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

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

Science.gov (United States)

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

2018-06-13

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

Principles of chemical kinetics

CERN Document Server

House, James E

2007-01-01

James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

First-order hydrothermal oxidation kinetics of digested sludge compared with raw sludge.

Science.gov (United States)

Shanableh, A; Imteaz, M

2008-09-01

This article presents an assessment of the first-order hydrothermal oxidation kinetics of a selected digested sludge at subcritical ( 374 degrees C) temperatures in the range of 250-460 degrees C. Furthermore, the results were compared with reported oxidation kinetics of raw sludge treated under identical experimental conditions. In the assessment, oxidation was considered to proceed in two steps: (1) decomposition of the particulate, or non-filterable, chemical oxygen demand (PCOD); followed by (2) ultimate oxidation and removal of the total, particulate and soluble, COD. The accumulation and removal of soluble COD (SCOD) was determined from the difference between the rates of sludge decomposition and ultimate oxidation. Using results from batch and continuous-flow hydrothermal treatment experiments, the reacting organic ingredients were separated into groups according to the ease or difficulty at which they were decomposed or removed, with Arrhenius-type activation energy levels assigned to the different groups. The analysis confirmed that within the treatment range of 75% to more than 97% COD removal, the oxidation kinetics of the digested and raw sludges were nearly identical despite differences in the proportions of their original organic ingredients. The original organic ingredients were mostly removed above 75% COD removal, and the oxidation kinetics appeared to be dominated by the removal of acetic acid, an intermediate by-product which constituted 50% to more than 80% of the remaining COD. Furthermore, the oxidation kinetics of both sludge types were consistent with reported first-order oxidation kinetics of pure acetic acid solutions. The resulting kinetic models adequately represented hydrothermal oxidation of digested sludge, in terms of COD and PCOD removals, as well as accumulation and removal of the soluble SCOD.

Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

KAUST Repository

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

2016-01-01

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

Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

KAUST Repository

Wang, Zhandong

2015-07-01

Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot

Directory of Open Access Journals (Sweden)

R. Prasad

2011-01-01

Full Text Available To comply with the stringent emission regulations on soot, diesel vehicles manufacturers more and more commonly use diesel particulate filters (DPF. These systems need to be regenerated periodically by burning soot that has been accumulated during the loading of the DPF. Design of the DPF requires rate of soot oxidation. This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions. Kinetics data were collected in a specially designed mini-semi-batch reactor. Under the high air flow rate assuming pseudo first order reaction the activation energy of soot oxidation was found to be, Ea = 160 kJ/ mol. ©2010 BCREC UNDIP. All rights reserved(Received: 14th June 2010, Revised: 18th July 2010, Accepted: 9th August 2010[How to Cite: R. Prasad, V.R. Bella. (2010. Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot. Bulletin of Chemical Reaction Engineering and Catalysis, 5(2: 95-101. doi:10.9767/bcrec.5.2.796.95-101][DOI:http://dx.doi.org/10.9767/bcrec.5.2.796.95-101 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/796]Cited by in: ACS 1 |

pyJac: Analytical Jacobian generator for chemical kinetics

Science.gov (United States)

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

2017-06-01

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

In situ photoemission spectroscopy using synchrotron radiation for O2 translational kinetic energy induced oxidation processes of partially-oxidized Si(001) surfaces

International Nuclear Information System (INIS)

Teraoka, Yuden; Yoshigoe, Akitaka

2001-01-01

The influence of translational kinetic energy of incident O 2 molecules for the passive oxidation process of partially-oxidized Si(001) surfaces has been studied by photoemission spectroscopy. The translational kinetic energy of O 2 molecules was controlled up to 3 eV by a supersonic seed beam technique using a high temperature nozzle. Two translational kinetic energy thresholds (1.0 eV and 2.6 eV) were found out in accordance with the first-principles calculation for the oxidation of clean surfaces. Si-2p photoemission spectra measured in representative translational kinetic energies revealed that the translational kinetic energy dependent oxidation of dimers and the second layer (subsurface) backbonds were caused by the direct dissociative chemisorption of O 2 molecules. Moreover, the difference in chemical bonds for oxygen atoms was found out to be as low and high binding energy components in O-1s photoemission spectra. Especially, the low binding energy component increased with increasing the translational kinetic energy that indicates the translational kinetic energy induced oxidation in backbonds. (author)

The oxidation kinetics and the structure of the oxide film on Zircaloy before and after the kinetic transition

International Nuclear Information System (INIS)

Arima, T.; Masuzumi, T.; Furuya, H.; Idemitsu, K.; Inagaki, Y.

2001-01-01

Oxidation kinetics of Zircaloy-4 have been measured using a micro-balance technique in CO-CO 2 gas mixtures between 450 deg. C and 600 deg. C. Oxidation kinetics of Zircaloy-4 obeyed a cubic rate law with time at 450-600 deg. C up to 24 h. At 600 deg. C, the kinetic transition occurred after about 36 h. After the transition, oxidation kinetics obeyed a linear rate law. X-ray diffraction patterns for the samples oxidized at 600 deg. C showed that the volume fraction of tetragonal phase of zirconia decreased with time until the kinetic transition occurred and was almost constant after that. In addition, stresses in the oxide films were found to be larger for the pre-transition samples than for the post-transition ones. (authors)

Kinetics of oxidic phase dissolution in acids

International Nuclear Information System (INIS)

Gorichev, I.G.; Kipriyanov, N.A.

1981-01-01

The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

Mathematical modelling of the kinetics of aerosol oxidation of sulfur dioxide upon electron-beam purification of power-plant flue gases from nitrogen and sulfur oxides

International Nuclear Information System (INIS)

Gerasimov, G.Ya.; Gerasimova, T.S.; Fadeev, S.A.

1996-01-01

A kinetic model of SO 2 oxidation in flue gases, irradiated with accelerated electron flux is proposed. The model comprises an optimized mechanism of gas phase radiation chemical oxidation of NO and SO 2 , kinetics circuit of SO 2 and NH 3 thermal interaction, kinetic models of volumetric condensation of water and sulfuric acid vapors and liquid-phase oxidation of SO 2 in aerosol drops, produced in the course of volumetric condensation. Calculation results are in a satisfactory agreement with experimental data. (author)

Oxidation kinetics of corium pool

International Nuclear Information System (INIS)

Sulatsky, A.A.; Smirnov, S.A.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu.; Fischer, M.; Hellmann, S.; Tromm, W.; Miassoedov, A.; Bottomley, D.; Piluso, P.; Barrachin, M.

2013-01-01

Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations

Oxidation kinetics of corium pool

Energy Technology Data Exchange (ETDEWEB)

Sulatsky, A.A., E-mail: andrei314@mail.ru [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Smirnov, S.A. [D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg (Russian Federation); Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Fischer, M.; Hellmann, S. [AREVA NP GmbH, Erlangen (Germany); Tromm, W.; Miassoedov, A. [Forschungzentrum Karlsruhe (FZK), Karlsruhe (Germany); Bottomley, D. [EUROPÄISCHE KOMMISSION, Joint Research Centre Institut für Transurane (ITU), Karlsruhe (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI, St.Paul-lez-Durance (France); Barrachin, M. [Institut de Radioprotection et Sûreté Nucléaire, St.Paul-lez-Durance (France)

2013-09-15

Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations.

Kinetic investigation of the oxidation of N-alkyl anilines by ...

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 6. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate. G P Panigrahi Jagannath Panda. Physical and Theoretical Volume 112 Issue 6 December 2000 pp 615-622 ...

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Science.gov (United States)

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

2018-03-01

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

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

Science.gov (United States)

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

2015-07-16

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

Kinetics and mechanism of oxidation of carbidized electrolytic chromium coatings

International Nuclear Information System (INIS)

Arkharov, V.I.; Yar-Mukhamedov, Sh.Kh.

1978-01-01

Thermal stability carbidized electrolytic chromium coatings has been studied depending on the conditions of their formation; the specific features of the mechanism of oxidation at 1200 deg in an air atmosphere have been elucidated. It has been established that kinetics of high temperature oxidation of the coatings depends essentially on the conditions of their formation and on the composition of steel to which the coating is applied. It has been shown that two oxidation mechanisms are possible: by diffusion of the residual chromium through a carbide layer along the carbide grain boundaries outwards or, when there is no residual chromium, by chemical reaction of carbon combustion and oxidation of the liberated chromium. The comparison of oxidation kinetic curves of the samples of 38KhMYuA, 35KhGSA, and DI-22 steels with and without coating has shown that the coatings under study have a better protective effect on 38KhMYuA steel than on 35KhGSA, although without coating oxidability of the first steel is higher than that of the second

Ab initio and kinetic modeling studies of formic acid oxidation

DEFF Research Database (Denmark)

Marshall, Paul; Glarborg, Peter

2015-01-01

A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...

Prediction of Combustion Instability with Detailed Chemical Kinetics

Science.gov (United States)

2014-12-01

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

The kinetic of photoreactions in zinc oxide microrods

Science.gov (United States)

Fiedot, M.; Rac, O.; Suchorska-Woźniak, P.; Nawrot, W.; Teterycz, H.

2016-01-01

Zinc oxide is the oldest sensing material used in the chemical resistive gas sensors which allow to detect many gases, such as carbon oxide, nitrogen oxides and other. This material is also widely used in medicine and daily life as antibacterial agent. For this reason this semiconductor is often synthesized on the polymer substrates such as foils and textiles. In presented results zinc oxide was deposited on the surface of poly(ethylene terephthalate) foil to obtain antibacterial material. As synthesis method chemical bath deposition was chosen. The growth of zinc oxide structures was carried out in water solution of zinc nitrate (V) and hexamethylenetetramine in 90°C during 9 h. Because antibacterial properties of ZnO are strongly depended on photocatalytic and electric properties of this semiconductor impedance spectroscopy measurements were carried out. During the measurements material was tested with and without UV light to determinate the kinetic of photoreactions in zinc oxide. Moreover the composite was analyzed by XRD diffraction and scanning electron microscope. The X-ray analysis indicated that obtained material has the structure of wurtzite which is typical of zinc oxide. SEM images showed that on the PET foil microrods of ZnO were formed. The impedance spectroscopy measurements of ZnO layer showed that in UV light significant changes in the conductivity of the material are observed.

The kinetic of photoreactions in zinc oxide microrods

International Nuclear Information System (INIS)

Fiedot, M; Rac, O; Suchorska-Woźniak, P; Nawrot, W; Teterycz, H

2016-01-01

Zinc oxide is the oldest sensing material used in the chemical resistive gas sensors which allow to detect many gases, such as carbon oxide, nitrogen oxides and other. This material is also widely used in medicine and daily life as antibacterial agent. For this reason this semiconductor is often synthesized on the polymer substrates such as foils and textiles. In presented results zinc oxide was deposited on the surface of poly(ethylene terephthalate) foil to obtain antibacterial material. As synthesis method chemical bath deposition was chosen. The growth of zinc oxide structures was carried out in water solution of zinc nitrate (V) and hexamethylenetetramine in 90°C during 9 h. Because antibacterial properties of ZnO are strongly depended on photocatalytic and electric properties of this semiconductor impedance spectroscopy measurements were carried out. During the measurements material was tested with and without UV light to determinate the kinetic of photoreactions in zinc oxide. Moreover the composite was analyzed by XRD diffraction and scanning electron microscope. The X-ray analysis indicated that obtained material has the structure of wurtzite which is typical of zinc oxide. SEM images showed that on the PET foil microrods of ZnO were formed. The impedance spectroscopy measurements of ZnO layer showed that in UV light significant changes in the conductivity of the material are observed

Chemical kinetic study of a novel lignocellulosic biofuel: Di-n-butyl ether oxidation in a laminar flow reactor and flames

KAUST Repository

Cai, Liming; Sudholt, Alena; Lee, Dongjoon; Egolfopoulos, Fokion N.; Pitsch, Heinz G.; Westbrook, Charles K.; Sarathy, Mani

2014-01-01

The combustion characteristics of promising alternative fuels have been studied extensively in the recent years. Nevertheless, the pyrolysis and oxidation kinetics for many oxygenated fuels are not well characterized compared to those of hydrocarbons. In the present investigation, the first chemical kinetic study of a long-chain linear symmetric ether, di-n-butyl ether (DBE), is presented and a detailed reaction model is developed. DBE has been identified recently as a candidate biofuel produced from lignocellulosic biomass. The model includes both high temperature and low temperature reaction pathways with reaction rates generated using appropriate rate rules. In addition, experimental studies on fundamental combustion characteristics, such as ignition delay times and laminar flame speeds have been performed. A laminar flow reactor was used to determine the ignition delay times of lean and stoichiometric DBE/air mixtures. The laminar flame speeds of DBE/air mixtures were measured in the stagnation flame configuration for a wide rage of equivalence ratios at atmospheric pressure and an unburned reactant temperature of 373. K. All experimental data were modeled using the present kinetic model. The agreement between measured and computed results is satisfactory, and the model was used to elucidate the oxidation pathways of DBE. The dissociation of keto-hydroperoxides, leading to radical chain branching was found to dominate the ignition of DBE in the low temperature regime. The results of the present numerical and experimental study of the oxidation of di-n-butyl ether provide a good basis for further investigation of long chain linear and branched ethers. © 2013 The Combustion Institute.

