is fast on the reaction time scale, the latter kinetics are far from conventional. The opposite situation when the reaction is fast and controlled by diffusion has been studied by using the Monte Carlo technique. The corresponding results indicate that the dependence of the reaction kinetics on the domain size may be weak.

  19. Reaction rates for reaction-diffusion kinetics on unstructured meshes

    Science.gov (United States)

    Hellander, Stefan; Petzold, Linda

    2017-02-01

    The reaction-diffusion master equation is a stochastic model often utilized in the study of biochemical reaction networks in living cells. It is applied when the spatial distribution of molecules is important to the dynamics of the system. A viable approach to resolve the complex geometry of cells accurately is to discretize space with an unstructured mesh. Diffusion is modeled as discrete jumps between nodes on the mesh, and the diffusion jump rates can be obtained through a discretization of the diffusion equation on the mesh. Reactions can occur when molecules occupy the same voxel. In this paper, we develop a method for computing accurate reaction rates between molecules occupying the same voxel in an unstructured mesh. For large voxels, these rates are known to be well approximated by the reaction rates derived by Collins and Kimball, but as the mesh is refined, no analytical expression for the rates exists. We reduce the problem of computing accurate reaction rates to a pure preprocessing step, depending only on the mesh and not on the model parameters, and we devise an efficient numerical scheme to estimate them to high accuracy. We show in several numerical examples that as we refine the mesh, the results obtained with the reaction-diffusion master equation approach those of a more fine-grained Smoluchowski particle-tracking model.

  20. Reaction rates for reaction-diffusion kinetics on unstructured meshes.

    Science.gov (United States)

    Hellander, Stefan; Petzold, Linda

    2017-02-14

    The reaction-diffusion master equation is a stochastic model often utilized in the study of biochemical reaction networks in living cells. It is applied when the spatial distribution of molecules is important to the dynamics of the system. A viable approach to resolve the complex geometry of cells accurately is to discretize space with an unstructured mesh. Diffusion is modeled as discrete jumps between nodes on the mesh, and the diffusion jump rates can be obtained through a discretization of the diffusion equation on the mesh. Reactions can occur when molecules occupy the same voxel. In this paper, we develop a method for computing accurate reaction rates between molecules occupying the same voxel in an unstructured mesh. For large voxels, these rates are known to be well approximated by the reaction rates derived by Collins and Kimball, but as the mesh is refined, no analytical expression for the rates exists. We reduce the problem of computing accurate reaction rates to a pure preprocessing step, depending only on the mesh and not on the model parameters, and we devise an efficient numerical scheme to estimate them to high accuracy. We show in several numerical examples that as we refine the mesh, the results obtained with the reaction-diffusion master equation approach those of a more fine-grained Smoluchowski particle-tracking model.

  1. Reaction wheels for kinetic energy storage

    Science.gov (United States)

    Studer, P. A.

    1984-01-01

    In contrast to all existing reaction wheel implementations, an order of magnitude increase in speed can be obtained efficiently if power to the actuators can be recovered. This allows a combined attitude control-energy storage system to be developed with structure mounted reaction wheels. The feasibility of combining reaction wheels with energy storage wwheels is demonstrated. The power required for control torques is a function of wheel speed but this energy is not dissipated; it is stored in the wheel. The I(2)R loss resulting from a given torque is shown to be constant, independent of the design speed of the motor. What remains, in order to efficiently use high speed wheels (essential for energy storage) for control purposes, is to reduce rotational losses to acceptable levels. Progress was made in permanent magnet motor design for high speed operation. Variable field motors offer more control flexibility and efficiency over a broader speed range.

  2. The Oxidation of 2-(2-Methoxyethoxyethanol and 2-(2-Ethoxyethoxyethanol by Ditelluratocuprate(III: A Kinetic and Mechanistic Study

    Directory of Open Access Journals (Sweden)

    Jin-huan Shan

    2013-01-01

    Full Text Available The oxidation of 2-(2-methoxyethoxyethanol (MEE and 2-(2-ethoxyethoxyethanol (EEE by ditelluratocuprate(III (DTC had been studied spectrophotometrically in alkaline medium. The reaction between and showed first-order dependence in DTC and fractional order in MEE and EEE. The rate constant of the pseudo-first-order reaction decreased with an increase of [TeO4  2−], whereas adding [OH−] enhanced the constant. In addition, the reaction had a negative salt effect. The rate of EEE was higher than that of MEE. A suitable assumption involving preequilibriums before the rate-controlling step and a free radical mechanism was proposed, based on the kinetic data. Activation parameters and the rate constant of the rate-determining step were calculated.

  3. Adsorption and kinetic studies on the removal of chromium and copper onto Chitosan-g-maliec anhydride-g-ethylene dimethacrylate.

    Science.gov (United States)

    Gopal Reddi, M R; Gomathi, T; Saranya, M; Sudha, P N

    2017-11-01

    The present work was designed to remove toxic metals chromium and copper using the double grafted copolymer Chitosan-g-Maleic anhydride-g-ethylene dimethacrylate. The graft copolymer was synthesized through chain polymerization reaction using ceric ammonium nitrate as the initiator. Prepared Chitosan-g-Maleic anhydride-g-ethylene dimethacrylate was used in order to remove the heavy metals chromium and copper from aqueous solutions of 200ppm/L concentration proceeding batch adsorption process by varying the parameters such as adsorbent dose, contact time, pH and initial concentration of the metal solution. The experimental data were equipped with isotherm models such as Langmuir and Freundlich and pseudo-first order and pseudo-second order kinetics. The calculated results revealed that the adsorption favours Freundlich isotherm and follows pseudo-second order kinetics. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Kinetics of ozone-initiated oxidation of textile dye, Amaranth in aqueous systems.

    Science.gov (United States)

    Dachipally, Purnachandar; Jonnalagadda, Sreekanth B

    2011-01-01

    The ozone facilitated oxidation mechanism of water soluble azo anionic dye, amaranth (Am) was investigated monitoring the depletion kinetics of the dye spectrometrically at 521 nm. The oxidation kinetics of the dye by ozone was studied under semi-batch conditions, by bubbling ozone enriched oxygen through the aqueous reaction mixture of dye, as function of flow rate, ionic strength, [O(3)] and pH variations. With excess concentration of ozone and other reagents and low [amaranth], reaction followed pseudo-first-order kinetics with respect to the dye. Added neutral salts had marginal effect on the reaction rate and the variation of pH from 7 to 2 and 7 to 12 exerted only small increases in the reaction rate suggesting molecular ozone possibly is the principle reactive species in oxidation of dye. The reaction order with respect ozone was near unity and it varied slightly with pH and flow rate variations. The overall second-order rate constant for the reaction was (105 ± 4) M(-1) min(-1). The main oxidation products immediately after amaranth decolorization were identified. The reaction mechanism and overall rate law were proposed. After spiking the seawater, river water and wastewaters with Amaranth dye, the reaction rates and trends in BOD and COD under control and natural conditions were investigated. The rate of depletion of the dye in natural waters was relatively lower, but the ozonation process significantly decreased both the BOD and COD levels.

  5. KINETICS OF SUBSTITUTION OF CIS-BIS(MALONATO ...

    African Journals Online (AJOL)

    Preferred Customer

    Effect of concentration of amino acids. The pseudo-first order rate constants were evaluated from the straight line plot of log (A∞-At) vs. time by using KINTOB software procedure. The rate of the reaction increases with increase in the concentration of amino acids (Table 1). In the amino acid variation studies the pH was kept.

  6. SABIO-RK--database for biochemical reaction kinetics.

    Science.gov (United States)

    Wittig, Ulrike; Kania, Renate; Golebiewski, Martin; Rey, Maja; Shi, Lei; Jong, Lenneke; Algaa, Enkhjargal; Weidemann, Andreas; Sauer-Danzwith, Heidrun; Mir, Saqib; Krebs, Olga; Bittkowski, Meik; Wetsch, Elina; Rojas, Isabel; Müller, Wolfgang

    2012-01-01

    SABIO-RK (http://sabio.h-its.org/) is a web-accessible database storing comprehensive information about biochemical reactions and their kinetic properties. SABIO-RK offers standardized data manually extracted from the literature and data directly submitted from lab experiments. The database content includes kinetic parameters in relation to biochemical reactions and their biological sources with no restriction on any particular set of organisms. Additionally, kinetic rate laws and corresponding equations as well as experimental conditions are represented. All the data are manually curated and annotated by biological experts, supported by automated consistency checks. SABIO-RK can be accessed via web-based user interfaces or automatically via web services that allow direct data access by other tools. Both interfaces support the export of the data together with its annotations in SBML (Systems Biology Markup Language), e.g. for import in modelling tools.

  7. The kinetics of substitution reaction of oxydiacetate and ...

    Indian Academy of Sciences (India)

    ... Journals; Journal of Chemical Sciences; Volume 127; Issue 10. The kinetics of substitution reaction of oxydiacetate and thiodiacetate copper(II) complexes with 1,10-phenanthroline and 2,2'-bipyridine. Joanna Pranczk Dagmara Jacewicz Dariusz Wyrzykowski Aleksandra Tesmar Lech Chmurzyński. Volume 127 Issue 10 ...

  8. 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)

  9. 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…

  10. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Variation of kinetic isotope effect in multiple proton transfer reactions. #. B SARITHA and M DURGA PRASAD. ∗. School of Chemistry, University of Hyderabad, Hyderabad 500 046, India e-mail: mdpsc@uohyd.ernet.in. Abstract. Recently, we had suggested that the motion along the promoter mode in the first part of the IRC.

  11. Complex Kinetics in the Reaction of Taurine with Aqueous Bromine ...

    African Journals Online (AJOL)

    Complex Kinetics in the Reaction of Taurine with Aqueous. Bromine and Acidic Bromate: A Possible Cytoprotective. Role against Hypobromous Acid. Reuben H. Simoyi1*, Kevin Streete2, Claudius Mundoma2 and Rotimi Olojo2. 1Department of Chemistry, University of Cape Town, Rondebosch, 7700 South Africa.

  12. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

  13. Kinetics of the Adsorption of Bovine Serum Albumin of White Wine ...

    African Journals Online (AJOL)

    This study investigates the kinetics of adsorption of bovine serum albumin, BSA, in white wine model solutions onto activated carbon, AC, and alumina, AL. Pseudo-first order and pseudo-second order models were applied to determine the rate and mechanism of adsorption of the white wine protein during the haze removal ...

  14. Kinetics of the Adsorption of Bovine Serum Albumin of White Wine ...

    African Journals Online (AJOL)

    NJD

    2008-11-07

    Nov 7, 2008 ... This study investigates the kinetics of adsorption of bovine serum albumin, BSA, in white wine model solutions onto activated carbon, AC, and alumina, AL. Pseudo-first order and pseudo-second order models were applied to determine the rate and mechanism of adsorption of the white wine protein during ...

  15. Kinetics and mechanism of the reaction between aquacobalamin and isoniazid

    Science.gov (United States)

    Tumakov, S. O.; Dereven'kov, I. A.; Salnikov, D. S.; Makarov, S. V.

    2017-10-01

    Kinetics of the reaction of aquacobalamin (H2OCbl) with isoniazid (isonicotinic acid hydrazide, INH) in weakly alkaline, neutral, and weakly acidic media was studied using UV-Vis spectroscopy. It is shown that the reversible formation of a complex more stable than those of cobalamin(III) with pyridine and hydrazine occurs during the reaction. A mechanism of the reaction includes reversible stages of binding a neutral INH molecule by cobalamin(III) through an oxygen atom with its subsequent deprotonation, along with the reversible interaction of H2OCbl and the negatively charged form of INH.

  16. Investigation and kinetic evaluation of the reactions of hydroxymethylfurfural with amino and thiol groups of amino acids.

    Science.gov (United States)

    Hamzalıoğlu, Aytül; Gökmen, Vural

    2018-02-01

    In this study, reactions of hydroxymethylfurfural (HMF) with selected amino acids (arginine, cysteine and lysine) were investigated in HMF-amino acid (high moisture) and Coffee-amino acid (low moisture) model systems at 5, 25 and 50°C. The results revealed that HMF reacted efficiently and effectively with amino acids in both high and low moisture model systems. High-resolution mass spectrometry (HRMS) analyses of the reaction mixtures confirmed the formations of Michael adduct and Schiff base of HMF with amino acids. Calculated pseudo-first order reaction rate constants were in the following order; k Cysteine >k Arginine >k Lysine for high moisture model systems. Comparing to these rate constants, the k Cysteine decreased whereas, k Arginine and k Lysine increased under the low moisture conditions of Coffee-amino acid model systems. The temperature dependence of the rate constants was found to obey the Arrhenius law in a temperature range of 5-50°C under both low and high moisture conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Kinetic study of DPPH scavenging in the presence of mixture of Zinc and Vitamin C as an antioxidant

    Directory of Open Access Journals (Sweden)

    M. Momen Heravi

    2012-08-01

    Full Text Available Reactions of free radicals and reactive oxygen species (ROS with biological molecules in vivo play an important physiological role in many diseases. 2,2-diphenyl-1-picrylhydrazyl (DPPH is a stable free radical and often used as a routine reagent to evaluate the antioxidant capacity of an antioxidant. This study was undertaken to investigate the free radical-scavenging and antioxidant activities of Zinc, Vitamin C and mixture of them. UV-Vis spectrophotometry method was used to evaluate the ability of Zinc, Vitamin C and mixture of them to scavenge DPPH radical. The kinetic parameters such as rate constant and activation energy in experimental conditions were calculated. The rate constants of the H atom abstraction by DPPH (, in the presence of Zinc, Vitamin C and mixture of them were obtained (0.4209, 2.092 and 1.82 min-1 respectively, under pseudo-first-order conditions at 25 oC.

  18. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  19. Removal of Dye (Blue 56 From Aqueous Solution via Adsorption onto Pistachio Shell: kinetic and isotherm study of removal process

    Directory of Open Access Journals (Sweden)

    A. Ravanpaykar

    2012-03-01

    Full Text Available In the present investigation, shells of pistachio are used as adsorbents and they have been successfully used for the removal of Blue 56, from water samples. The effect of various parameters such as: pH, amounts of adsorbents, size of adsorbent particles and contact time on removal processing were investigated. Inthisstudy Freundlichabsorptionisotherms and Langmuir were investigated. The experimental data were correlated reasonably well by the Freundlich adsorption isotherm and isotherm parameters were calculated. In order to investigate the efficiency of Blue 56 adsorption on the pistachio shell, pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion kinetic models were studied. Themodel that hadgoodcorrelationtoattractFreundlichwas chosenasthemodel. Its kineticsfollowsthepseudosecond order reaction.

  20. The reaction kinetics of amino radicals with sulfur dioxide

    DEFF Research Database (Denmark)

    Gao, Yide; Glarborg, Peter; Marshall, Paul

    2015-01-01

    Application of the laser photolysis-laser-induced fluorescence method to the reaction NH2+SO2 in argon bath gas yields pressure-dependent, third-order kinetics which may be summarized as k = (1.49 ± 0.15) × 10-31 (T/298 K)-0.83cm6 molecule-2 s-1 over 292-555K, where the uncertainty is the 95% con...

  1. High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation

    Science.gov (United States)

    Sabourin, Justin L.

    Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and

  2. Electrochemically responsive heterogeneous catalysis for controlling reaction kinetics.

    Science.gov (United States)

    Mao, Xianwen; Tian, Wenda; Wu, Jie; Rutledge, Gregory C; Hatton, T Alan

    2015-01-28

    We report a method to control reaction kinetics using electrochemically responsive heterogeneous catalysis (ERHC). An ERHC system should possess a hybrid structure composed of an electron-conducting porous framework coated with redox-switchable catalysts. In contrast to other types of responsive catalysis, ERHC combines all the following desired characteristics for a catalysis control strategy: continuous variation of reaction rates as a function of the magnitude of external stimulus, easy integration into fixed-bed flow reactors, and precise spatial and temporal control of the catalyst activity. Herein we first demonstrate a facile approach to fabricating a model ERHC system that consists of carbon microfibers with conformal redox polymer coating. Second, using a Michael reaction whose kinetics depends on the redox state of the redox polymer catalyst, we show that use of different electrochemical potentials permits continuous adjustment of the reaction rates. The dependence of the reaction rate on the electrochemical potential generally agrees with the Nernstian prediction, with minor discrepancies due to the multilayer nature of the polymer film. Additionally, we show that the ERHC system can be employed to manipulate the shape of the reactant concentration-time profile in a batch reactor through applying customized potential-time programs. Furthermore, we perform COMSOL simulation for an ERHC-integrated flow reactor, demonstrating highly flexible manipulation of reactant concentrations as a function of both location and time.

  3. Kinetic study of ozonation of molasses fermentation wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Coca, M. [Departamento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain)], E-mail: monica@iq.uva.es; Pena, M.; Gonzalez, G. [Departamento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain)

    2007-10-22

    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{sup 7} to 3.8 x 10{sup 7} L mol{sup -1} s{sup -1}, depending on the stirring rate and the inlet gas flow.

  4. Microdroplet fusion mass spectrometry for fast reaction kinetics.

    Science.gov (United States)

    Lee, Jae Kyoo; Kim, Samuel; Nam, Hong Gil; Zare, Richard N

    2015-03-31

    We investigated the fusion of high-speed liquid droplets as a way to record the kinetics of liquid-phase chemical reactions on the order of microseconds. Two streams of micrometer-size droplets collide with one another. The droplets that fused (13 μm in diameter) at the intersection of the two streams entered the heated capillary inlet of a mass spectrometer. The mass spectrum was recorded as a function of the distance x between the mass spectrometer inlet and the droplet fusion center. Fused droplet trajectories were imaged with a high-speed camera, revealing that the droplet fusion occurred approximately within a 500-μm radius from the droplet fusion center and both the size and the speed of the fused droplets remained relatively constant as they traveled from the droplet fusion center to the mass spectrometer inlet. Evidence is presented that the reaction effectively stops upon entering the heated inlet of the mass spectrometer. Thus, the reaction time was proportional to x and could be measured and manipulated by controlling the distance x. Kinetic studies were carried out in fused water droplets for acid-induced unfolding of cytochrome c and hydrogen-deuterium exchange in bradykinin. The kinetics of the former revealed the slowing of the unfolding rates at the early stage of the reaction within 50 μs. The hydrogen-deuterium exchange revealed the existence of two distinct populations with fast and slow exchange rates. These studies demonstrated the power of this technique to detect reaction intermediates in fused liquid droplets with microsecond temporal resolution.

  5. KINETICS OF PALM OIL TRANSESTERIFICATION IN METHANOL WITH POTASSIUM HYDROXIDE AS A CATALYST

    Directory of Open Access Journals (Sweden)

    Yoeswono Yoeswono

    2010-06-01

    Full Text Available A study on palm oil transesterification to evaluate the effect of some parameters in the reaction on the reaction kinetics has been carried out. Transesterification was started by preparing potassium methoxide from potassium hydroxide and methanol and then mixed it with the palm oil. An aliquot was taken at certain time interval during transesterification and poured into test tube filled with distilled water to stop the reaction immediately. The oil phase that separated from the glycerol phase by centrifugation was analyzed by 1H-NMR spectrometer to determine the percentage of methyl ester conversion. Temperature and catalyst concentration were varied in order to determine the reaction rate constants, activation energies, pre-exponential factors, and effective collisions. The results showed that palm oil transesterification in methanol with 0.5 and 1 % w/w KOH/palm oil catalyst concentration appeared to follow pseudo-first order reaction. The rate constants increase with temperature. After 13 min of reaction, More methyl esters were formed using KOH 1 % than using 0.5 % w/w KOH/palm oil catalyst concentration. The activation energy (Ea and pre-exponential factor (A for reaction using 1 % w/w KOH was lower than those using 0.5 % w/w KOH.   Keywords: palm oil, transesterification, catalyst, first order kinetics, activation energy, pre-exponential factor

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

    Science.gov (United States)

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

    2011-07-14

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

  7. Transient kinetics of heparin-catalyzed protease inactivation by antithrombin III. Characterization of assembly, product formation, and heparin dissociation steps in the factor Xa reaction.

    Science.gov (United States)

    Craig, P A; Olson, S T; Shore, J D

    1989-04-05

    The kinetics of alpha-factor Xa inhibition by antithrombin III (AT) were studied in the absence and presence of heparin (H) with high affinity for antithrombin by stopped-flow fluorometry at I 0.3, pH 7.4 and 25 degrees C, using the fluorescence probe p-aminobenzamidine (P) and intrinsic protein fluorescence to monitor the reactions. Active site binding of p-aminobenzamidine to factor Xa was characterized by a 200-fold enhancement and 4-nm blue shift of the probe fluorescence emission spectrum (lambda max 372 nm), 29-nm red shift of the excitation spectrum (lambda max 322 nm), and dissociation constant (KD) of about 80 microM. Under pseudo-first order conditions [( AT]0, [H]0, [P]0 much greater than [Xa]0), the observed factor Xa inactivation rate constant (kobs) measured by p-aminobenzamidine displacement or residual enzymatic activity increased linearly with the "effective" antithrombin concentration (i.e. corrected for probe competition) up to 300 microM in the absence of heparin, indicating a simple bimolecular process with a rate constant of 2.1 x 10(3) M-1 s-1. In the presence of heparin, a similar linear dependence of kobs on effective AT.H complex concentration was found up to 25 microM whether the reaction was followed by probe displacement or the quenching of AT.H complex protein fluorescence due to heparin dissociation, consistent with a bimolecular reaction between AT.H complex and free factor Xa with a 300-fold enhanced rate constant of 7 x 10(5) M-1 s-1. Above 25 microM AT.H complex, an increasing dead time displacement of p-aminobenzamidine and a downward deviation of kobs from the initial linear dependence on AT.H complex concentration were found, reflecting the saturation of an intermediate Xa.AT.H complex with a KD of 200 microM and a limiting rate of Xa-AT product complex formation of 140 s-1. Kinetic studies at catalytic heparin concentrations yielded a kcat/Km for factor Xa at saturating antithrombin of 7 x 10(5) M-1 s-1 in agreement with the

  8. Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

    Science.gov (United States)

    Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

    2011-10-18

    The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. Kinetics and deuterium kinetic isotope effects in 3,3- and 2,3-sigmatropic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Emrani, J.

    1985-01-01

    In previous work, Conrad, using ..cap alpha..-2/sup 0/ deuterium kinetic isotope effects (KIE), showed that variable transition states are involved in Cope and Claisen rearrangements, two groups of sigmatropic reactions. The variation could be understood in terms of substituents affecting the relative extents of bond making and bond breaking. The kinetics and KIEs have now been determined for rearrangements of allyl trimethyl silyl ketene actal (TMS-KA), diisopropyl allylamine-oxide (diamo), and 1,3- and 1,4-diphenyl-1,5-hexadienes. Measurements of KIE in the reaction of TMS-KA and diamo, have shown that the transition state of both these reactions involve much more bond breaking than bond making. Solvent and phenyl substituent effects have been measured for TMS-KA, and these verify a non-polar reaction with substantial bond cleavage. The origin of the behavior is discussed. Measurements of the activation free energies for Cope rearrangement of 1,3- and 1,4-diphenyl-1,5-hexadienes reveal parameters similar to that of 3-phenyl-1,5-hexadiene. The values are consistent with a theoretical model developed for substituent effects in these reactions.

  10. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    Science.gov (United States)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

  11. 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.

  12. Tunneling and reflection in unimolecular reaction kinetic energy release distributions

    Science.gov (United States)

    Hansen, K.

    2018-02-01

    The kinetic energy release distributions in unimolecular reactions is calculated with detailed balance theory, taking into account the tunneling and the reflection coefficient in three different types of transition states; (i) a saddle point corresponding to a standard RRKM-type theory, (ii) an attachment Langevin cross section, and (iii) an absorbing sphere potential at short range, without long range interactions. Corrections are significant in the one dimensional saddle point states. Very light and lightly bound absorbing systems will show measurable effects in decays from the absorbing sphere, whereas the Langevin cross section is essentially unchanged.

  13. Control of Reaction Kinetics During Friction Stir Processing

    Science.gov (United States)

    Das, Shamiparna; Martinez, Nelson Y.; Mishra, Rajiv S.; Grant, Glenn J.; Jana, Saumyadeep

    2017-05-01

    Friction stir processing (FSP) was used to successfully embed galfenol particles into aluminum (AA 1100 Al) matrix uniformly. However, intermetallic layer of Al3Fe was formed around the galfenol particles. Activation energy for Al3Fe formation during FSP was estimated, and attempts were made to minimize the Al3Fe layer thickness. By changing the processing conditions, FSP successfully eliminated the intermetallic layer. Hence, FSP, in addition to microstructural control, can successfully fabricate intermetallic-free embedded regions by controlling the reaction kinetics.

  14. 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.

  15. Python framework for kinetic modeling of electronically excited reaction pathways

    Science.gov (United States)

    Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew

    2012-10-01

    The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.

  16. Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.

    Science.gov (United States)

    Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

    2014-06-25

    Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps.

  17. 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.

  18. Kinetics of Adsorption of Nickel Ion on Kankara Kaolinite

    Directory of Open Access Journals (Sweden)

    Lawrence C. EDOMWONYI-OTU

    2013-06-01

    Full Text Available In this work, the kinetics and dynamics of nickel ion adsorption on calcined kaolinite clay were studied. The Kinetic models (k1=0.025, k2=0.00065 and ki=2.089 g/(mg·min were evaluated in order to identify potential adsorption mechanisms. The kinetic data were best represented by the pseudo first order model (R2=0.959 and the adsorption process is favored by decrease in pH i.e. Acidic condition (below 5.0. The Langmuir model was found to best suit the adsorption isotherm of nickel ion on clay than the Freundlich model. The maximum adsorption capacity of Kankara kaolinite was found to be 97.68% at a temperature of 50°C and pH of 2. The intra-particle diffusion model suggests that the process was diffusion controlled. The thermodynamic data indicates that the adsorption reaction is spontaneous with an increase in Gibbs free energy (∆G>0 and purely physisorption and exothermal in nature (∆H = -19.837 kJ/mol.

  19. 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.

  20. 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.

  1. 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.

  2. DETERMINATION OF REACTION KINETICS USING ONLINE X-RAY DIFFRACTION

    Directory of Open Access Journals (Sweden)

    Elida Purba

    2010-06-01

    Full Text Available X-ray diffraction (XRD is a powerful technique for the study of polymorphism and polymorphic phase transformations. Monitoring of phase transformation directly has been very limited to-date. The XRD system used in this study was used to determine the rate of transformation of pure glutamic acid a form to b form in a solution mediated phase. On every run starting from the pure a form, the transformation process was monitored continuously at fixed temperature, and separate experiments were performed as a function of temperature. The operating temperature was varied from 36 to 57 °C with 10% w/w solid concentration. Data were taken every 200 seconds until the transformation was completed. This paper is concerned with a study of the transformation of the alpha (a form of L-glutamic acid (L-GA to the beta (b form in order to determine the kinetic reaction. The rate constant (k, activation energy (Ea and pre-exponential factor (A were obtained. Sensitivity tests were also carried out to examine minimum detection limit when both a and b present in the mixture. In addition, effect of particle size on XRD patterns was also determined. The results show that XRD gives useful information to observe polymorphism for pharmaceutical industry.     Keywords: XRD, polymorphism, glutamic acid, reaction kinetics

  3. Metal accumulation kinetics by the estuarine macroalga, Fucus ceranoides

    Science.gov (United States)

    Varma, Ranjit; Turner, Andrew; Brown, Murray T.; Millward, Geoff E.

    2013-08-01

    The kinetics of Cu, Cd and Pb accumulation by the macroalga, Fucus ceranoides, was studied under simulated estuarine conditions. Accumulation of Cu and Pb proceeded via a pseudo-first-order reaction that was reversible, suggesting desorption or efflux of accumulated metal, with forward rate constants on the order of 0.1 h-1. For both metals, reaction reversibility increased and the equilibrium constant decreased with increasing salinity (from 1 to 33.5) and system response times were <10 h throughout. Accumulation of Cd proceeded via a first-order reaction that was irreversible, suggesting little desorption or efflux of metal, with rate constants that decreased with increasing salinity (from 0.023 to 0.015 h-1) and reaction half-lives ranging from approximately 30-50 h. Inorganic equilibrium speciation calculations suggest that interactions of Cu, Cd and Pb principally involve the respective free ions, but that additional ions (e.g. CdCl+) and biotic processes may also be significant.

  4. 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.

  5. Thermochemistry, reaction paths, and kinetics on the tert-isooctane radical reaction with O2.

    Science.gov (United States)

    Snitsiriwat, Suarwee; Bozzelli, Joseph W

    2014-07-03

    Thermochemical properties of tert-isooctane hydroperoxide and its radicals are determined by computational chemistry. Enthalpies are determined using isodesmic reactions with B3LYP density function and CBS QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the tert-isooctane hydroperoxide and its radicals in order to identify isomer energies. Recommended values derived from the most stable conformers of tert-isooctane hydroperoxide of are -77.85 ± 0.44 kcal mol(-1). Isooctane is a highly branched molecule, and its structure has a significant effect on its thermochemistry and reaction barriers. Intramolecular interactions are shown to have a significant effect on the enthalpy of the isooctane parent and its radicals on peroxy/peroxide systems, the R• + O2 well depths and unimolecular reaction barriers. Bond dissociation energies and well depths, for tert-isooctane hydroperoxide → R• + O2 are 33.5 kcal mol(-1) compared to values of ∼38 to 40 kcal mol(-1) for the smaller tert-butyl-O2 → R• + O2. Transition states and kinetic parameters for intramolecular hydrogen atom transfer and molecular elimination channels are characterized to evaluate reaction paths and kinetics. Kinetic parameters are determined versus pressure and temperature for the chemically activated formation and unimolecular dissociation of the peroxide adducts. Multifrequency quantum RRK (QRRK) analysis is used for k(E) with master equation analysis for falloff. The major reaction paths at 1000 K are formation of isooctane plus HO2 followed by cyclic ether plus OH. Stabilization of the tert-isooctane hydroperoxy radical becomes important at lower temperatures.

  6. 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

  7. 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

  8. Fundamental Studies of Novel Zwitterionic Hybrid Membranes: Kinetic Model and Mechanism Insights into Strontium Removal

    OpenAIRE

    Wen Zhu; Junsheng Liu; Meng Li

    2014-01-01

    A series of zwitterionic hybrid membranes were prepared via the ring opening of 1,3-propanesultone with the amine groups in the chains of TMSPEDA and a subsequent sol-gel process. Their kinetic models for strontium removal were investigated using three two-parameter kinetic equations (i.e., Lagergren pseudo-first order, pseudo-second order, and Elovich models). Adsorption mechanism was evaluated using intraparticle diffusion model, diffusion-chemisorption model, and Boyd equation. It was foun...

  9. Insights of ibuprofen electro-oxidation on metal-oxide-coated Ti anodes: Kinetics, energy consumption and reaction mechanisms.

    Science.gov (United States)

    Wang, Chong; Yu, Yanxin; Yin, Lifeng; Niu, Junfeng; Hou, Li-An

    2016-11-01

    Electrochemical degradation of ibuprofen (IBP) was performed on three types of Ti-based metal oxide electrodes. The degradation of IBP followed pseudo-first-order kinetics and the electrochemical degradation rate constant (k) over Ti/SnO2-Sb/Ce-PbO2 (9.4 × 10(-2) min(-1)) was 2.0 and 1.7 times of the values over Ti/Ce-PbO2 (4.7 × 10(-2) min(-1)) and Ti/SnO2-Sb (5.6 × 10(-2) min(-1)), respectively. The removal of total organic carbon and the energy consumption per order for IBP degradation were 93.2% and 13.1 Wh L(-1), respectively, under the optimal conditions using Ti/SnO2-Sb/Ce-PbO2 anode. Six aromatic intermediate products of IBP were identified by ultra-high-performance liquid chromatography coupled with a quadrupole time-of-flight mass spectrometer. The electrochemical mineralization mechanism of IBP was proposed. It was supposed that OH radicals produced on the surface of anode attacked IBP to form hydroxylated IBP derivatives that were then followed by a series of hydroxylation, loss of isopropanol and isopropyl, decarboxylation and benzene ring cleavage processes to form simple linear carboxylic acids. By successive hydroxylation, these carboxylic acids were then oxidized to CO2 and H2O, achieving the complete mineralization of IBP. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Reaction kinetics of the hydrothermal treatment of lignin.

    Science.gov (United States)

    Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri

    2008-03-01

    Lignins derived from abundant and renewable resources are nontoxic and extremely versatile in performance, qualities that have made them increasingly important in many industrial applications. We have shown recently that liquefaction of lignin extracted from aspen wood resulted in a 90% yield of liquid. In this paper, the hydrothermal treatment of five types of lignin and biomass residues was studied: Kraft pine lignin provided by MeadWestvaco, Kraft pine lignin from Sigma-Aldrich, organosolv lignin extracted from oat hull, the residues of mixed southern hardwoods, and switchgrass after hydrolysis. The yields were found dependent on the composition or structure of the raw materials, which may result from different pretreatment processes. We propose a kinetic model to describe the hydrothermal treatment of Kraft pine lignin and compare it with another model from the literature. The kinetic parameters of the presented model were estimated, including the reaction constants, the pre-exponential factor, and the activation energy of the Arrhenius equations. Results show that the presented model is well in agreement with the experiments.

  11. Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

    Science.gov (United States)

    Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

    2015-09-15

    Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. Kinetic study of the reactions between chloramine disinfectants and hydrogen peroxide: temperature dependence and reaction mechanism.

    Science.gov (United States)

    McKay, Garrett; Sjelin, Brittney; Chagnon, Matthew; Ishida, Kenneth P; Mezyk, Stephen P

    2013-09-01

    The temperature-dependent kinetics for the reaction between hydrogen peroxide and chloramine water disinfectants (NH2Cl, NHCl2, and NCl3) have been determined using stopped flow-UV/Vis spectrophotometry. Rate constants for the mono- and dichloramine-peroxide reaction were on the order of 10(-2)M(-1)s(-1) and 10(-5)M(-1)s(-1), respectively. The reaction of trichloramine with peroxide was negligibly slow compared to its thermal and photolytically-induced decomposition. Arrhenius expressions of ln(kH2O2-NH2Cl)=(17.3±1.5)-(51500±3700)/RT and ln(kH2O2-NHCl2)=(18.2±1.9)-(75800±5100)/RT were obtained for the mono- and dichloramine peroxide reaction over the temperature ranges 11.4-37.9 and 35.0-55.0°C, respectively. Both monochloramine and hydrogen peroxide were first-order in the rate-limiting kinetic step and concomitant measurements made using a chloride ion selective electrode showed that the chloride was produced quantitatively. These data will aid water utilities in predicting chloramine concentrations (and thus disinfection potential) throughout the water distribution system. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Sonication effect on the reaction of 4-bromo-1-methylbenzene with sodium sulfide in liquid-liquid multi-site phase-transfer catalysis condition - kinetic study.

    Science.gov (United States)

    Abimannan, Pachaiyappan; Selvaraj, Varathan; Rajendran, Venugopal

    2015-03-01

    The synthesis of di-p-tolylsulfane from the reaction of 4-bromo-1-methylbenzene (BMB) with sodium sulfide was carried out using a multi-site phase-transfer catalyst (MPTC) viz., 1,4-dihexyl-1,4-diazoniabicyclo[2.2.2]octanium dibromide and ultrasonic irradiation in a liquid-liquid reaction condition. The overall reaction rate is greatly enhanced when catalyzed by multi-site phase-transfer catalyst (MPTC) combined with sonication (40 kHz, 300 W) in a batch reactor than catalyzed by MPTC without sonication. Effects on the reaction due to various operating conditions, such as agitation speed, different ultrasound frequencies, different phase-transfer catalysts, different organic solvents, the amount of MPTC, temperature, amount of sodium sulfide, effect of sodium hydroxide, volume of n-hexane and the concentration of 4-bromo-1-methylbenzene. The reaction obeys a pseudo first-order rate law and a suitable mechanism was proposed based on the experimental observation. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Kinetics of adsorption of bovine serum albumin on magnetic carboxymethyl chitosan nanoparticles.

    Science.gov (United States)

    Wang, Zhouli; Yue, Tianli; Yuan, Yahong; Cai, Rui; Niu, Chen; Guo, Caixia

    2013-07-01

    The magnetic carboxymethyl chitosan nanoparticles (MNPs-CMC) were developed as effective magnetic affinity adsorbent for Bovine serum albumin and the adsorption reactions were investigated. The obtained experimental data were compared with the adsorption kinetics models and equilibrium isotherms. The experimental kinetic data were modeled using Pseudo-first order, Pseudo-second order, Bangham's equation, Intra-particle diffusion model and Elovich equations. It was found that the adsorption reactions followed the Pseudo-second order kinetics equation. The experimental isotherm data were analyzed using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin equations. By comparing the correlation coefficients determined for each linear transformation of isotherm analysis, it was found that the Langmuir equation was the best fit equilibrium model for the adsorption of BSA. Error functions have been used to determine the alternative single component parameters by nonlinear regression due to the inherent bias in using the correlation coefficient resulting from linearization. It showed that the Langmuir equation resulted in the lowest values for the error function and thus fitted the data better than the other isotherm. Various thermodynamic parameters such as enthalpy (ΔH°), entropy (ΔS°) and Gibbs free energy (ΔG°) were evaluated. MNPs-CMC nanoaprticles were shown to be a promising material for adsorption of BSA from aqueous solutions. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

  15. Equilibrium, hysteresis and kinetics of cadmium desorption from sodium-feldspar using rhamnolipid biosurfactant.

    Science.gov (United States)

    Aşçi, Yeliz; Açikel, Unsal; Açikel, Yeşim Sağ

    2012-09-01

    In this study, the sorption/desorption equilibruim and the desorption kinetics of Cd by rhamnolipid biosurfactant from Na-feldspar as a soil component were investigated. The linear, Langmuir and Freundlich isotherms adequately fitted the equilibrium sorption data with regression coefficients ranging from 0.9836 - 0.9879. However, both the sorption/desorption equilibria were well characterized by the Freundlich model. The extent of hysteresis was quantified based on the differences obtained from sorption and desorption isotherms regarding the quantity of Cd(II) sorbed, the Freundlich exponent, concentration-dependent metal distribution coefficients, and the irreversibility index based on the metal distribution coefficient. The kinetics of desorption of Cd from Na-feldspar was investigated using 77 mM rhamnolipid and at pH 6.8. The first-order, an empirical first-order desorption model (two-coefficient), Lagergren-pseudo-first-order, pseudo-second-order, Elovich and modified Freundlich models were used to describe the kinetic data to estimate the rate constants. To determine the rate-controlling step, the intra-particle diffusion model was also applied to the desorption process. The desorption kinetics of Cd(II) on Na-feldspar was represented better by the pseudo-second-order, Elovich and modified Freundlich equations with correlation coefficients ranging from 0.9941- 0.9982 than by first-order equations. The rate-controlling stage was suggested to be mainly the surface reaction mechanism.

  16. Wide Temperature Range Kinetics of Elementary Combustion Reactions for Army Models

    National Research Council Canada - National Science Library

    Fontijn, Arthur

    2002-01-01

    The goals of this program are to provide accurate kinetic data on isolated elementary reactions at temperatures relevant to Army combustion models, particularly for propellant combustion dark zones...

  17. UV and solar photo-degradation of naproxen: TiO{sub 2} catalyst effect, reaction kinetics, products identification and toxicity assessment

    Energy Technology Data Exchange (ETDEWEB)

    Jallouli, Nabil [University of Sfax, Laboratory of Water, Energy and Environment, National School of Engineers of Sfax (ENIS), Route de Soukra Km 3.5, PO Box 1173, 3038 Sfax (Tunisia); Elghniji, Kais [University of Gafsa, Research Unit of Materials, Environment and Energy, Campus Universitaire Sidi Ahmed Zarroug, 2112 Gafsa (Tunisia); Hentati, Olfa [University of Sfax, Laboratory of Water, Energy and Environment, National School of Engineers of Sfax (ENIS), Route de Soukra Km 3.5, PO Box 1173, 3038 Sfax (Tunisia); Higher Institute of Biotechnology of Sfax (ISBS), Route de Soukra Km 3, 5 PO Box 1175, 3038 Sfax (Tunisia); Ribeiro, Ana R.; Silva, Adrián M.T. [LCM – Laboratory of Catalysis and Materials – Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Ksibi, Mohamed, E-mail: mohamed.ksibi@isbs.rnu.tn [University of Sfax, Laboratory of Water, Energy and Environment, National School of Engineers of Sfax (ENIS), Route de Soukra Km 3.5, PO Box 1173, 3038 Sfax (Tunisia); Higher Institute of Biotechnology of Sfax (ISBS), Route de Soukra Km 3, 5 PO Box 1175, 3038 Sfax (Tunisia)

    2016-03-05

    Highlights: • Degradation kinetics and mineralization rate of naproxen (NPX) were studied. • Direct photolysis and TiO{sub 2}/UV approaches were evaluated. • The formation of by-products was followed by UHPLC-DAD-MS. • Ecological risk assessment of NPX-treated solutions was assessed using E. andrei. - Abstract: Direct photolysis and TiO{sub 2}-photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pH{sub initial} 6.5) was 83% after 3 h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO{sub 2}-UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant (k{sub app}) for NPX degradation by photolysis ranged from 0.0050 min{sup −1} at pH 3.5 to 0.0095 min{sup −1} at pH 6.5, while it was estimated to be 0.0063 min{sup −1} under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4 h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions.

  18. Kinetics of CN reactions with allene, butadiene, propylene and acrylonitrile

    Science.gov (United States)

    Butterfield, Michelle T.; Yu, T.; Lin, M. C.

    1993-01-01

    The two-laser pump-probe technique has been used to study the kinetics of the reaction of CN radicals with C 3H 6, CD 3C 2H 3, C 3D 6, C 2H 3CN, C 3H 4 and C 4H 6 at temperatures between 297 and 740 K. CN was generaged by 248-nm photolysis of ICN. Laser-induced fluorescence of the CN radical has been used for its detection by CN (B←X) excitation. The values for the rate constants, given in units of cm 3/s, are reported as: k(C 3H 6)=10 -9.88±0.10exp(+244±96.3/ T), k(C 3H 3D 3) = 10 -9.76±0.04 exp (+143.4±35.1/ T), k(C 3D 6)=10 -9.87±0.05exp(+231.4±47.01/ T, k(C 2H 3CN)=10 -10.52±0.02exp(+103.6±20.3/ T), k(C 3H 4)=10 -9.58±0.08 ×exp(+167.4±73.7/ T), k(C 4H 6)=10 -9.59±0.04exp(+169.2±33.1/ T). The absolute rates of CN reactions with CH 3CHCH 2, CD 3CHCH 2 and CD 3CDCD 2 are essentially the same and are somewhat faster than that of the CN+C 2H 4 reaction. This suggests that the CN+C 3H 6 reaction occurs primarily by addition to the unsaturated bond and the CH 3 group enhances the addition process slightly. The rate of the CN+CH 2CHCN reaction, however, was found to be a factor of six slower than that of CN+C 2H 4, indicating a substantial electron withdrawing effect of the CN group in vinyl cyanide which results in the reduction in the addition rate. The rates for CN reaction with CH 2CCH 2 and CH 2CHCHCH 2 are approximately the same and are twice that of CN+C 2H 4.

  19. Reaction Kinetics of HBr with HO2: A New Channel for Isotope Scrambling Reactions.

    Science.gov (United States)

    Church, Jonathan R; Skodje, Rex T

    2016-11-03

    The gas phase reaction kinetics of HBr with the HO2 radical are investigated over the temperature range of T = 200-1500 K using a theoretical approach based on transition state theory. The parameters for the potential energy surface are computed using density functional theory with the M11 exchange functional. The rate coefficient for the HBr + HO2 → Br + H2O2 abstraction channel is found to be somewhat larger than previous estimates at low temperatures due to quantum tunneling. The present study reveals the existence of a novel exchange pathway, HBr + H'O2 → H'Br + HO2, which exhibits a much lower reaction barrier than does the abstraction route. The transition state for this process is a symmetrical planar five-membered-ring-shaped structure. At low temperatures, this concerted double hydrogen transfer reaction is several orders of magnitude faster than the abstraction channel. The exchange process may be observed using isotope scrambling reactions; such reactions may contribute to observed isotope abundances in the atmosphere. The rate coefficients for the isotopically labeled reactions are computed.