Chemical kinetic study of a novel lignocellulosic biofuel: Di-n-butyl ether oxidation in a laminar flow reactor and flames

KAUST Repository

Cai, Liming

2014-03-01

The combustion characteristics of promising alternative fuels have been studied extensively in the recent years. Nevertheless, the pyrolysis and oxidation kinetics for many oxygenated fuels are not well characterized compared to those of hydrocarbons. In the present investigation, the first chemical kinetic study of a long-chain linear symmetric ether, di-n-butyl ether (DBE), is presented and a detailed reaction model is developed. DBE has been identified recently as a candidate biofuel produced from lignocellulosic biomass. The model includes both high temperature and low temperature reaction pathways with reaction rates generated using appropriate rate rules. In addition, experimental studies on fundamental combustion characteristics, such as ignition delay times and laminar flame speeds have been performed. A laminar flow reactor was used to determine the ignition delay times of lean and stoichiometric DBE/air mixtures. The laminar flame speeds of DBE/air mixtures were measured in the stagnation flame configuration for a wide rage of equivalence ratios at atmospheric pressure and an unburned reactant temperature of 373. K. All experimental data were modeled using the present kinetic model. The agreement between measured and computed results is satisfactory, and the model was used to elucidate the oxidation pathways of DBE. The dissociation of keto-hydroperoxides, leading to radical chain branching was found to dominate the ignition of DBE in the low temperature regime. The results of the present numerical and experimental study of the oxidation of di-n-butyl ether provide a good basis for further investigation of long chain linear and branched ethers. © 2013 The Combustion Institute.

Analysis of the kinetics of methanol oxidation in a porous Pt-Ru anode

Energy Technology Data Exchange (ETDEWEB)

Sun, Yan-Ping; Xing, Lei [Chemical Engineering Department, Taiyuan University of Technology, Shanxi 030024 (China); Scott, Keith [School of Chemical Engineering and Advanced Materials, Merz Court, University of Newcastle, Newcastle upon Tyne NE1 7RU (United Kingdom)

2010-01-01

A kinetic model of a porous Pt-Ru anode for methanol oxidation is presented. It was based on the dual-site mechanism for methanol oxidation and used to predict anode performance and the influence of species adsorption on the overall oxidation (macro-) kinetics. The performance of the porous Pt-Ru anode depended on the parameters of the intrinsic chemical kinetics of methanol oxidation and physical parameters such as electrode thickness, surface area, effective diffusion and charge transfer coefficients and concentration of methanol and temperature. The model was solved by using the finite difference method with a subroutine for solving a set of nonlinear algebraic equations in each step. Surface coverage ratio distributions of adsorbed species, effectiveness of the porous electrode and macro-polarisation curves were obtained. The simulated polarisation curves were compared to experimental polarisation data for methanol oxidation on Pt-Ru porous anodes at different temperatures and methanol concentrations. The intrinsic kinetic parameters were regressed from the corresponding experimental data. The predicted polarisation curves calculated by the model, were consistent with experimental polarisation data at lower current densities. The departure of experimental data from the predicted polarisation curves at high concentration and high apparent current densities was believed to be due to two-phase flow in the electrode. (author)

Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

DEFF Research Database (Denmark)

Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

2013-01-01

Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS......-spot downstream of a force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order...... in the aerobic wastewater....

Comparative kinetic and energetic modelling of phyllosemiquinone oxidation in Photosystem I.

Science.gov (United States)

Santabarbara, Stefano; Zucchelli, Giuseppe

2016-04-14

The oxidation kinetics of phyllo(semi)quinone (PhQ), which acts as an electron transfer (ET) intermediate in the Photosystem I reaction centre, are described by a minimum of two exponential phases, characterised by lifetimes in the 10-30 ns and 150-300 ns ranges. The fastest phase is considered to be dominated by the oxidation of the PhQ molecule coordinated by the PsaB reaction centre subunit (PhQB), and the slowest phase is dominated by the oxidation of the PsaA coordinated PhQ (PhQA). Testing different energetic schemes within a unified theory-based kinetic modelling approach provides reliable limit-values for some of the physical-chemical parameters controlling these ET reactions: (i) the value of ΔG(0) associated with PhQA oxidation is smaller than ∼+30 meV; (ii) the value of the total reorganisation energy (λt) likely exceeds 0.7 eV; (iii) different mean nuclear modes are coupled to PhQB and PhQA oxidation, the former being larger, and both being ≥100 cm(-1).

Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

International Nuclear Information System (INIS)

Westbrook, C.K.

2000-01-01

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

Bond-specific reaction kinetics during the oxidation of (111) Si: Effect of n-type doping

International Nuclear Information System (INIS)

Gokce, B.; Aspnes, D. E.; Lucovsky, G.; Gundogdu, K.

2011-01-01

It is known that a higher concentration of free carriers leads to a higher oxide growth rate in the thermal oxidation of silicon. However, the role of electrons and holes in oxidation chemistry is not clear. Here, we report real-time second-harmonic-generation data on the oxidation of H-terminated (111)Si that reveal that high concentrations of electrons increase the chemical reactivity of the outer-layer Si-Si back bonds relative to the Si-H up bonds. However, the thicknesses of the natural oxides of all samples stabilize near 1 nm at room temperature, regardless of the chemical kinetics of the different bonds.

Enhanced In Situ Chemical Oxidation Using Surfactants and Shear Thinning Fluids

Science.gov (United States)

Hauswirth, S.; Sadeghi, S.; Cerda, C. C.; Espinoza, I.; Schultz, P. B.; Miller, C. T.

2017-12-01

In situ chemical oxidation (ISCO) is an attractive approach for the remediation of recalcitrant contaminants, due to the fact that target compounds are degraded in place, precluding the need for ex situ treatment or disposal. However, field applications of ISCO approaches have been plagued by "rebound" of contaminant concentrations in groundwater weeks to months after treatment. The cause of rebound at a given site may vary, but is typically associated with back-diffusion from finer grained, low permeability units or the presence of non-aqueous phase liquids (NAPLs) that are incompletely degraded during treatment. Modifications to traditional ISCO methods have been proposed to overcome these challenges, including the use of shear-thinning polymers to improve delivery of oxidants to low permeability units and the addition of surfactants to improve dissolution of contaminants from NAPLs. In this work, we investigate the application of these approaches to the oxidation of manufactured gas plant (MGP) tars—NAPLs composed primarily of polycyclic aromatic hydrocarbons (PAHs). We conducted experiments to determine the mutual impact of each chemical component on the physical and chemical properties of the overall system. Specifically, experiments were designed to: determine the kinetics and overall effectiveness of contaminant-oxidant reactions for multiple oxidant-activator combinations; screen several common surfactants in terms of their ability to increase MGP tar solubility and their compatibility with oxidant systems; measure the impact of oxidants and surfactants on the rheology of several common polymer additives; and assess the effect of surfactants and polymers on the consumption of oxidants/activators and on the kinetics of contaminant-oxidant reactions. The results of this work provide insight into the chemical and physical mechanisms associated with enhanced ISCO approaches and an improved basis with which to model and design ISCO applications at both the lab

Selected readings in chemical kinetics

CERN Document Server

Back, Margaret H

2013-01-01

Selected Readings in Chemical Kinetics covers excerpts from 12 papers in the field of general and gas-phase kinetics. The book discusses papers on the laws of connexion between the conditions of a chemical change and its amount; on the reaction velocity of the inversion of the cane sugar by acids; and the calculation in absolute measure of velocity constants and equilibrium constants in gaseous systems. The text then tackles papers on simple gas reactions; on the absolute rate of reactions in condensed phases; on the radiation theory of chemical action; and on the theory of unimolecular reacti

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

International Nuclear Information System (INIS)

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

1995-01-01

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

Evolution of zirconium-based precipitates during oxidation and irradiation of Zr alloys (impact on the oxidation kinetics of Zr alloys)

International Nuclear Information System (INIS)

Pecheur, Dominique

1993-01-01

As the oxidation of the zircaloy sheath is one of the factors which limit the lifetime of nuclear fuel rods, this research thesis aims at a better knowledge of the involved oxidation mechanisms and to improve the oxidation resistance in order to increase rod lifetime. Oxidation test performed in autoclave to study zirconium alloy oxidation without irradiation showed that oxidation kinetics is significantly higher under irradiation. This difference is attributed to a different evolution of the sheath material under irradiation. Thus, this research focused on the role of precipitates in the oxidation process of zirconium alloys, and on the impact of their amorphization on this oxidation. After a detailed description of the context and of the various implemented experimental means, the author presents the results obtained on a reference material on the one hand, and on a material irradiated by ions or neutrons on the other hand. More particularly, the author studied in these both cases the introduction of precipitates in the oxide layer by transmission electronic microscopy, and oxidation kinetics obtained in autoclave on these two types of material. He reports the analysis of the introduction of precipitates in the oxide layer formed on the reference material. He proposes interpretations for the evolutions of structure and of chemical compositions of precipitates in the oxide layer. These observations are then correlated with oxidation kinetics in these alloys. Finally, the author discusses results of oxidation tests obtained on materials irradiated by ions and by neutrons [fr

Development of the kinetic model of platinum catalyzed ammonia oxidation in a microreactor

NARCIS (Netherlands)

Rebrov, E.V.; Croon, de M.H.J.M.; Schouten, J.C.

2002-01-01

The ammonia oxidation reaction on supported polycrystalline platinum catalyst was investigated in an aluminum-based microreactor. An extensive set of reactions was included in the chemical reactor modeling to facilitate the construction of a kinetic model capable of satisfactory predictions for a

Model-fitting approach to kinetic analysis of non-isothermal oxidation of molybdenite

International Nuclear Information System (INIS)

Ebrahimi Kahrizsangi, R.; Abbasi, M. H.; Saidi, A.

2007-01-01

The kinetics of molybdenite oxidation was studied by non-isothermal TGA-DTA with heating rate 5 d eg C .min -1 . The model-fitting kinetic approach applied to TGA data. The Coats-Redfern method used of model fitting. The popular model-fitting gives excellent fit non-isothermal data in chemically controlled regime. The apparent activation energy was determined to be about 34.2 kcalmol -1 With pre-exponential factor about 10 8 sec -1 for extent of reaction less than 0.5

Research in Chemical Kinetics, v.3

CERN Document Server

2012-01-01

This series of volumes aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the contributions and their top

Research in chemical kinetics, v.2

CERN Document Server

1994-01-01

This is the second volume in a new series, which aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the c

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

Science.gov (United States)

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

2013-01-01

The pyrolytic and oxidative behaviour of the biofuel 2,5-dimethylfuran (25DMF) has been studied in a range of experimental facilities in order to investigate the relatively unexplored combustion chemistry of the title species and to provide combustor relevant experimental data. The pyrolysis of 25DMF has been re-investigated in a shock tube using the single-pulse method for mixtures of 3% 25DMF in argon, at temperatures from 1200–1350 K, pressures from 2–2.5 atm and residence times of approximately 2 ms. Ignition delay times for mixtures of 0.75% 25DMF in argon have been measured at atmospheric pressure, temperatures of 1350–1800 K at equivalence ratios (ϕ) of 0.5, 1.0 and 2.0 along with auto-ignition measurements for stoichiometric fuel in air mixtures of 25DMF at 20 and 80 bar, from 820–1210 K. This is supplemented with an oxidative speciation study of 25DMF in a jet-stirred reactor (JSR) from 770–1220 K, at 10.0 atm, residence times of 0.7 s and at ϕ = 0.5, 1.0 and 2.0. Laminar burning velocities for 25DMF-air mixtures have been measured using the heat-flux method at unburnt gas temperatures of 298 and 358 K, at atmospheric pressure from ϕ = 0.6–1.6. These laminar burning velocity measurements highlight inconsistencies in the current literature data and provide a validation target for kinetic mechanisms. A detailed chemical kinetic mechanism containing 2768 reactions and 545 species has been simultaneously developed to describe the combustion of 25DMF under the experimental conditions described above. Numerical modelling results based on the mechanism can accurately reproduce the majority of experimental data. At high temperatures, a hydrogen atom transfer reaction is found to be the dominant unimolecular decomposition pathway of 25DMF. The reactions of hydrogen atom with the fuel are also found to be important in predicting pyrolysis and ignition delay time experiments. Numerous proposals are made on the mechanism and kinetics of the previously

Kinetics of plasma oxidation of germanium-tin (GeSn)

Science.gov (United States)

Wang, Wei; Lei, Dian; Dong, Yuan; Zhang, Zheng; Pan, Jisheng; Gong, Xiao; Tok, Eng-Soon; Yeo, Yee-Chia

2017-12-01

The kinetics of plasma oxidation of GeSn at low temperature is investigated. The oxidation process is described by a power-law model where the oxidation rate decreases rapidly from the initial oxidation rate with increasing time. The oxidation rate of GeSn is higher than that of pure Ge, which can be explained by the higher chemical reaction rate at the GeSn-oxide/GeSn interface. In addition, the Sn atoms at the interface region exchange positions with the underlying Ge atoms during oxidation, leading to a SnO2-rich oxide near the interface. The bandgap of GeSn oxide is extracted to be 5.1 ± 0.2 eV by XPS, and the valence band offset at the GeSn-oxide/GeSn heterojunction is found to be 3.7 ± 0.2 eV. Controlled annealing experiments demonstrate that the GeSn oxide is stable with respect to annealing temperatures up to 400 °C. However, after annealing at 450 °C, the GeO2 is converted to GeO, and desorbs from the GeSn-oxide/GeSn, leaving behind Sn oxide.

Study of internal oxidation kinetics of molybdenum base alloys

International Nuclear Information System (INIS)

Krushinskij, Yu.Yu.; Belyakov, B.G.; Belomyttsev, M.Yu.

1989-01-01

Metallographic and microdurometric method as well as new technique were used to study kinetics of internal oxidation (IO). It is shown that study of IO kinetics on the base of metallographic measurements of layers depth is not correct because it is related with insufficient sensitivity of the method. IO kinetics under conditions of formation of molybdenum oxide layer on saturated material surface as well as IO of alloy with high carbon content were investigated. Oxide film formation does not affect the IO kinetics; decarburization observed along with oxidation increases the apparent activation energy and K exponent on time dependence of diffusion layer depth

Chemical kinetics and reaction mechanism

International Nuclear Information System (INIS)

Jung, Ou Sik; Park, Youn Yeol

1996-12-01

This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

Inflation Rates, Car Devaluation, and Chemical Kinetics.

Science.gov (United States)

Pogliani, Lionello; Berberan-Santos, Mario N.

1996-01-01

Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)

Kinetic studies of oxidation of {gamma}-AlON-TiN composites

Energy Technology Data Exchange (ETDEWEB)

Zhang Zuotai; Wang Xidong; Li Wenchao

2005-01-25

The present article deals with the investigation of the oxidation kinetics of {gamma}-aluminum oxynitride-Titanium Nitride composites (AlON-TiN) in the temperature range of 1100-1300 deg. C by thermogravimetry. Oxidation experiments with AlON-TiN composite plates have been carried out in air both in isothermal and nonisothermal modes. The results showed that the rate of oxidation was negligible below 1000 deg. C, and showed an increase with increasing temperature at higher temperature. Both isothermal studies as well as experiments with ramped temperature clearly indicated that the mechanism of the reaction changes around 1400 deg. C. In the nonisothermal mode, the oxidation curve showed an increased reaction rate in this temperature range. Oxidation of AlON-TiN composite results in {alpha}-Al{sub 2}O{sub 3} and TiO{sub 2} at a low temperature and Al{sub 2}TiO{sub 5} at higher temperature. The buildup of the product layer leads to diffusion controlled kinetics. In the nonisothermal experiments, the phase transformation from Al{sub 2}O{sub 3} and TiO{sub 2}, to a Al{sub 2}TiO{sub 5} product layer at higher temperature would lead to crack formation, thereby leading to direct chemical reaction. From the experiments for the isothermal oxidation of AlON-TiN composite plates, the overall reactions are separated into three stages: chemistry reaction-controlling stage; chemical reaction- and diffusion-mixed-controlled stage; diffusion-controlled stage. The apparent activation energy for the experiments were calculated to be 10.109, 2.19 and 5.614 kJ mol{sup -1}, respectively, in the above three stages.

Kinetics of 25-hydroperoxycholesterol formation during photo-oxidation of crystalline cholesterol.

Science.gov (United States)

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

2014-06-01

25-Hydroxycholesterol (25-OH), a side-chain product of cholesterol oxidation, has emerged as one of the important issues in food chemistry and biochemistry, because of its involvement in several human pathologies. This oxysterol is derived from both enzymatic and non-enzymatic pathways. However, the latter mechanism has been scarcely studied in either food or model systems. In this work, a kinetic model was developed to evaluate the formation of 25-OH and its precursor 25-hydroperoxycholesterol (25-OOH) during photo-oxidation of cholesterol for 28 days under fluorescent light. 25-OOH was estimated by an indirect method, using thin-layer chromatography coupled with gas chromatography-mass spectrometry. Peroxide value (POV) and cholesterol oxidation products (COPs) were determined. POV showed a hyperbolic behavior, typical of a crystalline system in which the availability of cholesterol is the limiting factor. Further reactions of hydroperoxides were followed; in particular, after photo-oxidation, 25-OOH (0.55 mg g(-1) ) and 25-OH (0.08 mg g(-1) ) were found in cholesterol, as well as seven other oxysterols, including 7-hydroxy and 5,6-epoxy derivatives. The application of kinetic models to the data showed good correlation with theoretical values, allowing derivation of the kinetic parameters for each oxidation route. The results of this work confirm that cholesterol in the crystalline state involves different oxidation patterns as compared to cholesterol in solution. Moreover, the numerical fit proved that hydroperoxidation is the rate-limiting step in 25-OH formation. © 2013 Society of Chemical Industry.

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

Synthesis, electropolymerization and oxidation kinetics of an anthraquinone-functionalized poly(3,4-ethylenedioxythiophene)

International Nuclear Information System (INIS)

Arias-Pardilla, J.; Otero, T.F.; Blanco, R.; Segura, J.L.

2010-01-01

The chemical synthesis of an EDOT derivative endowed with an electron acceptor anthraquinone moiety (AQ-EDOT) is described. The electrochemical polymerization of the monomer has been studied by cyclic voltammetry, chronoamperometry and chronopotentiometry. The monomer oxidation-polymerization takes places on platinum at potentials more positive than 1.3 V vs. Ag/AgCl. The polymer film presents a stable redox process with E 0 = 0.22 V, that can be assigned to the characteristic exchange process of the parent unsubstituted PEDOT polymer. An unstable redox process at E 0 = -1.00 V, present decreasing charges on the consecutive cycles despite that the lost reduction charge is recovered by two irreversible oxidation processes taking place at high anodic potentials 0.00 and 0.16 V. A structural charge trapping effects occurring by reduction at -1.1 V and re-oxidation at 0.16 V of the anthraquinone moiety is suggested. The stable redox process is not affected by cycling allowing the obtention of the oxidation empirical kinetics, kinetic coefficients and reaction orders. Different initial states attained by reduction at different cathodic potentials for a constant time were explored for the kinetic study.

Synthesis, electropolymerization and oxidation kinetics of an anthraquinone-functionalized poly(3,4-ethylenedioxythiophene)

Energy Technology Data Exchange (ETDEWEB)

Arias-Pardilla, J. [Centre for Electrochemistry and Intelligent Materials (CEMI), Universidad Politecnica de Cartagena, ETSII, E-30203 Cartagena (Spain); Otero, T.F., E-mail: toribio.fotero@uptc.e [Centre for Electrochemistry and Intelligent Materials (CEMI), Universidad Politecnica de Cartagena, ETSII, E-30203 Cartagena (Spain); Blanco, R.; Segura, J.L. [Departamento de Quimica Organica, Facultad de Quimica, Universidad Complutense, E-28040 Madrid (Spain)

2010-02-01

The chemical synthesis of an EDOT derivative endowed with an electron acceptor anthraquinone moiety (AQ-EDOT) is described. The electrochemical polymerization of the monomer has been studied by cyclic voltammetry, chronoamperometry and chronopotentiometry. The monomer oxidation-polymerization takes places on platinum at potentials more positive than 1.3 V vs. Ag/AgCl. The polymer film presents a stable redox process with E{sup 0} = 0.22 V, that can be assigned to the characteristic exchange process of the parent unsubstituted PEDOT polymer. An unstable redox process at E{sup 0} = -1.00 V, present decreasing charges on the consecutive cycles despite that the lost reduction charge is recovered by two irreversible oxidation processes taking place at high anodic potentials 0.00 and 0.16 V. A structural charge trapping effects occurring by reduction at -1.1 V and re-oxidation at 0.16 V of the anthraquinone moiety is suggested. The stable redox process is not affected by cycling allowing the obtention of the oxidation empirical kinetics, kinetic coefficients and reaction orders. Different initial states attained by reduction at different cathodic potentials for a constant time were explored for the kinetic study.

Generalized first-order kinetic model for biosolids decomposition and oxidation during hydrothermal treatment.

Science.gov (United States)

Shanableh, A

2005-01-01

The main objective of this study was to develop generalized first-order kinetic models to represent hydrothermal decomposition and oxidation of biosolids within a wide range of temperatures (200-450 degrees C). A lumping approach was used in which oxidation of the various organic ingredients was characterized by the chemical oxygen demand (COD), and decomposition was characterized by the particulate (i.e., nonfilterable) chemical oxygen demand (PCOD). Using the Arrhenius equation (k = k(o)e(-Ea/RT)), activation energy (Ea) levels were derived from 42 continuous-flow hydrothermal treatment experiments conducted at temperatures in the range of 200-450 degrees C. Using predetermined values for k(o) in the Arrhenius equation, the activation energies of the various organic ingredients were separated into 42 values for oxidation and a similar number for decomposition. The activation energy values were then classified into levels representing the relative ease at which the organic ingredients of the biosolids were oxidized or decomposed. The resulting simple first-order kinetic models adequately represented, within the experimental data range, hydrothermal decomposition of the organic particles as measured by PCOD and oxidation of the organic content as measured by COD. The modeling approach presented in the paper provide a simple and general framework suitable for assessing the relative reaction rates of the various organic ingredients of biosolids.

Oxidation kinetics of (B6O) boron oxide

International Nuclear Information System (INIS)

Makarov, V.S.; Solov'ev, N.E.; Ugaj, Ya.A.

1987-01-01

Reactivity of B 6 O to oxygen is investigated. It is shown that the process of B 6 O oxidation in the air in the temperature range 760-1150 K results in the maximum transformation degree equal to 0.35. At the initial stages oxidation proceeds in kinetic regime, at final stages - in diffusion one, and high viscosity of B 2 O 3 probably affects the oxidation process

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

Science.gov (United States)

Fegley, Bruce, Jr.

1990-01-01

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

A combined kinetic and diffusion model for pyrite oxidation in tailings - a change in controls with time

International Nuclear Information System (INIS)

Elberling, B.; Nicholson, R.V.; Scharer, J.M.

1994-01-01

Acidic drainage from the oxidation of mine tailing wastes is an important environmental problem. The purpose of this paper is to develop a model (1) to simulate the rate of oxidation of pyrite over time, (2) to verify the importance of chemical kinetic control and diffusion control on the oxidation rate with time and, (3) to evaluate the sensitivity of the model to critical parameters of the tailings, such as grain size, pyrite content and the effective diffusion coefficient. The source code comprises four main modules including parameter allocation (kinetics, transport), sulphide oxidation (shrinking particle), oxygen transport and pyrite mass balance. The results show that high oxidation rates are observed in the initial time after tailings deposition. During this initial period of high rates, an apparent shift occurs from kinetic to diffusional control over a period of time that depends on the composition and properties of the tailings. Based on the simulation results, it is evident that the overall rate of oxidation after a few years will be controlled dominantly by the diffusion of oxygen rather than by biological or non-biological kinetics in the tailings

Mathematical modeling of the radiation-chemical oxidation of U(IV) in HClO4

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

Mathematical modeling of U(IV) oxidation in 0.5-12 M HClO 4 upon α, γ-radiolysis, based on the proposed scheme of radiation-chemical reactions, has been performed. The rate constants of the U(VI) + HO 2 , U(IV) + HO 2 , U(IV) + ClO 2 , and U(IV) + ClO 2 - reactions have been determined by the comparison of the calculated and experimental kinetic and dose curves and radiation-chemical yields of U(IV) oxidation or U(VI) formation. General equations for uranium (IV) oxidation constants at various HClO 4 concentrations, based on the analysis of the rates of particular radiation-chemical reactions composing oxidation process, have been obtained

KINETICS OF THE OXIDATION OF VITAMIN C

Directory of Open Access Journals (Sweden)

Sitti Rahmawati

2012-12-01

Full Text Available Vitamin C or ascorbic acid is needed by the human body but it is already damaged by the rise in temperature due to be oxidized to L-dehydroascorbic acid. This research aims to determine the kinetics of oxidation of ascorbic acid due to an increase if temperature (40-80 °C and to design an ascorbic acid oxidation reaction laboratory module to be applied in the senior high school reaction kinetics curriculum. The determination of the kinetics of the oxidation of ascorbic acid applies the integral and half-change time methods, while the concentration of the remained ascorbic acid in sixty minute intervals is determined by iodimetric titration method. Decomposition of ascorbic acid was measured at 40, 50, 60, 70 and 80 °C. The results of this research indicate that at 40, 50, 60, 70 and 80 °C the kinetics of the oxidation of ascorbic acid is a first-order reaction with rate constants of 4.55 x 10-4, 5.85 x 10-4, 8.4 x 10-4, 1.1 x 10-3 and 1.015 x 10-3 min-1, respectively. Pre-exponential factor or the frequency of collisions is a factor which is a measure of the collision rate. The activation energy and the pre-exponential factor for the oxidation of ascorbic acid were found to be 20.73 kJ.mol-1 and 1.372 min-1. The procedure used in this study was modified into a laboratory module will be applied in the teaching of reaction kinetics at the senior high school level.

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

International Nuclear Information System (INIS)

Adda, Y.

1955-06-01

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

Kinetic modeling of antimony(III) oxidation and sorption in soils.

Science.gov (United States)

Cai, Yongbing; Mi, Yuting; Zhang, Hua

2016-10-05

Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

Science.gov (United States)

Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

2017-06-01

The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

Chain radiation-chemical oxidation of aromatic amines in polyvinylchloride films

International Nuclear Information System (INIS)

Kolninov, O.V.; Lisovskaya, I.A.; Milinchuk, V.K.

1983-01-01

Radiation-chemical oxidation of tetramethyldiaminediphenylmethane in polyvinylchloride (PVC) and polystyrene (PS) films was investigated in the presence of CBr 4 at 300 K. Radiation yields (G) of 70 and 1 were obtained for an oxidized amine form (Am + ) in PVC and PS, resp. High yields of Am + in PVC matrix indicate the chain character of an oxidation reaction. Triplet states, which form exciplexes with CBr 4 were established to participate in oxidation reactions. The kinetic scheme suggested for the chain radiation oxidation of Am takes into account energy transfer, formation and degradation of the excited states of molecules resulting in the initiation and propagation of the chain on the account of active particles. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-30

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

A computational environment for creating and testing reduced chemical kinetic mechanisms

Energy Technology Data Exchange (ETDEWEB)

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

2002-02-01

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

Breaking up of pure and simulated 'burnt' mixed oxide fuel by chemical interaction with oxidized sodium

International Nuclear Information System (INIS)

Besnard, R.; Chaudat, J.P.