  20. Reaction kinetics and transformation of antipyrine chlorination with free chlorine.

    Science.gov (United States)

    Cai, Mei-Quan; Feng, Li; Jiang, Jin; Qi, Fei; Zhang, Li-Qiu

    2013-05-15

    Chlorine has been documented that it can effectively remove some pharmaceuticals. Recently, new active oxidants chlorine monoxide and molecular chlorine, which exist as free active chlorine in solution, were reported during pharmaceuticals chlorination. In this study, reaction kinetics, active oxidants, and transformation products during antipyrine chlorination were investigated with batch experiments. The reaction orders in [chlorine] were determined at various pH (6.53-7.62) and ranged from 1.13 ± 0.15 to 1.59 ± 0.08, which indicated that antipyrine chlorination is the concurrent existence of reactions appearing first-order and second-order in [chlorine]. The results by varying solution conditions (solution pH, chloride, ionic strength, and buffer concentration) show that chlorine monoxide and molecular chlorine play significant roles during the process of antipyrine chlorination. With kinetics modeling, the second-order rate constants for hypochlorous acid, chlorine monoxide, and molecular chlorine were obtained at 25 ± 2 °C (units: M(-1) s(-1)): kHOCl = 3.23 × 10(3), kCL2 = 2.86 × 10(7), kCL2O= 8.38 × 10(9) (R(2) = 0.9801). At pH 7, hypochlorous acid and chlorine monoxide are the main contributors to the degradation of antipyrine, about 80% and 20%, respectively (calculated by kHOCl, kCL2 and kCL2O. By applying these rate constants to predict the antipyrine elimination in real water matrixes (surface water, ground water), a good agreement was obtained, particularly in ground water. Moreover, liquid chromatography-tandems mass spectrometry (LC-MS/MS) and gas chromatograph-mass spectrometry (GC-MS) were used for products identification. Two main intermediate products and three stable products were observed during the process of antipyrine chlorination. The possible routes for antipyrine chlorination were proposed, which mainly consisted of halogenations, dealkylations and hydroxylations. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Chlorination of parabens: reaction kinetics and transformation product identification.

    Science.gov (United States)

    Mao, Qianhui; Ji, Feng; Wang, Wei; Wang, Qiquan; Hu, Zhenhu; Yuan, Shoujun

    2016-11-01

    The reactivity and fate of parabens during chlorination were investigated in this work. Chlorination kinetics of methylparaben (MeP), ethylparaben (EtP), propylparaben (PrP), and butylparaben (BuP) were studied in the pH range of 4.0 to 11.0 at 25 ± 1 °C. Apparent rate constants (k app) of 9.65 × 10-3 M-0.614·s-1, 1.77 × 10-2 M-1.019·s-1, 2.98 × 10-2 M-0.851·s-1, and 1.76 × 10-2 M-0.860·s-1 for MeP, EtP, PrP, and BuP, respectively, were obtained at pH 7.0. The rate constants depended on the solution pH, temperature, and NH4+ concentration. The maximum k app was obtained at pH 8.0, and the minimum value was obtained at pH 11.0. The reaction rate constants increased with increasing temperature. When NH4+ was added to the solution, the reaction of parabens was inhibited due to the rapid formation of chloramines. Two main transformation products, 3-chloro-parabens and 3,5-dichloro-parabens, were identified by GC-MS and LCMS-IT-TOF, and a reaction pathway was proposed. Dichlorinated parabens accumulated in solution, which is a threat to human health and the aqueous environment.

  2. Combustion reaction kinetics of guarana seed residue applying isoconversional methods and consecutive reaction scheme.

    Science.gov (United States)

    Lopes, Fernanda Cristina Rezende; Tannous, Katia; Rueda-Ordóñez, Yesid Javier

    2016-11-01

    This work aims the study of decomposition kinetics of guarana seed residue using thermogravimetric analyzer under synthetic air atmosphere applying heating rates of 5, 10, and 15°C/min, from room temperature to 900°C. Three thermal decomposition stages were identified: dehydration (25.1-160°C), oxidative pyrolysis (240-370°C), and combustion (350-650°C). The activation energies, reaction model, and pre-exponential factor were determined through four isoconversional methods, master plots, and linearization of the conversion rate equation, respectively. A scheme of two-consecutive reactions was applied validating the kinetic parameters of first-order reaction and two-dimensional diffusion models for the oxidative pyrolysis stage (149.57kJ/mol, 6.97×10(10)1/s) and for combustion stage (77.98kJ/mol, 98.611/s), respectively. The comparison between theoretical and experimental conversion and conversion rate showed good agreement with average deviation lower than 2%, indicating that these results could be used for modeling of guarana seed residue. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Reaction of NO(2) with selected conjugated alkenes.

    Science.gov (United States)

    Bernard, François; Cazaunau, Mathieu; Mu, Yujing; Wang, Xinming; Daële, Véronique; Chen, Jianmin; Mellouki, Abdelwahid

    2013-12-27

    The gas phase reactions of selected alkenes (isoprene, myrcene, ocimene, and 1,3-cyclohexadiene) with NO2 under dark condition have been investigated at T ∼ 298 K and P ∼ 760 Torr of purified air. The kinetic studies were performed under pseudo-first-order conditions using a large excess of NO2 concentration to those of the alkenes. The rate coefficients (in 10(-19) cm(3) molecule(-1) s(-1)) obtained are 1.1 ± 0.2 for isoprene, 2.5 ± 0.3 for myrcene, 8.5 ± 1.2 for ocimene, and 15 ± 1 for 1,3-cyclohexadiene. Several products were identified by using in situ Fourier transform infrared (FT-IR) spectrometry, and acetone was found to be the major product from the reactions of NO2 with myrcene and ocimene, with a formation yield of 22 ± 3% and 26 ± 7%, respectively. The oxidation products from the reactions of NO2 with isoprene and 1,3-cyclohexadiene were found to be mainly nitro compounds identified by FT-IR spectroscopy. Reaction mechanisms were proposed to account for the products observed.

  4. Kinetics and Mechanism of Micellar Catalyzed Oxidation of Dextrose by N-Bromosuccinimide in H2SO4 Medium

    Directory of Open Access Journals (Sweden)

    Minu Singh

    2014-01-01

    Full Text Available Kinetics and mechanism of micellar catalyzed N-bromosuccinimide oxidation of dextrose in H2SO4 medium was investigated under pseudo-first-order condition temperature of 40°C. The results of the reactions studied over a wide range of experimental conditions show that NBS shows a first order dependence, fractional order, on dextrose and negative fractional order dependence on sulfuric acid. The determined stoichiometric ratio was 1 : 1 (dextrose : N-bromosuccinimide. The variation of Hg(OAC2 and succinimide (reaction product has insignificant effect on reaction rate. Effects of surfactants, added acrylonitrile, added salts, and solvent composition variation have been studied. The Arrhenius activation energy and other thermodynamic activation parameters are evaluated. The rate law has been derived on the basis of obtained data. A plausible mechanism has been proposed from the results of kinetic studies, reaction stoichiometry, and product analysis. The role of anionic and nonionic micelle was best explained by the Berezin’s model.

  5. 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

  6. Kinetic Approach for the Adsorption of Organophosphorous Pesticides from Aqueous Solution Using “Waste” Jute Fiber Carbon

    OpenAIRE

    Senthilkumaar, S.; Krishna, S. K.; Kalaamanic, P.; Subburamaan, C. V.; N. Ganapathy Subramaniam; Kang, T W

    2010-01-01

    Chemically activated “Waste” Jute Fiber carbon has been effectively used for the removal of five organophosphorous pesticides (malathion, monocrotophos, methylparathion, phosphamidon and dimethoate) from aqueous solutions. The prepared activated jute fiber carbon was characterized by using Elemental analyzer and proximate analysis methods. The adsorption equilibrium was examined at 28 ºC. Three different kinetic models, the pseudo first order, pseudo second order and Elovich kinetic models we...

  7. Microsecond time-scale kinetics of transient biochemical reactions.

    Directory of Open Access Journals (Sweden)

    Sandra Mitić

    Full Text Available To afford mechanistic studies in enzyme kinetics and protein folding in the microsecond time domain we have developed a continuous-flow microsecond time-scale mixing instrument with an unprecedented dead-time of 3.8 ± 0.3 μs. The instrument employs a micro-mixer with a mixing time of 2.7 μs integrated with a 30 mm long flow-cell of 109 μm optical path length constructed from two parallel sheets of silver foil; it produces ultraviolet-visible spectra that are linear in absorbance up to 3.5 with a spectral resolution of 0.4 nm. Each spectrum corresponds to a different reaction time determined by the distance from the mixer outlet, and by the fluid flow rate. The reaction progress is monitored in steps of 0.35 μs for a total duration of ~600 μs. As a proof of principle the instrument was used to study spontaneous protein refolding of pH-denatured cytochrome c. Three folding intermediates were determined: after a novel, extremely rapid initial phase with τ = 4.7 μs, presumably reflecting histidine re-binding to the iron, refolding proceeds with time constants of 83 μs and 345 μs to a coordinatively saturated low-spin iron form in quasi steady state. The time-resolution specifications of our spectrometer for the first time open up the general possibility for comparison of real data and molecular dynamics calculations of biomacromolecules on overlapping time scales.

  8. Experimental and theoretical studies of the reaction between CF3 and NO2 at 298 K

    DEFF Research Database (Denmark)

    Pagsberg, P.; Jodkowski, J.T.; Ratajczak, E.

    1998-01-01

    ) was studied under pseudo-first-order conditions and the value of k(2a) = (1.53 +/- 0.10) X 10(-11) cm(3) molecule(-1) s(-1) was found to be independent of bath gas pressure in the range 4-22 mbar. Based on the characteristic absorption spectra of the products, the branching ratio of reaction (2a) was found......The title reaction has been studied by pulse radiolysis combined with time-resolved infrared diode laser spectroscopy. The kinetics of CF3 were analysed taking into account the two competing reactions CF3 + CF3 M --> C2F6 + M (1) and CF3 + NO2 --> CF2O + FNO (2a). Based on studies of the yield...... and kinetics of CF3 we determined values of the absorption cross section, sigma(CF3) = (1.96 +/- 0.20) X 10(-17) cm(2) molecule(-1) at 1263.567 cm(-1) and the bimolecular rate constant, k(1) = (1.04 +/- 0.12) X 10(-11) cm(3) molecule(-1) s(-1) with a bath gas pressure of 20 mbar at 298 K. Reaction (2a...

  9. Theory of Square-wave Voltammetry of Kinetically Controlled Two-step Electrode Reactions

    OpenAIRE

    Lovrić, Milivoj; Komorsky-Lovrić, Šebojka

    2012-01-01

    An influence of electron transfer kinetics on square-wave voltammograms of two-step electrode reaction is investigated theoretically. A phenomenon of “kinetic burden” of potential inversion is described for the case of equal kinetic parameters. A linear relationship between standard rate constant and the difference between standard potentials of the second and the first charge transfers is demonstrated for the reactions with thermodynamically unstable intermediate. (doi: 10.5562/cca2126)

  10. An assessment of the role of nonlinear reaction kinetics in parameterization of metamorphic fluid flow

    National Research Council Canada - National Science Library

    Zhao, Zhihong; Skelton, Alasdair

    2014-01-01

    ...) reaction order must be known for robust determination of time‐averaged net reaction rates based on reaction progress data and that underestimation of this term by more than 3 orders of magnitude can arise from assuming linear reaction kinetics, (3...

  11. Reactor model development: The removal performance of ferrous-catalysed photo-oxidation process by examining the reaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Chan, K.H. [Department of Civil and Structural Engineering, Research Centre for Environmental Technology and Management, Hong Kong Polytechnic University, Hunghom, Kowloon (Hong Kong); Chu, W., E-mail: cewchu@polyu.edu.hk [Department of Civil and Structural Engineering, Research Centre for Environmental Technology and Management, Hong Kong Polytechnic University, Hunghom, Kowloon (Hong Kong)

    2009-08-15

    The removal performance of the ferrous catalysed photo-oxidation process was investigated through the examination of major process parameters including pH levels and dosages of ferrous (Fe{sup 2+}) and hydrogen peroxide (H{sub 2}O{sub 2}). A common used herbicide, alachlor, was used as a target compound in the degradation process. In the study, alachlor was found to be effectively degraded by hydroxyl radicals (HO{center_dot}) which were generated by UV/Fe{sup 2+}/H{sub 2}O{sub 2} in the oxidation process. It was interesting to find that the pattern of reaction kinetics of alachlor varied depending on the initial concentrations of Fe{sup 2+} and H{sub 2}O{sub 2}. An optimum H{sub 2}O{sub 2} dosage was determined. This was practically useful because the overdose of H{sub 2}O{sub 2} would cause the process retardation. The conventional pseudo-first-order kinetics and two-stage first-order kinetics were observed at lower and higher Fe{sup 2+} concentrations, respectively. Models were proposed and used to stimulate the kinetic process. Thus, design charts were established for determining the reaction time (i.e., reactor sizing) required for predetermined removal performance of alachlor under different concentrations of H{sub 2}O{sub 2} and Fe{sup 2+}.

  12. Probing cluster surface morphology by cryo kinetics of N2 on cationic nickel clusters

    Science.gov (United States)

    Mohrbach, Jennifer; Dillinger, Sebastian; Niedner-Schatteburg, Gereon

    2017-11-01

    We present the stepwise N2 adsorption kinetics of size selected Nin + (n = 5-20) clusters at 26 K as obtained by a hybrid tandem ion trap instrument. Pseudo-first-order kinetic fits confirm consecutive adsorption steps without evidence of cluster isomers and up to adsorption limits, which scale with the cluster size. The reaction rates for the initial N2 adsorption increase smoothly with the cluster size and similar to hard sphere cluster modeling. The isothermal kinetics allow for the tentative elucidation of cluster surface morphologies and for their classification into highly symmetrical clusters with all smooth surfaces, small clusters with rough surfaces, and large clusters with partially rough and smooth surface areas. The parallel characterization of the vibrational spectroscopy of some cluster adsorbate complexes supports and refines the achieved conclusions and is published back to back with this contribution [S. Dillinger, J. Mohrbach, and G. Niedner-Schatteburg, J. Chem. Phys. 147, 184305 (2017)]. These two studies elucidate the adsorbate to cluster interaction, and they confirm and specify the sometimes considerable structural fluxionality of finite and curved metal surfaces in high detail. This work precedes further studies along the present lines of thought.

  13. Visible light photocatalytic water disinfection and its kinetics using Ag-doped titania nanoparticles.

    Science.gov (United States)

    Younas, Hassan; Qazi, Ishtiaq A; Hashmi, Imran; Awan, M Ali; Mahmood, Asif; Qayyum, Hafiz Adil

    2014-01-01

    The UN estimated about five million deaths every year due to water-borne diseases, accounting from four billion patients. Keeping in view, the ever increasing health issues and to undermine this statistics, a reliable and sustainable water-treatment method has been developed using visible light for water treatment. titania nanoparticles (NPs) have been synthesized successfully by a more applicable method Viz: liquid impregnation (LI) method. The bacterial death rate by photocatalysis under visible light was studied by employing a typical fluorescent source and was found to follow pseudo first-order reaction kinetics. The nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to deduce their size range, surface morphology, and elemental compositions, respectively. Among all the prepared grades, 1% Ag-TiO2 was found to be a very effective photocatalytic agent against Escherichia coli. The resulted photoinactivated data were also evaluated by different empirical kinetic models for bacterial inactivation. Hom, Hom-power, Rational, and Selleck models were not able to explain the disinfection kinetics but modified-Hom model fitted best with the experimentally obtained data by producing a shoulder, log-linear, and a tail region.

  14. Kinetic and thermodynamic studies of Hg(II) adsorption onto MCM-41 modified by ZnCl2

    Science.gov (United States)

    Raji, Foad; Pakizeh, Majid

    2014-05-01

    Kinetics and thermodynamics of mercury ions sorption onto ZnCl2-MCM-41 sorbent were studied. Several rate models in the form of two main classes of mathematic kinetic models (adsorption reaction models and adsorption diffusion models) were investigated. Pseudo-first-order, pseudo-second-order, Elovich, film and intraparticle diffusion models were used to analyze the kinetic data. Results showed that the pseudo-second order model can well describe the adsorption kinetic data. The thermodynamic parameters, such as Gibb's free energy change (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were also evaluated. Negative value of free energy at temperature range of 20-55 °C, indicates the spontaneous nature of Hg(II) sorption by ZnCl2-MCM-41 sorbent. The adsorption capacity which was found to decrease with temperature showed the exothermic nature of the mercury sorption process (ΔH° = -49.4 kJ mol-1). The negative ΔS° value (-148.9 J mol-1 K-1) revealed a decrease in the randomness at the solid/solution interface and also indicated the fast adsorption of the Hg(II) onto active sites.

  15. Four types of attenuation of phenol and cresols in microcosms under simulated marine conditions: A kinetic study.

    Science.gov (United States)

    Wang, Yuejie; Meng, Fanping; Lin, Yufei; Duan, Weiyan; Liu, Qunqun

    2017-10-01

    Phenol, o-cresol, m-cresol, and p-cresol were selected to conduct microcosm experiments to examine their attenuation under simulated marine conditions, aiming at estimating natural attenuation and the contribution of oxidation, photolysis, biodegradation, and volatilisation to total attenuation of phenol and three cresols in the marine environment. The development of attenuation in microcosms showed the relevance of the pseudo-first-order kinetic for all phenols. The half-lives of phenol, o-cresol, m-cresol, and p-cresol attenuation under optimal conditions were 7.9, 4.3, 5.3, and 4.4 d, respectively. Attenuation kinetics was proposed to analyse the natural attenuation of phenol and cresols. The leading attenuation type of phenol, o-cresol, and p-cresol was volatilisation, and the attenuation rate constants (Kv) were 0.0356, 0.0687, and 0.0710 d-1. Photolysis (Kp: 0.0584 d-1) was the major attenuation type for m-cresol. Biodegradation of phenol (Kb: 0.0021 d-1) and m-cresol (Kb: 0.0049 d-1) were extremely inhibited. The rank between the contributions of the four types of attenuation to total attenuation differed between phenol and the three cresols. The attenuation kinetics proposed in this study possibly demonstrated the attenuation of the phenol and cresols in microcosm. This new reaction kinetics can be used in the analysis of natural attenuation of chemical substances. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. [Influencing factors and reaction mechanism of chloroacetic acid reduction by cast iron].

    Science.gov (United States)

    Tang, Shun; Yang, Hong-Wei; Wang, Xiao-Mao; Xie, Yue-Feng

    2014-03-01

    The chloroacetic acids are ubiquitous present as a class of trace chlorinated organic pollutants in surface and drinking water. Most of chloroacetic acids are known or suspected carcinogens and, when at high concentrations, are of great concern to human health. In order to economically remove chloroacetic acids, the degradation of chloroacetic acids by cast iron was investigated. Moreover, the effect of iron style, pretreatment process, shocking mode and dissolved oxygen on chloroacetic acids reduced by cast iron was discussed. Compared to iron source and acid pretreatment, mass transfer was more important to chloroacetic acid removal. Dichloroacetic acid (DCAA) and monochloroacetic acid (MCAA) were the main products of anoxic and oxic degradation of trichloroacetic acid (TCAA) by cast iron during the researched reaction time, respectively. With longtitudinal shock, the reaction kinetics of chloroaectic acid removal by cast iron conformed well to the pseudo first order reaction. The anoxic reaction constants of TCAA, DCAA and MCAA were 0.46 h(-1), 0.03 h(-1) and 0, and their oxic constants were 1.24 h(-1), 0.79 h(-1) and 0.28 h(-1), respectively. The removal mechanisms of chloroacetic acids were different under various oxygen concentrations, including sequential hydrogenolysis for anoxic reaction and sequential hydrogenolysis and direct transformation possible for oxic reaction, respectively.

  17. Enhancement of activated sludge dewatering performance by combined composite enzymatic lysis and chemical re-flocculation with inorganic coagulants: Kinetics of enzymatic reaction and re-flocculation morphology.

    Science.gov (United States)

    Chen, Zhan; Zhang, Weijun; Wang, Dongsheng; Ma, Teng; Bai, Runying

    2015-10-15

    The feasibility of combined process of composite enzymatic treatment and chemical flocculation with inorganic salt coagulants was investigated in this study. The evolution of extracellular polymeric substances (EPS) distribution, composition and morphological properties were analyzed to unravel the sludge conditioning mechanism. It was found that sludge filtration performance was deteriorated due to release of a large amount of biopolymers after enzymatic treatment. The change in EPS followed the pseudo-first-order kinetic equation well under enzymatic treatment. The feeding modes of enzymes had a significant influence on sludge lysis efficiency under compound enzymes treatment. Alpha amylase + protease was more effective in solubilization than other two addition modes (protease + α-amylase or simultaneous addition). The sludge floc re-formed and macromolecule biopolymers were effectively removed through coagulation process. At the same time, both of filtration rate and cake solid content of sludge treated with enzymes were improved with increasing dosage of coagulants, and ferric iron (FeCl3) had better performance in sludge dewaterability enhancement than polyaluminium chloride (PACl). In addition, sludge filtration property was slightly deteriorated, while the cake moisture reduction was favored at the optimal dosage of inorganic coagulants. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. 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

  19. Nonlinear regression analysis of kinetics of the photocatalytic decolorization of an azo dye in aqueous TiO2 slurry.

    Science.gov (United States)

    Behnajady, Mohammad A; Modirshahla, Nasser

    2006-11-01

    The kinetics of decolorization of an anionic monoazo dye of acid class named C.I. Acid Red 27 (AR27) was investigated in the UV/TiO2 process with nonlinear regression analysis. The experimental results indicated that the kinetics of decolorization of AR27 in this process fit well by pseudo-first order kinetics. With nonlinear regression analysis a model was developed for pseudo-first order rate constant (k(ap,UV/TiO2)) as a function of operational parameters such as TiO2 dosage, initial concentration of AR27, concentration of O2 and UV-light intensity (I0) as following: k(ap,UV/TiO2) = 0.0025 [TiO2](0.65) [AR27]0(-0.96) [O2](0.16)I0. This rate expression can be used for predicting k(ap,UV/TiO2) at different conditions.

  20. 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.

  1. Kinetics and Mechanism of the Ligand Exchange Reaction Between ...

    African Journals Online (AJOL)

    NICO

    Visible spectrophotometry is used to study the kinetics of ligand exchange in the system Ni(salpn)/H2salen with or without triethylamine (NEt3) and ... coordination chemistry.4,5 However, the kinetics of polydentate ligands exchange ..... chlorides and tetraaza Schiff bases: synthesis and characterization of some novel tin(IV) ...

  2. Influence of relative humidity on heterogeneous reactions of O3 and O3/SO2 with soot particles: Potential for environmental and health effects

    Science.gov (United States)

    He, Xiang; Pang, Shufeng; Ma, Jiabi; Zhang, Yunhong

    2017-09-01

    The heterogeneous reactions of soot particles with O3 and the mixture of O3 and SO2 were studied as a function of relative humidities (RHs). The reactions were followed in real time using microscopic Fourier transform infrared (micro-FTIR) spectrometer to obtain kinetic data. The results show that the ketone (Cdbnd O) group is the main product of the O3/soot reaction, and the sulfate is identified on the surface of soot particles in the presence of O3/SO2. Both reactions are sensitive to RHs and surrounding water significantly promotes the proceeding of the heterogeneous reactions. For the O3/soot reaction, the pseudo-first-order rate constant increases from 3.2 × 10-4 s-1 to 7.1 × 10-4 s-1 with increasing RH in the range of 1%-82%. When O3 and SO2 exist simultaneously during the reaction, the reaction rate and uptake coefficient are all enhanced by about an order of magnitude as the RH increases from 1% to 83%. The high productions of the ketone and sulfate on soot surface are of highly hydrophilic, which play a key role in environmental effect under humid environment. The possible reaction mechanism speculates that products of aromatic carbonyls and dihydrofuran species on soot particles will be more harmful to human health.

  3. Faster rates with less catalyst in template-directed reactions

    Science.gov (United States)

    Kanavarioti, A.; Baird, E. E.

    1995-01-01

    We have recently shown that the polycytidylic acid-directed polymerization of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) is amenable to kinetic study and that rate determinations as a function of 2-MeImpG concentration can reveal much mechanistic detail (Kanavarioti et al. 1993). Here we report kinetic data which show that, once the reaction has been initiated by the formation of dimers, the elongation of dimers to form longer oligomers is accelerated by decreasing polycytidylate (poly(C)) concentration from 0.05 to 0.002 M. This result is consistent with the previously proposed mechanism. The increase in the observed pseudo-first order rate constant for formation of the trimer, k3', and the corresponding constant for formation of oligomers longer than the trimer, ki' (ki' is independent of oligomer length for i > or = 4), with decreasing template concentration for a given monomer concentration is attributed to an increase in template occupancy as template concentration is reduced.

  4. Some kinetics aspects of chlorine-solids reactions

    Directory of Open Access Journals (Sweden)

    Kanari, N.

    2010-02-01

    Full Text Available The present paper describes detailed kinetics investigations on some selected chlorine-solid reactions through thermogravimetric measurements. The solids studied in this article include chemical pure oxides and sulfides as well as their natural bearing materials. The chlorinating agents employed are gaseous mixtures of Cl2+N2 (chlorination, Cl2+O2 (oxychlorination, and Cl2+CO (carbochlorination. Results are presented as effects of various parameters on the reaction rate of these solids with these chlorinating agents. It was observed that the reactivity of these solids towards different chlorinating agents varied widely. Sulfides could be chlorinated at room temperature, while carbochlorination of chromium (III oxide was possible only above 500 °C. The variation of the chlorination rate of these complex materials with respect to gas velocity, composition and temperature enabled us to focus some light on the plausible reaction mechanisms and stoichiometries. The obtained results were used for selective removal of iron from chromite concentrates, extraction of valuable metals from sulfide materials, purification of MgO samples, etc.

    Este trabajo describe detalladas investigaciones cinéticas en algunas reacciones seleccionadas de cloro-sólido a través de medidas termogravimétricas. Los sólidos estudiados en este artículo incluyen óxidos químicos puros y sulfuros, así como sus materiales naturales de soporte. Los agentes de cloración empleados son mezclas de gases de Cl2+N2 (cloración, Cl2+O2 (oxicloración y Cl2+O2 (carbocloración. Los resultados se presentan como efecto de varios parámetros en el porcentaje de reacción de estos sólidos con los agentes de cloración. Se ha observado que la reactividad de estos sólidos a través de diferentes agentes de cloración varía ampliamente. Los sulfuros se pudieron

  5. New method for exploring deactivation kinetics in copper-catalyzed atom-transfer-radical reactions.

    Science.gov (United States)

    Zerk, Timothy J; Bernhardt, Paul V

    2014-11-03

    Copper polyamine complexes are among the most utilized catalysts for controlled radical polymerization reactions. Copper(I) complexes may react reversibly with an alkyl halide to form an alkyl radical, which promotes polymerization, and a copper(II) halido complex in a step known as activation. The kinetics of the reverse reaction between the alkyl radical and higher oxidation-state copper complex (deactivation) are less studied because these reactions approach diffusion-controlled rates, and it is difficult to isolate or quantify the concentration of the alkyl radical (R(•)) in situ. Herein we report a broadly applicable electrochemical technique for simultaneously measuring the kinetics of deactivation and kinetics of activation.

  6. Ultrasound promoted reaction of Rhodamine B with sodium hypochlorite using sonochemical and dental ultrasonic instruments.

    Science.gov (United States)

    Tiong, T Joyce; Price, Gareth J

    2012-03-01

    The sonochemical acceleration of bleaching of Rhodamine B by sodium hypochlorite has been studied using ultrasound intensities in the range 0-7 W cm(-2). Using a 20 kHz ultrasonic horn, it was shown that ultrasound could significantly shorten the treatment time and/or the concentration of hypochlorite required for the reaction. A number of intermediate species formed during the reaction have been identified. It was demonstrated that the same sonochemical reactions occur during the use of dental ultrasound instruments of the type used in endodontics where hypochlorite solutions act as disinfectants. Results showed pseudo-first order degradation kinetics for the degradation of Rhodamine B for both types of source. Both the distribution of cavitation and the resulting bleaching reactions were dependent on the design of the tips. The bleaching reaction can therefore be used to characterise the behaviour of dental instruments and aid in the optimisation of their performance. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Multichannel quench-flow microreactor for high-troughput reaction kinetics monitoring on a chip

    NARCIS (Netherlands)

    Bula, W.P.; Kristianto, K.; Kristianto, K.; Gardeniers, Johannes G.E.; Verboom, Willem; van den Berg, Albert; Reinhoudt, David

    2006-01-01

    A novel quench-flow microreactor with parallel reaction lines for high-throughput kinetic studies was designed, fabricated, and tested. The parallel organic reactions can be initiated, controlled and chemically quenched on the chip for each reaction line independently. The simultaneous conversion of

  8. Model for reaction kinetics in pyrolysis of wood

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S. [Banaras Hindu Univ., Varanasi (India)

    1996-12-31

    A reaction model for the pyrolysis of small and large particles of wood Is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The of heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 7 refs., 3 figs., 2 tabs.

  9. Model for reaction kinetics in pyrolysis of wood

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kuma, S. [Banaras Hindu Univ., Varanasi (India)

    1996-12-31

    A reaction model for the pyrolysis of small and large particles of wood is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 6 refs., 3 figs., 2 tabs.

  10. THE KINETICS OF THE BACTERIUM-BACTERIOPHAGE REACTION.

    Science.gov (United States)

    Krueger, A P; Northrop, J H

    1930-11-20

    " as applying to the maximal [P]'s. That is, they all are grouped within a narrow range of [P] values, those having been made with high Po's being of lower titre than those made with low initial [P]'s. (1) There is a significant difference in the temperature coefficients of P and B formation. Further, the temperature coefficients of P and B destruction during lysis differ in almost the same ratio. Consequently, while all experimental evidence postulates B growth as an essential conditioning factor for P formation, the temperature coefficient data suggest that the two processes are basically separate reactions. A similar interpretation holds in the case of B dissolution and P inactivation. (m) The major events in the complete process of "bacteriophagy" are mathematically predictable. The [B] at which lysis occurs under certain standard conditions for given values of Bo and Po may be calculated from the equation: See PDF for Equation Substitution of this value for log B in the equation: See PDF for Equation gives satisfactory agreement with observed values for t((lysis)). (n) The kinetic analysis of the P-B reaction predicts that the values of log Po plotted against t((lysis)) for a constant Bo will give a straight line. This plot is employed in a method for the quantitative estimation of P described in an earlier paper on the basis of experimental observation alone. Its use is made more rational by the facts given above.

  11. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    OpenAIRE

    Cobbs, Gary

    2012-01-01

    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 pote...

  12. Carrageenan-based semi-IPN nanocomposite hydrogels: Swelling kinetic and slow release of sequestrene Fe 138 fertilizer

    Directory of Open Access Journals (Sweden)

    Mohammad Kazem Bahrami

    2016-09-01

    Full Text Available Nanocomposite hydrogels based on kappa-carrageenan were synthesized by incorporating natural sodium montmorillonite (Cloisite nanoclay. Acrylamide (AAm and methylenebisacrylamide (MBA were used as a monomer and a crosslinker, respectively. Effects of reaction variables on the swelling kinetics were studied. The results revealed that the rate of swelling for nanocomposites with high content of MBA was higher than those of nanocomposites consisting of low content of MBA. Similar to the effect of MBA, the rate of swelling enhanced as the carrageenan content was decreased. The influence of clay content on swelling rate was not remarkable. The experimental swelling data were evaluated by pseudo-first-order and pseudo-second-order kinetic models. The swelling data described well by pseudo-second-order kinetic model. Sequestrene Fe 138 (Sq as an agrochemical was loaded into nanocomposites and releasing of this active agent from nanocomposites was studied. The clay-free hydrogel released the whole loaded Sq; whereas the presence of clay restricted the release of Sq.

  13. Understanding Active Metal Reaction Kinetics with Cu–Mg ...

    Indian Academy of Sciences (India)

    Metal substitution reactions are simple redox reactions. These reactions demonstrate the relative activity and the electro- chemical series of metals. In particular, the purpose of this study is to help students comprehend the displacement reac- tion among, Mg metal and solutions containing Cu+2, Ni+2,. Pb+2, Cd+2, Co+2.

  14. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    Science.gov (United States)

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  15. 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…

  16. On the theoretical limits of detecting cyclic changes in cardiac high-energy phosphates and creatine kinase reaction kinetics using in vivo ³¹P MRS.

    Science.gov (United States)

    Weiss, Kilian; Bottomley, Paul A; Weiss, Robert G

    2015-06-01

    Adenosine triphosphate (ATP) is absolutely required to fuel normal cyclic contractions of the heart. The creatine kinase (CK) reaction is a major energy reserve reaction that rapidly converts creatine phosphate (PCr) to ATP during the cardiac cycle and at times of stress and ischemia, but is significantly impaired in conditions such as hypertrophy and heart failure. Because the magnitudes of possible in vivo cyclic changes in cardiac high-energy phosphates (HEPs) during the cardiac cycle are not well known from previous work, this study uses mathematical modeling to assess whether, and to what extent, cyclic variations in HEPs and in the rate of ATP synthesis through CK (CK flux) could exist in the human heart, and whether they could be measured with current in vivo (31)P MRS methods. Multi-site exchange models incorporating enzymatic rate equations were used to study the cyclic dynamics of the CK reaction, and Bloch equations were used to simulate (31)P MRS saturation transfer measurements of the CK reaction. The simulations show that short-term buffering of ATP by CK requires temporal variations over the cardiac cycle in the CK reaction velocities modeled by enzymatic rate equations. The maximum variation in HEPs in the normal human heart beating at 60 min(-1) was approximately 0.4 mM and proportional to the velocity of ATP hydrolysis. Such HEP variations are at or below the current limits of detection by in vivo (31)P MRS methods. Bloch equation simulations show that (31)P MRS saturation transfer estimates the time-averaged, pseudo-first-order forward rate constant, k(f,ap)', of the CK reaction, and that periodic short-term fluctuations in kf ' and CK flux are not likely to be detectable in human studies employing current in vivo (31)P MRS methods. Copyright © 2015 John Wiley & Sons, Ltd.

  17. The kinetics of YOYO-1 intercalation into single molecules of double-stranded DNA.

    Science.gov (United States)

    Reuter, Marcel; Dryden, David T F

    2010-12-10

    The cyanine dye, YOYO-1, has frequently been used in single DNA molecule imaging work to stain double-stranded DNA as it fluoresces strongly when bound. The binding of YOYO-1 lengthens the DNA due to bis-intercalation. We have investigated the kinetics of binding, via this increase in DNA length, for single, hydrodynamically-stretched molecules of lambda DNA observed via Total Internal Reflection Fluorescence (TIRF) microscopy. The rate and degree of lengthening in 40mM NaHCO(3) (pH 8.0) buffer depend upon the free dye concentration with the reaction taking several minutes to reach completion even in relatively high, 40nM, concentrations of YOYO-1. In the absence of overstretching of the DNA molecule, we determine the second order rate constant to be 3.8±0.7×10(5)s(-1)M(-1), the dissociation constant to be 12.1±3.4nM and the maximum DNA molecule extension to be 36±4%. The intercalation time constant (inverse of the pseudo-first order rate constant), τ, decreased from 309 to 62s as YOYO-1 levels increased from 10 to 40nM. The kinetics of binding help with interpretation of the behavior of DNA-YOYO-1 complexes when overstretched and establish defined conditions for the preparation of DNA-YOYO-1 complexes. Copyright © 2010 Elsevier Inc. All rights reserved.

  18. Kinetics and equilibrium properties of the biosorption of Cu2+ by algae.

    Science.gov (United States)

    Wang, Qiong; Peckenham, John; Pinto, Jamie; Patterson, Howard

    2012-11-01

    The purpose of this study was to examine the kinetics and equilibrium properties of freshwater algae with Cu(2+). This was a model system to explore using algae as biosensors for water quality. Methods included making luminescence measurements (fluorescence) and copper ion-selective electrode (CuISE) measurements vs. time to obtain kinetic data. Results were analyzed using a pseudo-first-order model to calculate the rate constants of Cu(2+) uptake by algae: k (p(Cu-algae)) = 0.0025 ± 0.0006 s(-1) by CuISE and k (p(Cu-algae)) = 0.0034 ± 0.0011 s(-1) by luminescence. The binding constant of Cu-algae, K (Cu-algae), was 1.62 ± 0.07 × 10(7) M(-1). Fluorescence results analyzed using the Stern-Volmer relationship indicate that algae have two types of binding sites of which only one appears to affect quenching. The fluorescence-based method was found to be able to detect the reaction of algae with Cu(2+) quickly and at a detection limit of 0.1 mg L(-1).

  19. KINETICS OF THE PHOTOCATALYTIC DEGRADATION OF SELECTED ORGANIC MICROPOLLUTANTS IN THE WATER ENVIROMENT

    Directory of Open Access Journals (Sweden)

    Edyta Anna Kudlek

    2017-04-01

    Full Text Available The paper presents an assessment of the removal degree of selected polycyclic aromatic hydrocarbons (anthracene, benzo(apyrene, xenoestrogens (octylphenol, pentachlorophenol and pharmaceutical compounds (diclofenac in the process of heterogeneous photocatalysis of their water solutions, which were prepared on the base of deionized water. Titanium dioxide at a dose of 100 mg/dm3 was used as a photocatalyst of the process. The kinetics of the process was determined based on the Langmuir-Hinsherlwood equation, assuming the pseudo-first-order reaction of micropollutants decomposition. Furthermore a toxicological analysis of water samples of test compounds was performed by the use of the Microtox® test. It has been found that the micropollutant concentrations decreased with the increase of process time and their removal degree after 60 minutes exceeds 90%. The analysis of the proces kinetic showed that the oxidation of the compounds occurred with the greatest intensity in the first stage of the process up to 10 min. The preformed toxicological assessment confirmed the incomplete decomposition of pollutants and the generation of by-products, which contribute to the increase of the toxicity of treated water solutions.

  20. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  1. Kinetic Approach for the Adsorption of Organophosphorous Pesticides from Aqueous Solution Using “Waste” Jute Fiber Carbon

    Directory of Open Access Journals (Sweden)

    S. Senthilkumaar

    2010-01-01

    Full Text Available Chemically activated “Waste” Jute Fiber carbon has been effectively used for the removal of five organophosphorous pesticides (malathion, monocrotophos, methylparathion, phosphamidon and dimethoate from aqueous solutions. The prepared activated jute fiber carbon was characterized by using Elemental analyzer and proximate analysis methods. The adsorption equilibrium was examined at 28 ºC. Three different kinetic models, the pseudo first order, pseudo second order and Elovich kinetic models were selected to analyses the adsorption process. To compare the fitness of pseudo first order and pseudo second order, sum of the squares of the errors and correlation coefficient, r2 values were calculated. The Elovich model was used to confirm the chemisorptions.

  2. Incremental Identification of Reaction and Mass-Transfer Kinetics Using the Concept of Extents

    OpenAIRE

    Bhatt, Nirav; Amrhein, Michael; Bonvin, Dominique

    2011-01-01

    This paper proposes a variation of the incremental approach to identify reaction and mass-transfer kinetics (rate expressions and the corresponding rate parameters) from concentration measurements for both homogeneous and gas-liquid reaction systems. This incremental approach proceeds in two steps: (i) computation of the extents of reaction and mass transfer from concentration measurements without explicit knowledge of the reaction and mass-transfer rate expressions, and (ii) estimation of ...

  3. Reactions of polynuclear aromatic hydrocarbons with chlorine and chlorine dioxide in coal tar lined pipes

    Energy Technology Data Exchange (ETDEWEB)

    Merkel, T.; Maier, M.; Sacher, F.; Maier, D. [University of Karlsruhe, Karlsruhe (Germany). Engler Bunte Institut

    1997-12-31

    In the presence of disinfectants, PAH are remobilised from the coal tar lining of water distribution mains. Reactions of the PAH with chlorine and chlorine dioxide can lead to chlorinated PAH that might show higher mutagenic effects that the parent PAH. Detection limits in the lower nanogram-per-litre level for the determination of PAH and chlorinated PAH were achieved by using solid phase micro extraction and a gas chromatographic mass spectrometric device. Thus, the reactions of four PAH (anthracene, fluoranthene, fluorene and phenanthrene) with chlorine and chlorine dioxide under conditions and at concentrations of common practice in the drinking water distribution system could be investigated. In batch experiments with demineralised and drinking water at pH 7, the concentrations of fluoranthene, fluorene and phenanthrene remained constant, whereas anthracene reacted quantitatively with both disinfectants. The reaction of anthracene followed by pseudo-first order kinetics. In these reactions no chlorinated products could be detected, only monohydroxyanthracene and anthraquinone were identified. The toxic effect of a set of chlorinated and oxidised PAH was also examined.

  4. Advanced oxidation kinetics and mechanism of preservative propylparaben degradation in aqueous suspension of TiO2 and risk assessment of its degradation products.

    Science.gov (United States)

    Fang, Hansun; Gao, Yanpeng; Li, Guiying; An, Jibin; Wong, Po-Keung; Fu, Haiying; Yao, Side; Nie, Xiangping; An, Taicheng

    2013-03-19

    The absolute kinetic rate constants of propylparaben (PPB) in water with different free radicals were investigated, and it was found that both hydroxyl radicals (HO(•)) and hydrated electrons could rapidly react with PPB. The advanced oxidation kinetics and mechanisms of PPB were investigated using photocatalytic process as a model technology, and the degradation was found to be a pseudo-first-order model. Oxidative species, particularly HO(•), were the most important reactive oxygen species mediating photocatalytic degradation of PPB, and PPB degradation was found to be significantly affected by pH because it was controlled by the radical reaction mechanism and was postulated to occur primarily via HO(•)-addition or H-abstraction reactions on the basis of pulse radiolysis measurements and observed reaction products. To investigate potential risk of PPB to humans and aqueous organisms, the estrogenic assays and bioassays were performed using 100 μM PPB solution degraded by photocatalysis at specific intervals. The estrogenic activity decreased as PPB was degraded, while the acute toxicity at three trophic levels first increased slowly and then decreased rapidly as the total organic carbon decreased during photocatalytic degradation.

  5. Experimental and reaction kinetic investigation of 1-octene metathesis reaction with Hoveyda-Grubbs first generation precatalyst

    OpenAIRE

    Van der Gryp, Percy; Marx, Sanette; Vosloo, Hermanus C.M.

    2012-01-01

    In this study we report the catalytic performance, reaction engineering kinetics and elucidation of the reaction mechanism using density functional theory (DFT) for the metathesis reaction of 1-octene in the presence of the Hoveyda-Grubbs 2 [RuCl2(CHoOiPrC6H4)(H2IMes)] precatalyst. The study showed that reaction temperature (30-100 °C), 1-octene/precatalyst molar ratio (5000-14,000) and different solvents had a significant effect on the selectivity, activity and turnover number. Turnover numb...

  6. 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...... and 3D limiting cases. The analytical result is fully confirmed by kinetic Monte Carlo simulations....