1983-01-01

A large experimental program have permitted to investigate the behaviour of mixed oxide fuel coming in contact with hot oxidized sodium. The kinetic of the reaction, the size and the chemical nature of the particules after interaction have been studied. The main part of experiments have been performed using mixed oxide fuel non irradiated at first and with simulated fission products afterwards. Complementary informations have been obtained with UO 2 fuel pellets. After description of the experimental devices, the results are discussed and the importance of the main parameters, like temperature and fission products effect, are pointed out. (orig.)

Empiricism or self-consistent theory in chemical kinetics?

International Nuclear Information System (INIS)

Gutman, E.M.

2007-01-01

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

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

Modeling chemical kinetics graphically

NARCIS (Netherlands)

Heck, A.

2012-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-02-08

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

Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

Science.gov (United States)

2017-01-01

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

DEFF Research Database (Denmark)

Aranda, V.; Christensen, J. M.; Alzueta, Maria

2013-01-01

A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH...... the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

African Journals Online (AJOL)

acer

Kinetic Studies of Catalytic Oxidation of Cyclohexene Using Chromium VI Oxide in. Acetic Acid ... respect to the oxidant using pseudo-order approximation method. .... making the concentration of the cyclohexene in ..... on Titanium Silicate.

Chemical oxidation methods in the closure of paper mill water circulations; Hapetustekniikoiden kaeyttoe metsaeteollisuuden vesikiertojen sulkemisessa - EKT 04

Energy Technology Data Exchange (ETDEWEB)

Laari, A.; Kallas, J. [Lappeenranta Univ. of Technology (Finland); Korhonen, S. [Kuopio Univ. (Finland); Tuhkanen, T. [Mikkelin Ammattikorkeakoulu, Mikkeli (Finland)

1998-12-31

When water circulations are closed some harmful compounds tend to accumulate in the circulation waters. These compounds include lipophilic extractives, like resin and fatty acids, triglycerides and sterols, but also other compounds, like lignins, lignans and sugars. Microbial growth will increase due to elevated organic concentrations. The purpose of this project is to find out the possibilities of the use of ozonation and wet oxidation in the treatment of paper mill water circulations. In chemical oxidation organic matter is destroyed in oxidation reactions. Especially lipophilic extractives are selectively oxidated by ozone. Chemical oxidation reactions are carried out in gas-liquid reactors, where ozone or oxygen are transferred from gas to liquid phase where the oxidation reactions happen. One target of the project is to estimate kinetic parameters for different groups of compounds on the basis of experimental data. Kinetic parameters are then used in modelling of reactors and in estimation of process costs. (orig.)

Chemical oxidation methods in the closure of paper mill water circulations; Hapetustekniikoiden kaeyttoe metsaeteollisuuden vesikiertojen sulkemisessa - EKT 04

Energy Technology Data Exchange (ETDEWEB)

Laari, A; Kallas, J [Lappeenranta Univ. of Technology (Finland); Korhonen, S [Kuopio Univ. (Finland); Tuhkanen, T [Mikkelin Ammattikorkeakoulu, Mikkeli (Finland)

1999-12-31

When water circulations are closed some harmful compounds tend to accumulate in the circulation waters. These compounds include lipophilic extractives, like resin and fatty acids, triglycerides and sterols, but also other compounds, like lignins, lignans and sugars. Microbial growth will increase due to elevated organic concentrations. The purpose of this project is to find out the possibilities of the use of ozonation and wet oxidation in the treatment of paper mill water circulations. In chemical oxidation organic matter is destroyed in oxidation reactions. Especially lipophilic extractives are selectively oxidated by ozone. Chemical oxidation reactions are carried out in gas-liquid reactors, where ozone or oxygen are transferred from gas to liquid phase where the oxidation reactions happen. One target of the project is to estimate kinetic parameters for different groups of compounds on the basis of experimental data. Kinetic parameters are then used in modelling of reactors and in estimation of process costs. (orig.)

Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

Science.gov (United States)

Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

2018-02-01

High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

Developments in kinetic modelling of chalcocite particle oxidation

Energy Technology Data Exchange (ETDEWEB)

Jaervi, J; Ahokainen, T; Jokilaakso, A [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

1998-12-31

A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

Developments in kinetic modelling of chalcocite particle oxidation

Energy Technology Data Exchange (ETDEWEB)

Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

1997-12-31

A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

Science.gov (United States)

2009-05-01

methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

Science.gov (United States)

Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2018-08-01

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nonlinear oxidation kinetics of nickel cermets

International Nuclear Information System (INIS)

Galinski, Henning; Bieberle-Huetter, Anja; Rupp, Jennifer L.M.; Gauckler, Ludwig J.

2011-01-01

The oxidation of a cermet of screen-printed nickel (Ni) and gadolinia-doped ceria (CGO) with an approximate median porosity of 50 vol.% has been studied via in situ X-ray diffraction and focused ion beam nanotomography in the temperature range 773-848 K. The oxidation kinetics of Ni to NiO is found to be highly nonlinear with an apparent activation energy of 2.8(2) eV in this temperature range. The nonlinear oxidation kinetics found is in good agreement with theoretical works on oxide growth driven by nonlinear inbuilt fields. Stress-induced Kirkendall void formation has been identified as the physical process that enhances the oxidation of Ni/CGO cermets. Compressive stresses within the Ni matrix result from the thermal expansion mismatch of Ni and CGO and cause plastic deformation as they exceed the yield stress of the Ni matrix. The pore size distribution of Kirkendall voids formed has been measured by FIB nanotomography and shows a significant temperature dependence. It is shown that even one cycle of reoxidation changes irreversibly the microstructure of the cermet which can be interpreted as the onset and main contribution to the mechanical degradation of the cermet.

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

International Nuclear Information System (INIS)

Lunsford, J.L.

1977-10-01

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

Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

Science.gov (United States)

2007-12-01

natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE perchloroethylene HSO5− peroxymonosulfate PNDA p...properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and stability in the subsurface, and develop a standardized natural...chlorinated ethenes For contaminant oxidation by activated S2O82−, it is more difficult to develop a general description of kobs vs. T because there are

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

African Journals Online (AJOL)

The kinetics of oxidation of four aliphatic alcohols in acidic aqueous and micellar media were investigated. The reaction was found to be first-order with respect to both alcohol and oxidant. Pseudo-first-order kinetics were found to be perfectly applicable with ethanol, 1-propanol and 2-propanol while deviation was observed ...

Application of Chemical Kinetics to Deterioration of Foods.

Science.gov (United States)

Labuza, T. P.

1984-01-01

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

Chemical kinetics and oil shale process design

Energy Technology Data Exchange (ETDEWEB)

Burnham, A.K.

1993-07-01

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

The oxidation kinetics of zircaloy - 4 under isothermal conditions

International Nuclear Information System (INIS)

Santos, A.M.M. dos; Cardoso, P.E.

1982-01-01

The oxidation kinetics of zircaloy-4 tubes was studied by means of isothermal tests in the temperature interval 500 0 C to 900 0 C. Dry oxygen and water steam, were used as oxidant agents. The results show that the oxidation kinetics law exhibits a behaviour from cubic to parabolic in the range of the time and temperatures of the experiment. Dry oxygen shows a stronger oxidation effect than water steam. A special mechanical test to study the embrittlement effect in the small samples of zircaloy tubes was used. (Author) [pt

Computer-Aided Construction of Chemical Kinetic Models

Energy Technology Data Exchange (ETDEWEB)

Green, William H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

2014-12-31

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

Oxidation behaviour of Zr-Ce alloys. Kinetic and microstructure aspects

International Nuclear Information System (INIS)

Rouillon, Ludovic

1996-01-01

As Zircaloy alloys are used for fuel rods in pressurized water nuclear reactors, this research thesis aims at studying and improving corrosion resistance of zirconium alloys while maintaining their mechanical properties. It more precisely deals with the kinetic and microstructure aspects of the external corrosion of the cladding by the coolant. In the case of Zircaloys, this corrosion is characterized by a kinetic transition from an initially parabolic to a linear regime. This research aims at intervening on this transition by elaborating zirconium alloys containing an element which stabilizes zirconia, in this case cerium. After having reported a bibliographical study on sheath oxidation, on parameters which influence sheath oxidation kinetics, on zirconia stabilization by doping elements, on the interest of lanthanide oxides, the author reports a feasibility study on the use of cerium (choice and preparation, sintered ceramic characterization, annealing of stabilized zirconia), reports a metallurgical study of Zr-Ce alloys, reports the study of the oxidation behaviour of these alloys (in autoclave, in presence of oxygen, under oxygen and then water) and the characterization of the microstructures of the oxide layers. He finally discusses the relationship between microstructure and oxidation kinetics, the role of cerium in the oxidation process, and the role of water in the oxidation process [fr

Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate

Energy Technology Data Exchange (ETDEWEB)

Gail, S.; Sarathy, S.M.; Thomson, M.J. [Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, ON M5S 3G8 (Canada); Dievart, P.; Dagaut, P. [CNRS, 1C, Ave de la Recherche Scientifique, 45071 Orleans Cedex 2 (France)

2008-12-15

This study examines the effect of unsaturation on the combustion of fatty acid methyl esters (FAME). New experimental results were obtained for the oxidation of methyl (E)-2-butenoate (MC, unsaturated C{sub 4} FAME) and methyl butanoate (MB, saturated C{sub 4} FAME) in a jet-stirred reactor (JSR) at atmospheric pressure under dilute conditions over the temperature range 850-1400 K, and two equivalence ratios ({phi}=0.375,0.75) with a residence time of 0.07 s. The results consist of concentration profiles of the reactants, stable intermediates, and final products, measured by probe sampling followed by on-line and off-line gas chromatography analyses. The oxidation of MC and MB in the JSR and under counterflow diffusion flame conditions was modeled using a new detailed chemical kinetic reaction mechanism (301 species and 1516 reactions) derived from previous schemes proposed in the literature. The laminar counterflow flame and JSR (for {phi}=1.13) experimental results used were from a previous study on the comparison of the combustion of both compounds. Sensitivity analyses and reaction path analyses, based on rates of reaction, were used to interpret the results. The data and the model show that MC has reaction pathways analogous to that of MB under the present conditions. The model of MC oxidation provides a better understanding of the effect of the ester function on combustion, and the effect of unsaturation on the combustion of fatty acid methyl ester compounds typically found in biodiesel. (author)

Oxidation kinetics of amorphous AlxZr1−x alloys

International Nuclear Information System (INIS)

Weller, K.; Wang, Z.M.; Jeurgens, L.P.H.; Mittemeijer, E.J.

2016-01-01

The oxidation kinetics of amorphous Al x Zr 1−x alloys (solid solution) has been studied as function of the alloy composition (0.26 ≤ x ≤ 0.68) and the oxidation temperature (350 °C ≤ T ≤ 400 °C; at constant pO 2  = 1 × 10 5  Pa) by a combinatorial approach using spectroscopic ellipsometry (SE), Auger electron spectroscopy (AES) depth profiling, transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. Thermal oxidation of the am-Al x Zr 1−x alloys results in the formation of an amorphous oxide overgrowth with a thermodynamically preferred singular composition, corresponding to a constant Al ox /Zr ox ratio of 0.5. Both the solubility and the diffusivity of oxygen in the am-Al x Zr 1−x alloy substrate increase considerably with increasing Zr content, in particular for Zr contents above 49 at.% Zr. Strikingly, the oxidation kinetics exhibit a transition from parabolic oxide growth kinetics for Al-rich am-Al x Zr 1−x alloys (x ≥ 0.51) to linear oxide growth kinetics for Zr-rich am-Al x Zr 1−x alloys (x < 0.35). The underlying oxidation mechanism is discussed. It is concluded that the oxidation kinetics of the amorphous Al x Zr 1−x alloys for 0.26 ≤ x ≤ 0.68 and 350 °C ≤ T ≤ 400 °C are governed by: (i) the atomic mobilities of O and Al in the alloy substrate at the reacting oxide/alloy interface, (ii) the solubility of O in the substrate and (iii) the compositional constraint due to the thermodynamically preferred formation of an amorphous oxide phase of singular composition.

Isothermal Kinetics of Diesel Soot Oxidation over La0.7K0.3ZnOy Catalysts

Directory of Open Access Journals (Sweden)

Ram Prasad

2014-10-01

Full Text Available This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions (320-350 oC. Isothermal kinetics data were collected in a mini-semi-batch reactor. Experiments were performed over the best selected catalyst composition La0.7K0.3ZnOy prepared by sol-gel method. Characterization of the catalyst by XRD and FTIR confirmed that La1-xKxZnOy did not exhibit perovskite phase but formed mixed metal oxides. 110 mg of the catalyst-soot mixture in tight contact (10:1 ratio was taken in order to determine the kinetic model, activation energy and Arrhenius constant of the oxidation reaction under the high air flow rate assuming pseudo first order reaction. The activation energy and Arrhenius constant were found to be 138 kJ/mol and 6.46x1010 min-1, respectively. © 2014 BCREC UNDIP. All rights reservedReceived: 26th April 2014; Revised: 27th May 2014; Accepted: 28th June 2014How to Cite: Prasad, R., Kumar, A., Mishra, A. (2014. Isothermal Kinetics of Diesel Soot Oxidation over La0.7K0.3ZnOy Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 9(3: 192-200. (doi: 10.9767/bcrec.9.3.6773.192-200Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.6773.192-200

Radiation-chemical removal of exhaust gases of thermal power stations from nitrogen and sulfur oxides

International Nuclear Information System (INIS)

Gerasimov, G.Ya.; Gerasimova, T.S.; Tokmacheva, I.P.; Fadeev, S.A.; Faminskaya, M.V.

1991-01-01

Problem related to numerical simulation of kinetic processes occuring in waste flue gases of heat and power plants when they are treated by fast electrons are considered. The system of gas-phase chemical reactions describing kinetics of NO transformation in the presence of ammonia was studied. Different groups of reactions resulting in SO 2 oxidation were analyzed. Results of the calculations are compared with experimental data

Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

KAUST Repository

Yin, S. M.

2017-01-18

Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

KAUST Repository

Yin, S. M.; Duanmu, J. J.; Zhu, Yihan; Yuan, Y. F.; Guo, S. Y.; Yang, J. L.; Ren, Z. H.; Han, G. R.

2017-01-01

Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

Chemical kinetics and combustion modeling

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Chemical solution route to self-assembled epitaxial oxide nanostructures.

Science.gov (United States)

Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

2014-04-07

Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.

Effect of strain on bond-specific reaction kinetics during the oxidation of H-terminated (111) Si

International Nuclear Information System (INIS)

Gokce, Bilal; Aspnes, David E.; Gundogdu, Kenan

2011-01-01

Although strain is used in semiconductor technology for manipulating optical, electronic, and chemical properties of semiconductors, the understanding of the microscopic phenomena that are affected or influenced by strain is still incomplete. Second-harmonic generation data obtained during the air oxidation of H-terminated (111) Si reveal the effect of compressive strain on this chemical reaction. Even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si-H up bonds and Si-Si back bonds in the outer layer of Si atoms.

Finite element modelling of the oxidation kinetics of Zircaloy-4 with a controlled metal-oxide interface and the influence of growth stress

International Nuclear Information System (INIS)

Zumpicchiat, Guillaume; Pascal, Serge; Tupin, Marc; Berdin-Méric, Clotilde

2015-01-01

Highlights: We developed two finite element models of zirconium-based alloy oxidation using the CEA Cast3M code to simulate the oxidation kinetics of Zircaloy-4: the diffuse interface model and the sharp interface model. We also studied the effect of stresses on the oxidation kinetics. The main results are: • Both models lead to parabolic oxidation kinetics in agreement with the Wagner’s theory. • The modellings enable to calculate the stress distribution in the oxide as well as in the metal. • A strong effect of the hydrostatic stress on the oxidation kinetics has been evidenced. • The stress gradient effect changes the parabolic kinetics into a sub-parabolic law closer to the experimental kinetics because of the stress gradient itself, but also because of the growth stress increase with the oxide thickness. - Abstract: Experimentally, zirconium-based alloys oxidation kinetics is sub-parabolic, by contrast with the Wagner theory which predicts a parabolic kinetics. Two finite element models have been developed to simulate this phenomenon: the diffuse interface model and the sharp interface model. Both simulate parabolic oxidation kinetics. The growth stress effects on oxygen diffusion are studied to try to explain the gap between theory and experience. Taking into account the influence of the hydrostatic stress and its gradient into the oxygen flux expression, sub-parabolic oxidation kinetics have been simulated. The sub-parabolic behaviour of the oxidation kinetics can be explained by a non-uniform compressive stress level into the oxide layer.

Some concepts in condensed phase chemical kinetics

International Nuclear Information System (INIS)

Adelman, S.A.

1986-01-01

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

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

KAUST Repository

Ciottoli, Pietro P.

2017-08-14

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

Phase-field modeling of corrosion kinetics under dual-oxidants

Science.gov (United States)

Wen, You-Hai; Chen, Long-Qing; Hawk, Jeffrey A.

2012-04-01

A phase-field model is proposed to simulate corrosion kinetics under a dual-oxidant atmosphere. It will be demonstrated that the model can be applied to simulate corrosion kinetics under oxidation, sulfidation and simultaneous oxidation/sulfidation processes. Phase-dependent diffusivities are incorporated in a natural manner and allow more realistic modeling as the diffusivities usually differ by many orders of magnitude in different phases. Simple free energy models are then used for testing the model while calibrated free energy models can be implemented for quantitative modeling.

Ammonia removal in electrochemical oxidation: Mechanism and pseudo-kinetics

International Nuclear Information System (INIS)

Li Liang; Liu Yan

2009-01-01

This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO 2 /Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl - . The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L -1 h -1 and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl - . About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N 2 in the produced gas. The rate at which Cl - lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl - concentration affected the constant of the pseudo zero-order kinetics, expressed by k = 0.0024[Cl - ] x j. The ammonia was reduced to less than 0.5 mg N L -1 after 2 h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements

Kinetic Modeling of a Heterogeneous Fenton Oxidative Treatment of Petroleum Refining Wastewater

Science.gov (United States)

Basheer Hasan, Diya'uddeen; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2014-01-01

The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k 2′), their final oxidation step (k 1′), and the direct conversion to endproducts step (k 3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

Science.gov (United States)

Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

2015-11-05

Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides.

Science.gov (United States)

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-01

In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils. Copyright © 2015 Elsevier Inc. All rights reserved.

Kinetics and mechanism of synthetic CoS oxidation process

Directory of Open Access Journals (Sweden)

Štrbac N.

2006-01-01

Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

Directory of Open Access Journals (Sweden)

Junfeng Yang

2012-01-01

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

Kinetics of high-temperature oxidation of (Ti,Ta)(C,N)-based cermets

International Nuclear Information System (INIS)

Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

2016-01-01

Highlights: • The kinetic of high-temperature oxidation of (Ti,Ta)(C,N)-Co cermets was studied. • A parabolic oxidation kinetic was determined in cermets between 700 °C and 1200 °C. • This parabolic kinetic behaviour is due to the existence of a protective layer. • The protective layer formed was a complex Ti_xTa_1_−_xO_2 oxide with rutile structure. • The oxidation rate is controlled by the Ti and O_2 diffusion through the Ti_xTa_1_−_xO_2. - Abstract: The kinetics of the high-temperature oxidation of titanium–tantalum carbonitride-based cermets with different Ti/Ta ratios was studied. Isothermal oxidation tests were conducted under static air for 48 h at temperatures between 700 °C and 1200 °C. The oxidation satisfied the parabolic kinetics, characteristic of the existence of a protective oxide layer. The apparent activation energy suggests the rate-controlling process during oxidation is the simultaneous inward and outward diffusion of oxygen and titanium, respectively, through the formed protective layer, consisting mainly of a rutile phase. A higher Ta(V) content in the rutile decreased the oxygen diffusivity due to the reduction of oxygen vacancy concentration.

Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

African Journals Online (AJOL)

Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate constant and ...

Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

Energy Technology Data Exchange (ETDEWEB)

Chou, Wei-Lung, E-mail: wlchou@sunrise.hk.edu.tw [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China); Wang, Chih-Ta [Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan Hsien 717, Taiwan (China); Chang, Wen-Chun; Chang, Shih-Yu [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China)

2010-08-15

In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L{sup -1}). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

International Nuclear Information System (INIS)

Chou, Wei-Lung; Wang, Chih-Ta; Chang, Wen-Chun; Chang, Shih-Yu

2010-01-01

In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L -1 ). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation.

Science.gov (United States)

Chou, Wei-Lung; Wang, Chih-Ta; Chang, Wen-Chun; Chang, Shih-Yu

2010-08-15

In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L(-1)). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K. Copyright 2010 Elsevier B.V. All rights reserved.

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

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

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

The kinetics for ammonium and nitrite oxidation under the effect of hydroxylamine.

Science.gov (United States)

Wan, Xinyu; Xiao, Pengying; Zhang, Daijun; Lu, Peili; Yao, Zongbao; He, Qiang

2016-01-01

The kinetics for ammonium (NH4(+)) oxidation and nitrite (NO2(-)) oxidation under the effect of hydroxylamine (NH2OH) were studied by respirometry using the nitrifying sludge from a laboratory-scale sequencing batch reactor. Modified models were used to estimate kinetics parameters of ammonia and nitrite oxidation under the effect of hydroxylamine. An inhibition effect of hydroxylamine on the ammonia oxidation was observed under different hydroxylamine concentration levels. The self-inhibition coefficient of hydroxylamine oxidation and noncompetitive inhibition coefficient of hydroxylamine for nitrite oxidation was estimated by simulating exogenous oxygen-uptake rate profiles, respectively. The inhibitive effect of NH2OH on nitrite-oxidizing bacteria was stronger than on ammonia-oxidizing bacteria. This work could provide fundamental data for the kinetic investigation of the nitrification process.

Study of the oxidation kinetics of the MA 956 superalloy

International Nuclear Information System (INIS)

Garcia-Alonso, M.C.; Gonzalez-Carrasco, J.L.; Escudero, M.L.

1998-01-01

This work deals with the oxidation kinetics of the MA 956 superalloy in the temperature range of 800-1,200 degree centigree for up to 200 h exposure. During oxidation the alloy develops a fine, compact and very well adhered α-alumina layer, the thickness of which increases with increasing time and temperature. The oxidation kinetics obeys a sub parabolic type behaviour. The scale growth seems to occur by two different oxidation mechanisms; above 1,050 degree centigree, the oxidation process would be controlled by α-alumina, and below 900 degree centigree by γ-alumina. (Author) 17 refs

Oxidation kinetics of hazelnut oil treated with ozone

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H. Uzun

2018-01-01

Full Text Available The present study investigates the oxidation kinetics of hazelnut oil ozonated in different treatment periods (1, 5, 60 and 180 min. The kinetic rate constant (k was taken as the inverse of oxidation onset time (To observing a linear relationship from the plot of lnTo to isothermal temperatures (373, 383, 393, and 403 K carried out at differential scanning calorimetry. Kinetic parameters, activation energy (Ea, activation enthalpy (ΔH‡ and entropy (ΔS‡ were calculated based on the Arrhenius equation and activated complex theory. k values showed an exponential rise with the increase of ozone treatment time. The increase in k correlated well with the increase in the peroxide and free fatty acid values of all samples. Ea and ∆H‡ of the ozone treated oils showed a reducing trend and reflected an increased oxidation sensitivity after ozone treatment. Consistently, an increase in ∆S‡ indicated a faster oxidation reaction with an increase in ozone exposure time. However, no significant difference was observed in k, Ea, ΔH‡, ΔS‡ (p < 0.05 as a function of storage period, after the hazelnut oil was treated with ozone for 1 min.

Oxidation kinetics of hazelnut oil treated with ozone

International Nuclear Information System (INIS)

Uzun, H.; Ibanoglu, E.

2017-01-01

The present study investigates the oxidation kinetics of hazelnut oil ozonated in different treatment periods (1, 5, 60 and 180 min). The kinetic rate constant (k) was taken as the inverse of oxidation onset time (To) observing a linear relationship from the plot of ln To to isothermal temperatures (373, 383, 393, and 403 K) carried out at differential scanning calorimetry. Kinetic parameters, activation energy (Ea), activation enthalpy (ΔH‡) and entropy (ΔS‡) were calculated based on the Arrhenius equation and activated complex theory. k values showed an exponential rise with the increase of ozone treatment time. The increase in k correlated well with the increase in the peroxide and free fatty acid values of all samples. Ea and ΔH‡ of the ozone treated oils showed a reducing trend and reflected an increased oxidation sensitivity after ozone treatment. Consistently, an increase in ΔS‡ indicated a faster oxidation reaction with an increase in ozone exposure time. However, no significant difference was observed in k, Ea, ΔH‡, ΔS‡ (p < 0.05) as a function of storage period, after the hazelnut oil was treated with ozone for 1 min. [es

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

Science.gov (United States)

Nagy, Péter

2013-05-01

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

Recycling and Resistance of Petrogenic Particulate Organic Carbon: Implications from A Chemical Oxidation Method

Science.gov (United States)

Zhang, T.; Li, G.; Ji, J.