  7. Illustrating the Mass Transport Effect on Enzyme Cascade Reaction Kinetics Using a Rotating Ring Disk Electrode.

    Science.gov (United States)

    Wu, Zeng-Qiang; Liu, Jun-Jun; Li, Jin-Yi; Xu, Dan; Xia, Xing-Hua

    2017-11-07

    Electrochemical biosensors based on enzymatic reaction have been applied into a wide range of fields. As the trend continues to grow, these biosensors are approaching to the limit imposed by physics and chemistry. To further improve the performance of the biosensors, the interplay of mass transport and enzymatic reaction kinetics, especially in the enzyme cascade systems, should be considered at the design of biosensors. Herein, we propose a simple approach to the studying on the influence of mass transport and enzyme molecules motion on the kinetics of enzyme cascade reactions. β-galactosidase (β-Gal) and glucose oxidase (GOx) of the enzyme cascade reaction are precisely immobilized onto the disk and ring electrodes of rotating ring disk electrode (RRDE) via covalent attachment method, respectively. At a low rotating speed (<600 rpm), the convective transport promotes the enzyme cascade reaction. When the rotating speed is higher than 600 rpm, the cascade reaction develops into kinetics controlled. Further increase of the rotating speed results in slow decline in reaction rate possibly due to the production inhibition effect. In addition, the conformation change of the enzyme at higher centrifugal forces on enzyme activity should be considered. This study would shine lights on the effect of convective force on regulation of kinetics of enzyme cascade reaction, offering an ideal platform for studying other enzyme cascade reactions and providing fundamentals to design high performance of biosensors, biofuel cells and bioelectronics.

  8. Reaction kinetics of bioactive glass and a resorbable polysaccharide

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, I.; Hench, L.L. [Imperial Coll. of Science, Technology and Medicine, London (United Kingdom). Dept. of Materials

    2001-07-01

    The kinetics of bioactive glass systems has been well documented. The addition of a resorpable polysaccharide, dextran, has improved the handling properties of particulate glass. This paper describes the methodology that has shown the Bioglass {sup trademark} putty system increases the crystallisation of the amorphous calcium hydroxide layer by just 5 hours when compared to Bioglass {sup trademark} particles alone. (orig.)

  9. Microsecond reaction kinetics and catalytic mechanism of bacterial cytochrome oxidases

    NARCIS (Netherlands)

    Paulus, A.

    2017-01-01

    Fundamental biochemical research is of crucial importance for a complete and detailed
    understanding of what drives enzyme activity and how enzyme kinetic properties are
    optimized towards survival of the host organism. When cells fail to produce a fully functional
    enzyme, the organism’s

  10. Kinetics and mechanism of the ligand substitution reaction of di- ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3 ... The kinetics of the interaction between diethyldithiocarbamate (Et2DTC) and the title complex has been studied spectrophotometrically in aqueous medium as a function of nucleophile concentration, temperature and pH at constant ionic strength.

  11. Kinetically influenced terms for solute transport affected by heterogeneous and homogeneous classical reactions

    Science.gov (United States)

    Bahr, J.M.

    1990-01-01

    This paper extends a four-step derivation procedure, previously presented for cases of transport affected by surface reactions, to transport problems involving homogeneous reactions. Derivations for these classes of reactions are used to illustrate the manner in which mathematical differences between reaction classes are reflected in the mathematical derivation procedures required to identify kinetically influenced terms. Simulation results for a case of transport affected by a single solution phase complexation reaction and for a case of transport affected by a precipitation-dissolution reaction are used to demonstrate the nature of departures from equilibrium-controlled transport as well as the use of kinetically influenced terms in determining criteria for the applicability of the local equilibrium assumption. A final derivation for a multireaction problem demonstrates the application of the generalized procedure to a case of transport affected by reactions of several classes. -from Author

  12. Kinetics and mechanism for the substitution reactions of ...

    Indian Academy of Sciences (India)

    For the substitution with thiourea, a third reaction step, the displacement of the labilized amine, ... The activation parameters for all reactions studied suggest an ..... Its acid– base chemistry was characterized by fitting the poten- tiometric data to various acid–base models. The best fit model was found to be consistent with ...

  13. kinetics and mechanism of reaction of acidic chlorite with ...

    African Journals Online (AJOL)

    overall third order rate constants for the reaction of acidic chlorite with Nile blue and Meldola's blue were (0.363 ... of interest to investigate, how these differences affect the reaction rates of these dyes with acidic chlorite. .... To establish the order with respect to chlorite and acid, the effect of initial concentration of chlorite and ...

  14. Kinetic modelling of reactions in heated disaccharide-casein systems

    NARCIS (Netherlands)

    Brands, C.M.J.; Boekel, van M.A.J.S.

    2003-01-01

    The reactions occurring in disaccharide-casein reaction mixtures during heating at 120 degreesC and pH 6.8 were studied. The existence of two main degradation routes were established: (1) Isomerisation of the aldose sugars lactose and maltose in their ketose isomers lactulose and maltulose,

  15. Understanding Active Metal Reaction Kinetics with Cu–Mg ...

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 22; Issue 2. Understanding Active Metal Reaction Kinetis with Cu-Mg Replacement Reaction ... Author Affiliations. Ilhami Ceyhun1 Zafer Karagolge1. Ataturk University, Education Faculty, Department of Chemical Education, Erzurum, Turkey.

  16. Online Measurement of Oxygen-Dependent Enzyme Reaction Kinetics

    DEFF Research Database (Denmark)

    Meissner, Murray Peter; Nordblad, Mathias; Woodley, John M

    2018-01-01

    reaction rate constants and time-course progressions calculated from the oxygen mass balance were validated against conventional online methods of dissolved oxygen tension and pH titration measurements. A feasible operating window as well as the sensitivity to dynamic changes of reaction rates......As the application of biocatalysis to complement conventional chemical and catalytic approaches continues to expand, an increasing number of reactions involve poorly-water soluble substrates. At required industrial concentrations necessary for industrial implementation, this frequently leads...... to heterogeneous reaction mixtures composed of multiple phases. Such systems are challenging to sample and therefore it is problematic to measure representative component concentrations. In this work we demonstrate and validate an online method for following the progress of oxygen-dependent reactions through...

  17. Novel chemical kinetics for a single enzyme reaction: relationship between substrate concentration and the second moment of enzyme reaction time.

    Science.gov (United States)

    Jung, Won; Yang, Seongeun; Sung, Jaeyoung

    2010-08-05

    We report a robust quadratic relation between the inverse substrate concentration and the second moment, , of the catalytic turnover time distribution for enzyme reactions. The results hold irrespective of the mechanism and dynamics of the enzyme reaction and suggest a novel single molecule experimental analysis that provides information about reaction processes of the enzyme-substrate complex and ergodicity of the enzyme reaction system, which is beyond the reach of the conventional analysis for the mean reaction time, . It turns out that - 2(2) is linear in inverse substrate concentration for an ergodic homogeneous enzyme system given that the enzyme substrate encounter is a simple rate process, and its value at the high substrate concentration limit provides direct information about if any non-Poisson reaction process of the enzyme-substrate complex. For a nonergodic heterogeneous reaction system, the corresponding quantity becomes a quadratic function of the inverse substrate concentration. This leads us to suggest an ergodicity measure for single enzyme reaction systems. We obtain a simple analytic expression of the randomness parameter for the single catalytic turnover time, which could provide a quantitative explanation about the previously reported randomness data of the beta-galactosidase enzyme. In obtaining the results, we introduce novel chemical kinetics applicable to a non-Poisson reaction network with arbitrary connectivity, as a generalization of the conventional chemical kinetics.

  18. Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation.

    Science.gov (United States)

    Xie, Xiaofang; Zhang, Yongqing; Huang, Weilin; Huang, Shaobing

    2012-01-01

    Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature, persulfate concentration and pH conditions were examined in batch experiments. The results showed that, the aniline degradation followed pseudo first-order reaction model. Aniline degradation rate increased with increasing temperature or persulfate concentration. In the pH range of 3 to 11, a low aniline degradation rate was obtained at strong acid system (pH 3), while a high degradation rate was achieved at strong alkalinity (pH 11). Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5, 7 and 9). Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology. And nitrobenzene, 4-4'-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation mechanism of aniline was also tentatively proposed.

  19. Chlorination of oxybenzone: Kinetics, transformation, disinfection byproducts formation, and genotoxicity changes.

    Science.gov (United States)

    Zhang, Shujuan; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F

    2016-07-01

    UV filters are a kind of emerging contaminant, and their transformation behavior in water treatment processes has aroused great concern. In particular, toxic products might be produced during reaction with disinfectants during the disinfection process. As one of the most widely used UV filters, oxybenzone has received significant attention, because its transformation and toxicity changes during chlorine oxidation are a concern. In our study, the reaction between oxybenzone and chlorine followed pseudo-first-order and second-order kinetics. Three transformation products were detected by LC-MS/MS, and the stability of products followed the order of tri-chloro-methoxyphenoyl > di-chlorinated oxybenzone > mono-chlorinated oxybenzone. Disinfection byproducts (DBPs) including chloroform, trichloroacetic acid, dichloroacetic acid and chloral hydrate were quickly formed, and increased at a slower rate until their concentrations remained constant. The maximum DBP/oxybenzone molar yields for the four compounds were 12.02%, 6.28%, 0.90% and 0.23%, respectively. SOS/umu genotoxicity test indicated that genotoxicity was highly elevated after chlorination, and genotoxicity showed a significantly positive correlation with the response of tri-chloro-methoxyphenoyl. Our results indicated that more genotoxic transformation products were produced in spite of the elimination of oxybenzone, posing potential threats to drinking water safety. This study shed light on the formation of DBPs and toxicity changes during the chlorination process of oxybenzone. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Kinetic Study on Aminolysis of O-2-Pyridyl Thionobenzoate in Acetonitrile: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Reaction Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Min-Young; Um, Ik-Hwan [Ewha Womans University, Seoul (Korea, Republic of)

    2016-09-15

    Pseudo-first-order rate constants (k{sub obsd}) for nucleophilic substitution reaction of O-2-pyridyl thionobenzoate (7) with a series of secondary amines in MeCN at 25.0 ± 0.1 .deg. C have been measured spectrophotometrically. The plots of k{sub obsd} vs. [amine] curve upward, indicating that the reaction proceeds through a stepwise mechanism with a zwitterionic tetrahedral intermediate (T{sup ±}), which decomposes to the products through uncatalyzed and catalyzed routes. It has been proposed that the uncatalyzed reaction proceeds through a six-membered cyclic transition state (TS), in which expulsion of the leaving group occurs in the rate-determining step. The catalyzed reaction from T{sup ±} proceeds through a concerted mechanism with a six-membered cyclic TS rather than via a stepwise pathway with an anionic intermediate T{sup -}. This is in contrast to the report that the corresponding reaction of 2-pyridyl benzoate (6, a C=O analogue of 7) proceeds through a forced concerted mechanism. Comparison of the second-order rate constants for the uncatalyzed reaction of 7 with those reported previously for the corresponding reaction of 6 has revealed that 7 is much more reactive than 6. Factors that affect the reactivity and reaction mechanism are discussed in detail.

  1. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-06-05

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

  2. Kinetics of the reaction between dissolved sodium sulfide and biologically produced sulfur

    NARCIS (Netherlands)

    Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

    2005-01-01

    The kinetics of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied by measuring the formation of polysulfide ions, Sx2-, in time (pH = 8.0, T = 30-50 °C). Detailed knowledge of this reaction is essential to understand its effect on

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

    African Journals Online (AJOL)

    Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and Carbon. ... proceeds as written for high initial carbon contents but proceeds in the reverse direction for high initial silicon contents. The rate-limiting factors seem to be the surface chemical reactions, with rate of supply of silicon monoxide probably contributing.

  4. Microsecond reaction kinetics and catalytic mechanism of bacterial cytochrome oxidases

    OpenAIRE

    Paulus, A

    2017-01-01

    Fundamental biochemical research is of crucial importance for a complete and detailedunderstanding of what drives enzyme activity and how enzyme kinetic properties areoptimized towards survival of the host organism. When cells fail to produce a fully functionalenzyme, the organism’s ability to survive or thrive is impacted. In humans, for example, lowlevels or absence of lactase causes lactose intolerance, while decreased performance of theproton-pumping enzyme cytochrome aa3 oxidase in the m...

  5. Kinetic and mechanistic studies of free-radical reactions in combustion

    Energy Technology Data Exchange (ETDEWEB)

    Tully, F.P. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    Combustion is driven by energy-releasing chemical reactions. Free radicals that participate in chain reactions carry the combustion process from reactants to products. Research in chemical kinetics enables us to understand the microscopic mechanisms involved in individual chemical reactions as well as to determine the rates at which they proceed. Both types of information are required for an understanding of how flames burn, why engines knock, how to minimize the production of pollutants, and many other important questions in combustion. In this program the authors emphasize accurate measurements over wide temperature ranges of the rates at which ubiquitous free radicals react with stable molecules. The authors investigate a variety of OH, CN, and CH + stable molecule reactions important to fuel conversion, emphasizing application of the extraordinarily precise technique of laser photolysis/continuous-wave laser-induced fluorescence (LP/cwLIF). This precision enables kinetic measurements to serve as mechanistic probes. Since considerable effort is required to study each individual reaction, prudent selection is critical. Two factors encourage selection of a specific reaction: (1) the rates and mechanisms of the subject reaction are required input to a combustion model; and (2) the reaction is a chemical prototype which, upon characterization, will provide fundamental insight into chemical reactivity, facilitate estimation of kinetic parameters for similar reactions, and constrain and test the computational limits of reaction-rate theory. Most studies performed in this project satisfy both conditions.

  6. 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

    and confirmed by kinetic Monte Carlo (KMC) simulations. Here we report on KMC simulations investigating a different transition from 1D to 3D diffusion of 1D gliding loops for which their 1D migration is interrupted by occasional 2D migration due to conservative climb by dislocation core diffusion within a plane......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...... transverse to their 1D glide direction. Their transition from 1D to 3D kinetics is significantly different from that due to direction changes. The KMC results are compared to an analytical description of this diffusion mode in the form of a master curve relating the 1D normalized sink strength...

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

    Science.gov (United States)

    Heinisch, H. L.; Trinkaus, H.; Singh, B. N.

    2007-08-01

    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 and confirmed by kinetic Monte Carlo (KMC) simulations. Here we report on KMC simulations investigating a different transition from 1D to 3D diffusion of 1D gliding loops for which their 1D migration is interrupted by occasional 2D migration due to conservative climb by dislocation core diffusion within a plane transverse to their 1D glide direction. Their transition from 1D to 3D kinetics is significantly different from that due to direction changes. The KMC results are compared to an analytical description of this diffusion mode in the form of a master curve relating the 1D normalized sink strength to the frequency of disturbance of 1D migration.

  8. Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

    Science.gov (United States)

    Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana

    2013-09-01

    The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, Δ E a, Δ H #, Δ S #, Δ G ≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γmax), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (Πmax), Gibb's energy of micellization (Δ G M°), Gibb's energy of adsorption (Δ G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

  9. Reaction of a hydrated electron with gentamycin and collagen -a pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Pietrucha, K. [Technical Univ., Lodz (Poland). Inst. of Applied Radiation Chemistry; Gora, L. [Worcester Poltechnic Inst., MA (United States). Dept. of Chemical Engineering; Doillon, C.J. [Laval Univ., Quebec, PQ (Canada). Dept. of Surgery]|[Saint-Francois d`Assise Hospital, Quebec (Canada)

    1996-01-01

    The reactions of a hydrated electron (e{sub aq}{sup -}) with aminoglycoside antibiotic gentamycin and collagen in aqueous medium at different pH have been investigated employing a pulse radiolysis technique. The pseudo-first order equation of reaction kinetics was used to give an accurate description of the decay of e{sub aq}{sup -} in gentamycin solutions. The rate constant of the e{sub aq}{sup -}decay in collagen solutions was high and reached 3.2 x 10{sup 10} M{sup -1} s{sup -1}. The rate constants for the reaction of the e{sub aq}{sup -}with gentamycin were found to be influenced by pH, decreasing with the deprotonation of the -NH{sub 3} groups, while for pH > pK{sub a} which for gentamycin is equal to 7.8, the rate constant was unchanged. These observations suggest that when the amino groups are protonated, reductive deamination occurs, but for unprotonated non-reactive amino groups, a radical anion is formed on the glycoside moiety. (Author).

  10. 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.

  11. A new semi-empirical kinetic method for the determination of ion exchange constants for the counterions of cationic micelles.

    Science.gov (United States)

    Khan, M Niyaz

    2010-09-15

    A new method, based upon semi-empirical kinetic approach, for the determination of ion exchange constant for ion exchange processes occurring between counterions at the cationic micellar surface is described in this review article. Basically, the method involves a reaction kinetic probe which gives observed pseudo-first-order rate constants (k(obs)) for a nucleophilic substitution reaction between the nonionic and anionic reactants (R and S) in the presence of a constant concentration of both reactants as well as cationic micelles and varying concentrations of an inert inorganic or organic salt (MX). The observed data (k(obs), versus [MX]) fit satisfactorily (in terms of residual errors) to an empirical equation which could be derived from an equation explaining the mechanism of the reaction of the kinetic probe in terms of pseudophase micellar (PM) model coupled with another empirical equation. This (another) empirical equation explains the effect of [MX] on cationic micellar binding constant (K(S)) of the anionic reactant (say S) and gives an empirical constant, K(X/S). The magnitude of K(X/S) is the measure of the ability of X(-) to expel S(-) from a cationic micellar pseudophase to the bulk aqueous phase through ion exchange X(-)/S(-). The values of K(X/S) and K(Y/S) (where Y(-) is another inert counterion) give the ion exchange constant, K(X)(Y) (=K(X)/K(Y) where K(X) and K(Y) represent cationic micellar binding constants of X(-) and Y(-), respectively). The suitability of this method is demonstrated by the use of three different reaction kinetic probes and various MX. Copyright 2010 Elsevier B.V. All rights reserved.

  12. KINETIC STUDIES OF THE TWO LIGHT REACTIONS IN PHOTOSYNTHESIS

    Energy Technology Data Exchange (ETDEWEB)

    Kuntz Jr., I.D.; Calvin, Melvin

    1964-11-01

    The decay kinetics of the photo-induced absorbance changes in red and green algae are very sensitive to the wavelength of the actinic 11ght. A four to twofold increase in half-decay time is noted in going from short wavelength (550-650 mu) to long wavelength (> 700 mu) excitation. The slow decay ratios, produced by long wavelength light can be enhanced with a steady background of short wavelength light. A relationship between initial decay rates and 02 evolution rates is described. This relationship allows a direct correspondence between these spectroscopic studies and the 'red-drop' and 'enhancement' experiments of Emerson.

  13. Photocatalytic degradation kinetics and mechanism of environmental pharmaceuticals in aqueous suspension of TiO{sub 2}: A case of {beta}-blockers

    Energy Technology Data Exchange (ETDEWEB)

    Yang Hai [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Kehua Street, Tianhe District, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100049 (China); An Taicheng, E-mail: antc99@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Kehua Street, Tianhe District, Guangzhou 510640 (China); Li Guiying [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Kehua Street, Tianhe District, Guangzhou 510640 (China); Song Weihua; Cooper, William J. [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, CA 92697-2175 (United States); Luo Haiying [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Kehua Street, Tianhe District, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100049 (China); Guangzhou Product Quality Supervision and Testing Institute, National Centre for Quality Supervision and Testing of Processed Food (Guangzhou), Guangzhou 510110 (China); Guo Xindong [Guangzhou Product Quality Supervision and Testing Institute, National Centre for Quality Supervision and Testing of Processed Food (Guangzhou), Guangzhou 510110 (China)

    2010-07-15

    This study investigated the photocatalytic degradation of three {beta}-blockers in TiO{sub 2} suspensions. The disappearance of the compounds followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model and the rate constants were 0.075, 0.072 and 0.182 min{sup -1} for atenolol, metoprolol and propranolol, respectively. After 240 min irradiation, the reaction intermediates were completely mineralized to CO{sub 2} and the nitrogen was predominantly as NH{sub 4}{sup +}. The influence of initial pH and {beta}-blocker concentration on the kinetics was also studied. From adsorption studies it appears that the photocatalytic degradation occurred mainly on the surface of TiO{sub 2}. Further studies indicated that surface reaction with {center_dot}OH radical was principally responsible for the degradation of these three {beta}-blockers. The major degradation intermediates were identified by HPLC/MS analysis. Cleavage of the side chain and the addition of the hydroxyl group to the parent compounds were found to be the two main degradation pathways for all three {beta}-blockers.

  14. Stimulating kinetic of aerobic reactions skilled athlete in sport dance

    Directory of Open Access Journals (Sweden)

    Lee Bo

    2010-10-01

    Full Text Available Changes speed of development of reaction of frequency of heart-throbs are appraised under act of the program of trainings facilities. Directions stimulation of the cardiorespiratory system of sportsmen are rotined. In research took part 2 homogeneous groups of sportsmen for 12 sportsmen (6 pair. It is set that the high-rate of development of reactions of aerobic power providing reflects reactive properties of the cardiorespiratory system and influences on efficiency of functional preparation on the whole. Possibilities of estimation of reactive properties of the cardiorespiratory system are rotined in the natural terms of training process.

  15. A Numerical Study of Reaction Kinetics Model of Polymerization In ...

    African Journals Online (AJOL)

    The model which is a system of partial differential equations is analyzed numerically using the finite difference scheme to obtain results for1, 2, 3, 4, 10, 100, 1000 (where p is the order of reaction). Keywords: Frontal polymerization, Material diffusion. Journal of the Nigerian Association of Mathematical Physics, Volume 19 ...

  16. Kinetics and mechanism of the reactions of hexaaqua rhodium (III ...

    Indian Academy of Sciences (India)

    Unknown

    RhOH2. 3+ + SIV for which fast formation of the O- bonded sulphito complex was observed.9 Several. (aqua)(amine)cobalt (III) ions have been shown to undergo fast and reversible formation of the O-bon- ded sulphito complexes in the presence of SO2 in mild acidic media.8. On immediate acidification of the reaction mix-.

  17. The kinetics of substitution reaction of oxydiacetate and ...

    Indian Academy of Sciences (India)

    substitution reaction of Cu(II) oxydiactate and thio- diacetate complexes have also been investigated in. DMSO solution. The physico-chemical as well as acid- base properties of non-aqueous solvents including. DMSO affect coordinating properties of ligands such as pyridine derivatives and consequently it may influ-.

  18. Complex Kinetics in the Reaction of Taurine with Aqueous Bromine ...

    African Journals Online (AJOL)

    molecule is the only one that can engage in reactions.10 The range of taurine implication ... H2O2 and Cl–, some studies have shown that EPO is less active than MPO with .... taurine shows a strong absorption peak at 240 nm with an ab- sorptivity of 2713 ... Applying the Beer-Lambert law for monobromo- taurine at 288 nm ...

  19. Reactions on oxide catalysts—kinetics and mechanism

    Indian Academy of Sciences (India)

    The technique of competitive reactions has been used to establish that the catalytic ketonization is a bimolecular process on the surface of the catalyst. Keywords. ... the physical state of the catalyst, to provide a different environment for the catalyst and sometimes modify it by interaction. Mixed oxide systems, binary and ...

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

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    sensitive radical pair reactions occurring in the retina, the light-sensitive part of animal eyes. A photoreceptor, cryptochrome, has been suggested to endow birds with magnetoreceptive abilities as the protein has been shown to exhibit the biophysical properties required for an animal magnetoreceptor...

  1. Kinetics of the reaction of compound III of horseradish peroxidase ...

    African Journals Online (AJOL)

    Each reaction was first order with respect to the concentration of horseradish peroxidase. The observed rate constants were ionic strength dependent within the range of 0.06 – 0.30 M. The logarithmic values of the rate constants against the square root of the ionic strength showed that both NADPH and Compound III of ...

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

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

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

  3. Integration of Kinetic Analysis of Reaction Curve with a Proper Classical Approach for Enzymatic Analysis

    Directory of Open Access Journals (Sweden)

    Xiaolan Yang

    2012-01-01

    Full Text Available For enzymatic analysis to quantify a substrate or enzyme, kinetic analysis of reaction curve can be integrated with a proper classical approach. For their integration, they should have consistent slopes and intercepts of linear response and an overlapped region of analyte quantities measurable under optimized conditions. To quantify a substrate after optimizations of tool enzyme activity and reaction duration, the equilibrium method works when the reaction is completed within the reaction duration; otherwise, kinetic analysis of reaction curve applies providing at least seven data with sufficient consumption of substrate. To quantify an enzyme after optimizations of initial substrate concentration and reaction duration, the classical initial rate method works when an estimated initial rate locates within the linear range; otherwise, kinetic analysis of reaction curve applies after the conversion of the quantification index with optimized parameters. This integration strategy has ideal linear ranges and practical efficiency for quantifying an enzyme at moderate substrate levels and for quantifying a substrate at moderate cost on tool enzyme; it has promise to simultaneous assays of multiple enzymes in one reaction vessel each time and ,thus, potential applications to concurrently quantify multiple serum enzymes, screen inhibitors against multiple enzyme targets, and detect multiple serum components by enzymeimmunoassay.

  4. Complex Cure Kinetics of the Hydroxyl-Epoxide Reaction in DGEBA Epoxy Hardened with Diethanolamine

    Science.gov (United States)

    Ancipink, Windy; McCoy, John; Kropka, Jamie; Celina, Mathias

    The curing of a diglycidyl ether of bisphenol-A Epoxy (Epon 828) with diethanolamine (DEA) involves a fast amine-epoxide reaction followed by a slower hydroxyl-epoxide reaction. At curing temperatures below 100°C, the time scales of these two reactions are well separated, and the hydroxyl addition can be studied as an ''isolated'' reaction. The hydroxyl-epoxide reaction is of great interest due to the complex kinetics involved, which are brought about by competing reactions. The reaction kinetics are believed to be tertiary amine catalyzed and are well fit to a modified form of the Kamal-type equation. Here we study the complex long term reaction kinetics at various temperatures, by using isothermal modulated differential scanning calorimetry, micro calorimetry, and infrared spectroscopy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  5. Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

    Directory of Open Access Journals (Sweden)

    Xingxing Li

    2015-07-01

    Full Text Available Cuprous oxide (Cu2O nanocubes were synthesized by reducing Cu(OH2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area. The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.

  6. 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.

  7. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    DEFF Research Database (Denmark)

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...... lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches....... The parameter estimation problem is decomposed into five hierarchical steps, where the solution of each of the steps becomes the input for the subsequent step to achieve the final model with the corresponding regressed parameters. The model is further used for validating its performance and determining...

  8. Kinetics of diffusion-controlled enzymatic reactions with charged substrates

    OpenAIRE

    Lu, Benzhuo; McCammon, J. Andrew

    2010-01-01

    Abstract The Debye-Hückel limiting law (DHL) has often been used to estimate rate constants of diffusion-controlled reactions under different ionic strengths. Two main approximations are adopted in DHL: one is that the solution of the linearized Poisson-Boltzmann equation for a spherical cavity is used to estimate the excess electrostatic free energy of a solution; the other is that details of electrostatic interactions of the solutes are neglected. This ma...

  9. The Kinetics of Heterogeneous Electron Transfer Reactions in Polar Solvents

    Science.gov (United States)

    1994-04-20

    exp(-vei/ 2Vn )J (10) 2-exp(-vel/ 2Vn ) When Yel >> yn, jS is unity and the reaction is adiabatic. However, when ye, << yn, the expression for E becomes IC...approximation, IL is given by [31] TL - Em TD (13)Es where f, is the high frequency relative solvent permittivity and ID, the Debye relaxation time

  10. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    Science.gov (United States)

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Kinetics of diffusion-controlled enzymatic reactions with charged substrates.

    Science.gov (United States)

    Lu, Benzhuo; McCammon, J Andrew

    2010-01-18

    The Debye-Hückel limiting law (DHL) has often been used to estimate rate constants of diffusion-controlled reactions under different ionic strengths. Two main approximations are adopted in DHL: one is that the solution of the linearized Poisson-Boltzmann equation for a spherical cavity is used to estimate the excess electrostatic free energy of a solution; the other is that details of electrostatic interactions of the solutes are neglected. This makes DHL applicable only at low ionic strengths and dilute solutions (very low substrate/solute concentrations). We show in this work that through numerical solution of the Poisson-Nernst-Planck equations, diffusion-reaction processes can be studied at a variety of conditions including realistically concentrated solutions, high ionic strength, and certainly with non-equilibrium charge distributions. Reaction rate coefficients for the acetylcholine-acetylcholinesterase system are predicted to strongly depend on both ionic strength and substrate concentration. In particular, they increase considerably with increase of substrate concentrations at a fixed ionic strength, which is open to experimental testing. This phenomenon is also verified on a simple model, and is expected to be general for electrostatically attracting enzyme-substrate systems.PACS Codes: 82.45.Tv, 87.15.VvMSC Codes: 92C30.

  12. 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...... parameters. The model was validated with experimental data. As a conclusion, kinetic parameters with a possible positive impact on reaction performance were identified and assessed in relation to operating conditions. This resulted in the identification of suitable catalyst and process development targets...

  13. Soil solid materials affect the kinetics of extracellular enzymatic reactions

    Science.gov (United States)

    Lammirato, C.; Miltner, A.; Kästner, M.

    2009-04-01

    INTRODUCTION Soil solid materials affect the degradation processes of many organic compounds by decreasing the bioavailability of substrates and by interacting with degraders. The magnitude of this effect in the environment is shown by the fact that xenobiotics which are readily metabolized in aquatic environments can have long residence times in soil. Extracellular enzymatic hydrolysis of cellobiose (enzyme: beta-glucosidase from Aspergillus niger) was chosen as model degradation process since it is easier to control and more reproducible than a whole cell processes. Furthermore extracellular enzymes play an important role in the environment since they are responsible for the first steps in the degradation of organic macromolecules; beta-glucosidase is key enzyme in the degradation of cellulose and therefore it is fundamental in the carbon cycle and for soil in general. The aims of the project are: 1) quantification of solid material effect on degradation, 2) separation of the effects of minerals on enzyme (adsorption →change in activity) and substrate (adsorption →change in bioavailability). Our hypothesis is that a rate reduction in the enzymatic reaction in the presence of a solid phase results from the sum of decreased bioavailability of the substrate and decreased activity of enzyme molecules. The relative contribution of the two terms to the overall effect can vary widely depending on the chemical nature of the substrate, the properties of the enzyme and on the surface properties of the solid materials. Furthermore we hypothesize that by immobilizing the enzyme in an appropriate carrier the adsorption of enzymes to soil materials can be eliminated and that therefore immobilization can increase the overall reaction rate (activity loss caused by immobilization standard experimental conditions: 66 mM phosphate buffer, pH 5, 25°C, 20 mg solid/ml buffer). The enzyme in an immobilized form (covalent bonding to oxirane groups on the surfaces of macroporous

  14. Kinetics of transesterification of palm oil and dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base catalyst.

    Science.gov (United States)

    Zhang, Liping; Sheng, Boyang; Xin, Zhong; Liu, Qun; Sun, Shuzhen

    2010-11-01

    The transesterification of palm oil with dimethyl carbonate (DMC) for preparing biodiesel has been studied in solvent-free system at the catalysis of potassium hydroxide (KOH) as heterogeneous catalyst. Fatty acid methyl esters (FAMEs) were analyzed by GC with internal standard method. The effects of reaction conditions (molar ratio of DMC and palm oil, catalyst amount and time) on FAMEs yield were investigated. The highest FAMEs yield could reach 96.2% at refluxing temperature for 8h with molar ratio of DMC and oil 9:1 and 8.5% KOH (based on oil weight). Kinetics of the KOH-catalyzed transesterification of palm oil and DMC was researched over a temperature range of 65-75 degrees C. A pseudo first-order model was proposed. The activation energy (E(a)) was 79.1 kJ mo1(-1) and the pre-exponential factor (k(o)) was 1.26 x 10(9) min(-1) from Arrhenius equation. Further, a plausible reaction mechanism for the catalytic process with DMC as acyl acceptor was proposed. Copyright 2010 Elsevier Ltd. All rights reserved.

  15. Reaction diffusion and solid state chemical kinetics handbook

    CERN Document Server

    Dybkov, V I

    2010-01-01

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

  16. Degradation of aniline by heterogeneous Fenton's reaction using a Ni-Fe oxalate complex catalyst.

    Science.gov (United States)

    Liu, Yucan; Zhang, Guangming; Fang, Shunyan; Chong, Shan; Zhu, Jia

    2016-11-01

    A Ni-Fe oxalate complex catalyst was synthesized and characterized by means of Brunauer-Emmet-Teller (BET) method, scanning electron microscope (SEM) and X-ray photo-electron spectroscopy (XPS). The catalyst showed good catalytic activity for aniline degradation by heterogeneous Fenton's reaction, in which the synergetic index was 9.3. The effects of reaction temperature, catalyst dosage, hydrogen peroxide concentration and initial pH were investigated. Under the optimum conditions (T = 293 K, catalyst dosage = 0.2 g/L, H2O2 concentration = 4 mmol/L and initial pH = 5.4), 100% aniline could be removed within 35 min, and approximately 88% deamination efficiency was achieved in 60 min. The aniline degradation process followed the pseudo-first-order kinetic (k = 0.177 min(-1)) with activation energy (Ea) of 49.4 kJ mol(-1). Aniline could be removed in a broad initial pH (3-8) due to the excellent pH-tolerance property of the catalyst. The detected ammonium ion indicated that deamination occurred during aniline degradation. It was proposed that deamination synchronized with aniline removal, and aniline was attacked by free radicals to generate benzoquinonimine and phenol. This system is promising for the removal of aniline from water. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Self-triggering reaction kinetics between nitrates and aluminium powder

    Energy Technology Data Exchange (ETDEWEB)

    Demichela, Micaela [SAfeR-Centro Studi su Sicurezza Affidabilita e Rischi, Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi, 24, I 10129 Torino (Italy)], E-mail: micaela.demichela@polito.it

    2007-09-05

    During the night between the 19 and 20 September 2003, a loud explosion occurred at about 3 km from the town of Carignano that was clearly heard at a distance of some tens of kilometres. The explosion almost completely destroyed most of the laboratories of the Panzera Company that were used for the production of fireworks. The results of the research activities that were carried out using a differential scanning calorimeter (DSC) on the same raw materials that made up the pyrotechnical mixture that exploded are reported in this paper. This activity was carried out to identify the dynamics of the accident. It proved possible to verify how the event was produced because of a slow exothermic reaction which, after about 8 h, caused the self-triggering of 120 kg of finished product. The detonation can therefore be put down to a runaway reaction in the solid phase, whose primogenial causes can be attributed to a still craftsman type production system, not conformed to the rigorous controls and inspections as those required by a safety management system for major risk plants, as the Panzera Company was.

  18. Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction

    Directory of Open Access Journals (Sweden)

    Côrtes Carlos Eduardo S.

    2001-01-01

    Full Text Available The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm. It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C, different from all other values for this pKa proposed in the literature.

  19. Kinetic and thermodynamic studies of Hg(II) adsorption onto MCM-41 modified by ZnCl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Raji, Foad; Pakizeh, Majid, E-mail: pakizeh@um.ac.ir

    2014-05-01

    Highlights: • ZnCl{sub 2}-MCM-41 introduced itself as a high performance sorbent for Hg(II) removal. • Kinetics data were analyzed by pseudo-first and second order and diffusion models. • The adsorption kinetic data were described very well by pseudo-second-order model. • Sorption of Hg(II) by ZnCl{sub 2}-MCM-41 was an exothermic chemical process. • Hg(II) sorption was a spontaneous process since of minus free energy change. - Abstract: Kinetics and thermodynamics of mercury ions sorption onto ZnCl{sub 2}-MCM-41 sorbent were studied. Several rate models in the form of two main classes of mathematic kinetic models (adsorption reaction models and adsorption diffusion models) were investigated. Pseudo-first-order, pseudo-second-order, Elovich, film and intraparticle diffusion models were used to analyze the kinetic data. Results showed that the pseudo-second order model can well describe the adsorption kinetic data. The thermodynamic parameters, such as Gibb's free energy change (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were also evaluated. Negative value of free energy at temperature range of 20–55 °C, indicates the spontaneous nature of Hg(II) sorption by ZnCl{sub 2}-MCM-41 sorbent. The adsorption capacity which was found to decrease with temperature showed the exothermic nature of the mercury sorption process (ΔH° = −49.4 kJ mol{sup −1}). The negative ΔS° value (−148.9 J mol{sup −1} K{sup −1}) revealed a decrease in the randomness at the solid/solution interface and also indicated the fast adsorption of the Hg(II) onto active sites.

  20. 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.

  1. Sonocatalyzed synthesis of 2-phenylvaleronitrile under controlled reaction conditions--a kinetic study.

    Science.gov (United States)

    Vivekanand, P A; Wang, Maw-Ling

    2011-09-01

    In the current study, kinetics of synthesis of 2-phenylvaleronitrile (PVN) was successfully carried out by selective C-alkylation of benzyl cyanide (BC) with n-bromopropane (BP) using aqueous KOH and catalyzed by TBAB under ultrasonic (300W) assisted organic solvent-free conditions. Selective monoalkylation of benzyl cyanide has been achieved by controlling the reaction conditions and has been followed using gas chromatogram. The effects of various parameters such as agitation speed, catalyst concentration, KOH concentration, benzyl cyanide concentration, volume of water, ultrasonic frequency and temperature were studied systematically to understand their influence on the rate of the reaction. The experimental observations are consistent with an interfacial-type process. Further the kinetic results demonstrate clearly, that ultrasonic assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Decoupling diffusion from the bimolecular photoinduced electron transfer reaction: a combined ultrafast spectroscopic and kinetic analysis.

    Science.gov (United States)

    Mukherjee, Puspal; Sen, Pratik

    2017-05-10

    We have studied the bimolecular photoinduced electron transfer (PET) reaction between benzophenone (Bp) and DABCO using femtosecond broadband transient absorption spectroscopy in different compositions of acetonitrile/1-butanol binary solvent mixtures. With the increase in the 1-butanol percentage in the mixture, we have observed an increase in the onset delay time of Bp˙(-), which is the product of the reaction. As 1-butanol is more viscous than acetonitrile, we related the onset time to the change in medium viscosity. Moreover, we undertook a complete kinetic analysis of the bimolecular PET reaction under different conditions to show that from transient absorption spectroscopy, we can get the exact rate of electron transfer. This kind of kinetic analysis along with the experimental data is the first of its kind to prove that transient absorption spectroscopy is probably the most useful tool in studying the PET reaction.

  3. Decarboxylation of Δ 9-tetrahydrocannabinol: Kinetics and molecular modeling

    Science.gov (United States)

    Perrotin-Brunel, Helene; Buijs, Wim; van Spronsen, Jaap; van Roosmalen, Maaike J. E.; Peters, Cor J.; Verpoorte, Rob; Witkamp, Geert-Jan

    2011-02-01

    Efficient tetrahydrocannabinol (Δ 9-THC) production from cannabis is important for its medical application and as basis for the development of production routes of other drugs from plants. This work presents one of the steps of Δ 9-THC production from cannabis plant material, the decarboxylation reaction, transforming the Δ 9-THC-acid naturally present in the plant into the psychoactive Δ 9-THC. Results of experiments showed pseudo-first order reaction kinetics, with an activation barrier of 85 kJ mol -1 and a pre-exponential factor of 3.7 × 10 8 s -1. Using molecular modeling, two options were identified for an acid catalyzed β-keto acid type mechanism for the decarboxylation of Δ 9-THC-acid. Each of these mechanisms might play a role, depending on the actual process conditions. Formic acid proved to be a good model for a catalyst of such a reaction. Also, the computational idea of catalysis by water to catalysis by an acid, put forward by Li and Brill, and Churchev and Belbruno was extended, and a new direct keto-enol route was found. A direct keto-enol mechanism catalyzed by formic acid seems to be the best explanation for the observed activation barrier and the pre-exponential factor of the decarboxylation of Δ 9-THC-acid. Evidence for this was found by performing an extraction experiment with Cannabis Flos. It revealed the presence of short chain carboxylic acids supporting this hypothesis. The presented approach is important for the development of a sustainable production of Δ 9-THC from the plant.

  4. Organocatalytic kinetic resolution cascade reactions: new mechanistic and stereochemical manifold in diphenyl prolinol silyl ether catalysis.

    Science.gov (United States)

    McGarraugh, Patrick G; Johnston, Ryne C; Martínez-Muñoz, Aurora; Cheong, Paul Ha-Yeon; Brenner-Moyer, Stacey E

    2012-08-20

    A new cascade reaction involving an iminium-catalyzed intramolecular oxa-Michael addition followed by an enamine-catalyzed intermolecular Michael addition is reported herein. This cascade reaction generates enantiopure, highly functionalized tetrahydropyrans and tetrahydrofurans in a one-pot reaction and in up to 89 % combined yield and up to 99 % ee. This cascade reaction is catalyzed by diaryl prolinol silyl ethers, which are a privileged class of catalysts. The stereochemical outcome of these cascade reactions is unprecedented. Computational studies indicate that this stereochemical outcome arises from nonclassical hydrogen-bonding interactions between the electrophile and the substrate, and from entropic considerations of preorganization. The unprecedented configurations of the cascade products, combined with the computational models, reveal for the first time that asymmetric induction by diaryl prolinol silyl ether catalysts is not always exclusively reagent controlled. The stereochemical outcome also arises from a kinetic resolution or dynamic kinetic resolution of the β-stereocenter through an enamine-catalyzed intermolecular reaction. This unprecedented organocascade reaction mechanism may be adaptable to diaryl prolinol silyl ether-catalyzed cascade reactions, in which both the iminium- and enamine-catalyzed steps are intermolecular, an underdeveloped type of cascade reaction. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1997-01-01

    The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

  6. Kinetics and mechanism of the catalytic reaction between alcohols and dimethyl carbonate

    Science.gov (United States)

    Koledina, K. F.; Koledin, S. N.; Shchadneva, N. A.; Gubaidullin, I. M.

    2017-03-01

    The mechanism of the reaction between alcohols and dimethyl carbonate, catalyzed by dicobalt octacarbonyl Co2(CO)8, is studied by means of mathematical modeling. Kinetic models for possible schemes of chemical transformations are constructed at different initial concentrations of the catalyst. Based on a comparative analysis of activation energies of possible stages of chemical transformations, possible reaction pathways are determined and an appropriate mechanism is selected.

  7. 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...

  8. On the meaning of the impingement parameter in kinetic equations of diffusion controlled reactions

    OpenAIRE

    Starink, M.J.

    2001-01-01

    If certain preconditions are met, the Johnson-Mehl-Avrami-Kolmogorov (JMAK) kinetic equation is exactly accurate for nucleation and growth reactions with linear growth and is, at least, a good approximation for nucleation and growth reactions with parabolic growth. These preconditions include randomly distributed product phases, isotropic growth and constant equilibrium state. Mechanisms causing deviations from these preconditions include: capillarity effect, vacancy annihilation, blocking du...

  9. Selective reduction of Cr(VI) in chromium, copper and arsenic (CCA) mixed waste streams using UV/TiO2 photocatalysis

    National Research Council Canada - National Science Library

    Zheng, Shan; Jiang, Wenjun; Rashid, Mamun; Cai, Yong; Dionysiou, Dionysios D; O'Shea, Kevin E

    2015-01-01

    .... The reduction follows pseudo-first order kinetics and increases with decreasing solution pH. Saturation of the reaction solution with argon during UV/TiO2 photocatalysis had no significant effect on the Cr(VI...

  10. Kinetic studies on the reaction between dicyanocobinamide and hypochlorous acid.

    Directory of Open Access Journals (Sweden)

    Dhiman Maitra

    Full Text Available Hypochlorous acid (HOCl is a potent oxidant generated by myeloperoxidase (MPO, which is an abundant enzyme used for defense against microbes. We examined the potential role of HOCl in corrin ring destruction and subsequent formation of cyanogen chloride (CNCl from dicyanocobinamide ((CN2-Cbi. Stopped-flow analysis revealed that the reaction consists of at least three observable steps, including at least two sequential transient intermediates prior to corrin ring destruction. The first two steps were attributed to sequential replacement of the two cyanide ligands with hypochlorite, while the third step was the destruction of the corrin ring. The formation of (OCl(CN-Cbi and its conversion to (OCl2-Cbi was fitted to a first order rate equation with second order rate constants of 0.002 and 0.0002 µM(-1 s(-1, respectively. The significantly lower rate of the second step compared to the first suggests that the replacement of the first cyanide molecule by hypochlorite causes an alteration in the ligand trans effects changing the affinity and/or accessibility of Co toward hypochlorite. Plots of the apparent rate constants as a function of HOCl concentration for all the three steps were linear with Y-intercepts close to zero, indicating that HOCl binds in an irreversible one-step mechanism. Collectively, these results illustrate functional differences in the corrin ring environments toward binding of diatomic ligands.