2013-12-01

Petrogenic particulate organic carbon (OCpetro) represents a small fraction of photosynthetic carbon which escapes pedogenic-petrogenic degradation and gets trapped in the lithosphere. Exhumation and recycling of OCpetro are of significant importance in the global carbon cycle because OCpetro oxidation represents a substantial carbon source to the atmosphere while the re-burial of OCpetro in sediment deposits has no net effect. Though studies have investigated various behaviors of OCpetro in the surface environments (e.g., riverine mobilization, marine deposition, and microbial remineralization), less attention has been paid to the reaction kinetics and structural transformations during OCpetro oxidation. Here we assess the OCpetro-oxidation process based on a chemical oxidation method adopted from soil studies. The employed chemical oxidation method is considered an effective simulation of natural oxidation in highly oxidative environments, and has been widely used in soil studies to isolate the inert soil carbon pool. We applied this chemical method to the OCpetro-enriched black shale samples from the middle-lower Yangtze (Changjiang) basin, China, and performed comprehensive instrumental analyses (element analysis, Fourier transform infrared (FTIR) spectrum, and Raman spectrum). We also conducted step-oxidizing experiments following fixed time series and monitored the reaction process in rigorously controlled lab conditions. In this work, we present our experiment results and discuss the implications for the recycling and properties of OCpetro. Particulate organic carbon concentration of black shale samples before and after oxidation helps to quantify the oxidability of OCpetro and constrain the preservation efficiency of OCpetro during fluvial erosion over large river basin scales. FTIR and Raman analyses reveal clear structural variations on atomic and molecular levels. Results from the step-oxidizing experiments provide detailed information about the reaction

In-Situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes

Science.gov (United States)

2010-12-28

DATES COVERED (From - To) 1/29/10-9/30/10 4. TITLE AND SUBTITLE In situ optical studies of oxidation/reduction kinetics on SOFC cermet anodes 5a...0572 In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Department of Chemistry and Biochemistry Montana State University...of Research In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Principal Investigator Robert Walker Organization

High-temperature steam oxidation kinetics of the E110G cladding alloy

International Nuclear Information System (INIS)

Király, Márton; Kulacsy, Katalin; Hózer, Zoltán; Perez-Feró, Erzsébet; Novotny, Tamás

2016-01-01

In the course of recent years, several experiments were performed at MTA EK (Centre for Energy Research, Hungarian Academy of Sciences) on the isothermal high-temperature oxidation of the improved Russian cladding alloy E110G in steam/argon atmosphere. Using these data and designing additional supporting experiments, the oxidation kinetics of the E110G alloy was investigated in a wide temperature range, between 600 °C and 1200 °C. For short durations (below 500 s) or high temperatures (above 1065 °C) the oxidation kinetics was found to follow a square-root-of-time dependence, while for longer durations and in the intermediate temperature range (800–1000 °C) it was found to approach a cube-root-of-time dependence rather than a square-root one. Based on the results a new best-estimate and a conservative oxidation kinetics model were created. - Highlights: • Steam oxidation kinetics of E110G was studied at MTA EK based on old and new data. • New best-estimate and conservative steam oxidation kinetics were proposed for E110G. • The exponent of oxidation time changed depending on oxidation temperature. • A simple exponential curve was used instead of Arrhenius-type curve for the factor.

Oxidation kinetic changes of UO2 by additive addition and irradiation

International Nuclear Information System (INIS)

You, Gil-Sung; Kim, Keon-Sik; Min, Duck-Kee; Ro, Seung-Gy

2000-01-01

The kinetic changes of air-oxidation of UO 2 by additive addition and irradiation were investigated. Several kinds of specimens, such as unirradiated-UO 2 , simulated-UO 2 for spent PWR fuel (SIMFUEL), unirradiated-Gd-doped UO 2 , irradiated-UO 2 and -Gd-doped UO 2 , were used for these experiments. The oxidation results represented that the kinetic patterns among those samples are remarkably different. It was also revealed that the oxidation kinetics of irradiated-UO 2 seems to be more similar to that of unirradiated-Gd-doped UO 2 than that of SIMFUEL

Kinetics of the gas-phase tritium oxidation reaction

International Nuclear Information System (INIS)

Failor, R.A.

1989-01-01

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

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

Science.gov (United States)

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Chemical kinetics and modeling of planetary atmospheres

Science.gov (United States)

Yung, Yuk L.

1990-01-01

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

Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers

KAUST Repository

Bugler, John

2015-07-16

© 2015 American Chemical Society. This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the first- and second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight- and branched-chained alkanes.

Kinetics of Oxidation of Fe–6Si

Czech Academy of Sciences Publication Activity Database

Lashin, Abdel Rahman; Schneeweiss, Oldřich; Svoboda, Milan

2008-01-01

Roč. 69, č. 5-6 (2008), s. 359-374 ISSN 0030-770X R&D Projects: GA AV ČR IAA1041404 Institutional research plan: CEZ:AV0Z20410507 Keywords : iron silicon * Mössbauer spectroscopy * XRD * iron oxides * oxidation kinetics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.359, year: 2008

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

Science.gov (United States)

Bai, Shirong; Skodje, Rex T

2017-08-17

A new approach is presented for simulating the time-evolution of chemically reactive systems. This method provides an alternative to conventional modeling of mass-action kinetics that involves solving differential equations for the species concentrations. The method presented here avoids the need to solve the rate equations by switching to a representation based on chemical pathways. In the Sum Over Histories Representation (or SOHR) method, any time-dependent kinetic observable, such as concentration, is written as a linear combination of probabilities for chemical pathways leading to a desired outcome. In this work, an iterative method is introduced that allows the time-dependent pathway probabilities to be generated from a knowledge of the elementary rate coefficients, thus avoiding the pitfalls involved in solving the differential equations of kinetics. The method is successfully applied to the model Lotka-Volterra system and to a realistic H 2 combustion model.

Cure kinetics and chemorheology of EPDM/graphene oxide nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Allahbakhsh, Ahmad [Department of Polymer Engineering, Islamic Azad University, South Tehran Branch, 17776-13651 Tehran (Iran, Islamic Republic of); Mazinani, Saeedeh, E-mail: s.mazinani@aut.ac.ir [Amirkabir Nanotechnology Research Institute (ANTRI), Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Kalaee, Mohammad Reza [Department of Polymer Engineering, Islamic Azad University, South Tehran Branch, 17776-13651 Tehran (Iran, Islamic Republic of); Sharif, Farhad [Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of)

2013-07-10

Graphical abstract: - Highlights: • Graphene oxide content and dispersion as effective parameters on cure kinetics. • Graphene oxide as an effective controlling factor of crosslink density. • Interaction of graphene oxide with curing system (ZnO) during curing process. - Abstract: In this study, the effect of graphene oxide on cure behavior of ethylene–propylene–diene rubber (EPDM) nanocomposite is studied. In this regard, the cure kinetics of nanocomposite is studied employing different empirical methods. The required activation energy of nth-order cure process shows about 160 kJ/mol increments upon 5 phr graphene oxide loading compared to 1 phr graphene oxide loading. However, the required activation energy is significantly reduced followed by incorporation of graphene oxide in nanocomposites compared to neat EPDM sample. Furthermore, the effect of graphene oxide on structural properties of nanocomposites during the cure process is studied using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectrometry techniques. As the results show, graphene oxide interestingly affects the structure of zinc oxide during the vulcanization process. This behavior could be probably related to high tendency of zinc oxide to react with oxidized surface of graphene oxide.

To the problem on formation kinetics of absorption and polylayer films in anodic oxidation of cadmium in alkali hydroxides. Kinetics of irreversible absorption of oxide

International Nuclear Information System (INIS)

Grachev, D.K.

1978-01-01

An attempt is made to substantiate the formation of adsorption and polylayer films on cadmium electrode during its oxidation in KOH diluted solutions based on the interpretation of data from methods of the potential control. Using relaxation methods (voltammetry and chronoammetry) the conditions were determined at which irreversible abd sorption kinetics of the passivating oxide turns out to dominate the anodic dissolution process in the KOH 1-0.1 N solutions. Parts of monolayer and polylayer surface filling are shown. Kinetics of monolayer oxide growth is interpreted based on the Temkin-Zeldovich type equation for irreversible adsorption process. Ways of the kinetic equation precision are discussed for its full correspondence with the experiment obtained

Kinetics of oxidation of H2 and reduction of H2O in Ni-YSZ based solid oxide cells

DEFF Research Database (Denmark)

Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

2012-01-01

Reduction of H2O and oxidation of H2 was studied in a Ni-YSZ electrode supported Solid Oxide Cells produced at DTU Energy conversion (former Risø DTU). Polarisation (i-V) and electrochemical impedance spectroscopic characterisation show that the kinetics for reduction of H 2O is slower compared...... to oxidation of H2. The kinetic differences cannot be explained by the reaction mechanisms which are similar in the two cases but are rather an effect of the thermodynamics. The preliminary analysis performed in this study show that the slow kinetic for reduction is partly related to the endothermic nature...... of the reaction, cooling the active electrode, thereby leading to slower kinetics at low current densities. Likewise, the increased kinetic for oxidation was found to be related to the exothermic nature of the reaction, heating the active electrode, and thereby leading to faster kinetics. At higher current...

Generalized kinetic model of reduction of molecular oxidant by metal containing redox

International Nuclear Information System (INIS)

Kravchenko, T.A.

1986-01-01

Present work is devoted to kinetics of reduction of molecular oxidant by metal containing redox. Constructed generalized kinetic model of redox process in the system solid redox - reagent solution allows to perform the general theoretical approach to research and to obtain new results on kinetics and mechanism of interaction of redox with oxidants.

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.

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

African Journals Online (AJOL)

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

Thorium oxide dissolution kinetics for hydroxide and carbonate complexation

International Nuclear Information System (INIS)

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

2002-01-01

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

Kinetic Study of Zn2+ and Cd2+ Ions Sorption by Ceric Oxide Powder

International Nuclear Information System (INIS)

Hassan, H.S.; Abd El-Rahman, K.M.; El Sayed, A.A.

2008-01-01

Ceric Oxide powder was chemically synthesized and characterized using infrared spectra and x-ray diffraction. The sorptive removal of Zinc and Cadmium ions from aqueous waste solution using synthetic ceric oxide powder was investigated using batch technique. Experiments were carried out as a function of ph, particle size, solute concentration and temperature. The uptake of zinc was found to be greater than that of cadmium. A comparison of kinetic models applied to the sorption process of each ion was evaluated for the pseudo first order, the pseudo second order, and homogeneous particle diffusion kinetic models, respectively. The results showed that both the pseudo second order and the homogeneous particle diffusion model (HPDM) were found to best correlate the experimental rate data. The numerical values of the rate constants and particle diffusion coefficients were determined from the graphical representation of the proposed models. Activation energy (Ε a ) and entropy (δ S * ) of activation for each sorption process were also calculated from the linearized form of Arrhenius equation

Oxidative desulfurization: kinetic modelling.

Science.gov (United States)

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

2009-01-30

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

Oxidative desulfurization: Kinetic modelling

International Nuclear Information System (INIS)

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

2009-01-01

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

High temperature oxidation kinetics of dysprosium particles

Energy Technology Data Exchange (ETDEWEB)

Jaques, Brian J.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu

2015-09-25

Highlights: • The oxidation behavior of dysprosium particles was studied from 500 to 1000 °C. • Activation energy in initial region found as 8–25 kJ/mol, depending on atmosphere. • Activation energy in intermediate region found as 80–95 kJ/mol. • The oxide grows at the metal–oxide interface. • Generally, the formed oxide behaved as a p-type semiconductor. - Abstract: Rare earth elements have been recognized as critical materials for the advancement of many strategic and green technologies. Recently, the United States Department of Energy has invested many millions of dollars to enhance, protect, and forecast their production and management. The work presented here attempts to clarify the limited and contradictory literature on the oxidation behavior of the rare earth metal, dysprosium. Dysprosium particles were isothermally oxidized from 500 to 1000 °C in N{sub 2}–(2%, 20%, and 50%) O{sub 2} and Ar–20% O{sub 2} using simultaneous thermal analysis techniques. Two distinct oxidation regions were identified at each isothermal temperature in each oxidizing atmosphere. Initially, the oxidation kinetics are very fast until the reaction enters a slower, intermediate region of oxidation. The two regions are defined and the kinetics of each are assessed to show an apparent activation energy of 8–25 kJ/mol in the initial region and 80–95 kJ/mol in the intermediate oxidation reaction region. The effects of varying the oxygen partial pressure on the reaction rate constant are used to show that dysprosium oxide (Dy{sub 2}O{sub 3}) generally acts as a p-type semiconductor in both regions of oxidation (with an exception above 750 °C in the intermediate region)

Elimination kinetic model for organic chemicals in earthworms.

NARCIS (Netherlands)

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

2010-01-01

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

Chemical kinetics of detonation in some liquid mixtures

Energy Technology Data Exchange (ETDEWEB)

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

2005-09-01

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

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

KAUST Repository

Atef, Nour

2017-02-05

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

Kinetics and oxidation mechanisms of polycrystaline niobium

International Nuclear Information System (INIS)

Paschoal, J.O.A.

1979-01-01

The oxidation kinetics of annealed niobium was determined by thermogravimetric analysis between 450 and 800 0 C and for oxygen pressures varying from 20 to 700 mmHg. The oxidation kinetics of cold worked and/or irradiated niobium for temperatures between 500 and 700 0 C, with oxygen pressures varying from 100 to 300 mmHg. Was also determined. Using X-ray diffraction it was found that the oxide formed in the range of temperature and oxygen pressure considered in this research is γ-Nb 2 O 5 . Optical and scanning eletronic microscopy showed that for annealed niobium oxidized under 600 0 C there was formation of non-uniform oxide layers, containing cracks and pores, presenting very irregular metal/pentoxide interface. The presence of sub-oxide NbOsub(z) platelets was observed in this interface. This sub-oxide platelets where not observed in annealed oxidized niobium samples over 600 0 C; the oxide layers formed were compact. At 800 0 C and the beginning at 700 0 C the interfaces were quite regular. Through microhardness measurements for the metal near the metal/pentoxide interface, the formation of oxygen solid solution was found and the oxygen diffusion coefficient was calculated. The results showed that at 600 0 C the oxygen diffusion coefficient in cold worked niobium is three times larger than the value obtained for annealed niobium. The results suggest that the reaction between annealed niobium and oxygen undaer 600 0 C is controlled by reaction in interface where the oxide layers are not compacted, parcially due to Nb sub(z) platelets formation.(Author) [pt

Kinetic study of Cs+ and Eu3+ ions sorption by zirconium oxide powder

International Nuclear Information System (INIS)

Hanafi, H.A.; Hassan, H.S.; Hamed, M.M.