  11. 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.

  12. 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

  13. 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...

  14. Cyclo dehydration reaction of polyhydrazides. II. Kinetic parameters obtained from isothermal thermogravimetry

    NARCIS (Netherlands)

    Gebben, B.; Mulder, M.H.V.; Smolders, C.A.

    1988-01-01

    The kinetics of the thermal conversion reaction of poly-(1,3-phenyl-1,4-phenyl)-hydrazide into poly-(1,3-phenyl-1,4-phenyl)-1,3,4-oxadiazole have been studied with isothermal thermogravimetry in continuation of a study with nonisothermal thermogravimetry described in a previous paper. Although the

  15. The renneting of milk : a kinetic study of the enzymic and aggregation reactions

    NARCIS (Netherlands)

    Hooydonk, van A.C.M.

    1987-01-01

    The rennet-induced clotting of milk was studied under various conditions. The kinetics of the enzymic and aggregation reactions was analysed separately and, where possible, related to the physico-chemical properties of the casein micelle and its environment.

    The effects of important

  16. Marcus Theory: Thermodynamics CAN Control the Kinetics of Electron Transfer Reactions

    Science.gov (United States)

    Silverstein, Todd P.

    2012-01-01

    Although it is generally true that thermodynamics do not influence kinetics, this is NOT the case for electron transfer reactions in solution. Marcus Theory explains why this is so, using straightforward physical chemical principles such as transition state theory, Arrhenius' Law, and the Franck-Condon Principle. Here the background and…

  17. Spectroscopy and kinetics of germylene and digermene reactions photogenerated in the condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Plyusnin, V F; Kaletina, M V; Leshina, T V [Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2007-10-31

    The state of the art in the spectroscopic identification and kinetic analysis of condensed-phase reactions of bivalent germanium derivatives and their dimers is considered. Considerable attention is drawn to the comparison of results obtained by laser flash photolysis and spin chemistry methods.

  18. Kinetic and mechanistic studies on the Heck reaction using real-time near infrared spectroscopy

    NARCIS (Netherlands)

    Cruz, S. C.; Aarnoutse, P. J.; Rothenberg, G.; Westerhuis, J. A.; Smilde, A. K.; Bliek, A.

    2003-01-01

    In this paper, Fourier-transform near infrared (FT- NIR) spectroscopy is used to monitor the kinetics of complex catalytic reactions in liquid phase. Gas chromatography ( GC) is used as a reference method. Spectroscopic measurements generate large amounts of data and the calibration is usually

  19. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  20. Atmospheric chemistry of CF3COOH. Kinetics of the reaction with OH radicals

    DEFF Research Database (Denmark)

    Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.

    1994-01-01

    Two different experimental techniques were used to study the kinetics of the reaction of OH radicals with trifluoroacetic acid, CF3COOH. Using a pulse radiolysis absolute rate technique, rate constants at 315 and 348 K were determined to be (1.6 +/- 0.4) x 10(-13) and (1.5 +/- 0.2) x 10(-13) cm3...

  1. Employing Magnetic Levitation to Monitor Reaction Kinetics and Measure Activation Energy

    Science.gov (United States)

    Benz, Lauren; Cesafsky, Karen E.; Le, Tran; Park, Aileen; Malicky, David

    2012-01-01

    This article describes a simple and inexpensive undergraduate-level kinetics experiment that uses magnetic levitation to monitor the progress and determine the activation energy of a condensation reaction on a polymeric solid support. The method employs a cuvette filled with a paramagnetic solution positioned between two strong magnets. The…

  2. Parallel Kinetic Resolution of Racemic Aldehydes by Use of Asymmetric Horner-Wadsworth-Emmons Reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Jensen, Jakob Feldthusen; Humble, Rikke Eva

    2000-01-01

    A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy all...

  3. Sulfidation kinetics of silver nanoparticles reacted with metal sulfides.

    Science.gov (United States)

    Thalmann, Basilius; Voegelin, Andreas; Sinnet, Brian; Morgenroth, Eberhard; Kaegi, Ralf

    2014-05-06

    Recent studies have documented that the sulfidation of silver nanoparticles (Ag-NP), possibly released to the environment from consumer products, occurs in anoxic zones of urban wastewater systems and that sulfidized Ag-NP exhibit dramatically reduced toxic effects. However, whether Ag-NP sulfidation also occurs under oxic conditions in the absence of bisulfide has not been addressed, yet. In this study we, therefore, investigated whether metal sulfides that are more resistant toward oxidation than free sulfide, could enable the sulfidation of Ag-NP under oxic conditions. We reacted citrate-stabilized Ag-NP of different sizes (10-100 nm) with freshly precipitated and crystalline CuS and ZnS in oxygenated aqueous suspensions at pH 7.5. The extent of Ag-NP sulfidation was derived from the increase in dissolved Cu(2+) or Zn(2+) over time and linked with results from X-ray absorption spectroscopy (XAS) analysis of selected samples. The sulfidation of Ag-NP followed pseudo first-order kinetics, with rate coefficients increasing with decreasing Ag-NP diameter and increasing metal sulfide concentration and depending on the type (CuS and ZnS) and crystallinity of the reacting metal sulfide. Results from analytical electron microscopy revealed the formation of complex sulfidation patterns that seemed to follow preexisting subgrain boundaries in the pristine Ag-NP. The kinetics of Ag-NP sulfidation observed in this study in combination with reported ZnS and CuS concentrations and predicted Ag-NP concentrations in wastewater and urban surface waters indicate that even under oxic conditions and in the absence of free sulfide, Ag-NP can be transformed into Ag2S within a few hours to days by reaction with metal sulfides.

  4. 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

  5. Enzymatic kinetics of the quinol peroxidase of an aggressive periodontopathic bacterium.

    Science.gov (United States)

    Abe, Tasuku; Kawarai, Taketo; Takahashi, Yukihiro; Konishi, Kiyoshi

    2017-06-01

    Aggregatibacter actinomycetemcomitans is an oral pathogen for aggressive periodontitis, and encodes a triheme c-containing membrane-bound enzyme, quinol peroxidase (QPO) that catalyzes peroxidase activity using quinol in the respiratory chain. In the previous work, we have characterized recombinant QPO purified from the membrane fraction of Escherichia coli harboring a plasmid containing QPO gene. Irreversible inactivation of QPO by high concentration of H2O2 exhibited pseudo-first order kinetics. Analysis of initial-rate kinetics of QPO may suggest that enzyme catalytic mechanism is explained by a Ping Pong Bi Bi system rather than sequential systems. In addition, the redox reactions of cytochrome c in the presence of several values of [Q1H2]/[Q1] were at equilibrium, and only about 2/3 of the cytochrome c of QPO is reduced at high ratios of [Q1H2]/[Q1]. These results indicated that one of the three heme c moieties of QPO is maintained in an oxidized form even at increased ratios of [Q1H2]/[Q1], suggesting that QPO is reduced in the absence of H2O2 and only two of the three heme c moieties are reduced in the presence of high concentration of the Q1H2. Product inhibition of QPO accorded with our theoretical model for the reaction mechanism. Considered together, the enzymatic kinetics data for QPO confirm the Ping Pong Bi Bi system. © The Authors 2017. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

  6. Kinetics of collision-induced reactions between hard-sphere reactants.

    Science.gov (United States)

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

    2009-10-28

    We investigate the reaction kinetics of hard-sphere reactants that undergo reaction upon collision. When the reaction probability at a given collision is unity, the Noyes rate theory provides an exact expression of the rate coefficient. For the general case with the reaction probability less than unity, Noyes assumed that successive recollision times between a tagged pair of reactants are decorrelated. We show that with this renewal assumption, the rate theory of Wilemski and Fixman yields the same rate coefficient expression as the Noyes theory. To evaluate the validity of the renewal assumption, we carry out molecular dynamics simulations. Contrary to the usual expectation, we find that the renewal assumption works better at higher particle densities. The present study shows that the rate coefficient for collision-induced hard-sphere reactions can be estimated with great accuracy by using the first recollision time distribution alone, regardless of the magnitude of the reaction probability at a given collision.

  7. Automated Discovery of Complex Reaction Networks: Reaction Topology, Thermochemistry and Kinetics

    Science.gov (United States)

    2015-07-08

    Pfaendtner, “ Car –Parrinello Molecular Dynamics + Metadynamics Study of High- Temperature Methanol Oxidation Reactions Using Generic Collective Variables”, J...release. 13. SUPPLEMENTARY NOTES 14. ABSTRACT Understanding the combustion mechanism of jet fuel is essential for the design of stable, responsive...optimized reaction networks were generated. The methodology was applied to study methanol oxidation, prediction of ethylene combustion mechanism and

  8. Reaction reversibility in α-pinene thermal isomerization: improving the kinetic model

    Science.gov (United States)

    Chibiryaev, A. M.; Ermakova, A.; Kozhevnikov, I. V.

    2011-08-01

    Revision of the experimental data on α-pinene thermal isomerization attained in supercritical ethanol allowed us to expand the reaction scheme, which includes now six main products and eleven reversible reactions. The equilibrium constants of every reaction ( K T, j and K Φ, j) were calculated to allow for reversibility of reactions. The thermochemical data of the pure compounds required to calculate constants K T, j and K Φ, j (standard enthalpy and entropy of formation Δf H° (298.15 K), Δf S° (298.15 K), heat capacity C p ( T), critical parameters T cr and p cr, boiling point T b, and the acentric factor ω) were preliminary estimated using the empirical Joback and Benson methods. A kinetic model based on the new expanded scheme of reversible reactions was successfully identified and its kinetic parameters k j (600 K) and E j were determined. Detailed examination of the new kinetic model allowed us to refine the generally accepted mechanism of α-pinene thermal isomerization and to distinguish additional features of the multistep process.

  9. Kinetics of the Sabatier reaction over a nickel catalyst in a flow-circulation system

    Energy Technology Data Exchange (ETDEWEB)

    Naumov, V.A.; Krylov, O.V.

    1979-10-01

    The kinetics of the Sabatier reaction over a nickel catalyst in a flow-circulation system were studied in a continuation of previous experiments conducted in a differential flow reactor, with the same 58.3% Ni/35.7% Cr/sub 2/O/sub 3//5.5% graphite catalyst to derive a total kinetic equation for the reversible process of carbon dioxide hydrogenation to methane and water (the Sabatier reaction). The study was carried out at 200/sup 0/-400/sup 0/C and 1 atm. The reaction rate is a complex function of CO/sub 2/ and H/sub 2/ pressures, but becomes first order in CO/sub 2/ when CO/sub 2/ pressures are much smaller than those of H/sub 2/.

  10. Non-isothermal kinetic characterisation of a gas–solid reaction by TG analysis

    Directory of Open Access Journals (Sweden)

    ZELJKO CUPIC

    2005-11-01

    Full Text Available A series of silica-supported Ni-catalyst precursors was synthesized, with different SiO2/Nimole ratios between 0.2 and 1.15. The reduction of all the prepared samples was studied by thermogravimetry (TG in a hydrogen flow. The results of the TG analysis were analyzed by the multi-thermal history model-fitting method, with non-linear regression. The activation energies for the reduction of each sample were determined. The statistical F-test was performed to discriminate between various models. It was found that increasing the SiO2/Ni mole ratio leads to a change in the reaction mechanism of the nickel reduction, resulting finally in a change from second order reaction kinetics to three halves order reaction kinetics.

  11. 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…

  12. 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…

  13. 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 (CO2 ) to methanol (CH3 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 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 modeled 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 to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH3 OH, a TTN of 160 and BPR of 24 μmol CH3 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 CH3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

  14. Reaction rate constants of H-abstraction by OH from large ketones: measurements and site-specific rate rules.

    Science.gov (United States)

    Badra, Jihad; Elwardany, Ahmed E; Farooq, Aamir

    2014-06-28

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (C=O) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (C=O), and the prime is used to differentiate different neighboring environments of a methylene group):

  15. Equilibrium, kinetics and thermodynamics studies of textile dyes adsorption on modified Tunisian clay

    Directory of Open Access Journals (Sweden)

    naghmouchi nahed

    2016-04-01

    Full Text Available The adsorption capacity of two anionic textile dyes (RR120 and BB150 on DMSO intercalated Tunisian raw clay was investigated with respect to contact time, initial dye concentration, pH and Temperature. The equilibrium data were fitted into Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. The kinetic parameters were calculated using pseudo-first order, pseudo second-order, intra-particle diffusion and Elovich kinetic models. The thermodynamic parameters (DH°, DS° and DG° of the adsorption process were also evaluated.

  16. Measuring kinetic rate constants of multiple-component reactions with optical biosensors.

    Science.gov (United States)

    Edwards, David A; Evans, Ryan M; Li, Wenbin

    2017-09-15

    One may measure the kinetic rate constants associated with biochemical reactions using an optical biosensor: an instrument in which ligand molecules are convected through a flow cell over a surface to which receptors are immobilized. If there are multiple reactants, one is faced with the problem of fitting multiple kinetic rate constants to one signal, since data from all of the reacting species is lumped together. Even in the presence of ambiguous data, one may use a series of experiments to accurately determine the rate constants. Moreover, the true set of rate constants may be identified by either postprocessing the signals or adjusting the ligand inflow concentrations. Published by Elsevier Inc.

  17. Assessment of adsorption kinetics for removal potential of Crystal Violet dye from aqueous solutions using Moroccan pyrophyllite

    Directory of Open Access Journals (Sweden)

    Youssef Miyah

    2017-06-01

    Full Text Available This study involves the adsorption of Crystal Violet (CV dye adsorbed from solution on the pyrophyllite’s surface. The batch technique was used under a variety of conditions to produce quantitative adsorption, namely amount of adsorbent, dye concentration, contact time, pH solution and temperature. The maximum adsorption capacity of Crystal Violet on pyrophyllite was 9.58 mg/g for 10 mg/L of CV concentration, pH = 6.8 at a temperature 20 °C and 1 g/L of adsorbent. This study of adsorption kinetics was carried out within framework of three models: intraparticle diffusion, pseudo-first order and pseudo-second order. The experimental isotherm data were analyzed using Langmuir and Freundlich models. Different thermodynamic parameters have shown spontaneous reaction with endothermic nature (The estimated value for ΔG was −7.64 kJ/mol at 293 K. Various techniques for characterizing the adsorbent were applied including X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, scanning electron microscopy (SEM and transmission electron microscopy (TEM coupled by energy dispersive X-ray spectroscopy (EDX. In addition, the regenerated adsorbents technique was reused several times; this demonstrated an economical aspect of using pyrophyllite which underlines the re-use importance considering the material capacity to regenerate.

  18. Adsorption kinetics of NO on ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC)

    Science.gov (United States)

    Chen, Jinghuan; Cao, Feifei; Chen, Songze; Ni, Mingjiang; Gao, Xiang; Cen, Kefa

    2014-10-01

    Ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC) were prepared using evaporation-induced self-assembly (EISA) method and used to adsorb NO. N2 sorption, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to confirm their structures. The results showed that the ordered and uniform structures were successfully synthesized and with the introduction of cerium pore properties were not significantly changed. The NO adsorption capacity of OMC was two times larger than that of activated carbon (AC). With the introduction of cerium both the adsorption capacity and the adsorption rate were improved. The effects of residence time and oxygen concentration on NO adsorption were also investigated. Oxygen played an important role in the NO adsorption (especially in the form of chemisorption) and residence time had small influence on the NO adsorption capacity. The NO adsorption kinetics was analyzed using pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion models. The results indicated that the NO adsorption process can be divided into rapid adsorption period, slow adsorption period, and equilibrium adsorption period. The pseudo-second-order model was the most suitable model for NO adsorption on OMC and Ce-OMC. The rate controlling step was the intraparticle diffusion together with the adsorption reaction.

  19. Photocatalytic degradation of bisphenol A in the presence of Ce–ZnO: Evolution of kinetics, toxicity and photodegradation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Bechambi, Olfa [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Jlaiel, Lobna [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia); Najjar, Wahiba, E-mail: najjarwahiba2014@gmail.com [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Sayadi, Sami [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia)

    2016-04-15

    Ce–ZnO (2 mol %) and undoped ZnO catalysts have been synthesized through hydrothermal method and characterized by X-ray diffraction (XRD), Nitrogen physisorption at 77 K; Fourier transformed infrared spectroscopy (FTIR), UV–Visible spectroscopy, Photoluminescence spectra (PL), and Raman spectroscopy. Ce-doping reduces the average crystallite size, increases the BET surface area, shifts the absorption edge, reduces the electron–hole recombination and consequently improves photodegradation efficiency of Bisphenol A (BPA) in the presence of UV irradiation and hydrogen peroxide. The photocatalytic optimum conditions were established by studying the influence of various operational parameters including catalyst concentration, initial BPA concentration, H{sub 2}O{sub 2} concentration and initial pH. Under optimum conditions, Ce–ZnO (2%) achieved 100% BPA degradation and 61% BPA mineralization after 24 h of UV irradiation. BPA degradation reaction followed pseudo first-order kinetics according to the Langmuir–Hinshelwood model. Based on the identified intermediate products, the possible mechanism for BPA photodegradation is proposed. Toxicity under the optimum condition was also evaluated. - Graphical abstract: Proposed photocatalytic degradation pathway of BPA in the presence of Ce– ZnO (2%)/UV/H{sub 2}O{sub 2} system. - Highlights: • Influence of different parameters on the degradation and mineralization of BPA. • Identification of possible degradation products. • Toxicity tests conducted with Vibrio fischeri. • Simple and direct photodegradation mechanism of BPA is proposed.

  20. Development and application of a numerical model of kinetic and equilibrium microbiological and geochemical reactions (BIOKEMOD)

    Science.gov (United States)

    Salvage, Karen M.; Yeh, Gour-Tsyh

    1998-08-01

    This paper presents the conceptual and mathematical development of the numerical model titled BIOKEMOD, and verification simulations performed using the model. BIOKEMOD is a general computer model for simulation of geochemical and microbiological reactions in batch aqueous solutions. BIOKEMOD may be coupled with hydrologic transport codes for simulation of chemically and biologically reactive transport. The chemical systems simulated may include any mixture of kinetic and equilibrium reactions. The pH, pe, and ionic strength may be specified or simulated. Chemical processes included are aqueous complexation, adsorption, ion-exchange and precipitation/dissolution. Microbiological reactions address growth of biomass and degradation of chemicals by microbial metabolism of substrates, nutrients, and electron acceptors. Inhibition or facilitation of growth due to the presence of specific chemicals and a lag period for microbial acclimation to new substrates may be simulated if significant in the system of interest. Chemical reactions controlled by equilibrium are solved using the law of mass action relating the thermodynamic equilibrium constant to the activities of the products and reactants. Kinetic chemical reactions are solved using reaction rate equations based on collision theory. Microbiologically mediated reactions for substrate removal and biomass growth are assumed to follow Monod kinetics modified for the potentially limiting effects of substrate, nutrient, and electron acceptor availability. BIOKEMOD solves the ordinary differential and algebraic equations of mixed geochemical and biogeochemical reactions using the Newton-Raphson method with full matrix pivoting. Simulations may be either steady state or transient. Input to the program includes the stoichiometry and parameters describing the relevant chemical and microbiological reactions, initial conditions, and sources/sinks for each chemical species. Output includes the chemical and biomass concentrations

  1. Thermal decomposition of sugarcane straw, kinetics and heat of reaction in synthetic air.

    Science.gov (United States)

    Rueda-Ordóñez, Yesid Javier; Tannous, Katia

    2016-07-01

    The aim of this work was to analyze the thermal decomposition, kinetics and heat of reaction of sugarcane straw in synthetic air by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG and DSC experiments were carried out using heating rates of 2.5°C/min, 5°C/min, and 10°C/min, and particle diameter of 0.250mm. In the study of the smoldering reaction were identified three consecutive stages, drying, oxidative pyrolysis, and combustion. Thus, the kinetic pathway was composed by six independent parallel reactions, three for each stage after drying, in which the activation energies were 176, 313, 150, 80, 150, and 100kJ/mol. The heat of reaction in synthetic air was completely exothermic releasing 8MJ/kg. The modeled curves of thermal decomposition of sugarcane straw presented good agreement with experimental data. Then, the kinetic parameters obtained could be used to analyze different processes involving smoldering. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    Science.gov (United States)

    Kawa, S. Randolph; Stolarksi, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  3. Michaelis-Menten kinetics in shear flow: Similarity solutions for multi-step reactions.

    Science.gov (United States)

    Ristenpart, W D; Stone, H A

    2012-03-01

    Models for chemical reaction kinetics typically assume well-mixed conditions, in which chemical compositions change in time but are uniform in space. In contrast, many biological and microfluidic systems of interest involve non-uniform flows where gradients in flow velocity dynamically alter the effective reaction volume. Here, we present a theoretical framework for characterizing multi-step reactions that occur when an enzyme or enzymatic substrate is released from a flat solid surface into a linear shear flow. Similarity solutions are developed for situations where the reactions are sufficiently slow compared to a convective time scale, allowing a regular perturbation approach to be employed. For the specific case of Michaelis-Menten reactions, we establish that the transversally averaged concentration of product scales with the distance x downstream as x(5/3). We generalize the analysis to n-step reactions, and we discuss the implications for designing new microfluidic kinetic assays to probe the effect of flow on biochemical processes.

  4. 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

  5. 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.

  6. Removal of Cr(VI from Aqueous Solution Using Modified Pomegranate Peel : Equilibrium and Kinetic Studies

    Directory of Open Access Journals (Sweden)

    Tariq S. Najim

    2009-01-01

    Full Text Available The present investigation deals with the utilization of modified pomegrenate peel (MPGP and formaldehyde modified pomegrenate peel (FMPGP as adsorbents for the removal of chromium Cr(VI from aqueous solution. A series of experiments were conducted in a batch system to evaluate the effect of system variables. The effect of pH, initial Cr(VI concentration, contact time, adsorbent dosage and temperature were considered. The optimal pH values of Cr(VI removal by MPGP and FMPGP were 2.0 and 3.0 respectively. The time required for equilibrium was found to be about 100 minutes. The initial Cr(VI concentration and adsorbent dosage was found to have large effect on the adsorption of Cr(VI. The maximum uptake capacities were 13.01 and 22.28 mg of Cr(VI per gram of MPGP and FMPGP respectively. Adsorption kinetic data were tested using pseudo-first order, pseudo-second order, Elovich and intra-particle diffusion models. Kinetic studies showed that the adsorption followed a pseudo second order reaction due to the high correlation coefficient and the agreement between the experimental and calculated values of qe.The adsorption may follow intraparticle diffusion as well, due to the highest values of rate constants for the surface adsorption and intraparticle diffusion kinetic models, the higher values of rate constants are related to an improved bonding between Cr(VI ions and adsorbent particle.The Dubinin-radushkevich, Freundlich and Tempkin models were the closest fit for the equilibrium data of MPGP and FMPGP.

  7. Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study.

    Science.gov (United States)

    Li, Youji; Li, Xiaodong; Li, Junwen; Yin, Jing

    2006-03-01

    TiO2-coated activated carbon (AC) grain (TiO2/AC) was prepared through hydrolytic precipitation of TiO2 from Tetrabutylorthotitanate and following heat treatment. The TiO2/AC was characterized by BET, SEM, XRD and optical absorption spectroscopy. The samples were employed as catalysts for methyl orange photocatalytic oxidation degradation in aqueous suspension, used as probe reaction. The kinetics of methyl orange photodegradation was analyzed. The results indicate that BET surface area of TiO2-coated ACs decreased drastically in comparison with the original AC with increasing TiO2 coatings by more than 1 doped cycle. Nano-TiO2 particles were dispersed on the AC with the size of 20-40 nm. Crystalline TiO2 doped onto AC was from anatase to rutile with increase of heat-treatment temperature. The TiO2/AC was shown high photoactivity for the photodegradation of methyl orange (MO) dyestuff in aqueous solution under UV irradiation. The kinetics of photocatalytic MO dyestuff degradation was found to follow a pseudo-first-order rate law. It was observed that the presence of the AC enhanced the photoefficiency of the titanium dioxide catalyst. Different amount of TiO2 coatings induced different increases in the apparent first-order rate constant of the process. The kinetic behavior could be described in terms of a modified Langmuir-Hinshelwood model. The values of the adsorption equilibrium constants for the organic molecules, KC, and for the rate constants, kc, were certainly dependent on TiO2 content. At 47wt% TiO2 coatings with the highest rate constant, the KC and kc was 0.1116l mmol(-1) and 0.1872 mmol l(-1) min(-1), respectively. The mechanism of methyl orange degradation was discussed in terms of the titanium dioxide photosensitization by the AC.

  8. Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica

    Directory of Open Access Journals (Sweden)

    Atyaf Khalid Hameed

    2016-08-01

    Full Text Available Zero valent iron supported on mesoporous silicanano particles (NZVI/MSNs was prepared by the aqueous phase borohydride reduction methods. Prior to the reduction, mesoporous silica nanoparticles (MSNs were prepared through the activation of fumed silica with concentrated HCl by refluxing at 90 °C. FTIR, XRD, FESEM, EDX and BET were used to characterize theadsorbents prepared. BET surface areas of MSNs, NZVI, and NZVI/MSNs were 126, 41, and 72 m2/g for, respectively. The performance of NZVI/MSNs as adsorbent was examined by adsorption of methylene blue (MB, performed in series of batch experiments. In the kinetic studies, pseudo first order and pseudo second order kinetic models were examined. The pseudo second order equation provided the best fit with the experimental data. Thermodynamic studies indicated that the adsorption process is endothermic with ΔH° was 90.53 kJ/mol. Positive ΔS° (300 J/mol and negative ΔG° (-6.42 kJ/mol was recorded, indicating the spontaneous of the adsorption process and naturally favorable. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th March 2016; Revised: 18th March 2016; Accepted: 18th March 2016 How to Cite: Hameed, A.K., Dewayanto, N., Dongyun, D., Nordin, M.R., Mohd Hasbi Ab. Rahim, M.H.A. (2016. Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 250-261 (doi:10.9767/bcrec.11.2.443.250-261 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.443.250-261

  9. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  10. Role of reaction kinetics and mass transport in glucose sensing with nanopillar array electrodes

    OpenAIRE

    Rao Yeswanth L; Kim Euihyeon; Yang Xiaoling; Anandan Venkataramani; Zhang Guigen

    2007-01-01

    Abstract The use of nanopillar array electrodes (NAEs) for biosensor applications was explored using a combined experimental and simulation approach to characterize the role of reaction kinetics and mass transport in glucose detection with NAEs. Thin gold electrodes with arrays of vertically standing gold nanopillars were fabricated and their amperometric current responses were measured under bare and functionalized conditions. Results show that the sensing performances of both the bare and f...

  11. Kinetics of the reaction of Fe-II(EDTA) with oxygen in aqueous solutions

    NARCIS (Netherlands)

    Gambardella, F; Ganzeveld, IJ; Winkelman, JGM; Heeres, EJ; Heeres, H.J.

    2005-01-01

    The kinetics of the reaction of oxygen with aqueous Fe-II(EDTA) solutions has been determined in a range of process conditions (C-Fe(II)(EDTA) = 15-60 mol/m(3), P-O2 = 5-20 kPa, pH = 5-8, T = 298-328 K, C-NaCl = 0-15 kg/m(3)) using a gas-liquid stirred cell reactor. The oxygen absorption rates were

  12. Kinetic studies in solid state reactions by sample-controlled methods and advanced analysis procedures

    OpenAIRE

    Pérez-Maqueda, Luis A.; Criado, J. M.; Sánchez-Jiménez, P.E.; Perejón, Antonio

    2013-01-01

    A comparative study of both conventional rising temperature and sample-controlled methods, like constant rate thermal analysis (CRTA), is carried out after analyzing a set of solid state reactions using both methods. It is shown that CRTA avoids the influence of heat and mass transfer phenomena for a wide range of sample sizes leading to reliable kinetic parameters. On the other hand, conventional rising temperature methods yield α–T plots dependent on experimental conditions, even when using...

  13. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.

    OpenAIRE

    Hoggett, J G; Kellett, G L

    1992-01-01

    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kas...

  14. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  15. Kinetics of the reactions of alkyl radicals with HBr and DBr

    Science.gov (United States)

    Nicovich, J. M.; Van Dijk, C. A.; Kreutter, K. D.; Wine, P. H.

    1991-01-01

    The kinetics of the reactions CH3 + HBr, CD3 + HBr, CH3 + DBr, C2H5 + HBr, C2H5 + DBr, t-C4H9 + HBr, and t-C4H9 + DBr is studied as a function of temperature (257-430 K) and pressure (10-300 Torr of N2). Time-resolved resonance fluorescence detection of Br atom appearance following laser flash photolysis of RI was used in the experiments. Results show that the rates of all reactions increased as the temperature decreased.

  16. Approach Matters: The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions.

    Science.gov (United States)

    Sen, Rickdeb; Gahtory, Digvijay; Escorihuela, Jorge; Firet, Judith; Pujari, Sidharam P; Zuilhof, Han

    2017-09-21

    Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels-Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained by surface-bound mass spectrometry (DART-HRMS). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  17. Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics.

    Science.gov (United States)

    Bingaman, Jamie L; Messina, Kyle J; Bevilacqua, Philip C

    2017-05-01

    Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Consistency between kinetics and thermodynamics: general scaling conditions for reaction rates of nonlinear chemical systems without constraints far from equilibrium.

    Science.gov (United States)

    Vlad, Marcel O; Popa, Vlad T; Ross, John

    2011-02-03

    We examine the problem of consistency between the kinetic and thermodynamic descriptions of reaction networks. We focus on reaction networks with linearly dependent (but generally kinetically independent) reactions for which only some of the stoichiometric vectors attached to the different reactions are linearly independent. We show that for elementary reactions without constraints preventing the system from approaching equilibrium there are general scaling relations for nonequilibrium rates, one for each linearly dependent reaction. These scaling relations express the ratios of the forward and backward rates of the linearly dependent reactions in terms of products of the ratios of the forward and backward rates of the linearly independent reactions raised to different scaling powers; the scaling powers are elements of the transformation matrix, which relates the linearly dependent stoichiometric vectors to the linearly independent stoichiometric vectors. These relations are valid for any network of elementary reactions without constraints, linear or nonlinear kinetics, far from equilibrium or close to equilibrium. We show that similar scaling relations for the reaction routes exist for networks of nonelementary reactions described by the Horiuti-Temkin theory of reaction routes where the linear dependence of the mechanistic (elementary) reactions is transferred to the overall (route) reactions. However, in this case, the scaling conditions are valid only at the steady state. General relationships between reaction rates of the two levels of description are presented. These relationships are illustrated for a specific complex reaction: radical chlorination of ethylene.

  19. Atmospheric oxidation of halogenated aromatics: comparative analysis of reaction mechanisms and reaction kinetics.

    Science.gov (United States)

    Kovacevic, Goran; Sabljic, Aleksandar

    2017-03-22

    Atmospheric transport is the major route for global distribution of semi-volatile compounds such as halogenated aromatics as well as their major exposure route for humans. Their major atmospheric removal process is oxidation by hydroxyl radicals. There is very little information on the reaction mechanism or reaction-path dynamics of atmospheric degradation of halogenated benzenes. Furthermore, the measured reaction rate constants are missing for the range of environmentally relevant temperatures, i.e. 230-330 K. A series of recent theoretical studies have provided those valuable missing information for fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene. Their comparative analysis has provided additional and more general insight into the mechanism of those important tropospheric degradation processes as well as into the mobility, transport and atmospheric fate of halogenated aromatic systems. It was demonstrated for the first time that the addition of hydroxyl radicals to monohalogenated as well as to perhalogenated benzenes proceeds indirectly, via a prereaction complex and its formation and dynamics have been characterized including the respective transition-state. However, in fluorobenzene and chlorobenzene reactions hydroxyl radical hydrogen is pointing approximately to the center of the aromatic ring while in the case of hexafluorobenzene and hexachlorobenzene, unexpectedly, the oxygen is directed towards the center of the aromatic ring. The reliable rate constants are now available for all environmentally relevant temperatures for the tropospheric oxidation of fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene while pentachlorophenol, a well-known organic micropollutant, seems to be a major stable product of tropospheric oxidation of hexachlorobenzene. Their calculated tropospheric lifetimes show that fluorobenzene and chlorobenzene are easily removed from the atmosphere and do not have long-range transport potential while

  20. Kinetics and reaction pathways of total acid number reduction of cyclopentane carboxylic acid using subcritical methanol

    Directory of Open Access Journals (Sweden)

    Mandal Pradip C.

    2016-09-01

    Full Text Available Cyclopentane carboxylic acid (CPCA is a model compound of Naphthenic acids (NAs. This objective of this paper is to discover total acid number (TAN reduction kinetics and pathways of the reaction between CAPA and subcritical methanol (SubC-MeOH. The experiments were carried out in an autoclave reactor at temperatures of 180-220°C, a methanol partial pressure (MPP of 3 MPa, reaction times of 0-30 min and CPCA initial gas phase concentrations of 0.016-0.04 g/mL. TAN content of the samples were analyzed using ASTM D 974 techniques. The reaction products were identified and quantified with the help of GC/MS and GC-FID respectively. Experimental results reveal that TAN removal kinetics followed first order kinetics with an activation energy of 13.97 kcal/mol and a pre-exponential factor of 174.21 s-1. Subcritical methanol is able to reduce TAN of CPCA decomposing CPCA into new compounds such as cyclopentane, formaldehyde, methyl acetate and 3-pentanol.

  1. Refolded scFv Antibody Fragment against Myoglobin Shows Rapid Reaction Kinetics

    Directory of Open Access Journals (Sweden)

    Hyung-Nam Song

    2014-12-01

    Full Text Available Myoglobin is one of the early biomarkers for acute myocardial infarction. Recently, we have screened an antibody with unique rapid reaction kinetics toward human myoglobin antigen. Antibodies with rapid reaction kinetics are thought to be an early IgG form produced during early stage of in vivo immunization. We produced a recombinant scFv fragment for the premature antibody from Escherichia coli using refolding technology. The scFv gene was constructed by connection of the VH–VL sequence with a (Gly4Ser3 linker. The scFv fragment without the pelB leader sequence was expressed at a high level, but the solubility was extremely low. A high concentration of 8 M urea was used for denaturation. The dilution refolding process in the presence of arginine and the redox reagents GSH and GSSH successfully produced a soluble scFv protein. The resultant refolded scFv protein showed association and dissociation values of 9.32 × 10−4 M−1·s−1 and 6.29 × 10−3 s−1, respectively, with an affinity value exceeding 107 M−1 (kon/koff, maintaining the original rapid reaction kinetics of the premature antibody. The refolded scFv could provide a platform for protein engineering for the clinical application for diagnosis of heart disease and the development of a continuous biosensor.

  2. Kinetics of reaction of gold nanoparticles following partial removal of stabilizers

    Energy Technology Data Exchange (ETDEWEB)

    Dutta, Anushree [Indian Institute of Technology Guwahati, Department of Chemistry (India); Das, Subhojit [National Institute of Technology, Department of Chemistry (India); Paul, Anumita, E-mail: anumita@iitg.ernet.in; Chattopadhyay, Arun, E-mail: arun@iitg.ernet.in [Indian Institute of Technology Guwahati, Department of Chemistry (India)

    2015-06-15

    Citrate-stabilized gold nanoparticles (Au NPs) of 17-nm diameter were allowed to react following partial depletion of the stabilizer using dialysis. Kinetics of the reaction was investigated by following time-dependent changes in the visible extinction spectrum. Thus, surface plasmon resonance peak (SPR) of isolated Au NPs (reactant) at 522 nm decreased, while SPR peak due to product—which was agglomerated Au NPs—occurring at 600 nm increased with time. The reaction followed first-order kinetics with respect to concentration of reactant (Au NP) with a rate constant on the order of (2.10 ± 0.34) × 10{sup −3} min{sup −1}. Further, product concentration correspondingly increased with time. Transmission electron microscopy investigation indicated the presence of individual NPs, along with agglomerated structures in the beginning of reaction—the extent of which increased with time, rather than the formation of smaller agglomerates. A model has been proposed based on reaction of individual NPs with agglomerated structures which accounted for the observed kinetics.

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

    Science.gov (United States)

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

    2017-10-30

    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. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

  4. Quantum chemistry investigation of secondary reaction kinetics in acrylate-based copolymers.

    Science.gov (United States)

    Cuccato, Danilo; Mavroudakis, Evangelos; Moscatelli, Davide

    2013-05-30

    Recently, a growing amount of attention has been focused on the influence of secondary reactions on the free radical polymerization features and the properties and microstructure of the final polymer, particularly in the context of acrylate copolymers. One of the most challenging aspects of this research is the accurate determination of the corresponding reaction kinetics. In this paper, this problem is addressed using quantum chemistry. The reaction rate coefficients of various backbiting, propagation, and β-scission steps are estimated considering different chain configurations of a terpolymer system composed of methyl acrylate, styrene, and methyl methacrylate. The replacement of methyl acrylate radical units with styrene and methyl methacrylate globally decreases the backbiting probability and shifts the equilibrium toward the reactants, while the effect of replacing adjacent units is weaker and more dependent upon the specific substituting monomer. Propagation kinetics is affected primarily by the replacement of the radical units, while this effect appears to be particularly effective on midchain radical reactivity. The overall results clarify the different physicochemical behavior of chain-end, midchain, and short-branch radicals as a function of copolymer composition, providing new insights into free radical polymerization kinetics.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-16

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

  6. Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid.

    Science.gov (United States)

    Grimes, Travis S; Horne, Gregory P; Dares, Christopher J; Pimblott, Simon M; Mezyk, Stephen P; Mincher, Bruce J

    2017-07-17

    The rate of reduction of hexavalent 243 Am due to self-radiolysis was measured across a range of total americium and nitric acid concentrations. These so-called autoreduction rates exhibited zero-order kinetics with respect to the concentration of hexavalent americium, and pseudo-first-order kinetics with respect to the total concentration of americium. However, the rate constants did vary with nitric acid concentration, resulting in values of 0.0048 ± 0.0003, 0.0075 ± 0.0005, and 0.0054 ± 0.0003 h -1 for 1.0, 3.0, and 6.5 M HNO 3 , respectively. This indicates that reduction is due to reaction of hexavalent americium with the radiolysis products of total americium decay. The concentration changes of Am(III), Am(V), and Am(VI) were determined by UV-vis spectroscopy. The Am(III) molar extinction coefficients are known; however, the unknown values for the Am(V) and Am(VI) absorbances across the studied range of nitric acid concentrations were determined by sensitivity analysis in which a mass balance with the known total americium concentration was obtained. The new extinction coefficients and reduction rate constants have been tabulated here. Multiscale radiation chemical modeling using a reaction set with both known and optimized rate coefficients was employed to achieve excellent agreement with the experimental results, and indicates that radiolytically produced nitrous acid from nitric acid radiolysis and hydrogen peroxide from water radiolysis are the important reducing agents. Since these species also react with each other, modeling indicated that the highest concentrations of these species available for Am(VI) reduction occurred at 3.0 M HNO 3 . This is in agreement with the empirical finding that the highest rate constant for autoreduction occurred at the intermediate acid concentration.

  7. Adsorption of Pb(II) ions from aqueous solution by native and activated bentonite: kinetic, equilibrium and thermodynamic study.

    Science.gov (United States)

    Kul, Ali Riza; Koyuncu, Hülya

    2010-07-15

    In this study, the adsorption kinetics, equilibrium and thermodynamics of Pb(II) ions on native (NB) and acid activated (AAB) bentonites were examined. The specific surface areas, pore size and pore-size distributions of the samples were fully characterized. The adsorption efficiency of Pb(II) onto the NB and AAB was increased with increasing temperature. The kinetics of adsorption of Pb(II) ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 16.51 and 13.66 kJ mol(-1) for NB and AAB, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin-Redushkevich (D-R) isotherm equations at different temperatures. R(L) separation factor for Langmuir and the n value for Freundlich isotherm show that Pb(II) ions are favorably adsorbed by NB and AAB. Thermodynamic quantities such as Gibbs free energy (DeltaG), the enthalpy (DeltaH) and the entropy change of sorption (DeltaS) were determined as about -5.06, 10.29 and 0.017 kJ mol(-1) K(-1), respectively for AAB. It was shown that the sorption processes were an endothermic reactions, controlled by physical mechanisms and spontaneously. 2010 Elsevier B.V. All rights reserved.

  8. Nonenzymatic browning reaction of essential amino acids: effect of pH on caramelization and Maillard reaction kinetics.

    Science.gov (United States)

    Ajandouz, E H; Puigserver, A

    1999-05-01

    The interaction between glucose and essential amino acids at 100 degrees C at pH values ranging from 4.0 to 12.0 was investigated by monitoring the disappearance of glucose and amino acids as well as the appearance of brown color. Lysine was the most strongly destroyed amino acid, followed by threonine which induced very little additional browning as compared with that undergone by glucose. Around neutrality, the nonenzymatic browning followed pseudo-zero-order kinetics after a lag time, while the glucose and amino acid losses did not follow first-order kinetics at any of the pH values tested. Glucose was more strongly destroyed than all of the essential amino acids, the losses of which are really small at pH values lower than 9.0. However, glucose was less susceptible to thermal degradation in the presence of amino acids, especially at pH 8.0 with threonine and at pH 10.0 with lysine. The contribution of the caramelization reaction to the overall nonenzymatic browning above neutrality should lead to an overestimation of the Maillard reaction in foods.

  9. [Effects of particle size of zero-valent iron on the reactivity of activating persulfate and kinetics for the degradation of acid orange 7].

    Science.gov (United States)

    Li, Huan-xuan; Wan, Jin-quan; Ma, Yong-wen; Huang, Ming-zhiz; Wang, Yan; Chen Yang, Mei

    2014-09-01

    This research described the heterogeneous reactions of persulfate with different particle sizes of zero-valent iron (including 1 mm-ZVI,150 μm-ZVI,50 nm-ZVI) for degradation of acid orange 7(AO7) , and studied the kinetics and intermediate products of AO7 under these systems. The results demonstrated that these three types of ZVI were efficient in promoting the degradation of AO7, the degradation efficiencies of AO7 were 43% , 97% , and 100% within 90 min respectively, in the 1 mm-ZVI,150 μm-ZVI and 50 nm- ZVI systems, respectively. With the results of kinetic fitting models, the pseudo first-order kinetics exhibited better fitting results in the 1 mm-ZVI,150 μm-ZVI systems, while the second-order kinetics exhibited better fitting results in the 50 nm-ZVI system. And the different ZVI types exhibited difference on the AO7 degradation rate constant, which ranged as 50 nm-ZVI > 150 μm-ZVI > 1 mm-ZVI. The iron corrosion products coating on the ZVI after reaction were composed of α-Fe2 O3 and some Fe3O4 in the 1 mm-ZVI system while that consisted of Fe3O4 and α-Fe2O3, FeOOH respectively, in thel50 μm-ZVI and 50 nm-ZVI systems,. Which were identified by scanning electron microscope (SEM) with energy dispersive spectrometer (EDS) and Raman spectroscopy. Some intermediate products, including 2-naphthalenol, 2-methylphenol, 4-ethyl- 3-methyl-phenol, isoindole- 1,3-dione and phthalic acid et al. were identified by GC/MS measurement. Both UV-vis absorbance spectra and GC/MS determination indicated that there was difference in degradation paths of AO7 between the three systems.

  10. Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

    OpenAIRE

    Imit, Mokhtar; Yamamoto, Takakazu; Imin, Patigul

    2005-01-01

    Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant k obs of 1.4×10−5 s−1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

  11. Kinetics study of carbon dioxide absorption reaction into the promoted methyldiethanolamine solution

    Science.gov (United States)

    Sitorus, Yasmikha Tiurlan Susanti; Taurina, Hanna Sucita; Altway, Ali; Rahmawati, Yeni; Nurkhamidah, Siti

    2017-05-01

    The absorption of carbon dioxide (CO2) is important in the industrial world. In industries, especially petrochemical, oil, and natural gas sectors, separation process of CO2 gas which is a corrosive gas (acid gas) is required. So, the separation process of CO2 gas stream is important, one of the methods used to remove CO2 from the gas stream is reactive absorption process using the promoted methyldiethanolamine (MDEA) solution. Therefore, this study is aimed to obtain the reaction kinetics data of CO2 absorption in MDEA solution using arginine as a promoter. Arginine was chosen because of its amino acid molecule which is reactive, so it can accelerate the reaction rate of MDEA. Moreover, this study also made a comparison between the reactivity of MDEA solution using arginine and MDEA solution using other promoters (glycine and piperazine) for CO2 absorption. The method used is absorption using laboratory scale of Wetted Wall Column (WWC) equipment at 1 atm. This study provides the reaction kinetics data information in order to optimize the separation process of CO2 in the industrialized world. The experimental results show that CO2 absorption rate at 323.15 K without any additon of arginine is 2.33 × 10-7 kmol/sec. By addition of 0.5 and 1 wt% of arginine, the absorption rate becomes 4 × 10-7 kmol/sec (2 times larger) and 6 × 10-7 kmol/sec (3 times larger). These results show that the addition of arginine as a promoter can increase the absorption rate of CO2 in MDEA solution and cover the weaknesses of MDEA solution. Based on the experimental result, the reaction kinetics constant for arginine is 1.91 × 1025 exp (-12296/T) (m3/kmol.s). Although, arginine reaction rate constant is lower than glycine and piperazine.

  12. Electronic Effects versus Distortion Energies During Strain-Promoted Alkyne-Azide Cycloadditions: A Theoretical Tool to Predict Reaction Kinetics

    NARCIS (Netherlands)

    Garcia-Hartjes, J.; Dommerholt, J.; Wennekes, T.; Delft, van F.L.; Zuilhof, H.

    2013-01-01

    Second-order reaction kinetics of known strain-promoted azide–alkyne cycloaddition (SPAAC) reactions were compared with theoretical data from a range of ab initio methods. This produced both detailed insights into the factors determining the reaction rates and two straightforward theoretical tools

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

    Science.gov (United States)

    Sattsangi, Prem D.

    2011-01-01

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

  14. Very Tiny Rocks: Site-Specific, Size-Dependent Reaction Kinetics at Nanoparticle-Water Interfaces

    Science.gov (United States)

    Rustad, J. R.

    2008-12-01

    One of the most fundamental challenges in geochemistry is to be able to understand the rates and mechanisms of elementary reactions that describe chemical processes occurring at mineral-water interfaces. One of the reasons for the primitive conceptual state of reaction kinetics in solid earth geochemistry is that it is very difficult to identify defensible elementary reactions where theoretical predictions can be made and the results can tested experimentally at the same length and time scale of the prediction. For example, the most fundamental predictor of complexation kinetics in aqueous solution is the characteristic water exchange rate, which are well known for the aquo ions and vary by 20 orders of magnitude even for simple trivalent ions. In contrast, for interfacial reactions, it was not even known whether water exchange rates were faster or slower than equivalent metal sites in solution, prohibiting any quantitive understanding of mineral reaction kinetics at the molecular level. Recent advances in synthesis and characterization of materials at nanometer length scales has been able to bridge the gap in scale, and nanometer-sized minerals have given us our first quantitative understanding of elementary reaction rates for fundamental processes involving water and hydroxide exchange reactions. I describe the results of molecular dynamics calculation and experimental measurement of the rates of water, hydroxide, and proton exchange reactions on nanoparticle surfaces. The calculations already show that transition state theory is completely inadequate to understand the rates of even the simplest elementary reactions. Furthermore, the mechanistic implications of rate parameters such as activation volume and activation enthalpy may be different in moving from aquo ions to interfaces. Is a molecular understanding of geochemical processes really needed? One might have asked a biologist at the turn of the century whether studying the structure of proteins would ever

  15. A kinetic study of the oxidation by molecular oxygen of the cytochrome chain of intact yeast cells, Acetobacter suboxydans cells, and of particulate suspensions of heart muscle.

    Science.gov (United States)

    Ludwig, G D; Kuby, S A; Edelman, G M; Chance, B

    1983-01-01

    The pre-steady state kinetics of the cytochrome c oxidase reaction with oxygen were studied by a variation in the reaction time between approximately 6 and 25 ms at oxygen concentrations less than 6 mumol/l. For baker's yeast, a pseudo-first-order velocity constant of approximately 150 s-1 at 1.3 mumol/l O2 was obtained corresponding to a second-order reaction between O2 and a3 at a forward velocity constant (k+1) of approximately 3 X 10(7) liter equiv.-1s-1. Thus, the membrane-bound oxidase in the intact cell exhibits one of the most rapid enzyme-substrate reactions to be reported. The value is identical with that of Greenwood and Gibson on an isolated, solubilized cytochrome c oxidase. Similar values of k+1 are calculated from the turnover numbers [k+2 (a+2)] divided by the Km values (formula; see text) measured for these yeast preparations, which points to an almost negligible reverse reaction (k-1) compared to k+2(a+2). Similar calculations for the membrane-bound cytochrome c oxidase of heart muscle give a value of k+1 approximately equal to 10(7) liter equiv.-1s-1. The concordance of the different values of k+1 supports the view that the yeast cell wall does not impart a significant diffusion barrier to the transport of molecular oxygen. In contrast, Acetobacter suboxydans exhibits a much larger value for Km, and has a terminal oxidase of different kinetic parameters.

  16. Binding of dihydrostreptomycin to Escherichia coli ribosomes: kinetics of the reaction.

    Science.gov (United States)

    Chang, F N; Flaks, J G

    1972-10-01

    Investigations were carried out on the binding of dihydrostreptomycin to purified (and reassociated) 70S ribosomes and 30S subunits from streptomycin-susceptible strains, and the results were compared with those of similar studies with native (run-off) 70S ribosomes. At 0 C, only a small fraction of purified 70S ribosomes and 30S sub-units bound 1 molecule of the antibiotic tightly, and at a rate comparable to the binding occurring with native 70S ribosomes. At temperatures of 10 C and above, there was a temperature-dependent increase in the extent of antibiotic binding to purified 70S and 30S particles up to a maximum of 1 molecule/ribosomal particle, but the kinetics of binding was slow in comparison to that taking place at 0 C. These and other results suggest that a major fraction of 30S subunits and purified (or reassociated) 70S ribosomes are inactive in binding the antibiotic. This has been localized to an instability of the free 30S subunit, which in solution at 0 C has a half-life of 5 hr or less. Inactive 30S or 70S particles could be thermally activated, with the latter being identical in their streptomycin-binding properties to native 70S ribosomes. The activation kinetics were slow in comparison to the binding kinetics for the antibiotic and were indicative of a conformational change in ribosomal structure. There thus appears to be a reversible transition between active and inactive forms of the ribosomal particles for streptomycin binding, but additional binding sites for the antibiotic are not created by the transitions. The active form of the 30S subunit can be stabilized in the presence of polyuridylic acid, but much more effectively by association with the 50S subunit to form a 70S ribosome. The kinetics of dihydrostreptomycin binding were studied in both directions of the reaction, and the reaction in the direction of binding was found to be several orders of magnitude faster than that of the reverse, or debinding, direction. The kinetics of the

  17. Reaction mechanism and kinetics of the degradation of terbacil initiated by OH radical - A theoretical study

    Science.gov (United States)

    Ponnusamy, S.; Sandhiya, L.; Senthilkumar, K.

    2018-02-01

    The reaction of terbacil with OH radical is studied by using electronic structure calculations. The reaction of terbacil with OH radical is found to proceed by H-atom abstraction, Cl-atom abstraction and OH addition reactions. The initially formed alkyl radical will undergo atmospheric transformation in the presence of molecular oxygen leading to the formation of peroxy radical. The reaction of peroxy radical with other atmospheric oxidants, such as HO2 and NO radicals is studied. The rate constant is calculated for the H-atom abstraction reactions over the temperature range of 200-1000 K. The results obtained from electronic structure calculations and kinetic study show that the H-atom abstraction reaction is more favorable. The calculated lifetime of terbacil is 24 h in normal atmospheric OH concentration. The rate constant calculated for H-atom abstraction reactions is 6 × 10-12, 4.4 × 10-12 and 3.2 × 10-12 cm3molecule-1s-1, respectively which is in agreement with the previous literature value of 1.9 × 10-12 cm3molecule-1s-1.

  18. Microbial respiration and dissolution precipitation reactions of minerals: thermo-kinetics and reactive transport modelling

    Science.gov (United States)

    Azaroual, M. M.; Parmentier, M.; Andre, L.; Croiset, N.; Pettenati, M.; Kremer, S.

    2010-12-01

    Microbial processes interact closely with abiotic geochemical reactions and mineralogical transformations in several hydrogeochemical systems. Reactive transport models are aimed to analyze these complex mechanisms integrating as well as the degradation of organic matter as the redox reactions involving successive terminal electron acceptors (TEAPs) mediated by microbes through the continuum of unsaturated zone (soil) - saturated zone (aquifer). The involvement of microbial processes in reactive transport in soil and subsurface geologic greatly complicates the mastery of the major mechanisms and the numerical modelling of these systems. The introduction of kinetic constraints of redox reactions in aqueous phase requires the decoupling of equilibrium reactions and the redefinition of mass balance of chemical elements including the concept of basis species and secondary species of thermodynamic databases used in geochemical modelling tools. An integrated methodology for modelling the reactive transport has been developed and implemented to simulate the transfer of arsenic, denitrification processes and the role of metastable aqueous sulfur species with pyrite and organic matter as electron donors entities. A mechanistic rate law of microbial respiration in various geochemical environments was used to simulate reactive transport of arsenic, nitrate and organic matter combined to the generalized rate law of mineral dissolution - precipitation reactions derived from the transition state theory was used for dissolution - precipitation of silica, aluminosilicate, carbonate, oxyhydroxide, and sulphide minerals. The kinetic parameters are compiled from the literature measurements based on laboratory constrained experiments and field observations. Numerical simulations, using the geochemical software PHREEQC, were performed aiming to identify the key reactions mediated by microbes in the framework of in the first hand the concept of the unsaturated - saturated zones of an

  19. The effect of viscosity on the kinetics of redox reactions in highly viscous silicate liquids.

    Science.gov (United States)

    Kido, Ladislav; Müller, Matthias; Rüssel, Christian

    2012-06-14

    The kinetics of the temperature dependent redox reaction between chromium and manganese (Cr(6+) + 3Mn(2+)⇌Cr(3+) + 3Mn(3+)) in highly viscous silicate melts were studied by UV-vis-NIR spectroscopy at temperatures in the range from 25 to 800 °C. At high temperatures, the reaction is in equilibrium. During cooling, it is continuously shifted to the right. During cooling from Tg+50 K to Tg (Tg = glass transition temperature), a further decrease in the Cr(6+) concentration was obtained which, however, was less pronounced if larger cooling rates were applied. In this temperature range, the kinetics plays an important part. Finally, at a certain temperatures below Tg, the equilibrium was frozen. The temperature, the equilibrium is frozen in decreases with decreasing cooling rate. It also decreases with the glass transition temperature of the respective composition. The activation energies increase with the activation energies of the viscosity of the respective melt. The redox reaction is controlled by the viscosity, i.e., the rearrangement of the glass network and not by diffusion. The reason is a drastic change in the coordination spheres during the reaction which leads to a high inner reorganization energy according to Marcus' Theory.

  20. A First-Passage Kinetic Monte Carlo method for reaction-drift-diffusion processes

    Science.gov (United States)

    Mauro, Ava J.; Sigurdsson, Jon Karl; Shrake, Justin; Atzberger, Paul J.; Isaacson, Samuel A.

    2014-02-01

    Stochastic reaction-diffusion models are now a popular tool for studying physical systems in which both the explicit diffusion of molecules and noise in the chemical reaction process play important roles. The Smoluchowski diffusion-limited reaction model (SDLR) is one of several that have been used to study biological systems. Exact realizations of the underlying stochastic processes described by the SDLR model can be generated by the recently proposed First-Passage Kinetic Monte Carlo (FPKMC) method. This exactness relies on sampling analytical solutions to one and two-body diffusion equations in simplified protective domains. In this work we extend the FPKMC to allow for drift arising from fixed, background potentials. As the corresponding Fokker-Planck equations that describe the motion of each molecule can no longer be solved analytically, we develop a hybrid method that discretizes the protective domains. The discretization is chosen so that the drift-diffusion of each molecule within its protective domain is approximated by a continuous-time random walk on a lattice. New lattices are defined dynamically as the protective domains are updated, hence we will refer to our method as Dynamic Lattice FPKMC or DL-FPKMC. We focus primarily on the one-dimensional case in this manuscript, and demonstrate the numerical convergence and accuracy of our method in this case for both smooth and discontinuous potentials. We also present applications of our method, which illustrate the impact of drift on reaction kinetics.

  1. Maillard reaction and caramelization during hazelnut roasting: A multiresponse kinetic study.

    Science.gov (United States)

    Göncüoğlu Taş, Neslihan; Gökmen, Vural

    2017-04-15

    A comprehensive kinetic model indicating the elementary steps of Maillard reaction and caramelization during hazelnut roasting was proposed based on a multi-response kinetic modeling approach. Changes in the concentrations of sucrose, fructose, glucose, amino acids, 3-deoxyglucosone, 1-deoxyglucosone, 3,4-dideoxyglucosone, glyoxal, methylglyoxal, dimethylglyoxal, and 5-hydroxymethylfurfural were examined in hazelnuts during roasting at 150, 160 and 170°C for 15, 30, 60, 90, and 120min. The results suggested that 1,2-enolization was important in the interconversion of glucose and fructose, 5-hydroxymethylfurfural formation mainly proceeded via fructofuranosyl cation dehydration rather than 3-deoxglucosone, glucose contributed more than fructose and fructofuranosyl cation to the early stage of the Maillard reaction. Methylglyoxal and dimethylglyoxal were mainly formed from 1-deoxyglucosone with high reaction rate constants while glyoxal formed through glucose degradation. α-Dicarbonyl compounds could have a role in the formation of melanoidins. The temperature dependence of the reactions was complicated and could not be explained by the Arrhenius equation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. A constant-time kinetic Monte Carlo algorithm for simulation of large biochemical reaction networks

    Science.gov (United States)

    Slepoy, Alexander; Thompson, Aidan P.; Plimpton, Steven J.

    2008-05-01

    The time evolution of species concentrations in biochemical reaction networks is often modeled using the stochastic simulation algorithm (SSA) [Gillespie, J. Phys. Chem. 81, 2340 (1977)]. The computational cost of the original SSA scaled linearly with the number of reactions in the network. Gibson and Bruck developed a logarithmic scaling version of the SSA which uses a priority queue or binary tree for more efficient reaction selection [Gibson and Bruck, J. Phys. Chem. A 104, 1876 (2000)]. More generally, this problem is one of dynamic discrete random variate generation which finds many uses in kinetic Monte Carlo and discrete event simulation. We present here a constant-time algorithm, whose cost is independent of the number of reactions, enabled by a slightly more complex underlying data structure. While applicable to kinetic Monte Carlo simulations in general, we describe the algorithm in the context of biochemical simulations and demonstrate its competitive performance on small- and medium-size networks, as well as its superior constant-time performance on very large networks, which are becoming necessary to represent the increasing complexity of biochemical data for pathways that mediate cell function.

  3. 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 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 existing theories of the ET. Our alternative dynamic ET model for

  4. Quality by Design (QbD approach to develop HPLC method for eberconazole nitrate: Application oxidative and photolytic degradation kinetics

    Directory of Open Access Journals (Sweden)

    M. Vamsi Krishna

    2016-09-01

    Full Text Available Stability of eberconazole nitrate (EBZ was investigated using a stability indicating HPLC method. Quality by Design (QbD approach was used to facilitate method development. EBZ was exposed to different stress conditions, including hydrolytic (acid, base, neutral, oxidative, thermal and photolytic. Relevant degradation was found to take place in all the conditions. The degradation of EBZ followed (pseudo first-order kinetics under experimental conditions. The kinetic parameters (rate constant, t1/2, and t90 of the degradation of EBZ were calculated.

  5. Kinetic Studies of Inhibition of the Aβ(1–42) Aggregation Using a Ferrocene-tagged β-Sheet Breaker Peptide

    Science.gov (United States)

    Zhang, Lin; Yagnik, Gargey; Peng, Yong; Wang, Jianxiu; Xu, H. Howard; Hao, Yuanqiang; Liu, You-Nian; Zhou, Feimeng

    2013-01-01

    The aggregation of amyloidogenic proteins/peptides has been closely linked to the neuropathology of several important neurological disorders. In Alzheimer's disease (AD), amyloid beta (Aβ) peptides and their aggregation are believed to be at least partially responsible for the etiology of AD. The aggregate-inflicted cellular toxicity can be inhibited by short peptides whose sequence are homologous to segments of the Aβ(1–42) peptide responsible for β-sheet stacking (referred to as the β-sheet breaker peptides). Herein a water-soluble ferrocene (Fc)-tagged β-sheet breaker peptide (Fc-KLVFFK6) is used as an electrochemical probe for kinetic studies of the inhibition of the Aβ(1–42) fibrillation process and for determination of the optimal concentration of β-sheet breaker peptide for efficient inhibition. Our results demonstrated that Fc-KLVFFK6 interacts with the Aβ aggregates instantaneously in solution, and sub-stoichiometric amount of Fc-KLVFFK6 is sufficient to inhibit the formation of the Aβ oligomers and fibrils and to reduce the toxicity of Aβ(1–42). The interaction between Fc-KLVFFK6 and Aβ(1–42) follows a pseudo-first-order reaction, with a rate constant of 1.89 ± 0.05 × 10−4 s−1. Tagging β-sheet breaker peptides with a redox label facilitates design, screening, and rational use of peptidic inhibitors for impeding/altering Aβ aggregation. PMID:23232068

  6. Batch sorption dynamics, kinetics and equilibrium studies of Cr(VI), Ni(II) and Cu(II) from aqueous phase using agricultural residues

    Science.gov (United States)

    Kaur, Rajvinder; Singh, Joginder; Khare, Rajshree; Cameotra, Swaranjit Singh; Ali, Amjad

    2013-03-01

    In the present study, the agricultural residues viz., Syzygium cumini and Populus deltoides leaves powder have been used for the biosorption of Cu(II), Ni(II), and Cr(VI) from aqueous solutions. FTIR and SEM analysis of the biosorbents were performed to explore the type of functional groups available for metal binding and to study the surface morphology. Various physico-chemical parameters such as pH, adsorbent dosage, initial metal ion concentration, and equilibrium contact time were studied. Thermodynamic studies were carried out and the results demonstrated the spontaneous and endothermic nature of the biosorption process. The equilibrium data were tested using four isotherm models—Langmuir, Freundlich, Temkin and Dubinin-Radushkevich and the maximum biosorption capacities were evaluated. The Pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models were applied to study the reaction kinetics with pseudo-second order model giving the best fit ( R 2 = 0.99) to the experimental data.

  7. Decolorization of malachite green, decolorization kinetics and stoichiometry of ozone-malachite green and removal of antibacterial activity with ozonation processes

    Energy Technology Data Exchange (ETDEWEB)

    Kusvuran, Erdal, E-mail: erdalkusvuran@yahoo.com [Chemistry Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey); Gulnaz, Osman [Biology Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey); Samil, Ali [Chemistry Department, Arts and Sciences Faculty, Sutcu Imam University, 46100 Kahramanmaras (Turkey); Yildirim, Ozlem [Chemistry Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey)

    2011-02-15

    This study aimed to identify degradation intermediates and to investigate the stoichiometry of decolorization and degradation, decolorization kinetics, and removal of antibacterial activity of malachite green (MG) using ozonization processes. The decolorization of MG was optimal at an acidic pH value of 3 based on molecular ozone attack on MG molecules. The stoichiometric ratio of decolorization between ozone and MG was calculated to be 7.0 with a regression coefficient of 0.995, whereas the ratio for degradation was calculated as 13.1 with a regression coefficient of 0.998. With MG concentrations in the range of 0.30-1.82 mM, the concentration of decolorized MG increased with higher initial concentrations of MG, whereas the ozonolytic decolorization rates of MG, decreased with increasing initial concentration. The pseudo-first-order degradation rate constants (k') decreased with the initial concentration and ranged from 0.769 to 0.223 min{sup -1}. Twelve different intermediates were produced during the ozonation of MG with ozonation times between 5 min and 30 min and were identified by GC-MS. Although 86% of MG in the reaction mixture was removed by ozonation after 10 min, the decrease of antibacterial activity was very low (10%) for Bacillus subtilis and Staphylococcus epidermidis because the degradation intermediates, phenol and benzoic acid, also have antibacterial activity. The antibacterial activity of both MG and its intermediates were removed successfully with ozonation times above 26 min.

  8. Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics

    Science.gov (United States)

    Bose, Amartya; Makri, Nancy

    2017-10-01

    The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

  9. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H.

    Science.gov (United States)

    Meisner, Jan; Kästner, Johannes

    2016-05-07

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10(-20) to 4 ⋅ 10(-17) cm(3) s(-1), demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.

  10. Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

    Science.gov (United States)

    Bose, Amartya; Makri, Nancy

    2017-10-21

    The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

  11. Adsorption kinetic and desorption studies of Cd2+ on Multi-Carboxylic-Functionalized Silica Gel

    Science.gov (United States)

    Li, Min; Wei, Jian; Meng, Xiaojing; Wu, Zhuqiang; Liang, Xiuke

    2018-01-01

    In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed cadmium (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of cadmium (II) ion didn’t present an obvious decrease after five cycles.

  12. Adsorption kinetic and desorption studies of Cu2+ on Multi-Carboxylic-Functionalized Silica Gel

    Science.gov (United States)

    Li, Min; Meng, Xiaojing; Liu, Yushuang; Hu, Xinju; Liang, Xiuke

    2018-01-01

    In the present study, the adsorption behavior of copper (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of copper (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed copper (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of copper (II) ion didn’t present an obvious decrease after five cycles.

  13. 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

    . 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...... 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...... and concentration of sinks under mixed 1D/3D migration is shown to lie between that for pure 1D and pure 3D migration and varies with L, the average distance between direction changes of the gliding defects. It is shown that the sink strength in simulations for spherical sinks of radius R under mixed 1D/3D...

  14. A novel approach to modeling the reaction kinetics of tetracycline antibiotics with aqueous ozone.

    Science.gov (United States)

    Hopkins, Zachary R; Blaney, Lee

    2014-01-15

    Tetracycline antibiotics represent one of the most successful classes of pharmaceuticals and are extensively used around the world for human and veterinary health. Ozone-based processes have emerged as a selective water treatment process for many pharmaceuticals. The primary objective of this study was to determine the reaction kinetics for transformation of five tetracycline antibiotics (i.e., chlortetracycline, doxycycline, oxytetracycline, rolitetracycline, and tetracycline) by ozone across the pH2 to 9 range. The apparent second-order rate constant for tetracycline was on the order of 1-6 × 10(4) M(-1) s(-1) at low pH, and 0.6-2.0 × 10(6) M(-1) s(-1) at near neutral pH. The apparent second-order rate constants did not fit a conventional pKa-based model, presumably due to the complex acid/base speciation of tetracycline antibiotics. A model that considers the net charge on tetracycline molecules in solution provided a nice fit to experimental data for all five tetracyclines. The five tetracycline antibiotics demonstrated similar reaction kinetics with ozone, and a cumulative analysis of all kinetics data provides a baseline model for other tetracycline compounds. The ozone exposure required for complete transformation of tetracycline antibiotics (10(-5) M-s) is well below that achieved during ozone disinfection processes (10(-3) M-s), indicating that ozone is an effective treatment for tetracycline antibiotics. © 2013 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Schöpp, W; Aurich, H

    1976-01-01

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

  16. Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound.

    Science.gov (United States)

    Piiskop, Sander; Salmar, Siim; Tuulmets, Ants; Kuznetsov, Aleksei; Järv, Jaak

    2013-11-01

    The kinetics of the pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated with and without ultrasonic irradiation in acetonitrile-water binary mixtures containing 0.008 to 35 wt.% of acetonitrile and the kinetic sonication effects (kson/knon) were calculated. Molecular dynamics (MD) simulations of the structure of the solutions were performed with ethyl acetate as the model ester. The ester is preferentially solvated by acetonitrile. The excess of acetonitrile over water in the solvation shell grows fast with an increase in the co-solvent content in the bulk solution. In parallel, the formation of a second solvation shell rich in acetonitrile takes place. Significant kinetic sonication effects for the hydrolysis were explained with facile destruction of the diffuse second solvation shell followed by a rearrangement of the remaining solvent layer under sonication. The rate levelling effect of ultrasound was discussed. In an aqueous-organic binary solvent, independent of the solvent composition, the ultrasonic irradiation evokes changes in the reaction medium which result in an almost identical solvation state of the reagent thus leading to the reaction rate levelling. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Reaction Kinetics and Morphological Study of TiNb2O7 Synthesized by Solid-State Reaction

    Directory of Open Access Journals (Sweden)

    Choi S.H.

    2017-06-01

    Full Text Available Although TiNb2O7 is regarded as a material with high application potential in lithium-ion batteries (LIBs and solid-oxide fuel cells (SOFCs, it has been difficult to find suitable cost-effective conditions for synthesizing it on a commercial scale. In this study, TiNb2O7 compounds were synthesized by a solid state synthesis process. For stoichiometrically precise synthesis of the TiNb2O7 phase, the starting materials, TiO2 and Nb2O5 were taken in a 1:1 molar ratio. Activation energy and reaction kinetics of the system were investigated at various synthesis temperatures (800,1000,1200, and 1400°C and for various holding durations (1,5,10, and 20 h. Furthermore, change in the product morphology and particle size distribution were also evaluated as a function of synthesis temperature and duration. Additionally, quantitative phase analysis was conducted using the Rietveld refinement method. It was found that increases in the synthesis temperature and holding time lead to increase in the mean particle size from 1 to 4.5 μm. The reaction rate constant for the synthesis reaction was also calculated.

  18. Unravelling the kinetics of the formation of acrylamide in the Maillard reaction of fructose and asparagine by multiresponse modelling

    NARCIS (Netherlands)

    Knol, J.J.; Linssen, J.P.H.; Boekel, van M.A.J.S.

    2010-01-01

    A kinetic model for the formation of acrylamide in a fructose–asparagine reaction system at initial pH 5.5 is proposed, based on an approach called multiresponse kinetic modelling. The formation of acetic acid and formic acid from the degradation of fructose and its isomer glucose was included in

  19. Kinetic studies on the Rhizomucor miehei lipase catalyzed esterification reaction of oleic acid with 1-butanol in a biphasic system

    NARCIS (Netherlands)

    Kraai, G.N.; Winkelman, J.G.M.; de Vries, Johannes; Heeres, H.J.

    2008-01-01

    The kinetics of the esterification of oleic acid with 1 -butanol catalyzed by free Rhizomucor miehei lipase in a biphasic system was studied in a batch reactor. The reaction appeared to proceed via a Ping Pong bi-bi mechanism with I -butanol inhibition. The kinetic constants of the model were

  20. 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

  1. Kinetics of acrylamide formation/elimination reactions as affected by water activity.

    Science.gov (United States)

    De Vleeschouwer, Kristel; Van der Plancken, Iesel; Van Loey, Ann; Hendrickx, Marc E

    2007-01-01

    The influence of water activity on the kinetics of acrylamide formation and elimination reaction was investigated using low-moisture equimolar asparagine-glucose model systems, which were heated at temperatures between 120 and 200 degrees C for variable heating times. To determine the water content corresponding to the water activities tested, a sorption moisture isotherm was constructed experimentally. The acrylamide concentrations measured at different water activities could be modeled on the basis of a reaction scheme including not only acrylamide formation and elimination reactions but also an alternative Maillard reaction between both reactants. The corresponding rate constants and activation energies were estimated using nonlinear regression analysis. Whereas the rate constant for acrylamide formation varied only slightly with the initial water activity of the model system, the elimination rate constant showed a clear minimum around a water activity of 0.82. The opposite trend, namely, a maximum at a water activity of 0.82, was found for the Maillard reaction rate constant as a function of water activity, which confirms data from literature. The activation energies for the different reactions changed in a comparable way as the corresponding rate constant with water activity.

  2. Reaction from dimethyl carbonate (DMC) to diphenyl carbonate (DPC). Part 2: Kinetics of the reactions from DMC via Methyl Phenyl Carbonate (MPC) to DPC

    NARCIS (Netherlands)

    Haubrock, J.; Wermink, W.; Versteeg, Geert; Kooijman, H.A.; Taylor, R.; van Sint Annaland, M.; Hogendoorn, Kees

    2008-01-01

    The kinetics of the reaction of dimethyl carbonate (DMC) and phenol to methyl phenyl carbonate (MPC) and the subsequent disproportion and transesterification reaction of methyl phenyl carbonate (MPC) to diphenyl carbonate (DPC) have been studied. Experiments were carried out in a closed batch

  3. Reaction from Dimethyl Carbonate (DMC) to Diphenyl Carbonate (DPC). 2. Kinetics of the Reactions from DMC via Methyl Phenyl Carbonate to DPC

    NARCIS (Netherlands)

    Haubrock, J.; Wermink, W.; Versteeg, G.F.; Kooijman, H.A.; Taylor, R.; Sint Annaland, M. van; Hogendoorn, J.A.

    2008-01-01

    The kinetics of the reaction of dimethyl carbonate (DMC) and phenol to methyl phenyl carbonate (MPC) and the subsequent disproportion and transesterification reaction of methyl phenyl carbonate (MPC) to diphenyl carbonate (DPC) have been studied. Experiments were carried out in a closed batch

  4. HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges

    Energy Technology Data Exchange (ETDEWEB)

    Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N. [Rensselaer Polytechnic Institute, Troy, NY (United States)

    1993-12-01

    The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.

  5. Hydrolysis of inulin: a kinetic study of the reaction catalyzed by an inulinase from Aspergillus ficuum.

    Science.gov (United States)

    Carniti, P; Beltrame, P L; Guardione, D; Focher, B; Marzetti, A

    1991-03-15

    A kinetic study of the hydrolysis of inulin was performed by using as catalyst a commercial inulinase from Aspergillus ficuum. The reaction was studied carrying out initial rate as well as time course measurements. Both inulinase and invertase activities of the enzyme were taken into account, and the corresponding kinetic parameters were determined in the temperature range 30-50 degrees C. The activation energies of the turnover constant for inulinase and invertase activities were found to be similar (56-57 kJ x mol(-1)). The ratio S/I of invertase to inulinase activity was 1.6 regardless of temperature. The thermal degradation of the enzyme was also investigated up to 70 degrees C, and an activation energy of 350-370 kJ x mol(-1) was evaluated.

  6. Multiple ion binding equilibria, reaction kinetics, and thermodynamics in dynamic models of biochemical pathways.

    Science.gov (United States)

    Vinnakota, Kalyan C; Wu, Fan; Kushmerick, Martin J; Beard, Daniel A

    2009-01-01

    The operation of biochemical systems in vivo and in vitro is strongly influenced by complex interactions between biochemical reactants and ions such as H(+), Mg(2+), K(+), and Ca(2+). These are important second messengers in metabolic and signaling pathways that directly influence the kinetics and thermodynamics of biochemical systems. Herein we describe the biophysical theory and computational methods to account for multiple ion binding to biochemical reactants and demonstrate the crucial effects of ion binding on biochemical reaction kinetics and thermodynamics. In simulations of realistic systems, the concentrations of these ions change with time due to dynamic buffering and competitive binding. In turn, the effective thermodynamic properties vary as functions of cation concentrations and important environmental variables such as temperature and overall ionic strength. Physically realistic simulations of biochemical systems require incorporating all of these phenomena into a coherent mathematical description. Several applications to physiological systems are demonstrated based on this coherent simulation framework.

  7. The investigation reaction kinetic for polyurethanes based on different types of diisocyanate and castor oil

    Directory of Open Access Journals (Sweden)

    Ristić Ivan S.

    2012-01-01

    Full Text Available The formation of polyurethanes based on vegetable oils is very complex and thus for industrial production of this materials it is important to determine the optimal temperature for polymerisation and finally to obtain materials with the proper mechanical properties. The goal of this work was to assess the kinetic of catalysed and noncatalysed reactions for polyurethanes based on castor oil as the polyol component and different types of diisocyanates. Due to the presences of hydroxyl groups on ricinoleic acid, castor oil is suitable for polyurethane preparation. The differential scanning calorimetry has been employed to study the polyurethane formation reaction using Ozawa isoconversion method. It was estimated that the catalyst addition decreases the activation energy. The highest reduction of activation energy was observed for the reactive systems with hexamethylene diisocyanate. Validity of obtained kinetic model was examined by FTIR spectroscopy following the apsorption of reactive groups. Obtained results of mechanical characteristics of the polyuretahane networks (with different NCO/OH ratio confirmed that applied method could be used for prediction of optimal reaction condition in polyurethane networks synthesis.

  8. Pyrolysis, kinetics analysis, thermodynamics parameters and reaction mechanism of Typha latifolia to evaluate its bioenergy potential.

    Science.gov (United States)

    Ahmad, Muhammad Sajjad; Mehmood, Muhammad Aamer; Taqvi, Syed Taha Haider; Elkamel, Ali; Liu, Chen-Guang; Xu, Jianren; Rahimuddin, Sawsan Abdulaziz; Gull, Munazza

    2017-12-01

    This work was focused on understanding the pyrolysis of Typha latifolia. Kinetics, thermodynamics parameters and pyrolysis reaction mechanism were studied using thermogravimetric data. Based on activation energies and conversion points, two regions of pyrolysis were established. Region-I occurred between the conversion rate 0.1-0.4 with peak temperatures 538K, 555K, 556K at the heating rates of 10Kmin-1, 30Kmin-1, and 50Kmin-1, respectively. Similarly, the Region-II occurred between 0.4 and 0.8 with peak temperatures of 606K, 621K, 623K at same heating rates. The best model was diffusion mechanism in Region-I. In Region-II, the reaction order was shown to be 2nd and 3rd. The values of activation energy calculated using FWO and KAS methods (134-204kJmol-1) remained same in both regions reflecting that the best reaction mechanism was predicted. Kinetics and thermodynamic parameters including E, ΔH, ΔS, ΔG shown that T. latifolia biomass is a remarkable feedstock for bioenergy. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. 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.

  10. Reaction Kinetics of CO2 Carbonation with Mg-Rich Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Dr. Soonchul [Georgia Institute of Technology; Fan, Maohong [University of Wyoming, Laramie; DaCosta, Dr. Herbert F.M. [Chem-Innovations Inc; Russell, Dr. Armistead [Georgia Institute of Technology; Tsouris, Costas [ORNL

    2011-01-01

    Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO{sub 2}. Direct carbonation of CO{sub 2} with Mg-rich minerals reported in this research for the first time could be considerably superior to conventional liquid extraction processes from an energy consumption perspective due to its avoidance of the use of a large amount of water with high specific heat capacity and latent heat of vaporization. Kinetic models of the reactions of the direct CO{sub 2} carbonation with Mg-rich minerals and within simulated flue gas environments are important to the scale-up of reactor designs. Unfortunately, such models have not been made available thus far. This research was initiated to fill that gap. Magnesium silicate (Mg{sub 2}SiO{sub 4}), a representative compound in Mg-rich minerals, was used to study CO{sub 2} carbonation reaction kinetics under given simulated flue gas conditions. It was found that the chosen sorbent deactivation model fits well the experimental data collected under given conditions. A reaction order of 1 with respect to CO{sub 2} is obtained from experimental data. The Arrhenius form of CO{sub 2} carbonation with Mg{sub 2}SiO{sub 4} is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.

  11. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.

    Science.gov (United States)

    Su, Chia-Hung

    2013-02-01

    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Reaction kinetics, P-T-t paths and rates of tectonic processes

    Energy Technology Data Exchange (ETDEWEB)

    Bohlen, S.R.; Hankins, W.B.; Eckert, J.O. Jr.; Kirby, S.H.; Liu, J. (Geological Survey, Menlo Park, CA (United States)); Hacker, B.R.; Mosenfelder, J.L. (Stanford Univ., Stanford, CA (United States). Dept. of Geology)

    1992-01-01

    The interpretation of portions of P-T-time (t) paths in metamorphic rocks assumes that continuous and discontinuous reactions record local equilibrium as P-T conditions change, implying that the kinetics of many reactions are rapid relative to dT/dt and dP/dt. Occurrence of eclogite veins in granulites from Bergen, Norway as well as occurrences of coesite and diamond in crustal rocks imply that, under certain conditions, this assumption is wrong. Knowledge of the kinetics of important reactions under appropriate conditions would provide limits on the duration of relatively narrowly defined P-T conditions, allow inference of the rates of exhumation of rocks containing high-pressure phases, and allow the calculation of the time required for the conversion of gabbro to eclogite in the lower crust as a function of P-T-t. The authors are currently assessing the rates of key phase transformations: calcite to aragonite, albite to jadeite + quartz, coesite to quartz, opx[sub Fs[sup 80

  13. Fractional Viscosity Dependence of Reaction Kinetics in Glass-Forming Liquids

    Science.gov (United States)

    Kwon, Seulki; Cho, Hyun Woo; Kim, Jeongmin; Sung, Bong June

    2017-08-01

    The diffusion of molecules in complex systems such as glasses and cell cytoplasm is slow, heterogeneous, and sometimes nonergodic. The effects of such intriguing diffusion on the kinetics of chemical and biological reactions remain elusive. In this Letter, we report that the kinetics of the polymer loop formation reaction in a Kob-Andersen (KA) glass forming liquid is influenced significantly by the dynamic heterogeneity. The diffusion coefficient D of a KA liquid deviates from the Stokes-Einstein relation at low temperatures and D shows a fractional dependence on the solvent viscosity ηs, i.e., D ˜ηs-ξD with ξD=0.85 . The dynamic heterogeneity of a KA liquid affects the rate constant krxn of the loop formation and leads to the identical fractional dependence of krxn on ηs with krxn˜ηs-ξ and ξ =ξD, contrary to reactions in dynamically homogeneous solutions where krxn˜ηs-1.

  14. Understanding the reaction of nuclear graphite with molecular oxygen: Kinetics, transport, and structural evolution

    Science.gov (United States)

    Kane, Joshua J.; Contescu, Cristian I.; Smith, Rebecca E.; Strydom, Gerhard; Windes, William E.

    2017-09-01

    For the next generation of nuclear reactors, HTGRs specifically, an unlikely air ingress warrants inclusion in the license applications of many international regulators. Much research on oxidation rates of various graphite grades under a number of conditions has been undertaken to address such an event. However, consequences to the reactor result from the microstructural changes to the graphite rather than directly from oxidation. The microstructure is inherent to a graphite's properties and ultimately degradation to the graphite's performance must be determined to establish the safety of reactor design. To understand the oxidation induced microstructural change and its corresponding impact on performance, a thorough understanding of the reaction system is needed. This article provides a thorough review of the graphite-molecular oxygen reaction in terms of kinetics, mass and energy transport, and structural evolution: all three play a significant role in the observed rate of graphite oxidation. These provide the foundations of a microstructurally informed model for the graphite-molecular oxygen reaction system, a model kinetically independent of graphite grade, and capable of describing both the observed and local oxidation rates under a wide range of conditions applicable to air-ingress.

  15. Kinetics of Electrocatalytic Reactions from First-Principles: A Critical Comparison with the Ab Initio Thermodynamics Approach.

    Science.gov (United States)

    Exner, Kai S; Over, Herbert

    2017-05-16

    Multielectron processes in electrochemistry require the stabilization of reaction intermediates (RI) at the electrode surface after every elementary reaction step. Accordingly, the bond strengths of these intermediates are important for assessing the catalytic performance of an electrode material. Current understanding of microscopic processes in modern electrocatalysis research is largely driven by theory, mostly based on ab initio thermodynamics considerations, where stable reaction intermediates at the electrode surface are identified, while the actual free energy barriers (or activation barriers) are ignored. This simple approach is popular in electrochemistry in that the researcher has a simple tool at hand in successfully searching for promising electrode materials. The ab initio TD approach allows for a rough but fast screening of the parameter space with low computational cost. However, ab initio thermodynamics is also frequently employed (often, even based on a single binding energy only) to comprehend on the activity and on the mechanism of an electrochemical reaction. The basic idea is that the activation barrier of an endergonic reaction step consists of a thermodynamic part and an additional kinetically determined barrier. Assuming that the activation barrier scales with thermodynamics (so-called Brønsted-Polanyi-Evans (BEP) relation) and the kinetic part of the barrier is small, ab initio thermodynamics may provide molecular insights into the electrochemical reaction kinetics. However, for many electrocatalytic reactions, these tacit assumptions are violated so that ab initio thermodynamics will lead to contradictions with both experimental data and ab initio kinetics. In this Account, we will discuss several electrochemical key reactions, including chlorine evolution (CER), oxygen evolution reaction (OER), and oxygen reduction (ORR), where ab initio kinetics data are available in order to critically compare the results with those derived from a

  16. Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, and Vinylic, Alkoxy, and Alkylperoxy Radicals.

    Science.gov (United States)

    Yommee, Suriyakit; Bozzelli, Joseph W

    2016-01-28

    Cyclopentadienone has one carbonyl and two olefin groups resulting in 4n + 2 π-electrons in a cyclic five-membered ring structure. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone-hydroperoxides, alcohols, and alkenyl, alkoxy, and peroxy radicals were determined by use of computational chemistry. The CBS-QB3 composite and B3LYP density functional theory methods were used to determine the enthalpies of formation (ΔfH°298) using the isodesmic reaction schemes with several work reactions for each species. Entropy and heat capacity, S°(T) and Cp°(T) (50 K ≤ T ≤ 5000 K) are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations. Standard enthalpies of formation are reported for parent molecules as cyclopentadienone, cyclopentadienone with alcohol, hydroperoxide substituents, and the cyclopentadienone-yl vinylic, alkoxy, and peroxy radicals corresponding to loss of a hydrogen atom from the carbon and oxygen sites. Entropy and heat capacity vs temperature also are reported for the parent molecules and for radicals. The thermochemical analysis shows The R(•) + O2 well depths are deep, on the order of 50 kcal mol(-1), and the R(•) + O2 reactions to RO + O (chain branching products) for cyclopentadienone-2-yl and cyclopentadienone-3-yl have unusually low reaction (ΔHrxn) enthalpies, some 20 or so kcal/mol below the entrance channels. Chemical activation kinetics using quantum RRK analysis for k(E) and master equation for falloff are used to show that significant chain branching as a function of temperature and pressure can occur when these vinylic radicals are formed.

  17. 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.

  18. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  19. Photochemistry and kinetics of gas phase reactions involving HO and Cl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, H.H.

    1980-11-01

    The kinetics of the reaction of the HO radical with HNO/sub 3/ and H/sub 2/O/sub 2/, the kinetics of Cl atom reactions with ClNO and ClNO/sub 2/, and the photochemistry of ClNO/sub 2/ and ClONO/sub 2/ were examined. The ultraviolet absorption cross sections of HNO/sub 3/ and ClNO/sub 2/ were also determined as part of the kinetics work. The rate constant for the reaction of HO with HNO/sub 3/ at room temperature was measured to be (8.2 +- 1.8) x 10/sup -14/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty reported here and in all cases reflects twice the experimental standard deviation plus an estimate of systematic errors. The rate constant for the reaction HO + H/sub 2/O/sub 2/ was measured as (1.57 +- 0.23) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This agrees well with the two latest determinations and serves as a calibration of the experimental apparatus used. The Cl + ClNO reaction rate constant was determined to be (1.65 +- 0.32) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The rate constant for the reaction of Cl + ClNO/sub 2/ was found to be (5.05 +- 0.75) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This is the first direct measurement of this rate constant. The photodissociation of ClNO/sub 2/ was studied in great detail. The absorption cross sections were measured in the ultraviolet and found to be substantially lower than the literature values in the Cl/sub 2/ absorption region (300 to 360 nm). Two product channels were investigated; products representative of the two channels were Cl and O atoms. Absolute calibration for the product detection systems was provided by Cl/sub 2/ and NO/sub 2/ photolysis respectively. The quantum uields measured for photolysis at 350 nm, calcualted using the absorption spectrum measured in this work, are: 0.93 +- 0.1 for Cl and less than or equal to 0.025 for O. An upper limit of 0.1 was measured for the O atom channel in ClOHO/sub 2/ photolysis.

  20. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2008-08-01

    Full Text Available This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006/07. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appendices containing the data sheets, which provide information upon which the recommendations are made.

  1. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2004-01-01

    Full Text Available This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

  2. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2006-01-01

    Full Text Available This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

  3. Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

    Science.gov (United States)

    Zaera, Francisco

    2017-05-01

    In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H2 with O2 and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. Sections 6 and 7 of this review deal with the advances made in the use of molecular beams with

  4. 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

  5. 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

    Enzymatic reduction of carbon dioxide (CO2 ) to methanol (CH3 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...... 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...

  6. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  7. Kinetics of the Sabatier reaction over a nickel catalyst in a flow system

    Energy Technology Data Exchange (ETDEWEB)

    Naumov, V.A.; Krylov, O.V.; Gavrilov, L.I.

    1979-07-01

    Methanation of carbon dioxide (the Sabatier reaction) over a 58.3Vertical Bar3< Ni/35.7Vertical Bar3< Cr/sub 2/O/sub 3//5.5Vertical Bar3< graphite catalyst was studied in a differential flow reactor at 200/sup 0/-300/sup 0/C, 1 atm, and 0-9:1 H/sub 2//CO/sub 2/ molar ratio (R). Dilution of the reactants with methane or steam, the reaction products, which were not adsorbed on nickel under the reaction conditions, did not inhibit the reaction. Analysis of an empirical kinetic equation showed that the reaction rate was a nonlinear function of R and passed through a temperature-dependent maximum at R = 0.0386 (72.1Vertical Bar3< CO/sub 2/ in the feed) at 250/sup 0/C and at R = 0.575 (63.5Vertical Bar3< CO/sub 2/) at 300/sup 0/C, which was in good agreement with experiment.

  8. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    Science.gov (United States)

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan; Xu, Donghai

    2017-03-01

    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Kinetics and Thermodynamic Studies of Depolymerization of Nylon Waste by Hydrolysis Reaction

    Directory of Open Access Journals (Sweden)

    D. B. Patil

    2014-01-01

    Full Text Available Depolymerization reaction of nylon waste was carried out by hydrolysis reaction. Yield of depolymerization products was up to 72.20% for a two-hour reaction time. The products obtained were characterized by melting point and FTIR spectra. The values obtained for dibenzoyl derivative of hexamethylenediamine (DBHMD agreed with those of the pure substance. Chemical kinetics of this reaction shows that it is a first-order reaction with respect to hexamethylenediamine (HMD concentration with velocity constant 7.32×10-3 min−1. The energy of activation and Arrhenius constant obtained by Arrhenius plot were 87.22 KJg−1 and 0.129, respectively. The other thermodynamic parameters such as enthalpy of activation (ΔH‡ and entropy of activation (ΔS‡ and free energy of activation were 5975.85 J and −270.86 J·K−1·mol−1 and 101.59 KJ·mol−1, respectively.

  10. Reaction mechanism and kinetics of sulfide copper concentrate oxidation at elevated temperatures

    Directory of Open Access Journals (Sweden)

    Aleksandra Mitovski

    2017-09-01

    Full Text Available Sulfide copper concentrate from domestic ore deposit (Bor, Serbia was subjected to oxidation in the air atmosphere due to a better understanding of reaction mechanism and oxidation of various sulfides present in the copper concentrate at elevated temperatures. Results of the initial sample characterization showed that concentrate is chalcopyrite–enargite-tennantite type, with an increased arsenic content. Characterization of the oxidation products showed the presence of sulfates, oxysulfates, and oxides. Based on predominance area diagrams for Me-S-O systems (Me = Cu, Fe, As combined with thermal analysis results, the reaction mechanism of the oxidation process was proposed. The reactions which occur in the temperature range 25 – 1000 °C indicate that sulfides are unstable in the oxidative conditions. Sulfides from the initial sample decomposed into binary copper and iron sulfides and volatile arsenic oxides at lower temperatures. Further heating led to oxidation of sulfides into iron oxides and copper sulfates and oxysulfates. At higher temperatures sulfates and oxysulfates decomposed into oxides. Kinetic analysis of the oxidation process was done using Ozawa’s method in the non-isothermal conditions. The values for activation energies showed that the reactions are chemically controlled and the temperature is the most influential parameter on the reaction rates.

  11. 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.

  12. Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.

    Science.gov (United States)

    da Silva, Gabriel; Bozzelli, Joseph W

    2012-12-14

    The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can β-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but

  13. A thermodynamic and kinetic study of hydride transfer of a caffeine derivative.

    Science.gov (United States)

    Han, Xiaozhen; Hao, Weifang; Zhu, Xiao-Qing; Parker, Vernon D

    2012-08-03

    One representative type of heterocyclic compound that can release a hydride ion is 7,8-dihydro-9-methylcaffeine (CAFH). The one-electron oxidation potential of CAFH [-0.294 (V vs Fc(+/0))] and the one-electron reduction potential of CAF(+) [-2.120 (V vs Fc(+/0))] were obtained using two different methods, CV and OSWV. Applying titration calorimetry data in thermodynamic cycles, the enthalpies of CAFH releasing a hydride ion [57.6 kcal/mol] and releasing a hydrogen atom [80.3 kcal/mol] and of its radical cation CAFH(•+) releasing a proton [33.0 kcal/mol] and releasing a hydrogen atom [38.4 kcal/mol] have been determined. Several conclusions can be drawn from the thermodynamic results: (1) CAFH is a very good single-electron donor whose single-electron oxidation potential is much less positive than that of NAD(P)H model compound BNAH [E(ox) = 0.219 V vs Fc(+/0)]. (2) The single-electron reduction potential of CAF(+) is much more negative than that of BNA(+) [E(red) = -1.419 V], which means that CAF(+) is not a good electron acceptor. Furthermore, CAFH is a very good hydride donor compared to BNAH. The results of non-steady-state kinetic studies, for the reaction of CAFH and AcrH(+)ClO(4)(-), show that the ratio of t(0.50)/t(0.05) is larger than 13.5 and the ratio of k(init)/k(pfo) is larger than 1. The pseudo-first-order rate constants obtained at different reaction stages decrease with the time, and the kinetic isotope was observed to be small at a short reaction time and slowly increases to 3.72 with the progress of the reaction. These kinetic results clearly display that the hydride transfer of CAFH to AcrH(+) in acetonitrile is not a one-step mechanism, while the thermodynamic results show that CAFH is a very good electron donor. The combination of the kinetic results with the thermodynamics analysis shows that the hydride transfer of the caffeine derivative CAFH takes place by a two-step reversible mechanism and there is an intermediate in the reaction.

  14. Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

    Science.gov (United States)

    Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena

    2008-10-01

    The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors

  15. Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers

    Science.gov (United States)

    Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Tian, Zemin; Zhang, Yingjia; Huang, Zuohua

    2016-10-01

    The ground-state potential energy surface (PES) of isomerization philosophy of ten normal-chain hexadiene isomers is computed by density functional methods using the geometries optimized at B3LYP/6-311++G (d, p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization reactions by transition state theory (TST) in the temperature range of 500-2500 K. Difference of rate constant between each hexadiene isomer is interpreted through the PES and Ḣ atom transfer, and only 2,4-hexadiene readily fulfills cis-cis to trans-trans conformation conversion. All the conversions are kinetically interpreted from the PES and ST geometry.

  16. Specific anion binding to sulfobetaine micelles and kinetics of nucleophilic reactions.

    Science.gov (United States)

    Marte, Luisa; Beber, Rosane C; Farrukh, M Akhyar; Micke, Gustavo A; Costa, Ana C O; Gillitt, Nicholas D; Bunton, Clifford A; Di Profio, Pietro; Savelli, Gianfranco; Nome, Faruk

    2007-08-23

    With fully micellar bound substrates reactions of OH- with benzoic anhydride, Bz(2)O, and of Br- with methyl naphthalene-2-sulfonate, MeONs, in micellized sulfobetaines are strongly inhibited by NaClO4 which displaces the nucleophilic anions from the micellar pseudophases. Micellar incorporations of ClO4- and Br- are estimated with an ion-selective electrode and by electrophoresis, and partitioning of Br- between water and micelles is related to changes in NMR spectral (79)Br- line widths. Extents of inhibition by ClO4- of these nucleophilic reactions in the micellar pseudophase are related to quantitative displacement of the reactive anions from the micelles by ClO4-. The kinetic data are correlated with physical evidence on the strong interactions between sulfobetaines and ClO4-, which turn sulfobetaine micelles anionic and effectively provoke displacement of OH- and Br-.

  17. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  18. On the Upscaling of Reaction-Transport Processes in Porous Media with Fast Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Kechagi, P.; Tsimpanogiannis, I.; Yortsos, Y.C.; Lichtner, P.

    2001-01-09

    This report is organized as follows: Provide a brief review of the upscaling constraints of the type (2) for a typical diffusion-reaction system. In this an analogy with two-phase flow in porous media was drawn. Then, using the methodology of QW a problem at the unit cell for the computation of the effective mass transfer coefficient, in processes where local thermodynamic equilibrium applies was derived. This problem is found to be different than in QW, as it depends on the gradients of the macroscale variable, and can be cast in terms of an eigenvalue problem. Two simple, examples, one involving advection-dissolution and another involving drying in a pore network, was presented to illustrate the coupling between scales and to show the quantitative effect in case this coupling was neglected. Finally, similar ideas and an illustrative example was applied to reaction-diffusion systems with fast kinetics, where an equilibrium state is approached.

  19. Reaction of a sterically hindered iron(III porphyrin with peroxyacetic acid: degradation kinetics

    Directory of Open Access Journals (Sweden)

    P. PRAKASH

    2005-09-01

    Full Text Available A kinetic analysis of the reaction between peracetic acid (AcOOH, and tetrakis (pentafluorophenyl - 21H, 23H-porphine iron(III chloride, Fe(F20TPPCl, in acetonitrile showed that the peracetic acid oxidatively destroys Fe(F20TPPCl. This is in contrast to an assumption that the oxidative degradation of metalloporphyrins can be prevented by the introduction of electron-withdrawing substituents into the phenyl groups of the porphyrin ligand. A UV-visible spectroscopic study showed a degree of macro cycle destruction of the tetrapyrrole conjucation of the metalloporphyrin. The degradation takes place via oxoperferryl species. The first step of the reaction mechanism is the reversible formation of an adduct ’X’(k1/k-1 between Fe(F20TPPCl and peracetic acid, followed by an irreversible step (k2 for the formation of oxoperferryl species.

  20. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  1. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

    Science.gov (United States)

    Wang, Heng; Bozzelli, Joseph W

    2016-07-04

    Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination. The enthalpies of formation of the transition states are determined and evaluated using six popular Density Functional Theory (DFT) calculation methods (B3LYP, B2PLYP, M06, M06-2X, ωB97X, ωB97XD), each combined with three different basis sets. The DFT enthalpy values are compared with five composite calculation methods (G3, G4, CBS-QB3, CBS-APNO, W1U), and by CCSD(T)/aug-cc-pVTZ. Kinetic parameters are determined versus pressure and temperature for the unimolecular dissociation pathways of an oxiranyl radical, which include the chemical activation reactions of the ring-opened oxiranyl radical relative to the ring-opening barrier. Multifrequency quantum Rice Ramsperger Kassel (QRRK) analysis is used to determine k(E) with master equation analysis for falloff. The major overall reaction pathway at lower combustion temperatures is oxiranyl radical dissociation to a methyl radical and carbon monoxide. Oxiranyl radical dissociation to a ketene and hydrogen atom is the key reaction path above 700 K. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Polychlorinated ethane reaction with zero-valent zinc: pathways and rate control

    Science.gov (United States)

    Arnold, William A.; Ball, William P.; Roberts, A. Lynn

    1999-12-01

    Efficient design of zero-valent metal permeable `barriers' for the reduction of organohalides requires information regarding the pertinent reaction rates as well as an understanding of the resultant distribution of products. In this study, the pathways and kinetics for reaction of polychlorinated ethanes with Zn(0) have been examined in batch reactors. Reductive β-elimination was the only route through which hexachloroethane (HCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,2-trichloroethane (1,1,2-TCA) and 1,2-dichloroethane (1,2-DCA) reacted. Pentachloroethane (PCA) reacted via concurrent reductive β-elimination (93%) and hydrolysis (7%). As previously demonstrated, 1,1,1-trichloroethane (1,1,1-TCA) and 1,1-dichloroethane (1,1-DCA) reacted predominantly via reductive α-elimination. Attempts to correlate BET surface area-normalized rate constants ( kSA-BET) with one-electron reduction potential ( E1) met with limited success, as HCA, PCA, 1,1,1,2-TeCA, and 1,1,1-TCA reacted at nearly identical rates despite substantial differences in E1 values. Comparison of the pseudo-first-order rate constants ( kobs) for these species with rate constants ( kLa) obtained from a correlation for mass transfer to suspended particles revealed that the reaction of these species was mass transfer limited even though reaction rates were unaffected by mixing speed. Calculations suggest that mass transfer limitations may also play a role in the design of treatment systems for highly reactive species, with overall rate constants predicted to increase with flow velocity.

  3. Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

    Science.gov (United States)

    Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

    1997-01-01

    Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-01-17

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

  5. Does phenomenological kinetics provide an adequate description of heterogeneous catalytic reactions?

    Science.gov (United States)

    Temel, Burcin; Meskine, Hakim; Reuter, Karsten; Scheffler, Matthias; Metiu, Horia

    2007-05-01

    Phenomenological kinetics (PK) is widely used in the study of the reaction rates in heterogeneous catalysis, and it is an important aid in reactor design. PK makes simplifying assumptions: It neglects the role of fluctuations, assumes that there is no correlation between the locations of the reactants on the surface, and considers the reacting mixture to be an ideal solution. In this article we test to what extent these assumptions damage the theory. In practice the PK rate equations are used by adjusting the rate constants to fit the results of the experiments. However, there are numerous examples where a mechanism fitted the data and was shown later to be erroneous or where two mutually exclusive mechanisms fitted well the same set of data. Because of this, we compare the PK equations to "computer experiments" that use kinetic Monte Carlo (kMC) simulations. Unlike in real experiments, in kMC the structure of the surface, the reaction mechanism, and the rate constants are known. Therefore, any discrepancy between PK and kMC must be attributed to an intrinsic failure of PK. We find that the results obtained by solving the PK equations and those obtained from kMC, while using the same rate constants and the same reactions, do not agree. Moreover, when we vary the rate constants in the PK model to fit the turnover frequencies produced by kMC, we find that the fit is not adequate and that the rate constants that give the best fit are very different from the rate constants used in kMC. The discrepancy between PK and kMC for the model of CO oxidation used here is surprising since the kMC model contains no lateral interactions that would make the coverage of the reactants spatially inhomogeneous. Nevertheless, such inhomogeneities are created by the interplay between the rate of adsorption, of desorption, and of vacancy creation by the chemical reactions.

  6. A kinetics and mechanistic study on the role of the structural rigidity of the linker on the substitution reactions of chelated dinuclear Pt(II) complexes.

    Science.gov (United States)

    Mambanda, Allen; Jaganyi, Deogratius

    2012-01-21

    Substitution reactions of platinum complexes bearing cyclohexylamine/diamine moieties viz., [Pt(H(2)O)(N,N-bis(2-pyridylmethyl)cyclohexylamine)](CF(3)SO(3))(2), bpcHna; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-trans-1,4-cyclohexyldiamine)](CF(3)SO(3))(4), cHn and [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-4,4'-dicyclohexylmethanediamine)](CF(3)SO(3))(4), dcHnm and phenylamine/diamine moieties viz., ([Pt(H(2)O)N,N-bis(2-pyridylmethyl)phenylamine)](CF(3)SO(3))(2), bpPha; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-phenyldiamine)](CF(3)SO(3))(4), mPh; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-1,4-phenyldiamine)](CF(3)SO(3))(4), pPh and [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-4,4'-diphenylmethanediamine)](CF(3)SO(3))(4)), dPhm with thiourea nucleophiles were studied in acidified 0.01 M LiCF(3)SO(3) aqueous medium under pseudo-first-order conditions using stopped-flow and UV-visible spectrophotometric techniques. The rate of substitution follows a similar trend in the two sets of complexes and decreases in the order: bpcHna > dcHnm > cHn and bpPha > dPhm ≈ pPh ≈ mPh), respectively. The result of this study has shown that the rigidity and/or the planarity of a diamine bridge linking the two (2-pyridylmethyl)amine-chelated Pt(II) centres, influences the reactivity of the metal centres by protracting similar symmetry elements within the complexes, which determines the amount of steric influences felt on the coordination square-plane. Hence, the order of reactivity is controlled by both the steric hindrance and the magnitude of the trans σ-inductive effect originating from the linker towards the metal centre. These two factors also impact on the acidity of the complexes. The high negative entropies and low positive enthalpies support an associative mode of activation.

  7. 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

  8. Ground reaction forces and knee kinetics during single and repeated badminton lunges.

    Science.gov (United States)

    Lam, Wing Kai; Ding, Rui; Qu, Yi

    2017-03-01

    Repeated movement (RM) lunge that frequently executed in badminton might be used for footwear evaluation. This study examined the influence of single movement (SM) and RM lunges on the ground reaction forces (GRFs) and knee kinetics during the braking phase of a badminton lunge step. Thirteen male university badminton players performed left-forward lunges in both SM and RM sessions. Force platform and motion capturing system were used to measure GRFs and knee kinetics variables. Paired t-test was performed to determine any significant differences between SM and RM lunges regarding mean and coefficient of variation (CV) in each variable. The kinetics results indicated that compared to SM lunges, the RM lunges had shorter contact time and generated smaller maximum loading rate of impact force, peak knee anterior-posterior force, and peak knee sagittal moment but generated larger peak horizontal resultant forces (Ps < 0.05). Additionally, the RM lunges had lower CV for peak knee medial-lateral and vertical forces (Ps < 0.05). These results suggested that the RM testing protocols had a distinct loading response and adaptation pattern during lunge and that the RM protocol showed higher within-trial reliability, which may be beneficial for the knee joint loading evaluation under different interventions.

  9. Neural networks for modelling of chemical reaction systems with complex kinetics: oxidation of 2-octanol with nitric acid

    NARCIS (Netherlands)

    Molga, E.J.; van Woezik, B.A.A.; Westerterp, K.R.

    2000-01-01

    Application of neural networks to model the conversion rates of a heterogeneous oxidation reaction has been investigated — oxidation of 2-octanol with nitric acid has been considered as a case study. Due to a more complex and unknown kinetics of the investigated reaction the proposed approach based

  10. Oxidation of ferrous nitrilotriacetic acid with oxygen : A model for oxygen mass transfer parallel to reaction kinetics

    NARCIS (Netherlands)

    Demmink, J.F; Beenackers, A.A C M

    1997-01-01

    The kinetics of the reaction of ferrous chelate of nitrilotriacetic acid (NTA) and gaseous oxygen were studied in a stirred-cell reactor. The initial concentration of ferrous chelate was 0.100 kmol/m(3). Other reaction conditions include 293

  11. Kinetics and mechanism of the chain reaction between N-phenyl-1,4-benzoquinone monoimine and thiophenol

    Science.gov (United States)

    Varlamov, V. T.; Gadomsky, S. Ya.

    2017-05-01

    The kinetics of the reaction between N-phenyl-1,4-benzoquinone monoimine (quinone monoimine) and thiophenol is studied in chlorobenzene at 343 K. The reaction has the same mechanism proposed earlier for a similar reaction involving N,N'-diphenyl-1,4-benzoquinone diimine (quinone diimine). This mechanism has two paths: chain and nonchain. An important difference between the kinetics of the two reactions is the apparent reversible nature of the chain reaction in the quinone monoimine + thiophenol system. This nature reveals itself when the concentrations of thiophenol are comparable to or slightly higher than the concentrations of quinone imine. In light of this, kinetic research is conducted under conditions where the concentrations of thiophenol are significantly higher than those of quinone monoimine, allowing us to simplify the kinetic features and obtain interpretable data. The rate constants of the reaction's elementary steps are estimated and found to be three to five times lower for the reaction involving quinone monoamine than for the one involving quinone diimine. Both reactions have relatively short chains whose lengths do not exceed several tens of units.

  12. 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)

  13. Microwave treatment of dairy manure for resource recovery: Reaction kinetics and energy analysis.

    Science.gov (United States)

    Srinivasan, Asha; Liao, Ping H; Lo, Kwang V

    2016-12-01

    A newly designed continuous-flow 915 MHz microwave wastewater treatment system was used to demonstrate the effectiveness of the microwave enhanced advanced oxidation process (MW/H2O2-AOP) for treating dairy manure. After the treatment, about 84% of total phosphorus and 45% of total chemical oxygen demand were solubilized with the highest H2O2 dosage (0.4% H2O2 per %TS). The reaction kinetics of soluble chemical oxygen demand revealed activation energy to be in the range of 5-22 kJ mole-1. The energy required by the processes was approximately 0.16 kWh per liter of dairy manure heated. A higher H2O2 dosage used in the system had a better process performance in terms of solids solubilization, reaction kinetics, and energy consumption. Cost-benefit analysis for a farm-scale MW/H2O2-AOP treatment system was also presented. The results obtained from this study would provide the basic knowledge for designing an effective farm-scale dairy manure treatment system.

  14. Kinetic modelling for zinc (II) ions biosorption onto Luffa cylindrica

    Science.gov (United States)

    Oboh, I.; Aluyor, E.; Audu, T.

    2015-03-01

    The biosorption of Zinc (II) ions onto a biomaterial - Luffa cylindrica has been studied. This biomaterial was characterized by elemental analysis, surface area, pore size distribution, scanning electron microscopy, and the biomaterial before and after sorption, was characterized by Fourier Transform Infra Red (FTIR) spectrometer. The kinetic nonlinear models fitted were Pseudo-first order, Pseudo-second order and Intra-particle diffusion. A comparison of non-linear regression method in selecting the kinetic model was made. Four error functions, namely coefficient of determination (R2), hybrid fractional error function (HYBRID), average relative error (ARE), and sum of the errors squared (ERRSQ), were used to predict the parameters of the kinetic models. The strength of this study is that a biomaterial with wide distribution particularly in the tropical world and which occurs as waste material could be put into effective utilization as a biosorbent to address a crucial environmental problem.

  15. Kinetic modelling for zinc (II) ions biosorption onto Luffa cylindrica

    Energy Technology Data Exchange (ETDEWEB)

    Oboh, I., E-mail: innocentoboh@uniuyo.edu.ng [Department of Chemical and Petroleum Engineering, University of Uyo, Uyo (Nigeria); Aluyor, E.; Audu, T. [Department of Chemical Engineering, University of Uyo, BeninCity, BeninCity (Nigeria)

    2015-03-30

    The biosorption of Zinc (II) ions onto a biomaterial - Luffa cylindrica has been studied. This biomaterial was characterized by elemental analysis, surface area, pore size distribution, scanning electron microscopy, and the biomaterial before and after sorption, was characterized by Fourier Transform Infra Red (FTIR) spectrometer. The kinetic nonlinear models fitted were Pseudo-first order, Pseudo-second order and Intra-particle diffusion. A comparison of non-linear regression method in selecting the kinetic model was made. Four error functions, namely coefficient of determination (R{sup 2}), hybrid fractional error function (HYBRID), average relative error (ARE), and sum of the errors squared (ERRSQ), were used to predict the parameters of the kinetic models. The strength of this study is that a biomaterial with wide distribution particularly in the tropical world and which occurs as waste material could be put into effective utilization as a biosorbent to address a crucial environmental problem.

  16. Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1988-01-01

    The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

  17. Study on the Size-Dependent Oxidation Reaction Kinetics of Nanosized Zinc Sulfide

    Directory of Open Access Journals (Sweden)

    Qing-Shan Fu

    2014-01-01

    Full Text Available Numerous oxidation problems of nanoparticles are often involved during the preparation and application of nanomaterials. The oxidation rate of nanomaterials is much faster than bulk materials due to nanoeffect. Nanosized zinc sulfide (nano-ZnS and oxygen were chosen as a reaction system. The influence regularities were discussed and the influence essence was elucidated theoretically. The results indicate that the particle size can remarkably influence the oxidation reaction kinetics. The rate constant and the reaction order increase, while the apparent activation energy and the preexponential factor decrease with the decreasing particle size. Furthermore, the logarithm of rate constant, the apparent activation energy and the logarithm of preexponential factor are linearly related to the reciprocal of particle diameter, respectively. The essence is that the rate constant is influenced by the combined effect of molar surface energy and molar surface entropy, the reaction order by the molar surface area, the apparent activation energy, by the molar surface energy, and the preexponential factor by the molar surface entropy. The influence regularities and essence can provide theoretical guidance to solve the oxidation problems involved in the process of preparation and application of nanomaterials.

  18. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-01-01

    Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

  19. Kinetic sonication effects in light of molecular dynamics simulation of the reaction medium.

    Science.gov (United States)

    Salmar, Siim; Kuznetsov, Aleksei; Tuulmets, Ants; Järv, Jaak; Piiskop, Sander

    2013-03-01

    Molecular dynamics (MD) simulation of the structure of ethyl acetate solutions in two water-ethanol mixtures was performed at 280 and 330K. The MD simulations revealed that ethyl acetate was preferentially solvated by ethanol, water being mainly located in the next solvation layer. With increasing temperature ethanol was gradually replaced by water in the first solvation shell. These findings explain the decrease in the rate of ester hydrolysis with increasing molar ratio of ethanol in the solution as the reaction rate was linearly dependent on the relative ethanol content in the first solvation shell of the ester. Predominance of ethanol results in decreased polarity and water activity in the shell and accordingly in a decreased reaction rate. Based on the results of the MD simulations, the principal conclusion of this work is that ultrasound enhances the kinetic energy (the effective temperature) of species in the solution and, in this way, evokes shifts in the solvation equilibria thus affecting the reaction rate. It appears that ultrasound does not completely break down the solvent shells or clusters in the solution as previously believed. Phenomena of thermo-solvatochromism and reaction rate levelling by ultrasound in binary solvents are described. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Research on the Thermal Decomposition Reaction Kinetics and Mechanism of Pyridinol-Blocked Isophorone Diisocyanate

    Directory of Open Access Journals (Sweden)

    Sen Guo

    2016-02-01

    Full Text Available A series of pyridinol-blocked isophorone isocyanates, based on pyridinol including 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, was synthesized and characterized by 1H-NMR, 13C-NMR, and FTIR spectra. The deblocking temperature of blocked isocyanates was established by thermo-gravimetric analysis (TGA, differential scanning calorimetry (DSC, and the CO2 evaluation method. The deblocking studies revealed that the deblocking temperature was increased with pyridinol nucleophilicity in this order: 3-hydroxypyridine > 4-hydroxypyridine > 2-hydroxypyridine. The thermal decomposition reaction of 4-hydroxypyridine blocked isophorone diisocyanate was studied by thermo-gravimetric analysis. The Friedman–Reich–Levi (FRL equation, Flynn–Wall–Ozawa (FWO equation, and Crane equation were utilized to analyze the thermal decomposition reaction kinetics. The activation energy calculated by FRL method and FWO method was 134.6 kJ·mol−1 and 126.2 kJ·mol−1, respectively. The most probable mechanism function calculated by the FWO method was the Jander equation. The reaction order was not an integer because of the complicated reactions of isocyanate.

  1. Kinetics of the reactions of NO/sub 3/ with OH and HO/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Mellouki, A.; Le Bras, G.; Poulet, G.

    1988-04-21

    The kinetics of the title reactions have been studied by using the discharge flow method at 298 K. NO/sub 3/ was used in excess over OH and HO/sub 2/ and was titrated with NO or 2,3-dimethyl-2-butene. Since OH was found to be produced in the reaction of HO/sub 2/ with NO/sub 3/, the OH and HO/sub 2/ decays were analyzed by computer simulations to obtain the rate constants for the reactions OH + NO/sub 3/ ..-->.. HO/sub 2/ + NO/sub 2/ (1), HO/sub 2/ + NO/sub 3/ ..-->.. OH + NO/sub 2/ + O/sub 2/ (2a), and HO/sub 2/ + NO/sub 3/ ..-->.. HNO/sub 3/ + O/sub 2/ (2b). The results are k/sub 1/ = (2.6 +- 0.6) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 2a/ = (3.6 +- 0.9) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, and k/sub 2b/ = (9.2 +- 4.8) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The data for reaction 2 are discussed in relation with the HNO/sub 3/ nighttime production in the atmospheric gas phase.

  2. Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

    Science.gov (United States)

    Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique

    2017-03-01

    This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super-Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature. This article is part of

  3. Kinetics of hydroperoxy radical reactions with acetone/HO2 adduct and with acetonylperoxy radical

    Science.gov (United States)

    Grieman, F. J.; VanDerGeest, K.; Newenhouse, E.; Watkins, K.; Noell, A. C.; Hui, A.; Sander, S. P.; Okumura, M.

    2013-12-01

    Reactions of hydroperoxy radical, HO2, with acetone and with acetonylperoxy radical, CH3C(O)CH2OO, may play an important role in the oxidation chemistry of the troposphere. Using a temperature-controlled slow-flow tube cell and laser flash photolysis of Cl2 to produce HO2 and CH3C(O)CH2OO from methanol and acetone, respectively, we studied the chemical kinetics involved over the temperature range of 215 to 298 K at 100 Torr. Rates of chemical reactions were determined by monitoring the HO2 concentration as a function of time by near-IR diode laser wavelength modulation spectroscopy. (See Fig.1.) The primary reactions are rapid (reactions to form the adducts HO2-CH3OH and HO2-CH3C(O)CH3 followed by HO2 reactions with itself, the adducts (chaperone mechanisms), and acetonylperoxy radical. The equilibrium constants for adduct formation were determined in previous work.1,2 In this work, rate coefficients were determined for the acetone chaperone mechanism over the entire temperature range. (E.g., see Fig. 2.) The rate coefficients and energies obtained are very similar to those found for the methanol case.1 Rate coefficients for the CH3C(O)CH2OO/HO2 reaction were also determined over a smaller temperature range, extending the measured value beyond room temperature, and yielding an activation energy. 1. Christensen et al. J. Phys. Chem. A 2006, 110, 6948-6959. 2. Grieman et al. J. Phys. Chem. A 2011, 115, 10527-10538. Fig.1. HO2 decay for HO2/Acetone chemistry at T = 298 K. Fig.2. Determining rate coefficient (k") for HO2/acetone chaperone effect at T = 222.5 K.

  4. Kinetics, mechanism, and thermochemistry of the gas-phase reaction of atomic chlorine with pyridine.

    Science.gov (United States)

    Zhao, Z; Huskey, D T; Olsen, K J; Nicovich, J M; McKee, M L; Wine, P H

    2007-08-21

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of atomic chlorine with pyridine (C(5)H(5)N) as a function of temperature (215-435 K) and pressure (25-250 Torr) in nitrogen bath gas. At T> or = 299 K, measured rate coefficients are pressure independent and a significant H/D kinetic isotope effect is observed, suggesting that hydrogen abstraction is the dominant reaction pathway. The following Arrhenius expression adequately describes all kinetic data at 299-435 K for C(5)H(5)N: k(1a) = (2.08 +/- 0.47) x 10(-11) exp[-(1410 +/- 80)/T] cm(3) molecule(-1) s(-1) (uncertainties are 2sigma, precision only). At 216 K rate coefficients are pressure dependent and are much faster than computed from the above Arrhenius expression for the H-abstraction pathway, suggesting that the dominant reaction pathway at low temperature is formation of a stable adduct. Over the ranges of temperature, pressure, and pyridine concentration investigated, the adduct undergoes dissociation on the time scale of our experiments (10(-5)-10(-2) s) and establishes an equilibrium with Cl and pyridine. Equilibrium constants for adduct formation and dissociation are determined from the forward and reverse rate coefficients. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the addition reaction: Delta(r)H = -47.2 +/- 2.8 kJ mol(-1), Delta(r)H = -46.7 +/- 3.2 kJ mol(-1), and Delta(r)S = -98.7 +/- 6.5 J mol(-1) K(-1). The enthalpy changes derived from our data are in good agreement with ab initio calculations reported in the literature (which suggest that the adduct structure is planar and involves formation of an N-Cl sigma-bond). In conjunction with the well-known heats of formation of atomic chlorine and pyridine, the above Delta(r)H values lead to the following heats of formation for C(5)H(5)N-Cl at 298 K and 0 K: Delta(f)H = 216.0 +/- 4.1 kJ mol(-1), Delta(f)H = 233.4 +/- 4.6 k

  5. Kinetics and isotherm studies of Cd(II) adsorption from aqueous solution utilizing seeds of bottlebrush plant ( Callistemon chisholmii)

    Science.gov (United States)

    Rao, Rifaqat Ali Khan; Kashifuddin, Mohammad

    2014-12-01

    Seeds of bottlebrush, a novel plant material, were found to exhibit excellent adsorption capacity over a wide range of Cd(II) concentration. It was characterized by Fourier transform infrared spectroscopy and Scanning Electron Microscopy to support the adsorption of Cd(II) ions. Effect of various parameters like pH, contact time, initial concentration and different electrolytes was investigated using batch process to optimize conditions for maximum adsorption. The adsorbent data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Redushkeuich isotherm equations at 30°, 40° and 50 °C. Thermodynamic parameters such as standard enthalpy change (Δ H°), free energy change (Δ G°) and entropy change (Δ S°) were also evaluated and the results indicated that adsorption of Cd(II) are spontaneous and endothermic. Various kinetics models including the Pseudo-first-order kinetics, Pseudo-second-order kinetics and Intraparticle diffusion models have been applied to the experimental data to predict the adsorption kinetics. Kinetic study was carried out by varying initial concentration of Cd(II) at constant temperature and it was found that pseudo-second-order rate equation was better obeyed than pseudo-first-order equation supporting that chemisorption process was involved.

  6. Methylidyne radical reactions with hydrocarbons: kinetics at low temperature and product branching ratios

    Science.gov (United States)

    Bergeat, Astrid; Caubert, Philippe; Costes, Michel; Daugey, Nicolas; Loison, Jean-Christophe

    CH radical reactions with hydrocarbons could play a role in the atmospheres of Titan, Pluto or Triton as well as in interstellar clouds (ISCs), where the hydrocarbon compounds were detected and the temperatures are very low, i.e. ~ 95 K down to ~ 38 K at the surface of these satellites and planet and from 50 K down to 10 K in ISCs. In fact, in modelling the processes occurring in these low-temperature environments, researchers generally still have to extrapolate the high-temperature kinetic data mainly obtained in the temperature range above 300 K. However, for many neutral-neutral reactions studied, the rate constants exhibit essentially non-Arrhenius behaviour at low temperatures. The temperature dependences of the methylidyne radical reactions with methane, allene, methylacetylene and propene were studied in our new supersonic flow reactor coupled with pulsed laser photolysis (PLP) and laser induced fluorescence (LIF) techniques. Three Laval nozzles were designed to provide uniform supersonic expansions down to 77 K. The rate constants for the CH + CH4 reaction are in good agreement with the temperature dependence proposed by A. Canosa et al., i.e. 3.96 × 10-8 ×(T/K)-1.04 exp(-36.1K/T) in the range 23-298 K. The rate constants of the CH + C3H4 (allene), CH + C3H4 (methylacetylene) and CH + C3H6 (propene) reactions exhibit a small temperature dependence between 77 and 170 K, are close to the gas kinetic limit and could thus contribute to the chemistry in the dense molecular clouds or outer planets atmospheres (Titan, Pluto and Triton for example) rich in hydrocarbons. The reactions of CH radical with several saturated and unsaturated hydrocarbons were studied, at room temperature, in a low-pressure fast-flow reactor. The absolute atomic hydrogen productions were determined at 300 K by V.U.V. resonance fluorescence, the reference used being the H production from the CH + CH4 and H2S reactions. Ab initio studies of the different stationary points relevant to some

  7. Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    M. L. Santee

    2009-11-01

    Full Text Available The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007 are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen

  8. Kinetics of decolorization of azo dye by bipolar pulsed barrier discharge in a three-phase discharge plasma reactor

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Ruobing [Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)]. E-mail: zrbingdut@163.com; Zhang Chi [Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Cheng Xingxin [Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Wang Liming [Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Wu Yan [Institute of Electrostatics and Special Power, Dalian University of Technology, Dalian 116024 (China); Guan Zhicheng [Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2007-04-02

    Removal of amaranth, a commercial synthetic azo dye widely used in the dye and food industry, was examined as a possible remediation technology for treating dye-contaminated water. Effects of various parameters such as gas flow rate, solution conductivity, pulse repetition frequency, etc., on decolorization kinetics were investigated. Experimental results show that an aqueous solution of 24 mg/l dye is 81.24% decolorized following 30 min plasma treatment for a 50 kV voltage and 0.75 m{sup 3}/h gas flow rate. Decolorization reaction of amaranth in the plasma reactor is a pseudo first order reaction. Rate constant (k) of decolorization increases quickly with increasing the applied voltage, pulse repetition frequency and the gas flow rate. However, when the applied voltage is beyond 50 kV and increases further, increase rate of k decreases. In addition, k decreases quickly when the solution conductivity increases from 200 to 1481 {mu}S/cm. The decolorization reaction has a high rate constant (k = 0.0269 min{sup -1}) when the solution pH is beyond 10. Rate constant k decreases with the decrease of pH and reaches minimum at a pH of about 5 (k {sub min} = 0.01603 min{sup -1}), then increases to 0.02105 min{sup -1} when pH decreases to 3.07. About 15% of the initial TOC can be degraded only in about 120 min non-thermal plasma treatment.

  9. Behavior and kinetic of hydrolysis of amine boranes in acid media employed in chemical vapor generation.

    Science.gov (United States)

    D'Ulivo, Lucia; Spiniello, Roberto; Onor, Massimo; Campanella, Beatrice; Mester, Zoltan; D'Ulivo, Alessandro

    2018-01-15

    The behavior of NaBH4 (THB) and the amine boranes, NH3BH3 (AB), tertbutylNH2BH3 (TBAB), Me2NHBH3 (DMAB) was investigated in continuous flow chemical vapor generation of H2Se from aqueous Se(IV) coupled with atomic absorption spectrometry. Unexpected higher efficiency of H2Se generation was obtained with amine boranes compared to THB (TBAB > AB > THB) using millimolar concentration of reductant (0.001-0.1 mol L(-1)) under strongly acidic conditions (HCl, HClO4, H2SO4, HNO3, 0.5-5 mol L(-1) H(+)). Analytical applicability of the CVG system was tested by the determination of Se(IV) in natural water samples certified reference materials, using 0.01 mol L(-1) TBAB in 0.5 M H2SO4. In order to explain this unexpected higher efficiency of amine boranes with respect of THB, the kinetic of hydrolysis of AB, TBAB and DMAB was investigated in acid media typically employed in chemical vapor generation for trace element determination. The kinetic was investigated by monitoring the rate the hydrogen gas evolved during hydrolysis, using a laboratory made thermostated reaction cell. Kinetics were measured for AB, TBAB and DMAB in 0.1, 0.5, 5 mol L(-1) HCl or HClO4 reaction media and in 0.1 mol L(-1) cysteine +0.1 mol L(-1) HCl or HClO4 buffer, for reaction times from 0 to 30 min. Under strongly acidic conditions, the rates of hydrogen evolution produced by amine boranes hydrolysis appear to be much slower than those predicted by a pseudo-first order reaction and using the rate constants reported in the literature. This suggests that, at elevated acidities (5 mol L(-1) HCl or HClO4), the hydrolysis of amine boranes takes place in two steps, generating a first amount of H2 (0.67-1.15 mol) much faster than the remaining about 2 mol. This evidence indicates a different mechanism of hydrolysis to the one accepted in the literature for amine boranes. The relatively high efficiencies of H2Se observed with amine borane reduction of inorganic Se(IV) at elevated

  10. Oxidation of triclosan by ferrate: Reaction kinetics, products identification and toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Yang Bin [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Ying Guangguo, E-mail: guang-guo.ying@csiro.au [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhao Jianliang; Zhang Lijuan; Fang Yixiang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Nghiem, Long Duc [School of Civil Mining and Environmental Engineering, University of Wollongong, Wollongong, NSW 2522 (Australia)

    2011-02-15

    Research highlights: {yields} Triclosan reacted rapidly with ferrate. {yields} Oxidation resulted in a decrease in algal toxicity. {yields} No inhibition of algae growth from ferrate. - Abstract: The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k{sub app}, being 754.7 M{sup -1} s{sup -1} at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7({+-}1.9) x 10{sup 2} M{sup -1} s{sup -1}, while that measured for anionic triclosan was 7.6({+-}0.6) x 10{sup 3} M{sup -1} s{sup -1}. The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth.

  11. Kinetics of reactions of the Actinomadura R39 DD-peptidase with specific substrates.

    Science.gov (United States)

    Adediran, S A; Kumar, Ish; Nagarajan, Rajesh; Sauvage, Eric; Pratt, R F

    2011-01-25

    The Actinomadura R39 DD-peptidase catalyzes the hydrolysis and aminolysis of a number of small peptides and depsipeptides. Details of its substrate specificity and the nature of its in vivo substrate are not, however, well understood. This paper describes the interactions of the R39 enzyme with two peptidoglycan-mimetic substrates 3-(D-cysteinyl)propanoyl-D-alanyl-D-alanine and 3-(D-cysteinyl)propanoyl-D-alanyl-D-thiolactate. A detailed study of the reactions of the former substrate, catalyzed by the enzyme, showed DD-carboxypeptidase, DD-transpeptidase, and DD-endopeptidase activities. These results confirm the specificity of the enzyme for a free D-amino acid at the N-terminus of good substrates and indicated a preference for extended D-amino acid leaving groups. The latter was supported by determination of the structural specificity of amine nucleophiles for the acyl-enzyme generated by reaction of the enzyme with the thiolactate substrate. It was concluded that a specific substrate for this enzyme, and possibly the in vivo substrate, may consist of a partly cross-linked peptidoglycan polymer where a free side chain N-terminal un-cross-linked amino acid serves as the specific acyl group in an endopeptidase reaction. The enzyme is most likely a DD-endopeptidase in vivo. pH-rate profiles for reactions of the enzyme with peptides, the thiolactate named above, and β-lactams indicated the presence of complex proton dissociation pathways with sticky substrates and/or protons. The local structure of the active site may differ significantly for reactions of peptides and β-lactams. Solvent kinetic deuterium isotope effects indicate the presence of classical general acid/base catalysis in both acylation and deacylation; there is no evidence of the low fractionation factor active site hydrogen found previously in class A and C β-lactamases.

  12. Thermodynamic and kinetic considerations for the reaction of semiquinone radicals to form superoxide and hydrogen peroxide

    Science.gov (United States)

    Song, Yang; Buettner, Garry R.

    2010-01-01

    The quinone/semiquinone/hydroquinone triad (Q/SQ•−/H2Q) represents a class of compounds that has great importance in a wide range of biological processes. The half-cell reduction potentials of these redox couples in aqueous solutions at neutral pH, E°′, provide a window to understanding the thermodynamic and kinetic characteristics of this triad and their associated chemistry and biochemistry in vivo. Substituents on the quinone ring can significantly influence the electron density “on the ring” and thus modify E°′ dramatically. E°′ of the quinone governs the reaction of semiquinone with dioxygen to form superoxide. At near-neutral pH the pKa's of the hydroquinone are outstanding indicators of the electron density in the aromatic ring of the members of these triads (electrophilicity) and thus are excellent tools to predict half-cell reduction potentials for both the one-electron and two-electron couples, which in turn allow estimates of rate constants for the reactions of these triads. For example, the higher the pKa's of H2Q, the lower the reduction potentials and the higher the rate constants for the reaction of SQ•− with dioxygen to form superoxide. However, hydroquinone autoxidation is controlled by the concentration of di-ionized hydroquinone; thus, the lower the pKa's the less stable H2Q to autoxidation. Catalysts, e.g., metals and quinone, can accelerate oxidation processes; by removing superoxide and increasing the rate of formation of quinone, superoxide dismutase can accelerate oxidation of hydroquinones and thereby increase the flux of hydrogen peroxide. The principal reactions of quinones are with nucleophiles via Michael addition, for example, with thiols and amines. The rate constants for these addition reactions are also related to E°′. Thus, pKa's of a hydroquinone and E°′ are central to the chemistry of these triads. PMID:20493944

  13. A Shock Tube Study of the CO + OH Reaction Near the Low-Pressure Limit

    KAUST Repository

    Nasir, Ehson Fawad

    2016-05-16

    Rate coefficients for the reaction between carbon monoxide and hydroxyl radical were measured behind reflected shock waves over 700 – 1230 K and 1.2 – 9.8 bar. The temperature/pressure conditions correspond to the predicted low-pressure limit of this reaction, where the channel leading to carbon dioxide formation is dominant. The reaction rate coefficients were inferred by measuring the formation of carbon dioxide using quantum cascade laser absorption near 4.2 µm. Experiments were performed under pseudo-first order conditions with tert-butyl hydroperoxide (TBHP) as the OH precursor. Using ultraviolet laser absorption by OH radicals, the TBHP decomposition rate was measured to quantify potential facility effects under extremely dilute conditions used here. The measured CO + OH rate coefficients are provided in Arrhenius form for three different pressure ranges: kCO+OH (1.2 – 1.6 bar) = 9.14 x 10-13 exp(-1265/T) cm3 molecule-1 s-1 kCO+OH (4.3 – 5.1 bar) = 8.70 x 10-13 exp(-1156/T) cm3 molecule-1 s-1 kCO+OH (9.6 – 9.8 bar) = 7.48 x 10-13 exp(-929/T) cm3 molecule-1 s-1 The measured rate coefficients are found to be lower than the master equation modeling results by Weston et al. [J. Phys. Chem. A, 117 (2013) 821] at 819 K and in closer agreement with the expression provided by Joshi and Wang [Int. J. Chem. Kinet., 38 (2006) 57].

  14. Mitoxantrone removal by electrochemical method: A comparison of homogenous and heterogenous catalytic reactions

    Directory of Open Access Journals (Sweden)

    Abbas Jafarizad

    2017-08-01

    Full Text Available Background: Mitoxantrone (MXT is a drug for cancer therapy and a hazardous pharmaceutical to the environment which must be removed from contaminated waste streams. In this work, the removal of MXT by the electro-Fenton process over heterogeneous and homogenous catalysts is reported. Methods: The effects of the operational conditions (reaction medium pH, catalyst concentration and utilized current intensity were studied. The applied electrodes were carbon cloth (CC without any processing (homogenous process, graphene oxide (GO coated carbon cloth (GO/CC (homogenous process and Fe3O4@GO nanocomposite coated carbon cloth (Fe3O4@GO/CC (heterogeneous process. The characteristic properties of the electrodes were determined by atomic force microscopy (AFM, field emission scanning electron microscopy (FE-SEM and cathode polarization. MXT concentrations were determined by using ultraviolet-visible (UV-Vis spectrophotometer. Results: In a homogenous reaction, the high concentration of Fe catalyst (>0.2 mM decreased the MXT degradation rate. The results showed that the Fe3O4@GO/CC electrode included the most contact surface. The optimum operational conditions were pH 3.0 and current intensity of 450 mA which resulted in the highest removal efficiency (96.9% over Fe3O4@GO/CC electrode in the heterogeneous process compared with the other two electrodes in a homogenous process. The kinetics of the MXT degradation was obtained as a pseudo-first order reaction. Conclusion: The results confirmed the high potential of the developed method to purify contaminated wastewaters by MXT.

  15. Reaction of the m-THPC triplet state with the antioxidant Trolox and the anesthetic Propofol: modulation of photosensitization mechanisms relevant to photodynamic therapy?

    Science.gov (United States)

    Friaa, O; Maillard, P; Brault, D

    2012-04-01

    Antioxidants may affect the outcome of photodynamic therapy (PDT) through the inactivation of reactive oxygen species. Their direct interaction with photosensitizers excited at the triplet state is also worthy of interest. This process is investigated by laser flash photolysis of m-THPC (meso-tetra(3-hydroxyphenyl)chlorin, Foscan) hydroalcoholic solutions added with Trolox (TrOH), a standard antioxidant or Propofol (PfOH, Diprivan(®)), a common anesthetic agent also characterized for its antioxidant properties. Transient UV-visible absorption spectra, kinetics at selected wavelengths and final spectra after extensive laser irradiation show that both compounds react with the m-THPC triplet state, (3)m-THPC, to ultimately restore the photosensitizer in its ground state. For PfOH, this process mainly appears as a single step obeying pseudo-first order kinetics. The bimolecular rate constant for the quenching of (3)m-THPC by PfOH is around 2 × 10(6) M(-1) s(-1), a value increased to some extent by the water content of the solution. A bimolecular reaction between (3)m-THPC and TrOH is observed with a rate constant of similar magnitude and dependence upon water. However, the reaction leads, at least partly, to intermediate species assigned to the TrO˙ radical and the m-THPC anion radical. Within a few ms, these species back react to yield m-THPC in its ground state. A general mechanism involving an intermediate activated complex with some charge transfer character is proposed. Depending on the redox potentials for the oxidation of the antioxidant, this complex evolves predominantly either toward the formation of radicals (TrOH) or back to the photosensitizer ground state (PfOH). Notably, the kinetics data suggest that Propofol may quench (3)m-THPC at concentrations relevant of clinical situation in PDT involving anesthesia.

  16. Inverse problem analysis for identification of reaction kinetics constants in microreactors for biodiesel synthesis

    Science.gov (United States)

    Pontes, P. C.; Naveira-Cotta, C. P.

    2016-09-01

    The theoretical analysis for the design of microreactors in biodiesel production is a complicated task due to the complex liquid-liquid flow and mass transfer processes, and the transesterification reaction that takes place within these microsystems. Thus, computational simulation is an important tool that aids in understanding the physical-chemical phenomenon and, consequently, in determining the suitable conditions that maximize the conversion of triglycerides during the biodiesel synthesis. A diffusive-convective-reactive coupled nonlinear mathematical model, that governs the mass transfer process during the transesterification reaction in parallel plates microreactors, under isothermal conditions, is here described. A hybrid numerical-analytical solution via the Generalized Integral Transform Technique (GITT) for this partial differential system is developed and the eigenfunction expansions convergence rates are extensively analyzed and illustrated. The heuristic method of Particle Swarm Optimization (PSO) is applied in the inverse analysis of the proposed direct problem, to estimate the reaction kinetics constants, which is a critical step in the design of such microsystems. The results present a good agreement with the limited experimental data in the literature, but indicate that the GITT methodology combined with the PSO approach provide a reliable computational algorithm for direct-inverse analysis in such reactive mass transfer problems.

  17. Adjusting the Chemical Bonding of SnO2 @CNT Composite for Enhanced Conversion Reaction Kinetics.

    Science.gov (United States)

    Cheng, Yayi; Huang, Jianfeng; Qi, Hui; Cao, Liyun; Yang, Jun; Xi, Qiao; Luo, Xiaomin; Yanagisawa, Kazumichi; Li, Jiayin

    2017-08-01

    Carbon nanotubes (CNTs) with excellent electron conductivity are widely used to improve the electrochemical performance of the SnO2 anode. However, the chemical bonding between SnO2 and CNTs is not clearly elucidated despite it may affect the lithiation/delithiation behavior greatly. In this work, an SnO2 @CNT composite with SnC and SnOC bonds as a linkage bridge is reported and the influence of the SnC and SnOC bonds on the lithium storage properties is revealed. It is found that the SnC bond can act as an ultrafast electron transfer path, facilitating the reversible conversion reaction between Sn and Li2 O to form SnO2 . Therefore, the SnO2 @CNT composite with more SnC bond shows high reversible capacity and nearly half capacity contributes from conversion reaction. It is opposite for the SnO2 @CNT composite with more SnOC bond that the electrons cannot be transferred directly to CNTs, resulting in depressed conversion reaction kinetics. Consequently, this work can provide new insight for exploration and design of metal oxide/carbon composite anode materials in lithium-ion battery. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Use of model peptide reactions for the characterization of kinetically controlled ligation.

    Science.gov (United States)

    Lee, Joongoo; Kwon, Yoonjin; Pentelute, Brad L; Bang, Duhee

    2011-08-17

    Since the introduction of kinetically controlled ligation (KCL), a chemoselective reaction between a peptide-(α)thioarylester and a Cys-peptide-(α)thioalkylester, KCL has been utilized for the total chemical synthesis of large proteins (i.e., lysozyme and HIV-protease) by providing fully convergent synthetic routes. Although KCL has the potential to become an important chemistry for protein synthesis, the principle of KCL is not fully characterized. In particular, prior work on KCL has focused on the reactivity difference of the two different -(α)thioester forms-alkyl vs aryl. Another equally important feature of KCL, Xaa-Cys ligation sites, has not been investigated. The work reported here describes combinatorial KCL reactions using model peptides to dissect the interplay of the Xaa(1), Xaa(2), -(α)thioarylester, and -(α)thioalkylester. Results from these studies provide fundamental insights into the KCL reaction, and will lead to the optimal synthetic route for the routine chemical synthesis of large target protein molecules.

  19. Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

    KAUST Repository

    Rachidi, Mariam El

    2015-01-01

    This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.

  20. Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions.

    Science.gov (United States)

    Menzeleev, Artur R; Bell, Franziska; Miller, Thomas F

    2014-02-14

    We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.

  1. 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)

  2. Investigation of the profile and kinetics of degradation of rivaroxaban using HPLC, TLC-densitometry and LC/MS/MS: Application to pre-formulation studies

    Directory of Open Access Journals (Sweden)

    Mohamed A. Abdallah

    2015-06-01

    Full Text Available Rivaroxaban (RIVA, an amide group-containing oral anticoagulant was subjected to stress conditions commonly required for the registration of pharmaceuticals: base and acid-catalyzed hydrolysis (0.1 M, 60 °C, 3–6 h, oxidation (10% H2O2, 24 h, photodegradation (300–800 nm, 24 h and thermal decomposition (50 °C, 6 h. Two major degradation products were separated and identified using TLC and LC/MS/MS, respectively. An orthogonal stability-indicating testing protocol (RP-HPLC and NP-TLC-densitometry was developed and validated according to ICH guidelines. Both assays enabled the determination of RIVA in the presence of its degradation products as well as the kinetics of degradation. Determination was carried out over a concentration range of (5.00–50.00 μg/mL and (0.40–12.00 μg/band with an accuracy of (100.81% ± 1.03 and (100.29% ± 1.08 for HPLC and TLC-densitometry, respectively. Results indicated that RIVA was stable towards oxidation, photodegradation and thermal decomposition but extremely sensitive to hydrolysis. Two major degradation products were detected in the case of base-catalyzed hydrolysis while only one degradation product was detected upon acid-catalyzed hydrolysis. This could be attributed to the presence of amide groups in RIVA structure of different stability profiles. The kinetics of hydrolysis was investigated in more detail and the reaction was found to follow the pseudo first order kinetics, as confirmed by the results of both HPLC and TLC-densitometric assays. The applicability of the assay for the determination of RIVA content and dissolution pattern of the innovator product as well as three generic formulations was demonstrated.

  3. The Photocatalytic Kinetics of the Methyl Orange Degradation in the Aqueous Suspension of Irradiated TiO2

    OpenAIRE

    Mazyar Peyda; Nahid Nabavi; Gholam Reza Sadeghi

    2017-01-01

    Background: In the present study, the photocatalytic (TiO2/UV) batch process has been used for the methyl orange (MO) degradation. Methods: In the catalyst range from 0.25 to 1.5 g/L, the optimum concentration of TiO2 was found to be 0.5 g/L. The kinetic behavior of MO degradation has been evaluated using the non-linear form of pseudo-first order and pseudo-second order models. Results: The goodness of the fit was evaluated using the correlation coefficient R2 value and the mean square ...

  4. Kinetic properties of Cellulomonas sp. purine nucleoside phosphorylase with typical and non-typical substrates: implications for the reaction mechanism.

    Science.gov (United States)

    Wielgus-Kutrowska, Beata; Bzowska, Agnieszka

    2005-01-01

    Phosphorolysis catalyzed by Cellulomonas sp. PNP with typical nucleoside substrate, inosine (Ino), and non-typical 7-methylguanosine (m7Guo), with either nucleoside or phosphate (Pd) as the varied substrate, kinetics of the reverse synthetic reaction with guanine (Gua) and ribose-1-phosphate (R1P) as the varied substrates, and product inhibition patterns of synthetic and phosphorolytic reaction pathways were studied by steady-state kinetic methods. It is concluded that, like for mammalian trimeric PNP, complex kinetic characteristics observed for Cellulomonas enzyme results from simultaneous occurrence of three phenomena. These are sequential but random, not ordered binding of substrates, tight binding of one substrate purine bases, leading to the circumstances that for such substrates (products) rapid-equilibrium assumptions do not hold, and a dual role of Pi, a substrate, and also a reaction modifier that helps to release a tightly bound purine base.

  5. 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.

  6. Molecular beam study of the kinetics of the fluorine--uranium dioxide reaction

    Energy Technology Data Exchange (ETDEWEB)

    Machiels, A.J.

    1976-12-01

    The kinetics of uranium dioxide fluorination were studied using an experimental system in which a molecular beam of fluorine was directed at a heated uranium dioxide single crystal wafer maintained in high vacuum. Gaseous reaction products desorbed from the uranium dioxide were monitored by a quadrupole mass spectrometer with an off-axis electron multiplier. The fluorine beam was modulated; ac phase-lock detection and pulse counting were employed to enhance the signal-to-noise ratio. The uranium dioxide targets were heated from the rear by electron bombardment to a maximum of 1800/sup 0/K. Fluorination of the uranium dioxide was found to produce uranium tetrafluoride in the 900/sup 0/ to 1600/sup 0/K temperature range, confirming the results obtained from thermodynamic considerations (quasi-equilibrium analysis). Fluorination of the uranium dioxide was found to be affected by some process acting as a flywheel smoothing the phase response of the interaction as the modulation frequency was varied.

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

    Science.gov (United States)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  8. Kinetic and Reaction Pathway Analysis in the Application of Botulinum Toxin A for Wound Healing

    Directory of Open Access Journals (Sweden)

    Frank J. Lebeda

    2012-01-01

    Full Text Available A relatively new approach in the treatment of specific wounds in animal models and in patients with type A botulinum toxin is the focus of this paper. The indications or conditions include traumatic wounds (experimental and clinical, surgical (incision wounds, and wounds such as fissures and ulcers that are signs/symptoms of disease or other processes. An objective was to conduct systematic literature searches and take note of the reactions involved in the healing process and identify corresponding pharmacokinetic data. From several case reports, we developed a qualitative model of how botulinum toxin disrupts the vicious cycle of muscle spasm, pain, inflammation, decreased blood flow, and ischemia. We transformed this model into a minimal kinetic scheme for healing chronic wounds. The model helped us to estimate the rate of decline of this toxin's therapeutic effect by calculating the rate of recurrence of clinical symptoms after a wound-healing treatment with this neurotoxin.

  9. Mitigating the Hook Effect in Lateral Flow Sandwich Immunoassays Using Real-Time Reaction Kinetics.

    Science.gov (United States)

    Rey, Elizabeth G; O'Dell, Dakota; Mehta, Saurabh; Erickson, David

    2017-05-02

    The quantification of analyte concentrations using lateral flow assays is a low-cost and user-friendly alternative to traditional lab-based assays. However, sandwich-type immunoassays are often limited by the high-dose hook effect, which causes falsely low results when analytes are present at very high concentrations. In this paper, we present a reaction kinetics-based technique that solves this problem, significantly increasing the dynamic range of these devices. With the use of a traditional sandwich lateral flow immunoassay, a portable imaging device, and a mobile interface, we demonstrate the technique by quantifying C-reactive protein concentrations in human serum over a large portion of the physiological range. The technique could be applied to any hook effect-limited sandwich lateral flow assay and has a high level of accuracy even in the hook effect range.

  10. Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

    DEFF Research Database (Denmark)

    Joelsson, Lars Magnus Torvald; Forecast, Roslyn; Schmidt, Johan Albrecht

    2014-01-01

    The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D is found to be 1.60 ± 0.04. In addition, a quantum chemistry/transition state theory model with tunneling...... correction is constructed and the primary cause for α13CH3D is found to be the substantially reduced reactivity of the D atom, which, in turn, can be explained by a significant increase in the reaction barrier due to changes in the vibrational zero point energy and to a lesser extent tunneling....

  11. A simplified kinetic model for the side reactions occurring during the enzymatic synthesis of ampicillin

    Directory of Open Access Journals (Sweden)

    A.L.O. Ferreira

    2000-12-01

    Full Text Available This work presents a kinetic study of the side reactions of the ampicillin enzymatic synthesis, from phenylglycine methyl ester and 6-aminopenicillanic acid using penicillin G acylase immobilized on agarose. A Michaelis-Menten model with competitive inhibition was fitted to initial rates of ester and antibiotic hydrolysis, at pH 6.5 and 25ºC. Inherent kinetic parameters were estimated for low enzymatic loads, to assure that diffusional resistance was not important. It was observed that ampicillin inhibits the hydrolysis of PGME, but the inhibitory effect of the ester on ampicillin hydrolysis was almost negligible. The obtained parameters were: k cat1= 0.025 mM/UI min, Km1 = 155.4mM, K AE = 16.18mM, k cat2= 4.67x10-3 mM/UI min, Km2 = 11.47, K EA = 0.68 mM. Parameter values are in the range reported in the literature, except for Km1, which is much higher. The large confidence interval for this parameter denotes that the model presents low sensitivity with respect to it.

  12. Chitosan modification persimmon tannin bioadsorbent for highly efficient removal of Pb(II) from aqueous environment: the adsorption equilibrium, kinetics and thermodynamics.

    Science.gov (United States)

    Li, Xiaojuan; Wang, Zhongmin; Liang, Haijun; Ning, Jingliang; Li, Guiyin; Zhou, Zhide

    2017-10-04

    Lead (Pb) pollution has triggered a great threat to ecological system as well as public health due to its highly toxic and mutagenic properties. In this study, chitosan surface modified persimmon tannin (PT-CS) biomass composite as an environmental-friendly bioadsorbent for highly efficient removal of Pb(II) from aqueous solutions was investigated. Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, Brunauer-Emmett-Teller, X-ray photoelectron spectroscopy and Zeta potential were used to elucidate the adsorption mechanism. Combining oxidation reaction, electrostatic interaction and chelation reaction, PT-CS exhibited fine adsorption to Pb(II). The maximum adsorption capacity was 179.3 mg/g. Equilibrium isotherm for the adsorption of Pb(II) was analyzed by the Langmuir, Freundlich and Temkin models, and the Langmuir isotherm (R2 > 0.99) was the best. The pseudo-first-order, pseudo-second-order and intraparticle diffusion equations were used to analyze the kinetic data of the adsorption process and the pseudo-second-order kinetic (Rs2 > 0.98) model was fitted well. Moreover, thermodynamic parameters including ΔG0  0 and ΔS0 (456.13 J/mol K) > 0 showed that the process of Pb(II) adsorption by PT-CS was spontaneous and endothermic. All these results illustrated that PT-CS would be a promising and low-cost alternative bioadsorbent of Pb(II) in wastewater treatment.

  13. On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Evangelos Mavroudakis

    2015-09-01

    Full Text Available Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP with growing interest. Nowadays, quantum chemistry (QC can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

  14. An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

    KAUST Repository

    Giri, Binod

    2016-06-24

    Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

  15. Coupled transport and reaction kinetics control the nitrate source-sink function of hyporheic zones

    Science.gov (United States)

    Zarnetske, Jay P.; Haggerty, Roy; Wondzell, Steven M.; Bokil, Vrushali A.; GonzáLez-Pinzón, Ricardo

    2012-11-01

    The fate of biologically available nitrogen (N) and carbon (C) in stream ecosystems is controlled by the coupling of physical transport and biogeochemical reaction kinetics. However, determining the relative role of physical and biogeochemical controls at different temporal and spatial scales is difficult. The hyporheic zone (HZ), where groundwater-stream water mix, can be an important location controlling N and C transformations because it creates strong gradients in both the physical and biogeochemical conditions that control redox biogeochemistry. We evaluated the coupling of physical transport and biogeochemical redox reactions by linking an advection, dispersion, and residence time model with a multiple Monod kinetics model simulating the concentrations of oxygen (O2), ammonium (NH4), nitrate (NO3), and dissolved organic carbon (DOC). We used global Monte Carlo sensitivity analyses with a nondimensional form of the model to examine coupled nitrification-denitrification dynamics across many scales of transport and reaction conditions. Results demonstrated that the residence time of water in the HZ and the uptake rate of O2 from either respiration and/or nitrification determined whether the HZ was a source or a sink of NO3 to the stream. We further show that whether the HZ is a net NO3 source or net NO3 sink is determined by the ratio of the characteristic transport time to the characteristic reaction time of O2 (i.e., the Damköhler number, DaO2), where HZs with DaO2 < 1 will be net nitrification environments and HZs with DaO2 ≪ 1 will be net denitrification environments. Our coupling of the hydrologic and biogeochemical limitations of N transformations across different temporal and spatial scales within the HZ allows us to explain the widely contrasting results of previous investigations of HZ N dynamics which variously identify the HZ as either a net source or sink of NO3. Our model results suggest that only estimates of residence times and O2uptake rates

  16. Synthesis Of Magnesium-Aluminum Layered Double Hydroxides By Mechanochemical Method And Its Solid State Reaction Kinetics

    Directory of Open Access Journals (Sweden)

    Hongbo Y.

    2015-06-01

    Full Text Available A mechanochemical method is developed in preparing magnesium-aluminum-layered double hydroxides (MgAl-LDHs. This approach includes activation process and diffusion process. In order to verify the LDHs structure and study the reaction kinetics, X-ray diffraction (XRD patterns, inductively coupled plasma(ICP and physical adsorption instrument were characterized. The results show that activation time can change the surface of particles and affect the reaction grade. During the diffusion process, reaction time is the most important factor. The reaction energy (ΔQ was calculated that is 6kJ/mol.

  17. Thermochemistry is not a lower bound to the activation energy of endothermic reactions: a kinetic study of the gas-phase reaction of atomic chlorine with ammonia.

    Science.gov (United States)

    Gao, Yide; Alecu, I M; Hsieh, P-C; Morgan, Brad P; Marshall, Paul; Krasnoperov, Lev N

    2006-06-01

    The rate constant for Cl + NH3 --> HCl + NH2 has been measured over 290-570 K by the time-resolved resonance fluorescence technique. Ground-state Cl atoms were generated by 193 nm excimer laser photolysis of CCl4 and reacted under pseudo-first-order conditions with excess NH3. The forward rate constant was fit by the expression k1 = (1.08 +/- 0.05) x 10(-11) exp(-11.47 +/- 0.16 kJ mol(-1)/RT) cm3 molecule(-1) s(-1), where the uncertainties in the Arrhenius parameters are +/-1 sigma and the 95% confidence limits for k1 are +/-11%. To rationalize the activation energy, which is 7.4 kJ mol(-1) below the endothermicity in the middle of the 1/T range, the potential energy surface was characterized with MPWB1K/6-31++G(2df,2p) theory. The products NH2 + HCl form a hydrogen-bonded adduct, separated from Cl + NH3 by a transition state lower in energy than the products. The rate constant for the reverse process k(-1) was derived via modified transition state theory, and the computed k(-1) exhibits a negative activation energy, which in combination with the experimental equilibrium constant yields k1 in fair accord with experiment.

  18. 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.

  19. Kinetics and reaction pathways of formaldehyde degradation using the UV-fenton method.

    Science.gov (United States)

    Liu, Xiangxuan; Liang, Jiantao; Wang, Xuanjun

    2011-05-01

    This study was based on the purpose of investigating the reaction rules of formaldehyde (HCHO) as an intermediate product in the degradation of many other organic wastewaters. The process conditions of UV-Fenton method for the degradation of the low concentrations of HCHO were studied in a batch photochemical reactor. The results showed that, when the original HCHO concentration was 30 mg/L, at an operating temperature of 23 degrees C, pH = 3, an H202 dosage of 68 mg/L, and an H2O2-to-Fe2+ mole ratio (H2O2:Fe2+) of 5, 91.89% of the HCHO was removed after 30 minutes. The degradation of HCHO in the UV-Fenton system was basically in accordance with the exponential decay. The kinetic study results showed that the reaction orders of HCHO, Fe2+, and H2O2 in the system were 1.054, 0.510, and 0.728, respectively, and the activation energy (Ea) was 9.85 kJ/mol. The comparison of UV/H2O2, Fenton, and UV-Fenton systems for the degradation of HCHO, and the results of iron catalyst tests showed that the mechanism of UV-Fenton on the degradation of HCHO was through a synergistic effect of Fe2+ and UV light to catalyze the decomposition of H2O2. The introduction of UV irradiation to the Fenton system largely increased the degradation rate of HCHO, mainly as a result of the accelerating effect on the formation of the Fe2+/Fe3+ cycle. The reaction products were analyzed by gas chromatography-mass spectrometry and a chemical oxygen demand (COD) analyzer. The effluent gases also were analyzed by gas chromatography. Based on those results, the reaction pathways of HCHO in the UV-Fenton system were proposed. The qualitative and quantitative analysis of the reaction products and the COD showed that the main intermediate product of the reaction was formic acid, and the further oxidation of it was the rate-limiting step for the degradation of HCHO.

  20. Stability of an anti-stroke peptide: driving forces and kinetics in chemical degradation.

    Science.gov (United States)

    Li, Rui; Wang, Fengzhen; Chen, Li; Zhu, Shuning; Wu, Lin; Jiang, Sunmin; Xu, Qunwei; Zhu, Dongya

    2014-09-10

    NR2B9c (Lys-Leu-Ser-Ser-Ile-Glu-Ser-Asp-Val) is a 9-amino acid peptide that has been illustrated to be a potential anti-stroke drug. For more effective treatment, suitable drug delivery systems should be developed. However, little is known about the stability of NR2B9c which is essential to its formulation. In this study, a reversed-phase high-performance liquid chromatography (HPLC) was applied to study the forced degradation behavior and stability of NR2B9c. HPLC studies were performed with an C8 column using a mobile phase consisting of acetonitrile (14.5:85.5, v/v) and aqueous solution (0.1% trifluoroacetic acid (TFA) and 0.05 M KH2PO4). The flow rate and the wavelength set during HPLC detection were 1.0 mL/min and 205 nm, respectively. The degradation pattern of NR2B9c aqueous solution followed pseudo first-order kinetics. The degradation rate at pH 7.5 was the slowest according to the plotting V-shaped pH-rate profile. The influence of temperature on the rate of reactions was interpreted in terms of Arrhenius equation (r(2)>0.98). Thermodynamic parameters were calculated based on Eyring equation (r(2)>0.98). The concentrations of drug, buffer species, buffer concentrations, oxidation and organic solvents have noticeable effects on the degradation of NR2B9c while ultrasound shows little impact under the experimental conditions. In a word, this study may give a detailed description of stability of NR2B9c. Copyright © 2014. Published by Elsevier B.V.

  1. Kinetics and products of gas-phase reactions of ozone with methyl methacrylate, methyl acrylate, and ethyl acrylate.

    Science.gov (United States)

    Bernard, F; Eyglunent, G; Daële, V; Mellouki, A

    2010-08-19

    The kinetics and products of the gas-phase reactions of ozone with methyl methacrylate, methyl acrylate, and ethyl acrylate have been investigated at 760 Torr total pressure of air and 294 +/- 2 K. The rate coefficients obtained (in cm(3) molecule(-1) s(-1) units) were as follows: k(methyl methacrylate) = (6.7 +/- 0.9) x 10(-18), k(methyl acrylate) = (0.95 +/- 0.07) x 10(-18), and k(ethyl acrylate) = (1.3 +/- 0.1) x 10(-18). In addition to formaldehyde being observed as a product of the three reactions, the other major reaction products were methyl pyruvate from reaction of ozone with methyl methacrylate, methyl glyoxylate from reaction of ozone with methyl acrylate, and ethyl glyoxylate from reaction of ozone with ethyl acrylate. Possible reaction mechanisms leading to the observed products are presented and discussed.

  2. Thermochemistry and Kinetics of the Cl+O2 Association Reaction

    Science.gov (United States)

    Nicovich, J. M.; Kreutter, K. D.; Shackelford, C. J.; Wine, P. H.

    1997-01-01

    Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).

  3. Interplay between excitation kinetics and reaction-center dynamics in purple bacteria

    Science.gov (United States)

    Caycedo-Soler, Felipe; Rodríguez, Ferney J.; Quiroga, Luis; Johnson, Neil F.

    2010-09-01

    Photosynthesis is arguably the fundamental process of life, since it enables energy from the Sun to enter the food chain on the Earth. It is a remarkable non-equilibrium process in which photons are converted to many-body excitations, which traverse a complex biomolecular membrane, where they are captured and fuel chemical reactions within a reaction center (RC) in order to produce nutrients. The precise nature of these dynamical processes—which lie at the interface between quantum and classical behavior and involve both noise and coordination—is still being explored. Here, we focus on a striking recent empirical finding concerning an illumination-driven transition in the biomolecular membrane architecture of the purple bacteria Rsp. photometricum. Using stochastic realizations to describe a hopping rate model for excitation transfer, we show numerically and analytically that this surprising shift in preferred architectures can be traced to the interplay between the excitation kinetics and the RC dynamics. The net effect is that the bacteria profit from efficient metabolism at low illumination intensities while using dissipation to avoid an oversupply of energy at high illumination intensities.

  4. Kinetic analysis of ski turns based on measured ground reaction forces.

    Science.gov (United States)

    Vaverka, Frantisek; Vodickova, Sona; Elfmark, Milan

    2012-02-01

    The objective of this study was to devise a method of kinetic analysis of the ground reaction force that enables the durations and magnitudes of forces acting during the individual phases of ski turns to be described exactly. The method is based on a theoretical analysis of physical forces acting during the ski turn. Two elementary phases were defined: (1) preparing to turn (initiation) and (2) actual turning, during which the center of gravity of the skier-ski system moves along a curvilinear trajectory (steering). The starting point of the turn analysis is a dynamometric record of the resultant acting ground reaction force applied perpendicularly on the ski surface. The method was applied to six expert skiers. They completed a slalom course comprising five gates arranged on the fall line of a 26° slope at a competition speed using symmetrical carving turns (30 evaluated turns). A dynamometric measurement system was placed on the carving skis (168 cm long, radius 16 m, data were recorded at 100 Hz). MATLAB procedures were used to evaluate eight variables during each turn: five time variables and three force variables. Comparison of the turn analysis results between individuals showed that the method is useful for answering various research questions associated with ski turns.

  5. Kinetic comparison of two basic heterogenous catalysts obtained from sustainable resources for transesterification of waste cooking oil

    Directory of Open Access Journals (Sweden)

    G.R. Moradi

    2015-06-01

    Full Text Available Alkaline earth metal oxides are appropriate catalysts for biodiesel production and among them, CaO and MgO are known for possessing the best efficiency. In this study, catalysts synthesized from economical and sustainable resources were used for biodiesel production. More specifically, waste mussel shells and demineralized (DM water treatment precipitates as calcium and magnesium carbonate sources, were converted into calcium and magnesium oxides at temperatures above 900 oC. Methanol and waste cooking oil were reacted in a 250 mL two-necked flask at 24:1 and 22.5:1 ratios in presence of 12 and 9.08 wt% of mussel shell-based and DM water treatment precipitates-based catalysts, respectively. The effects of temperature (328, 333, 338, 343 and 348 K and time (1, 3, 5, 7 and 8 h at a stirrer speed of 350 rpm on the conversion of the oil into biodiesel were investigated. The results obtained indicated a pseudo-first order kinetics for the transesterification reaction using both catalysts. The activation energies in the presence of the DM water treatment precipitates and mussel shell catalysts were measured at 77.09 and 79.83 kJ.mol-1, respectively. Accordingly, the DM water treatment precipitates catalyst resulted in a faster reaction due to its lower activation energy value. Moreover, the catalysts were reused five times and the results obtained showed that the methanol-driven extraction of CaO contained in the DM water treatment precipitates catalyst was lower than the waste mussel shell catalyst proving the higher stability of the new heterogeneous catalyst i.e. the calcinated DM water treatment precipitates.

  6. Evaluation of reaction mechanisms and the kinetic parameters for the transesterification of castor oil by liquid enzymes

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy

    2017-01-01

    methanolysis rates of glycerides obtained, indicated that transesterification dominates over hydrolysis. The mechanism among the four models proposed that gave the best fit could be simplified, eliminating the kinetic parameters with negligible effects on the reaction rates. This model was able to fit......The use of liquid enzymes for the production of biodiesel as an alternative to chemical catalysts requires significant investigation due to the lack of experimental data for the various feedstock and catalyst combinations. In this paper, reaction rates and kinetic modeling...... the concentration data, four different reaction mechanistic models were compared to determine the mechanism that best fitted the experimental data. Mechanisms where the methanolysis and hydrolysis reactions occurred simultaneously in the system were best at describing the concentration profiles. The high...

  7. HYDROBIOGEOCHEM: A coupled model of HYDROlogic transport and mixed BIOGEOCHEMical kinetic/equilibrium reactions in saturated-unsaturated media

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, G.T.; Salvage, K.M. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil and Environmental Engineering; Gwo, J.P. [Oak Ridge National Lab., TN (United States); Zachara, J.M.; Szecsody, J.E. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-07-01

    The computer program HYDROBIOGEOCHEM is a coupled model of HYDROlogic transport and BIOGEOCHEMical kinetic and/or equilibrium reactions in saturated/unsaturated media. HYDROBIOGEOCHEM iteratively solves the two-dimensional transport equations and the ordinary differential and algebraic equations of mixed biogeochemical reactions. The transport equations are solved for all aqueous chemical components and kinetically controlled aqueous species. HYDROBIOGEOCHEM is designed for generic application to reactive transport problems affected by both microbiological and geochemical reactions in subsurface media. Input to the program includes the geometry of the system, the spatial distribution of finite elements and nodes, the properties of the media, the potential chemical and microbial reactions, and the initial and boundary conditions. Output includes the spatial distribution of chemical and microbial concentrations as a function of time and space, and the chemical speciation at user-specified nodes.

  8. Influence of various metallic oxides on the kinetic of the oxygen evolution reaction on platinum electrodes

    Directory of Open Access Journals (Sweden)

    Kambire Ollo

    2015-08-01

    Full Text Available Pt, 50Pt-50RuO2 and 50Pt-50IrO2 electrodes were prepared on titanium (Ti substrate by thermal decomposition techniques. The micrographs of 50Pt-50RuO2 and 50Pt-50IrO2 have revealed that their surfaces are rough with cracked structures. That of platinum was smooth, compact and homogeneous. The richer the electrode ‘surface in platinum, thinner is the crack size and also more compact is the electrode’surface. The electrodes have also been characterized electrochemically by cyclic voltammetry in acid (HClO4 and in alkaline (KOH electrolytes. These characterizations showed that the surface of the 50Pt-50RuO2 and 50Pt-50IrO2 electrodes were composed by platinum and metal dioxide active sites. The Tafel slope obtained on Pt, 50Pt-50RuO2 and 50Pt-50IrO2 for the oxygen evolution reaction (OER were respectively 120, 90 and 44 mV/dec in acid electrolyte. In the alkaline electrolyte, they were 119, 87 and 42 mV/dec respectively on Pt, 50Pt-50RuO2 and 50Pt-50IrO2 electrodes indicating that for the prepared electrodes, Tafel slopes are the same in acid and in alkaline media. Moreover, in acid and in alkaline media, the kinetic of the oxygen evolution reaction was rapid on 50Pt-50RuO2 and 50Pt-50IrO2 than Pt owing to a synergetic effect of Pt and the oxides. That additional effect of the surface component 50Pt-50RuO2 and 50Pt-50IrO2 electrodes let them possess high electrocatalytic activity towards OER than Pt in the two media. Though the kinetic of the oxygen evolution reaction is practically the same in acidic and alkaline media for all the electrodes, OER occurred at lower overpotential in alkaline electrolyte than in acidic electrolyte on the prepared electrodes.

  9. Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.

    Science.gov (United States)

    Dybeck, Eric C; Plaisance, Craig P; Neurock, Matthew

    2017-04-11

    A novel algorithm is presented that achieves temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate time scales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC were designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the time scales of the slow kinetically relevant nonequilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation, and the reaction rate constants are rescaled accordingly. The algorithm was utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple time-scale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems, and the computational cost is not limited by the magnitude of the time scale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.

  10. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    NARCIS (Netherlands)

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

    2005-01-01

    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  11. Real-time monitoring of mass-transport-related enzymatic reaction kinetics in a nanochannel-array reactor.

    Science.gov (United States)

    Li, Su-Juan; Wang, Chen; Wu, Zeng-Qiang; Xu, Jing-Juan; Xia, Xing-Hua; Chen, Hong-Yuan

    2010-09-03

    To understand the fundamentals of enzymatic reactions confined in micro-/nanosystems, the construction of a small enzyme reactor coupled with an integrated real-time detection system for monitoring the kinetic information is a significant challenge. Nano-enzyme array reactors were fabricated by covalently linking enzymes to the inner channels of a porous anodic alumina (PAA) membrane. The mechanical stability of this nanodevice enables us to integrate an electrochemical detector for the real-time monitoring of the formation of the enzyme reaction product by sputtering a thin Pt film on one side of the PAA membrane. Because the enzymatic reaction is confined in a limited nanospace, the mass transport of the substrate would influence the reaction kinetics considerably. Therefore, the oxidation of glucose by dissolved oxygen catalyzed by immobilized glucose oxidase was used as a model to investigate the mass-transport-related enzymatic reaction kinetics in confined nanospaces. The activity and stability of the enzyme immobilized in the nanochannels was enhanced. In this nano-enzyme reactor, the enzymatic reaction was controlled by mass transport if the flux was low. With an increase in the flux (e.g., >50 microL min(-1)), the enzymatic reaction kinetics became the rate-determining step. This change resulted in the decrease in the conversion efficiency of the nano-enzyme reactor and the apparent Michaelis-Menten constant with an increase in substrate flux. This nanodevice integrated with an electrochemical detector could help to understand the fundamentals of enzymatic reactions confined in nanospaces and provide a platform for the design of highly efficient enzyme reactors. In addition, we believe that such nanodevices will find widespread applications in biosensing, drug screening, and biochemical synthesis.

  12. Atmospheric chemistry of HFC-134a. Kinetic and mechanistic study of the CF3CFHO2 + NO2 reaction

    DEFF Research Database (Denmark)

    Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.

    1994-01-01

    A pulse radiolysis system was used to study the kinetics of the reaction of CF3CFHO2 with NO2. By monitoring the rate of the decay of NO2 using its absorption at 400 nm the reaction rate constant was determined to be k = (5.0 +/- 0.5) x 10(-12) cm3 molecule-1 s-1. A long path length Fourier...

  13. Pre-steady state of reaction of nucleoside diphosphate kinase with anti-HIV nucleotides.

    Science.gov (United States)

    Schneider, B; Xu, Y W; Sellam, O; Sarfati, R; Janin, J; Veron, M; Deville-Bonne, D

    1998-05-08

    The pre-steady-state reaction of Dictyostelium nucleoside diphosphate (NDP) kinase with dideoxynucleotide triphosphates (ddNTP) and AZT triphosphate was studied by quenching of protein fluorescence after manual mixing or by stopped flow. The fluorescence signal, which is correlated with the phosphorylation state of the catalytic histidine in the enzyme active site, decreases upon ddNTP addition according to a monoexponential time course. The pseudo-first order rate constant was determined for different concentrations of the various ddNTPs and was found to be saturable. The data are compatible with a two-step reaction scheme, where fast association of the enzyme with the dideoxynucleotide is followed by a rate-limiting phosphorylation step. The rate constants and dissociation equilibrium constants determined for each dideoxynucleotide were correlated with the steady-state kinetic parameters measured in the enzymatic assay in the presence of the two substrates. It is shown that ddNTPs and AZT triphosphate are poor substrates for NDP kinase with a rate of phosphate transfer of 0.02 to 3.5 s-1 and a KS of 1-5 mM. The equilibrium dissociation constants for ADP, GDP, ddADP, and ddGDP were also determined by fluorescence titration of a mutant F64W NDP kinase, where the introduction of a tryptophan at the nucleotide binding site provides a direct spectroscopic probe. The lack of the 3'-OH in ddNTP causes a 10-fold increase in KD. Contrary to "natural" NTPs, NDP kinase discriminates between various ddNTPs, with ddGTP the more efficient and ddCTP the least efficient substrate within a range of 100 in kcat values.

  14. CRF-PEPICO: Double velocity map imaging photoelectron photoion coincidence spectroscopy for reaction kinetics studies

    Science.gov (United States)

    Sztáray, Bálint; Voronova, Krisztina; Torma, Krisztián G.; Covert, Kyle J.; Bodi, Andras; Hemberger, Patrick; Gerber, Thomas; Osborn, David L.

    2017-07-01

    Photoelectron photoion coincidence (PEPICO) spectroscopy could become a powerful tool for the time-resolved study of multi-channel gas phase chemical reactions. Toward this goal, we have designed and tested electron and ion optics that form the core of a new PEPICO spectrometer, utilizing simultaneous velocity map imaging for both cations and electrons, while also achieving good cation mass resolution through space focusing. These optics are combined with a side-sampled, slow-flow chemical reactor for photolytic initiation of gas-phase chemical reactions. Together with a recent advance that dramatically increases the dynamic range in PEPICO spectroscopy [D. L. Osborn et al., J. Chem. Phys. 145, 164202 (2016)], the design described here demonstrates a complete prototype spectrometer and reactor interface to carry out time-resolved experiments. Combining dual velocity map imaging with cation space focusing yields tightly focused photoion images for translationally cold neutrals, while offering good mass resolution for thermal samples as well. The flexible optics design incorporates linear electric fields in the ionization region, surrounded by dual curved electric fields for velocity map imaging of ions and electrons. Furthermore, the design allows for a long extraction stage, which makes this the first PEPICO experiment to combine ion imaging with the unimolecular dissociation rate constant measurements of cations to detect and account for kinetic shifts. Four examples are shown to illustrate some capabilities of this new design. We recorded the threshold photoelectron spectrum of the propargyl and the iodomethyl radicals. While the former agrees well with a literature threshold photoelectron spectrum, we have succeeded in resolving the previously unobserved vibrational structure in the latter. We have also measured the bimolecular rate constant of the CH2I + O2 reaction and observed its product, the smallest Criegee intermediate, CH2OO. Finally, the second

  15. Inactivation of human antithrombin by neutrophil elastase. Kinetics of the heparin-dependent reaction.

    Science.gov (United States)

    Jordan, R E; Nelson, R M; Kilpatrick, J; Newgren, J O; Esmon, P C; Fournel, M A

    1989-06-25

    Human neutrophil elastase catalyzes the inactivation of antithrombin by a specific and limited proteinolytic cleavage. This inactivation reaction is greatly accelerated by an active anticoagulant heparin subfraction with high binding affinity for antithrombin. A potentially complex reaction mechanism is suggested by the binding of both neutrophil elastase and antithrombin to heparin. The in vitro kinetic behavior of this system was examined under two different conditions: 1) at a constant antithrombin concentration in which the active anticoagulant heparin was varied from catalytic to saturating levels; and 2) at a fixed, saturating heparin concentration and variable antithrombin levels. Under conditions of excess heparin, the inactivation could be continuously monitored by a decrease in the ultraviolet fluorescence emission of the inhibitor. A Km of approximately 1 microM for the heparin-antithrombin complex and a turnover number of approximately 200/min was estimated from these analyses. Maximum acceleratory effects of heparin on the inactivation of antithrombin occur at heparin concentrations significantly lower than those required to saturate antithrombin. The divergence in acceleratory effect and antithrombin binding contrasts with the anticoagulant functioning of heparin in promoting the formation of covalent antithrombin-enzyme complexes and is likely to derive from the fact that neutrophil elastase is not consumed in the inactivation reaction. A size dependence was observed for the heparin effect since an anticoagulantly active octasaccharide fragment of heparin, with avid antithrombin binding activity, was without effect on the inactivation of antithrombin by neutrophil elastase. Despite the completely nonfunctional nature of elastase-cleaved antithrombin and the altered physical properties of the inhibitor as indicated by fluorescence and sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the inactivated inhibitor exhibited a circulating half

  16. Kinetics and Mechanism of Mn(II Catalyzed Periodate Oxidation of p-anisidine: Effect of pH

    Directory of Open Access Journals (Sweden)

    Rajneesh Dutt Kaushik

    2014-10-01

    Full Text Available The stoichiometry for the initial part of the reaction, Mn(II catalysed periodate oxidation of p-anisidine (PMA, has been found to be 1 mol of PMA consuming 2 mol of periodate ion. The kinetic-mechanistic study of reaction in acetone-water medium was made spectrophotometrically by noting the increase in the absorbance of reaction intermediate. Reaction is first order in reactants and catalyst each. A decrease in dielectric constant of the medium results in decrease in the rate of reaction suggesting an ion-dipole type interaction. Free radical scavengers do not affect the reaction rate. A special type of rate-pH profile shows a maximum at pH = 7.0. This pH effect also suggests the involvement of at least three differently reactive reactant species in the reaction and this fact has been considered by us while deriv-ing the rate law. Under pseudo first order conditions [IO4-] >> [PMA] and in agreement with the derived rate law, the 1/kcat versus [H+] plot passes through the minimum and the results can be fitted to the equation: 1/kcat = (K2 / k K3 K4 [H+] + {(Kw + Kb K2 / k K3 K4 Kw} + Kb [H+] / k K3 K4 Kw, where kK3K4 is the empirical composite rate constant, Kw is ionic product of water, K2 is acid dissociation constant of H4IO6- and Kb is base dissociation constant of PMA. The experimental value of [H+]min is in good agreement with the value calculated by using the derived rate law equation and is character-istic of the substrate involved relating to the base dissociation constant of PMA. The value of thermo-dynamic parameters have been evaluated. © 2014 BCREC UNDIP. All rights reservedReceived: 2nd May 2014; Revised: 2nd July 2014; Accepted: 5th July 2014How to Cite: Kaushik, R.D., Singh, J., Manila, M., Kaur, M., Singh, P. (2014. Kinetics and Mechanism of MnII Catalyzed Periodate Oxidation of p-anisidine: Effect of pH. Bulletin of Chemical Reaction En-gineering & Catalysis, 9(3: 182-191. (doi: 10.9767/bcrec.9.3.6823.182-191Permalink

  17. Validation of a kinetic-diffusive model to characterize pozzolanic reaction kinetics in sugar cane straw-clay ash/lime systems

    Directory of Open Access Journals (Sweden)

    Villar-Cociña, E.

    2005-06-01

    Full Text Available A kinetic-diffusive model proposed by the authors in previous papers to describe pozzolanic reaction kinetics in sugar cane straw-clay ash (SCSCA/calcium hydroxide (CH systems is validated in this study. Two different methods (direct and indirect for determining pozzolanic activity were applied and their effect on pozzolanic reaction rate kinetic constants evaluated. Determined by fitting a model to the data, these constants are used to quantitatively characterize pozzolanic activity. The values of the kinetic constants calculated with the model were similar for the two methods. Classic kinetic models, such as the Jander, modified Jander and Zhuravlev models, were also applied to the system studied and the results were compared to the figures calculated with the model proposed. The kinetic-diffusive approach proposed was found to be valid regardless of the method for determining pozzolanic activity used, and to be the most suitable model for describing pozzolanic reaction kinetics in the SCSCA/lime system.

    Se valida la aplicación de un modelo cinético-difusivo propuesto por los autores en trabajos anteriores para describir la cinética de reacción puzolánica en sistemas ceniza de paja de caña-arcilla (CPCAñúdróxido de calcio (CH. Se aplican 2 métodos diferentes de actividad puzolánica (directo e indirecto y se valora el efecto que pudieran tener los mismos sobre las constantes cinéticas de velocidad de reacción de la reacción puzolánica. Estas constantes cinéticas son determinadas en el proceso de ajuste del modelo y permiten caracterizar cuantitativamente la actividad puzolánica. Los resultados muestran la similitud de las constantes cinéticas de velocidad de reacción calculadas, aplicando el modelo a los resultados experimentales obtenidos por ambos métodos. Además, fueron aplicados al sistema estudiado modelos cinéticos el chicos como: modelo de Jander, modelo de Jander Modificado y el modelo de Zhuravlev y

  18. Charge separation kinetics in isolated photosynthetic reaction centers of Chloroflexus aurantiacus (with Q A reduced) at low temperatures

    Science.gov (United States)

    Schweitzer, Gerd; Hucke, Mathias; Griebenow, Kai; Müller, Marc G.; Holzwarth, Alfred R.

    1992-02-01

    The picosecond fluorescence kinetics of closed (quinone acceptor Q A reduced) reaction centers isolated from the phototrophic bacterium Chloroflexus aurantiacus shows time constants of ≈ 20 and ≈ 300 ps (amplitude ratio ≈ 1:1), which are nearly independent of temperature (7 to 80 K). Assuming a three-state kinetic model, we tested various assignments of the kinetics to the electron transfer processes. Only two of these assignments seem to be physically reasonable. One of these includes a fast reversible electron transfer between P* and H M, the pheophytin(s) in the M branch of the reaction center which up to now has been considered virtually inactive in electron transfer. The other possible model involves the formation of a monomeric bacteriochlorophyll anion.

  19. Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

    Science.gov (United States)

    Al-Rubaiey, Najem A.; Walsh, Robin

    2017-03-01

    Silylenes (silanediyls) have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD) of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2) are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas) at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using Lindemann

  20. Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

    Directory of Open Access Journals (Sweden)

    Al-Rubaiey Najem A.

    2017-01-01

    Full Text Available Silylenes (silanediyls have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2 are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using

  1. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

    Science.gov (United States)

    Bittker, David A.; Radhakrishnan, Krishnan

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  2. Kinetic Analysis of Parallel-Consecutive First-Order Reactions with a Reversible Step: Concentration-Time Integrals Method

    Science.gov (United States)

    Mucientes, A. E.; de la Pena, M. A.

    2009-01-01

    The concentration-time integrals method has been used to solve kinetic equations of parallel-consecutive first-order reactions with a reversible step. This method involves the determination of the area under the curve for the concentration of a given species against time. Computer techniques are used to integrate experimental curves and the method…

  3. 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...

  4. Analyzing General Chemistry Texts' Treatment of Rates of Change Concepts in Reaction Kinetics Reveals Missing Conceptual Links

    Science.gov (United States)

    Seethaler, Sherry; Czworkowski, John; Wynn, Lynda

    2018-01-01

    Change over time is a crosscutting theme in the sciences that is pivotal to reaction kinetics, an anchoring concept in undergraduate chemistry, and students' struggles with rates of change are well-documented. Informed by the education scholarship in chemistry, physics, and mathematics, a research team with members from complementary disciplinary…

  5. A cellular automata model for traffic flow based on kinetics theory, vehicles capabilities and driver reactions

    Science.gov (United States)

    Guzmán, H. A.; Lárraga, M. E.; Alvarez-Icaza, L.; Carvajal, J.

    2018-02-01

    In this paper, a reliable cellular automata model oriented to faithfully reproduce deceleration and acceleration according to realistic reactions of drivers, when vehicles with different deceleration capabilities are considered is presented. The model focuses on describing complex traffic phenomena by coding in its rules the basic mechanisms of drivers behavior, vehicles capabilities and kinetics, while preserving simplicity. In particular, vehiclés kinetics is based on uniform accelerated motion, rather than in impulsive accelerated motion as in most existing CA models. Thus, the proposed model calculates in an analytic way three safe preserving distances to determine the best action a follower vehicle can take under a worst case scenario. Besides, the prediction analysis guarantees that under the proper assumptions, collision between vehicles may not happen at any future time. Simulations results indicate that all interactions of heterogeneous vehicles (i.e., car-truck, truck-car, car-car and truck-truck) are properly reproduced by the model. In addition, the model overcomes one of the major limitations of CA models for traffic modeling: the inability to perform smooth approach to slower or stopped vehicles. Moreover, the model is also capable of reproducing most empirical findings including the backward speed of the downstream front of the traffic jam, and different congested traffic patterns induced by a system with open boundary conditions with an on-ramp. Like most CA models, integer values are used to make the model run faster, which makes the proposed model suitable for real time traffic simulation of large networks.

  6. Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

    Science.gov (United States)

    Wanty, R.B.; Goldhaber, M.B.

    1992-01-01

    A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (VIV) and vanadium[V] (VV) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of VIV to VIII H2S were studied. Although H2S is predicted from thermodynamic data to be capable of reducing VIV to VIII, this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45??C), pH (3.6-6.8), ionic strength (0.05-0.1 m), and V concentrations (9.8-240 ??molar) likely to be found in nature. Because the reaction is very slow, H2S concentrations in excess of natural conditions were used (8.1 ?? 10-4 to 0.41 atm). The results show that VIV is reduced to VIII under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the

  7. Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV–vis spectra: A comparative kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Ankamwar, Balaprasad, E-mail: bankamwar@yahoo.com [Bio-inspired Materials Research Laboratory, Department of Chemistry, Savitribai Phule Pune University, Ganeshkhind, Pune 411007 (India); Kamble, Vaishali; Sur, Ujjal Kumar [Bio-inspired Materials Research Laboratory, Department of Chemistry, Savitribai Phule Pune University, Ganeshkhind, Pune 411007 (India); Santra, Chittaranjan [Department of Chemistry, Netaji Nagar Day College, Regent Park, Kolkata 700092 (India)

    2016-03-15

    Graphical abstract: - Highlights: • The biosynthesized silver nanoparticles were stable for 6 months and used as effective SERS active substrate. • They are effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. • Comparative catalytic efficiency of both silver and gold nanoparticles was studied spectrophotometrically. • Our results demonstrate surface morphology dependent catalytic activity of both nanoparticles. - Abstract: The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV–vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir–Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.

  8. The browning kinetics of the non-enzymatic browning reaction in L-ascorbic acid/basic amino acid systems

    Directory of Open Access Journals (Sweden)

    Ai-Nong YU

    Full Text Available Abstract Under the conditions of weak basis and the reaction temperature range of 110-150 °C, lysine, arginine and histidine were reacted with L-ascorbic acid at equal amount for 30-150 min, respectively and the formation of browning products was monitored with UV–vis spectrometry. The kinetic characteristics of their non-enzymatic browning reaction were investigated. The study results indicated that the non-enzymatic browning reaction of these three amino acids with L-ascorbic acid to form browning products was zero-order reaction. The apparent activation energies for the formation of browning products from L-ascorbic acid/lysine, L-ascorbic acid/arginine and L-ascorbic acid/histidine systems were 54.94, 50.08 and 35.31kJ/mol. The activation energy data indicated the degree of effects of reaction temperature on non-enzymatic browning reaction. Within the temperature range of 110-150 °C, the reaction rate of L-ascorbic acid/lysine system was the fastest one, followed by that of the L-ascorbic acid/arginine system. The reaction rate of L-ascorbic acid/histidine system was the slowest one. Based on the observed kinetic data, the formation mechanisms of browning products were proposed.

  9. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    Methane is an potent greenhouse gas, second only to carbon dioxide of the anthropogenic greenhouse gases in its influence on Earth’s radiative budget. Although less abundant in the atmosphere, methane’s global warming potential is about twentyeight times that of carbon dioxide. Sources of methane....... In Papers I and II, isotopically-labeled methane was used and the reactions were studied using Fourier Transform Infrared spectroscopy (FTIR). In Paper III; natural abundance methane was used and only the reaction yield was measured with FTIR spectroscopy. Meanwhile, the isotopic compositions were measured...... the clumping effect by a reaction, the apparent clumpiness is defined as the deviation of the Kinetic Isotope Effect (KIE) of the reaction with the clumped isotope (13CH3D) from the combination of KIEs of reactions with the single substituted isotopologues (13CH4 and 12CH3D). If the KIE of the reaction with 13...

  10. Kinetic modeling and determination of reaction constants of Alzheimer's beta-amyloid fibril extension and dissociation using surface plasmon resonance.

    Science.gov (United States)

    Hasegawa, Kazuhiro; Ono, Kenjiro; Yamada, Masahito; Naiki, Hironobu

    2002-11-19

    To establish the kinetic model of the extension and dissociation of beta-amyloid fibrils (f(A)beta) in vitro, we analyzed these reactions using a surface plasmon resonance (SPR) biosensor. Sonicated f(A)beta were immobilized on the surface of the SPR sensor chip as seeds. The SPR signal increased linearly as a function of time after amyloid beta-peptides (Abeta) were injected into the f(A)beta-immobilized chips. The extension of f(A)beta was confirmed by atomic force microscopy. When flow cells were washed with running buffer, the SPR signal decreased with time after the extension reaction. The curve fitting resolved the dissociation reaction into the fast exponential and slow linear decay phases. Kinetic analysis of the effect of Abeta/f(A)beta concentrations on the reaction rate indicated that both the extension reaction and the slow linear phase of the dissociation were consistent with a first-order kinetic model; i.e., the extension/dissociation reactions proceed via consecutive association/dissociation of Abeta onto/from the end of existing fibrils. On the basis of this model, the critical monomer concentration ([M](e)) and the equilibrium association constant (K) were calculated, for the first time, to be 20 nM and 5 x 10(7) M(-1), respectively. Alternatively, [M](e) was directly measured as 200 nM, which may represent the equilibrium between the extension reaction and the fast phase of the dissociation. The SPR biosensor is a useful quantitative tool for the kinetic and thermodynamic study of the molecular mechanisms of f9A)beta formation in vitro.

  11. 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.

  12. Kinetics of the reaction of F atoms with O2 and UV spectrum of FO2 radicals in the gas phase at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics...

  13. Application of a two-state kinetic model to the heterogeneous kinetics of reaction between cysteine and hydrogen peroxide in amorphous lyophiles.

    Science.gov (United States)

    Luo, Dayong; Anderson, Bradley D

    2008-09-01

    The bimolecular reaction between cysteine (CSH) and hydrogen peroxide (H(2)O(2)) in amorphous PVP and trehalose lyophiles has been examined at different reactant and excipient concentrations and at varying pH and temperature. Initial rates of product formation and complete reactant and product concentration-time profiles were generated by HPLC analyses of reconstituted solutions of lyophiles stored for various periods of time. While only cystine (CSSC) forms in aqueous solutions, cysteine sulfinic (CSO(2)H) and sulfonic (CSO(3)H) acids are significant degradants in amorphous solids. The formation of alternative degradants was consistent with the solution reaction mechanism, which involves a reactive sulfenic acid (CSOH) intermediate, coupled with the restricted mobility in the amorphous solid-state, which favors reaction of CSOH with the smaller, mobility-advantaged H(2)O(2) over its reaction with cysteine. Complex rate laws (i.e., deviations from 1st order for each reactant) observed in initial rate studies and biphasic concentration-time profiles in PVP were successfully fitted by a two-state kinetic model assuming two reactant populations with different reactivities. The highly reactive population forms CSSC preferentially while the less reactive population generates primarily sulfinic and sulfonic acids. Reactions in trehalose could be described by a simple one-state model. In contrast to the reaction in aqueous solutions, the 'pH' effect was minimal in amorphous solids, suggesting a change in the rate-determining step to diffusion control for the model reaction occurring in amorphous lyophiles.

  14. Iron Reduction and Radionuclide Immobilization: Kinetic, Thermodynamic and Hydrologic controls & Reaction-Based Modeling - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    William D. Burgos

    2004-06-18

    that the hydrated surface of nano-particles of hematite (prepared according to well-cited recipes and confirmed to be 100% hematite by Mossbauer spectroscopy and XRD) exhibited the solubility of hydrous ferric oxide (HFO). Jang (2004) also demonstrated that the sorptive reactivity of hematite and HFO were identical except for different specific surface area and pHzpc, and that the reduction of U(VI) by sorbed Fe(II) in the presence of the two phases was also similar in spite of theoretical predictions of large differences in Nernst potential. These results are consistent with the modeling of hematite bioreduction experiments where the thermodynamic potential of hematite had to be adjusted to represent a more disordered surface phase in order to accurately model bioreduction kinetics (Burgos et al, 2002, 2003). We have demonstrated that humic substances enhance solid-phase Fe(III) bioreduction via both electron shuttling and Fe(II) complexation(Royer et al, 2002a, b). We have found that humic substances were shown to inhibit the bioreduction of dissolved U(VI) and that soluble humic-U(IV) complexes were likely formed (Burgos et al, 2004). Kirkham (2004) measured and modeled complexation of U(VI) by humic substances as a function of pH, pCO2, U(VI) concentration, and humic concentration, and demonstrated that humic substances can complex U(VI) even at neutral pH values and in the presence of high (ca.30 mM) carbonate concentrations. Jang(2004) measured the abiotic reduction of U(VI) by Fe(II) sorbed to Fe(III) oxides in the presence/absence of humic substances and demonstrated that humic substances inhibited the heterogeneous reduction of U(VI). We have recently developed, validated, and documented a series of diagonalized reaction-based reactive transport computer models (HYDROGEOCHEM; Yeh et al,2004a,b). We demonstrated that parallel kinetic reactions could be modeled if separate experiments are used to independently measure each contributing kinetic reaction (Burgos

  15. Theoretical and kinetic study of the hydrogen atom abstraction reactions of unsaturated C6 methyl esters with hydroxyl radical

    Science.gov (United States)

    Wang, Quan-De; Ni, Zhong-Hai

    2016-04-01

    This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydroxyl radical (OH) on typical isomers of unsaturated C6 methyl esters at the CBS/QB3 level of theory. The high-pressure limit rate constants at different reaction sites for all the methyl esters in the temperature range from 500 to 2000 K are calculated via transition-state theory with the Wigner method for quantum tunneling effect and fitted to the modified three parameters Arrhenius expression using least-squares regression. Further, a branching ratio analysis for each reaction site has been performed.

  16. The browning kinetics of the non-enzymatic browning reaction in L-ascorbic acid/basic amino acid systems

    OpenAIRE

    YU,Ai-Nong; Li, Ya; Yang, Yan; Yu, Ke

    2017-01-01

    Abstract Under the conditions of weak basis and the reaction temperature range of 110-150 °C, lysine, arginine and histidine were reacted with L-ascorbic acid at equal amount for 30-150 min, respectively and the formation of browning products was monitored with UV–vis spectrometry. The kinetic characteristics of their non-enzymatic browning reaction were investigated. The study results indicated that the non-enzymatic browning reaction of these three amino acids with L-ascorbic acid to ...

  17. New Dihydro OO′Bis(Salicylidene) 2,2′ Aminobenzothiazolyl Borate Complexes: Kinetic and Voltammetric Studies of Dimethyltin Copper Complex with Guanine, Adenine, and Calf Thymus DNA

    Science.gov (United States)

    Arjmand, Farukh; Mohani, Bhawana; Parveen, Shamima

    2006-01-01

    The newly synthesized ligand, dihydro OO′bis(salicylidene) 2,2′ aminobenzothiazolyl borate (2), was derived from the reaction of Schiff base of 2-aminobenzothiazole and salicylaldehyde with KBH4. CuII (3) and ZnII (4) complexes of (2) were synthesized and further metallated with dimethyltindichloride to yield heterobimetallic complexes (5) and (6). All complexes have been thoroughly characterized by elemental analysis, and IR, NMR, EPR, and UV-Vis spectroscopy and conductance measurements. The spectroscopic data support square planar environment around the CuII atom, while the SnIV atom acquires pentacoordinate geometry. The interaction of complex (5) with guanine, adenine, and calf thymus DNA was studied by spectrophotometric, electrochemical, and kinetic methods. The absorption spectra of complex (5) exhibit a remarkable “hyperchromic effect” in the presence of guanine and calf thymus DNA. Indicative of strong binding of the complex to calf thymus DNA preferentially binds through N7 position of guanine base, while the adenine shows binding to a lesser extent. The kinetic data were obtained from the rate constants, kobs, values under pseudo-first-order conditions. Cyclic voltammetry was employed to study the interaction of complex (5) with guanine, adenine, and calf thymus DNA. The CV of complex (5) in the absence and in the presence of guanine and calf thymus DNA altered drastically, with a positive shift in formal peak potential Epa and Epc values and a significant increase in peak current. The positive shift in formal potentials with increase in peak current favours strong interaction of complex (5) with calf thymus DNA. The net shift in E 1/2 has been used to estimate the ratio of equilibrium constants for the binding of Cu(II) and Cu(I) complexes to calf thymus DNA. PMID:17497007

  18. New Dihydro OO'Bis(Salicylidene) 2,2' Aminobenzothiazolyl Borate Complexes: Kinetic and Voltammetric Studies of Dimethyltin Copper Complex with Guanine, Adenine, and Calf Thymus DNA.

    Science.gov (United States)

    Arjmand, Farukh; Mohani, Bhawana; Parveen, Shamima

    2006-01-01

    The newly synthesized ligand, dihydro OO'bis(salicylidene) 2,2' aminobenzothiazolyl borate (2), was derived from the reaction of Schiff base of 2-aminobenzothiazole and salicylaldehyde with KBH(4). Cu(II) (3) and Zn(II) (4) complexes of (2) were synthesized and further metallated with dimethyltindichloride to yield heterobimetallic complexes (5) and (6). All complexes have been thoroughly characterized by elemental analysis, and IR, NMR, EPR, and UV-Vis spectroscopy and conductance measurements. The spectroscopic data support square planar environment around the Cu(II) atom, while the Sn(IV) atom acquires pentacoordinate geometry. The interaction of complex (5) with guanine, adenine, and calf thymus DNA was studied by spectrophotometric, electrochemical, and kinetic methods. The absorption spectra of complex (5) exhibit a remarkable "hyperchromic effect" in the presence of guanine and calf thymus DNA. Indicative of strong binding of the complex to calf thymus DNA preferentially binds through N(7) position of guanine base, while the adenine shows binding to a lesser extent. The kinetic data were obtained from the rate constants, k(obs), values under pseudo-first-order conditions. Cyclic voltammetry was employed to study the interaction of complex (5) with guanine, adenine, and calf thymus DNA. The CV of complex (5) in the absence and in the presence of guanine and calf thymus DNA altered drastically, with a positive shift in formal peak potential E(pa) and E(pc) values and a significant increase in peak current. The positive shift in formal potentials with increase in peak current favours strong interaction of complex (5) with calf thymus DNA. The net shift in E(1/2) has been used to estimate the ratio of equilibrium constants for the binding of Cu(II) and Cu(I) complexes to calf thymus DNA.

  19. Adsorptive, thermodynamic and kinetic performances of Al/Ti and Al/Zr-pillared clays from the Brazilian Amazon region for zinc cation removal

    Energy Technology Data Exchange (ETDEWEB)

    Guerra, Denis L. [Instituto de Quimica, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, Sao Paulo (Brazil); Airoldi, Claudio [Instituto de Quimica, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, Sao Paulo (Brazil)], E-mail: airoldi@iqm.unicamp.br; Lemos, Vanda P.; Angelica, Romulo S. [Universidade Federal do Para, Centro de Geociencia, Caixa Postal 1611, 66075-110 Belem, Para (Brazil)

    2008-06-30

    Smectite clay samples from the Amazon region, Brazil, were pillarized by intercalating the species obtained from the chemical reactions: (i) AlCl{sub 3}.6H{sub 2}O/NaOH, (ii) titanium ethoxide in hydrochloric acid and (iii) direct use of ZrOCl{sub 2}.8H{sub 2}O solution. The natural matrices and the pillaring solutions were maintained under vigorous stirring at 298 K for 3 h and then subjected to calcination at temperatures of 723 and 873 K. Natural and pillared matrices were characterized by XRD, FTIR, TG-DTG and nitrogen adsorption-desorption isotherms. The resulting materials were used for zinc adsorption from aqueous solution at room temperature. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data and the Freundlich model is limited for higher concentrations. The pillaring process increases the thermal stability, the basal spacing of the natural clay sample (A{sub 1}) from 1.55 to 2.06 nm and the surface area from 44.30 to 223.73 m{sup 2} g{sup -1}. Kinetic studies demonstrated an equilibrium time of 180 min for zinc adsorption on the pillared matrices. Pseudo-first-order, Lagergren pseudo-second-order and Elovich equations demonstrated a better agreement with second-order kinetics was obtained with K{sub 2} = 4.17-10.43 x 10{sup -3} g mg{sup -1} min{sup -1} for the A{sub 1} sample.

  20. Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction.

    Science.gov (United States)

    Coutinho, Nayara D; Silva, Valter H C; de Oliveira, Heibbe C B; Camargo, Ademir J; Mundim, Kleber C; Aquilanti, Vincenzo

    2015-05-07

    The OH + HBr → H2O + Br reaction, prototypical of halogen-atom liberating processes relevant to mechanisms for atmospheric ozone destruction, attracted frequent attention of experimental chemical kinetics: the nature of the unusual reactivity drop from low to high temperatures eluded a variety of theoretical efforts, ranking this one among the most studied four-atom reactions. Here, inspired by oriented molecular-beams experiments, we develop a first-principles stereodynamical approach. Thermalized sets of trajectories, evolving on a multidimensional potential energy surface quantum mechanically generated on-the-fly, provide a map of most visited regions at each temperature. Visualizations of rearrangements of bonds along trajectories and of the role of specific angles of reactants' mutual approach elucidate the mechanistic change from the low kinetic energy regime (where incident reactants reorient to find the propitious alignment leading to reaction) to high temperature (where speed hinders adjustment of directionality and roaming delays reactivity).

  1. Is the Gas-phase OH+H2CO Reaction a Source of HCO in Interstellar Cold Dark Clouds? A Kinetic, Dynamic, and Modeling Study

    Science.gov (United States)

    Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.

    2017-11-01

    The chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T ˜ 10-100 K). Scarce kinetic information is currently available for these kinds of reactions at T environments are also addressed.

  2. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk

    2014-12-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  3. Kinetics and product analysis of the reaction catalysed by recombinant homoaconitase from Thermus thermophilus.

    Science.gov (United States)

    Jia, Yunhua; Tomita, Takeo; Yamauchi, Kazuma; Nishiyama, Makoto; Palmer, David R J

    2006-06-15

    HACN (homoaconitase) is a member of a family of [4Fe-4S] cluster-dependent enzymes that catalyse hydration/dehydration reactions. The best characterized example of this family is the ubiquitous ACN (aconitase), which catalyses the dehydration of citrate to cis-aconitate, and the subsequent hydration of cis-aconitate to isocitrate. HACN is an enzyme from the alpha-aminoadipate pathway of lysine biosynthesis, and has been identified in higher fungi and several archaea and one thermophilic species of bacteria, Thermus thermophilus. HACN catalyses the hydration of cis-homoaconitate to (2R,3S)-homoisocitrate, but the HACN-catalysed dehydration of (R)-homocitrate to cis-homoaconitate has not been observed in vitro. We have synthesized the substrates and putative substrates for this enzyme, and in the present study report the first steady-state kinetic data for recombinant HACN from T. thermophilus using a (2R,3S)-homoisocitrate dehydrogenase-coupled assay. We have also examined the products of the reaction using HPLC. We do not observe HACN-catalysed 'homocitrate dehydratase' activity; however, we have observed that ACN can catalyse the dehydration of (R)-homocitrate to cis-homoaconitate, but HACN is required for subsequent conversion of cis-homoaconitate into homoisocitrate. This suggests that the in vivo process for conversion of homocitrate into homoisocitrate requires two enzymes, in simile with the propionate utilization pathway from Escherichia coli. Surprisingly, HACN does not show any activity when cis-aconitate is substituted for the substrate, even though other enzymes from the alpha-aminoadipate pathway can accept analogous tricarboxylic acid-cycle substrates. The enzyme shows no apparent feedback inhibition by L-lysine.

  4. Kinetics and energetics of electron transfer in reaction centers of the photosynthetic bacterium Roseiflexus castenholzii.

    Science.gov (United States)

    Collins, Aaron M; Kirmaier, Christine; Holten, Dewey; Blankenship, Robert E

    2011-03-01

    The kinetics and thermodynamics of the photochemical reactions of the purified reaction center (RC)-cytochrome (Cyt) complex from the chlorosome-lacking, filamentous anoxygenic phototroph, Roseiflexus castenholzii are presented. The RC consists of L- and M-polypeptides containing three bacteriochlorophyll (BChl), three bacteriopheophytin (BPh) and two quinones (Q(A) and Q(B)), and the Cyt is a tetraheme subunit. Two of the BChls form a dimer P that is the primary electron donor. At 285K, the lifetimes of the excited singlet state, P*, and the charge-separated state P(+)H(A)(-) (where H(A) is the photoactive BPh) were found to be 3.2±0.3 ps and 200±20 ps, respectively. Overall charge separation P*→→ P(+)Q(A)(-) occurred with ≥90% yield at 285K. At 77K, the P* lifetime was somewhat shorter and the P(+)H(A)(-) lifetime was essentially unchanged. Poteniometric titrations gave a P(865)/P(865)(+) midpoint potential of +390mV vs. SHE. For the tetraheme Cyt two distinct midpoint potentials of +85 and +265mV were measured, likely reflecting a pair of low-potential hemes and a pair of high-potential hemes, respectively. The time course of electron transfer from reduced Cyt to P(+) suggests an arrangement where the highest potential heme is not located immediately adjacent to P. Comparisons of these and other properties of isolated Roseiflexus castenholzii RCs to those from its close relative Chloroflexus aurantiacus and to RCs from the purple bacteria are made. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Ozonation of benzotriazole and methylindole: Kinetic modeling, identification of intermediates and reaction mechanisms.

    Science.gov (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldán, Gloria; Rodríguez, Elena

    2015-01-23

    The ozonation of 1H-benzotriazole (BZ) and 3-methylindole (ML), two emerging contaminants that are frequently present in aquatic environments, was investigated. The experiments were performed with the contaminants (1μM) dissolved in ultrapure water. The kinetic study led to the determination of the apparent rate constants for the ozonation reactions. In the case of 1H-benzotriazole, these rate constants varied from 20.1 ± 0.4M(-1)s(-1) at pH=3 to 2143 ± 23 M(-1)s(-1) at pH=10. Due to its acidic nature (pKa=8.2), the degree of dissociation of this pollutant was determined at every pH of work, and the specific rate constants of the un-dissociated and dissociated species were evaluated, being the values of these rate constants 20.1 ± 2.0 and 2.0 ± 0.3 × 10(3)M(-1)s(-1), respectively. On the contrary, 3-methylindole does not present acidic nature, and therefore, it can be proposed an average value for its rate constant of 4.90 ± 0.7 × 10(5)M(-1)s(-1) in the whole pH range 3-10. Further experiments were performed to identify the main degradation byproducts (10 mg L(-1) of contaminants, 0.023 gh(-1) of ozone). Up to 8 intermediates formed in the ozonation of 3-methylindole were identified by LC-TOFMS, while 6 intermediates were identified in the ozonation of 1H-benzotriazole. By considering these intermediate compounds, the reaction mechanisms were proposed and discussed. Finally, evaluated rate constants allowed to predict and modeling the oxidation of these micropollutants in general aquatic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Modeling of reaction kinetics in bubbling fluidized bed biomass gasification reactor

    Energy Technology Data Exchange (ETDEWEB)

    Thapa, R.K.; Halvorsen, B.M. [Telemark University College, Kjolnes ring 56, P.O. Box 203, 3901 Porsgrunn (Norway); Pfeifer, C. [University of Natural Resources and Life Sciences, Vienna (Austria)

    2013-07-01

    Bubbling fluidized beds are widely used as biomass gasification reactors as at the biomass gasification plant in Gussing, Austria. The reactor in the plant is a dual circulating bubbling fluidized bed gasification reactor. The plant produces 2MW electricity and 4.5MW heat from the gasification of biomass. Wood chips as biomass and olivine particles as hot bed materials are fluidized with high temperature steam in the reactor. As a result, biomass undergoes endothermic chemical reaction to produce a mixture of combustible gases in addition to some carbon-dioxide (CO2). The combustible gases are mainly hydrogen (H2), carbon monoxide (CO) and methane (CH4). The gas is used to produce electricity and heat via utilization in a gas engine. Alternatively, the gas is further processed for gaseous or liquid fuels, but still on the process of development level. Composition and quality of the gas determine the efficiency of the reactor. A computational model has been developed for the study of reaction kinetics in the gasification rector. The simulation is performed using commercial software Barracuda virtual reactor, VR15. Eulerian-Lagrangian approach in coupling of gas-solid flow has been implemented. Fluid phase is treated with an Eulerian formulation. Discrete phase is treated with a Lagrangian formulation. Particle-particle and particle-wall interactions and inter-phase heat and mass transfer have been taken into account. Series of simulations have been performed to study model prediction of the gas composition. The composition is compared with data from the gasifier at the CHP plant in Güssing, Austria. The model prediction of the composition of gases has good agreements with the result of the operating plant.

  7. 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.

  8. In situ laser measurement of oxygen concentration and flue gas temperature utilizing chemical reaction kinetics.

    Science.gov (United States)

    Viljanen, J; Sorvajärvi, T; Toivonen, J

    2017-12-01

    Combustion research requires detailed localized information on the dynamic combustion conditions to improve the accuracy of the simulations and, hence, improve the performance of the combustion processes. We have applied chemical reaction kinetics of potassium to measure the local temperature and O 2 concentration in flue gas. An excess of free atomic potassium is created in the measurement volume by a photofragmenting precursor molecule such as potassium chloride or KOH which are widely released from solid fuels. The decay of the induced potassium concentration is followed with an absorption measurement using a narrow-linewidth diode laser. The temperature and O 2 concentration are solved from the decay curve features using equations obtained from calibration measurements in a temperature range of 800°C-1000°C and in O 2 concentrations of 0.1%-21%. The local flue gas temperature and O 2 concentration were recorded in real time during devolatilization, char burning, and ash cooking phases of combustion in a single-particle reactor with a 5 Hz repetition rate. The method can be further extended to other target species and applications where the chemical dynamics can be disturbed with photofragmentation.

  9. Contact properties and surface reaction kinetics of single ZnO nanowire devices fabricated by dielectrophoresis

    Science.gov (United States)

    Pau, J. L.; García Núñez, C.; García Marín, A.; Guerrero, C.; Rodríguez, P.; Borromeo, S.; Piqueras, J.

    2014-03-01

    This work describes the development of ZnO nanowire (NW) devices for ultraviolet detection and cost-effective gas sensing. A dielectrophoresis (DEP) flow cell fabricated for the integration of NWs on different substrates is presented. The system includes the possibility to set characteristic parameters such as alternating current (AC) frequency, amplitude or flow speed in order to control NW trapping on specific sites defined by micro-gapped electrodes. The electrical characteristics of the rectifying metal/NW contact fabricated by DEP are investigated in darkness and under direct illumination of the metal-NW interface through the ZnO NW. A significant downshift of the turn-on voltage is observed in the current-voltage characteristics during the illumination with photon energies higher than the ZnO bandgap. The reduction is attributed to a barrier height lowering induced by interface charge emission. The effects of AC bias on the thermal drift of the DC average current in NW devices are also discussed. Finally, the reaction kinetics of ethanol and water vapors on the NW surface are compared through the analysis of the DC current under direct exposure to gas flows. Device responses to more complex compound mixtures such as coffee or mint are also monitored over time, showing different performance in both cases.

  10. Influence of surface acoustic waves induced acoustic streaming on the kinetics of electrochemical reactions

    Science.gov (United States)

    Tietze, Sabrina; Schlemmer, Josefine; Lindner, Gerhard

    2013-12-01

    The kinetics of electrochemical reactions is controlled by diffusion processes of charge carriers across a boundary layer between the electrode and the electrolyte, which result in a shielding of the electric field inside the electrolyte and a concentration gradient across this boundary layer. In accumulators the diffusion rate determines the rather long time needed for charging, which is a major drawback for electric mobility. This diffusion boundary can be removed by acoustic streaming in the electrolyte induced by surface acoustic waves propagating of the electrode, which results in an increase of the charging current and thus in a reduction of the time needed for charging. For a quantitative study of the influence of acoustic streaming on the charge transport an electropolishing cell with vertically oriented copper electrodes and diluted H3PO4-Propanol electrolytes were used. Lamb waves with various excitation frequencies were exited on the anode with different piezoelectric transducers, which induced acoustic streaming in the overlaying electrolytic liquid. An increase of the polishing current of up to approximately 100 % has been obtained with such a set-up.

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

    Science.gov (United States)

    Krix, David; Nienhaus, Hermann

    2013-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Krix, David [Faculty of Physics, University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE), Lotharstr. 1, 47057 Duisburg (Germany); Nienhaus, Hermann, E-mail: hermann.nienhaus@uni-due.de [Faculty of Physics, University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE), Lotharstr. 1, 47057 Duisburg (Germany)

    2013-04-01

    Clean and oxidized alkali metal films have been studied using X-ray photoelectron spectroscopy (XPS). Thin films, typically 10 nm thick, of lithium, sodium, potassium, rubidium and cesium have been deposited on silicon substrates and oxidized at 120 K. Plasmon losses were found to dress the primary photo emission structures of the metals’ core lines which confirms the metallic, bulk like nature of the films. The emission from the O 1s core levels was used to determine the chemical composition and the reaction kinetics during the exposure to molecular oxygen at low pressures. Molecular oxide ions O{sub 2}{sup −} and O{sub 2}{sup 2−} as well as atomic oxygen ions O{sup 2−} were detected in varying amounts depending on the alkali metal used. Diffusive transport of material in the film is shown to greatly determine the composition of the oxides. Especially, the growth of potassium superoxide is explained by the diffusion of potassium atoms to the surface and growth at the surface in a Deal–Grove like model.

  13. Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics: Effect of Franck-Condon States.

    Science.gov (United States)

    Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K

    2017-09-21

    Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches for ETRK and NESD, respectively, predict both of the processes to be independent of λex. The above said lacuna in these theories prompted us to develop a novel theory in 1D space, where the effect of innumerable Franck-Condon states is included through λex. The present theory not only sheds light on the origin of failure of the existing theories but also gives the correct trend for the effect of λex on ETRK and NESD. More importantly, the calculated results of NESD are in excellent agreement with the experimental results for different values of λex. The new theory will therefore advance the knowledge of scientific community on the dynamics of photoinduced nonequilibrium processes.

  14. Primary Ion Depletion Kinetics (PIDK) Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS.

    Science.gov (United States)

    Schuhfried, Erna; Märk, Tilmann D; Biasioli, Franco

    2013-01-01

    We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS), which we name primary ion depletion kinetics (PIDK). PTR-MS is a chemical ionization mass spectrometric (CIMS) technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H3O(+), and constant MH(+). Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H3O(+) leads to reduced heating of H3O(+) in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N) variation studies). Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (kinetics allows for the identification of dehydrogenation [MH(+) -H2] and adduct formation (RMH(+)) as low abundant fragmentation channels in monosulfides.

  15. kinetics

    Directory of Open Access Journals (Sweden)

    D. E. Panayotounakos

    2002-01-01

    Full Text Available We present the construction of the general solutions concerning the one-dimensional (1D fully dynamic nonlinear partial differential equations (PDEs, for the erosion kinetics. After an uncoupling procedure of the above mentioned equations a second–order nonlinear PDE of the Monge type governing the porosity is derived, the general solution of which is constructed in the sense that a full complement of arbitrary functions (as many as the order is introduced. Afterwards, we specify the above solution according to convenient initial conditions.

  16. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented 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 in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  17. Ozonolysis of mixed oleic-acid/stearic-acid particles: reaction kinetics and chemical morphology.

    Science.gov (United States)

    Katrib, Y; Biskos, G; Buseck, P R; Davidovits, P; Jayne, J T; Mochida, M; Wise, M E; Worsnop, D R; Martin, S T

    2005-12-08

    The ozonolysis of mixed oleic-acid/stearic-acid (OL/SA) aerosol particles from 0/100 to 100/0 wt % composition is studied. The magnitude of the divergence of the particle beam inside an aerosol mass spectrometer shows that, in the concentration range 100/0 to 60/40, the mixed OL/SA particles are liquid prior to reaction. Upon ozonolysis, particles having compositions of 75/25 and 60/40 change shape, indicating that they have solidified during reaction. Transmission electron micrographs show that SA(s) forms needles. For particles having compositions of 75/25, 60/40, and greater SA content, the reaction kinetics exhibit an initial fast decay of OL for low O(3) exposure with no further loss of OL at higher O(3) exposures. For compositions from 50/50 to 10/90, the residual OL concentration remains at 28 +/- 2% of its initial value. The initial reactive uptake coefficient for O(3), as determined by OL loss, decreases linearly from 1.25 (+/-0.2) x 10(-3) to 0.60 (+/-0.15) x 10(-3) for composition changes of 100/0 to 60/40. At 50/50 composition, the uptake coefficient drops abruptly to 0.15 (+/-0.1) x 10(-3), and there are no further changes with increased SA content. These observations can be explained with a combination of three postulates: (1) Unreacted mixed particles remain as supersaturated liquids up to 60/40 composition, and the OL in this form rapidly reacts with O(3). (2) SA, as it solidifies, locks into its crystal structure a significant amount of OL, and this OL is completely inaccessible to O(3). (3) Accompanying crystallization, some stearic acid molecules connect as a filamentous network to form a semipermeable gel containing liquid OL but with a reduced uptake coefficient because of the decrease in molecular diffusivity in the gel. An individual particle of 50/50 to 90/10 is hypothesized as a combination of SA crystals having OL impurities (postulate 2) that are partially enveloped by an SA/OL gel (postulate 3) to explain (a) the abrupt drop in the

  18. Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

    Directory of Open Access Journals (Sweden)

    Karla Herrera Delgado

    2015-05-01

    Full Text Available An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented in a one-dimensional flow field description of a fixed bed reactor. The model is evaluated by comparison of numerical simulations with data derived from isothermal experiments in a flow reactor over a powdered nickel-based catalyst using varying inlet gas compositions and operating temperatures. Furthermore, the influence of hydrogen and water as co-feed on methane dry reforming with CO2 is also investigated.

  19. Reaction Kinetics of Acetone Peroxide Formation and Structure Investigations Using Raman Spectroscopy and X-ray Diffraction

    DEFF Research Database (Denmark)

    Jensen, Lars; Mortensen, Peter Mølgaard; Trane, Rasmus

    2009-01-01

    that at 25 degrees C the reaction between acetone and hydrogen peroxide proceeds to form intermediates within one day. Based on the assumption that a likely reaction path involves a sequence of reaction steps between acetone and hydrogen peroxide, calculations of Raman spectra were performed using a density...... products and that the rate determining step is the ring closure. The reaction rate of TATP formation was found to increase with temperature and with sulfuric acid additions to the acetone/hydrogen peroxide mixture. By correlation of the induction time of TATP crystallization against pH it was shown......Triacetone triperoxide (TATP) has been prepared in order to study the effect of pH and temperature on the reaction kinetics. Raman spectra of liquid mixtures of acetone and hydrogen peroxide were recorded versus time throughout the experiments. The spectral data of the liquid phases indicate...

  20. 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.