2009-01-01

Full text: Zirconium oxide powder was chemically synthesized by sol-gel method and characterized using infrared spectra and x-ray diffraction. The sorptive removal of cesium and europium ions from aqueous waste solution using synthetic zirconium oxide powder was investigated using batch technique. Experiments were carried out as a function of pH, time and temperature. The uptake of europium was found to be greater than that of cesium. A comparison of kinetic models applied to the sorption process of each ion was evaluated for the pseudo first order, the pseudo second order, and homogeneous particle diffusion kinetic models, respectively. The results showed that both the pseudo second order and the homogeneous particle diffusion models (HPDM) were found to best correlate the experimental rate data. The numerical values of the rate constants and particle diffusion coefficients were determined from the graphical representation of the proposed models. Activation energy (Ea) and entropy (Δ S*) of activation for each sorption process were also calculated from the linearized form of Arrhenius equation. (author)

Influence of oxalic acid on the dissolution kinetics of manganese oxide

Science.gov (United States)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

Corrosion mechanisms of zirconium alloys - study of the initial oxidation kinetics and of the mechanical behaviour of the metal/oxide system

International Nuclear Information System (INIS)

Parise, M.

1996-12-01

Nuclear fuel claddings are made of zirconium alloys. The conditions of use lead the cladding oxidize outside. The so-formed layers behaves like a thermal barrier and prevents from using oxidized claddings with an oxide thickness larger than 100 μm. The oxidation kinetic is approximately cubic for oxide thicknesses smaller than about 2μm, linear beyond. A kinetic model has been proposed which estimates the post-transition growth rate from the kinetic parameters of the pre-transition state and morphological features of post-transition layers. This work aims at providing the necessary elements to validate this model and studying the layers around the kinetic transition, in order to determine whether the oxidation mechanisms before and after the transition are similar. Thicknesses of the 50 - 500 nm range of the oxide layers are measured by an optical method; pre-transition kinetics are thus precisely determined. The effect of the composition, the thermal treatment and the presence of oxygen in solid solution is studied. The morphological and crystallographic study of the layers show that they exhibit a lot of similarities before and after the kinetic transition. The results concerning the kinetic aspects and the morphology of the post-transition layers point out that the proposed model leads to realistic post-transition growth rates. Furthermore, the kinetic transition corresponds to the appearance of cracks in the oxide layer. The mechanical behaviour of the metal/oxide system has been modelled at different scales. When the specific behaviours of the metal and the oxide are taken into account together with the interface geometry, radial stresses appear, which are high enough to locally open cracks. The appearance and localization of cracks depend on both the interface geometry and the stress distribution in the metal/oxide system. (author)

Chemical Kinetic Modeling of 2-Methylhexane Combustion

KAUST Repository

Mohamed, Samah Y.

2015-03-30

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

Kinetics of chemical reactions initiated by hot atoms

International Nuclear Information System (INIS)

Firsova, L.P.

1977-01-01

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

CHEMSIMUL: A simulator for chemical kinetics

DEFF Research Database (Denmark)

Kirkegaard, P.; Bjergbakke, E.

1999-01-01

CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving theresulting coupled nonlinear ordinary...

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

Science.gov (United States)

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

2015-01-01

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

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

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

Kinetic studies of isooctane partial oxidation over a nickel-based catalyst

International Nuclear Information System (INIS)

Ibrahim, Hussameldin; Idem, Raphael; Aboudheir, Ahmed

2006-01-01

The production of hydrogen (H 2 ) for fuel cell applications in mobile vehicles by reforming technologies such as partial oxidation of various fossil fuels has gained much attention recently. In this study, the production of H 2 by the catalytic partial oxidation of isooctane ((C 8 H 18 ) used here as a surrogate for gasoline) was investigated over alumina (AI 2 O 3 )supported nickel (Ni) catalyst. The work investigated the kinetics of the partial oxidation of isooctane over a stable Ni/□-AI 2 O 3 catalyst in the range of 863 to 913 K, at atmospheric pressure, W/F i c8 in the range of 1.97 to 8.58 g h mol - 1, and molar feed ratio in the range of 2.0 to 8.0 experiments to obtain kinetic data were performed in a 12.7 mm diameter Inconel micro-reactor housed in an electrically controlled furnace. The chemical reaction was then modeled using rate models developed from the Langmuir-Hinshelwood-hougen-Watson (LHHW) and Eley-Rideal (ER) formulations. The model parameters were estimated using an adaptive Gauss-Newton and Marquardi-Levenberg minimization algorithm. Rival models were screened for their thermodynamic consistency and physicochemical significance of estimated parameters. Langmuir-Hinshelwood-hougen-Watson mechanism requiring the dissociative adsorption of isooctane and oxygen on two different sites appeared to be the most likely pathway for the partial oxidation reaction of isooctane. Reaction order with respect to isooctane indicates the strong coverage of nickel by isooctane. The activation energy of 73±3.1 kJ mol - 1 estimated from the LHHW model is consistent with the trend observed with lower hydrocarbons.(Author)

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

Science.gov (United States)

2013-01-01

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

Thermodynamic controls on the kinetics of microbial low-pH Fe(II) oxidation.

Science.gov (United States)

Larson, Lance N; Sánchez-España, Javier; Kaley, Bradley; Sheng, Yizhi; Bibby, Kyle; Burgos, William D

2014-08-19

Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems.

Uranium oxidation kinetics monitored by in-situ X-ray diffraction

Energy Technology Data Exchange (ETDEWEB)

Zalkind, S., E-mail: shimonzl@nrcn.org.il; Rafailov, G.; Halevy, I.; Livneh, T.; Rubin, A.; Maimon, H.; Schweke, D.

2017-03-15

The oxidation kinetics of U-0.1 wt%Cr at oxygen pressures of 150 Torr and the temperature range of 90–150 °C was studied by means of in-situ X-ray diffraction (XRD). A “breakaway” in the oxidation kinetics is found at ∼0.25 μm, turning from a parabolic to a linear rate law. At the initial stage of oxidation the growth plane of UO{sub 2}(111) is the prominent one. As the oxide thickens, the growth rate of UO{sub 2}(220) plane increases and both planes grow concurrently. The activation energies obtained for the oxide growth are Q{sub parabolic} = 17.5 kcal/mol and Q{sub linear} = 19 kcal/mol. Enhanced oxidation around uranium carbide (UC) inclusions is clearly observed by scanning electron microscopy (SEM).

KinChem: A Computational Resource for Teaching and Learning Chemical Kinetics

Science.gov (United States)

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

2014-01-01

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

Kinetic and reaction pathways of methanol oxidation on platinum

International Nuclear Information System (INIS)

McCabe, R.W.; McCready, D.F.

1986-01-01

Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

Chemical and kinetic equilibrations via radiative parton transport

International Nuclear Information System (INIS)

Zhang Bin; Wortman, Warner A

2011-01-01

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

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

Science.gov (United States)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

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

Science.gov (United States)

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

2015-09-01

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

Mechanism and kinetics of the oxidation of synthetic alpha-NiS

Directory of Open Access Journals (Sweden)

BOYAN BOYANOV

2008-02-01

Full Text Available The results of an investigation of the mechanism and kinetics of the oxidation process of synthetic a-NiS are presented in this paper. The mechanism of a-NiS oxidation was investigated based on the comparative analysis of DTA–TG–DTG and XRD results, as well as the constructed phase stability diagrams (PSD for the Ni–S–O system. The kinetic investigations of the oxidation process were performed under isothermal conditions (temperature range 823–1073 K. The obtained degrees of desulfurization were used in the calculation process according to the Sharp model and the kinetic parameters, including the activation energies and the rate constants of the characteristic reactions, for the oxidation of a-NiS were determined. These results enabled the formulation of a kinetic equation for the desulfurization process: ‑ln(1−a = k1t = 27.89 exp(–9860/Tt, with an activation energy of 82±4 kJ mol-1, for the first stage of the process and –ln (1 − a = k2t = 1.177 exp(–4810/Tt, with an activation energy of 40±2 kJ mol-1, for the second stage.

Kinetics of molybdenite oxidizing leaching in alkali medium by ozone

International Nuclear Information System (INIS)

Medvedev, A.S.; Sokratova, N.B.; Litman, I.V.; Zelikman, A.N.

1985-01-01

On the basis of investigation of the process kinetics proposed is a model of oxidizing leaching of molybdenite in alkali medium while ozonization of the solution by ozoneair mixture. A kinetic equation is derived, that describes experimental data satisfactorily

Kinetics and mechanism of oxidation of chloramphenicol by 1

Indian Academy of Sciences (India)

Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with ...

Study the oxidation kinetics of uranium using XRD and Rietveld method

Science.gov (United States)

Zhang, Yanzhi; Guan, Weijun; Wang, Qinguo; Wang, Xiaolin; Lai, Xinchun; Shuai, Maobing

2010-03-01

The surface oxidation of uranium metal has been studied by X-ray diffraction (XRD) and Rietveld method in the range of 50~300°C in air. The oxidation processes are analyzed by XRD to determine the extent of surface oxidation and the oxide structure. The dynamics expression for the formation of UO2 was derived. At the beginning, the dynamic expression was nonlinear, but switched to linear subsequently for uranium in air and humid oxygen. That is, the growth kinetics of UO2 can be divided into two stages: nonlinear portion and linear portion. Using the kinetic data of linear portion, the activation energy of reaction between uranium and air was calculated about 46.0 kJ/mol. However the content of oxide as a function of time was linear in humid helium ambience. Contrast the dynamics results, it prove that the absence of oxygen would accelerate the corrosion rate of uranium in the humid gas. We can find that the XRD and Rietveld method are a useful convenient method to estimate the kinetics and thermodynamics of solid-gas reaction.

A new quantitative analysis on nitriding kinetics in the oxidized Zry-4 at 900-1200 .deg. C

Energy Technology Data Exchange (ETDEWEB)

Park, Sanggi [ACT Co. Ltd., Daejeon (Korea, Republic of)

2016-10-15

Two major roles of nitrogen on the zirconium based cladding degradation were identified: mechanical degradation of the cladding, and the additional chemical heat release. It has long been known that accelerated oxidation can occur in air due to the nitrogen. In addition, significant uptake of nitrogen can also occur. The nitriding of pre-oxidized zirconium based alloys leads to micro porous and less coherent oxide scales. This paper aims to quantitatively investigate the nitriding mechanism and kinetics by proposing a new methodology that is coupled with the mass balance analysis and the optical microscope image processing analysis. A new quantitative analysis methodology is described in chapter 2 and the investigation of the nitriding kinetics is performed in chapter 3. The experimental details are previously reported in. Previously only qualitative analysis was performed in, and hence the quantitative analysis will be performed in this paper. In this paper, the nitriding kinetics and mechanism were quantitatively analyzed by the new proposed analysis methods: the mass balance analysis and the optical microscope image processing analysis. Using these combined methods, the mass gain curves and the optical microscopes are analyzed in very detail, and the mechanisms of nitriding accelerated, stabilized and saturated behaviors were well understood. This paper has two very distinctive achievements as follows: 1) Development of very effective quantitative analysis methods only using two main results of oxidation tests: No detailed analytical sample measurements (e.g. TEM, EPMA and so on.) were required. These methods can effectively reduce the cost and effort of the post-test investigation. 2) The first identification of the nitriding behaviors and its very accurate analysis in a quantitative way. Based on this quantitative analysis results on the nitriding kinetics, these new findings will contribute significantly the understanding the air oxidation behaviors and model

Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

Directory of Open Access Journals (Sweden)

Anna Kachina

2007-01-01

Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

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

International Nuclear Information System (INIS)

Lalauze, Rene

1973-01-01

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

Time-dependent postirradiation oxidative chemical changes in dehydrated egg products

International Nuclear Information System (INIS)

Katusin-Razem, B.; Mihaljevic, B.; Razem, D.

1992-01-01

Radiation-induced oxidative chemical changes in whole egg and egg yolk powder were followed in time after irradiation as a function of dose, dose rate, and storage atmosphere. In evacuated samples of whole egg powder the decay of lipid hydroperoxides (LOOH) was pseudo-first order (kappa = 0.088 day-1), while carotenoids did not decay at all. In the presence of air both lipid hydroperoxides and carotenoids decayed during postirradiation storage. The decay of LOOH could be treated by dispersive kinetics with the measure of dispersion, alpha = 0.51 +/- 0.05, independent of dose, and the effective lifetime tau inversely related to dose. The decay of carotenoids could also be treated by dispersive kinetics, with the values of alpha decreasing with increasing dose. The effective lifetimes of carotenoids did not depend on dose in samples irradiated in vacuum. In samples irradiated and stored in air the effective lifetimes decreased with dose, faster in egg yolk than in whole egg powder. The complex nature of postirradiation kinetics in solid food systems is discussed

Kinetic investigations of quinoline oxidation by ferrate(VI).

Science.gov (United States)

Luo, Zhiyong; Li, Xueming; Zhai, Jun

2016-01-01

Quinoline is considered as one of the most toxic and carcinogenic compounds and is commonly found in industrial wastewaters, which require treatment before being discharged. Removal of quinoline by the use of an environmentally friendly oxidant, potassium ferrate(VI) (K2FeO4), was assessed by studying the kinetics of the oxidation of quinoline by ferrate(VI) (Fe(VI)) as a function of pH (8.53-10.53) and temperature (21-36°C) in this work. The reaction of quinoline with Fe(VI) was found to be first order in Fe(VI), half order in quinoline, and 1.5 order overall. The observed rate constant at 28°C decreased non-linearly from 0.5334 to 0.2365 M(-0.5) min(-1) with an increase in pH from 8.53 to 10.03. Considering the equilibria of Fe(VI) and quinoline, the reaction between quinoline and Fe(VI) contained two parallel reactions under the given pH conditions. The individual rate constants of these two reactions were determined. The results indicate that the protonated species of Fe(VI) reacts more quickly with quinoline than the deprotonated form of Fe(VI). The reaction activation energy Ea was obtained to be 51.44 kJ·mol(-1), and it was slightly lower than that of conventional chemical reaction. It reveals that the oxidation of quinoline by Fe(VI) is feasible in the routine water treatment.

Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change

Directory of Open Access Journals (Sweden)

I. J. George

2007-08-01

Full Text Available The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NO_x-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl sebacate (BES particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS and scanning mobility particle sizer (SMPS was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O₃ in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ₀=1.3 (±0.4, confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.

Fundamental aspects of plasma chemical physics kinetics

CERN Document Server

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

2016-01-01

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

Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

National Research Council Canada - National Science Library

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

2002-01-01

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

Port wine oxidation management: a multiparametric kinetic approach.

Science.gov (United States)

Martins, Rui Costa; Monforte, Ana Rita; Silva Ferreira, António

2013-06-05

Port wine is a flagship fortified wine of Portugal, which undergoes a particularly long aging period, developing a dynamic sensory profile over time, responsible for several wine categories, which is dependent upon the type of aging (bottle or barrel). Therefore, the quality of the product is dependent upon the chemical mechanisms occurring during the aging process, such as oxidation or Maillard reactions. To attain the desired quality management, it is necessary to understand how technological parameters, such as temperature or oxygen exposure, affect the kinetics of the formation of key odorants, such as sotolon. There is a lack of information about the impact of the storage conditions (oxygen and temperature) on Port wine quality. In this study, the effect of these two parameters were investigated to increase the knowledge database concerning aging management of Port wines. It was found that sotolon formation is highly dependent upon oxygen and temperature. There is however a synergistic effect between these two parameters that could significantly increase the concentration. The kinetic parameters of oxygen, sotolon, and other compounds related to Port aging (cis- and trans-5-hydroxy-2-methyl-1,3-dioxan, 2-furfural, 5-hydroxy-methyl-furfural, and 5-methyl-furfural) are also reported. Kinetic models with Monte Carlo simulations, where the oxygen permeability dispersion and temperature are the parameters under evaluation, were applied. On the basis of the modeling predictions, it would seem that the temperature of a cellar would have a more significant impact on the Port wines stored in containers where the oxygen intake is higher (barrels) when compared to containers with low oxygen permeability (bottles using cork stoppers).

Hungarian University Students' Misunderstandings in Thermodynamics and Chemical Kinetics

Science.gov (United States)

Turanyi, Tamas; Toth, Zoltan

2013-01-01

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

Operational High Resolution Chemical Kinetics Simulation, Phase I

Data.gov (United States)

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

Modelling of elementary kinetics of H2 and CO oxidation on ceria pattern cells

International Nuclear Information System (INIS)

Patel, HC; Tabish, AN; Aravind, PV

2015-01-01

Elementary kinetic mechanisms of fuel oxidation on ceria have not been dealt with in detail in literature. An elementary kinetic model is developed considering charge transfer and adsorption steps for electrochemical H 2 and CO oxidation on ceria. The reaction chemistry is solved by fitting previously obtained impedance spectra for H 2 and CO oxidation on ceria. The rate determining step is found to be the charge transfer rather than the adsorption for both H 2 and CO. A method is presented to extend the kinetics obtained from pattern anodes to macroscopic simulations in which the activation overvoltage can be calculated on the basis of elementary kinetics.

Study the oxidation kinetics of uranium using XRD and Rietveld method

Energy Technology Data Exchange (ETDEWEB)

Zhang Yanzhi; Guan Weijun; Wang Qinguo; Wang Xiaolin; Lai Xinchun; Shuai Maobing, E-mail: yanzhizh@163.com [China Academy of Engineering Physics, PO Box 919-71, Mianyang, Sichuan, 621900 (China)

2010-03-15

The surface oxidation of uranium metal has been studied by X-ray diffraction (XRD) and Rietveld method in the range of 50{approx}300deg. C in air. The oxidation processes are analyzed by XRD to determine the extent of surface oxidation and the oxide structure. The dynamics expression for the formation of UO{sub 2} was derived. At the beginning, the dynamic expression was nonlinear, but switched to linear subsequently for uranium in air and humid oxygen. That is, the growth kinetics of UO{sub 2} can be divided into two stages: nonlinear portion and linear portion. Using the kinetic data of linear portion, the activation energy of reaction between uranium and air was calculated about 46.0 kJ/mol. However the content of oxide as a function of time was linear in humid helium ambience. Contrast the dynamics results, it prove that the absence of oxygen would accelerate the corrosion rate of uranium in the humid gas. We can find that the XRD and Rietveld method are a useful convenient method to estimate the kinetics and thermodynamics of solid-gas reaction.

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

Science.gov (United States)

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

2018-02-01

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

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.

2010-11-04

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

2010-01-01

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations.

Science.gov (United States)

Gould, Ian R; Wosinska, Zofia M; Farid, Samir

2006-01-01

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

Levofloxacin oxidation by ozone and hydroxyl radicals: kinetic study, transformation products and toxicity.

Science.gov (United States)

Hamdi El Najjar, Nasma; Touffet, Arnaud; Deborde, Marie; Journel, Romain; Leitner, Nathalie Karpel Vel

2013-10-01

This work was carried out to investigate the fate of the antibiotic levofloxacin upon oxidation with ozone and hydroxyl radicals. A kinetic study was conducted at 20 °C for each oxidant. Ozonation experiments were performed using a competitive kinetic method with carbamazepin as competitor. Significant levofloxacin removal was observed during ozonation and a rate constant value of 6.0×10(4) M(-1) s(-1) was obtained at pH 7.2. An H2O2/UV system was used for the formation of hydroxyl radicals HO. The rate constant of HO was determined in the presence of a high H2O2 concentration. The kinetic expressions yielded a [Formula: see text] value of 4.5×10(9) M(-1) s(-1) at pH 6.0 and 5.2×10(9) M(-1) s(-1) at pH 7.2. These results were used to develop a model to predict the efficacy of the ozonation process and pharmaceutical removal was estimated under different ozonation conditions (i.e. oxidant concentrations and contact times). The results showed that levofloxacin was completely degraded by molecular ozone during ozonation of water and that hydroxyl radicals had no effect in real waters conditions. Moreover, LC/MS/MS and toxicity assays using Lumistox test were performed to identify ozonation transformation products. Under these conditions, four transformation products were observed and their chemical structures were proposed. The results showed an increase in toxicity during ozonation, even after degradation of all of the observed transformation products. The formation of other transformation products not identified under our experimental conditions could be responsible for the observed toxicity. These products might be ozone-resistant and more toxic to Vibrio fisheri than levofloxacin. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

NARCIS (Netherlands)

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

2017-01-01

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

Influence of chemical composition of zirconium alloy E110 on embrittlement under LOCA conditions - Part 1: Oxidation kinetics and macrocharacteristics of structure and fracture

Science.gov (United States)

Nikulin, S. A.; Rozhnov, A. B.; Belov, V. A.; Li, E. V.; Glazkina, V. S.

2011-11-01

Exploratory investigations of the influence of alloying and impurity content in the E110 alloy cladding tubes on the behavior under conditions of Loss of Coolant Accidents (LOCA) has been performed. Three alloys of E110 type have been tested: E110 alloy of nominal composition Zr-1%Nb (E110), E110 alloy of modified composition Zr-1%Nb-0.12%Fe-0.13%O (E110M), E110 alloy of nominal composition Zr-1%Nb with reduced impurity content (E110G). Alloys E110 and E110M were manufactured on the electrolytic basis and alloy E110G was manufactured on the basis of zirconium sponge. The high temperature oxidation tests in steam ( T = 1100 °C, 18% of equivalent cladding reacted (ECR)) have been conducted, kinetics of oxidation was investigated. Quantitative research of structure and fracture macrocharacteristics was performed by means of optical and electron microscopy. The results received were compared with the residual ductility of specimens. The results of the investigation showed the existence of "breakaway oxidation" kinetics and white spalling oxide in E110 and E110M alloys while the specimen oxidation kinetics in E110G alloy was characterized by a parabolic law and specimens had a dense black oxide. Oxygen and iron alloying in the E110 alloy positively changed the macrocharacteristics of structure and fracture. However, in general, it did not improve the resistance to embrittlement in LOCA conditions apparently because of a strong impurity influence caused by electrolytic process of zirconium production.

Composition dependence of the kinetics and mechanisms of thermal oxidation of titanium-tantalum alloys

International Nuclear Information System (INIS)

Park, Y.S.; Butt, D.P.

1999-01-01

The oxidation behavior of titanium-tantalum alloys was investigated with respective concentrations of each element ranging from 0 to 100 wt.%. Alloys were exposed to argon-20% oxygen at 800 to 1400 C. The slowest oxidation rates were observed in alloys with 5--20% Ta. The oxidation kinetics of alloys containing less than approximately 40% Ta were approximately parabolic. Pure Ta exhibited nearly linear kinetics. Alloys containing 50% or more Ta exhibited paralinear kinetics. The activation energies for oxidation ranged between 232 kJ/mole for pure Ti and 119 kJ/mole for pure Ta, with the activation energies of the alloys falling between these values and generally decreasing with increasing Ta content. The activation energies for oxidation of the end members, Ti and Ta, agree well with published values for the activation energies for diffusion of oxygen in α-Ti and Ta. Scale formation in the alloys was found to be complex exhibiting various layers of Ti-, Ta-, and TiTa-oxides. The outermost layer of the oxidized alloys was predominantly rutile (TiO 2 ). Beneath the TiO 2 grew a variety of other oxides with the Ta content generally increasing with proximity to the metal-oxide interface. It was found that the most oxidation-resistant alloys had compositions falling between Ti-5Ta and Ti-15Ta. Although Ta stabilizes the β-phase of Ti, the kinetics of oxidation appeared to be rate limited by oxygen transport through the oxygen-stabilized α-phase. However, the kinetics are complicated by the formation of a complex oxide, which cracks periodically. Tantalum appears to increase the compositional range of oxygen-stabilized α-phase and reduces both the solubility of oxygen and diffusivity of Ti in the α- and β-phases

A physiologically based kinetic model for bacterial sulfide oxidation.

Science.gov (United States)

Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

2013-02-01

In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics and mechanism of methane oxidation in supercritical water

International Nuclear Information System (INIS)

Rofer, C.K.; Streit, G.E.

1988-10-01

This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

Kinetic study of the alkaline metals oxidation by dry oxygen

International Nuclear Information System (INIS)

Touzain, Ph.

1967-06-01

The oxidation of lithium, sodium, potassium, rubidium, cesium and sodium-potassium alloys by dry oxygen is studied at several temperatures and in the oxygen pressure range 40 to 400 mmHg. One distinguishes three different oxidation behaviours (inflammation, ignition and slow combustion) whose zones are precised in function of the temperature. The slow oxidation kinetic laws, the composition of oxides and the motive of oxides colorations are determined. At least, the experimental data are construed theoretically. (author) [fr

Kinetic studies on the degradation of crystal violet by the Fenton oxidation process.

Science.gov (United States)

Wu, H; Fan, M M; Li, C F; Peng, M; Sheng, L J; Pan, Q; Song, G W

2010-01-01

The degradation of dye crystal violet (CV) by Fenton oxidation process was investigated. The UV-Vis spectrogram has shown that CV can be degraded effectively by Fenton oxidation process. Different system variables namely initial H(2)O(2) concentration, initial Fe(2 + ) concentration and reaction temperature, which have effect on the degradation of CV by Fenton oxidation process, have been studied systematically. The degradation kinetics of CV was also elucidated based on the experimental data. The degradation of CV obeys the first-order reaction kinetics. The kinetic model can be described as k=1.5 exp(-(7.5)/(RT))[H(2)O(2)](0)(0.8718)[Fe(2+)](0)(0.5062). According to the IR spectrogram, it is concluded that the benzene ring of crystal violet has been destroyed by Fenton oxidation. The result will be useful in treating dyeing wastewater containing CV by Fenton oxidation process.

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

Science.gov (United States)

Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

Smouldering Combustion of Soil Organic Matter: Inverse Modelling of the Thermal and Oxidative Degradation Kinetics

Science.gov (United States)

Huang, Xinyan; Rein, Guillermo

2013-04-01

Smouldering combustion of soil organic matter (SOM) such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this work, a kinetic model, including 3-step chemical reactions and 1-step water evaporation is proposed to describe drying, pyrolysis and oxidation behaviour of peat. Peat is chosen as the most important type of SOM susceptible to smoudering, and a Chinese boreal peat sample is selected from the literature. A lumped model of mass loss based on four Arrhenius-type reactions is developed to predict its thermal and oxidative degradation under a range of heating rates. A genetic algorithm is used to solve the inverse problem, and find a group of kinetic and stoichiometric parameters for this peat that provides the best match to the thermogravimetric (TG) data from literature. A multi-objective fitness function is defined using the measurements of both mass loss and mass-loss rate in inert and normal atmospheres under a range of heating rates. Piece-wise optimization is conducted to separate the low temperature drying (450 K). Modelling results shows the proposed 3-step chemistry is the unique simplest scheme to satisfy all given TG data of this particular peat type. Afterward, this kinetic model and its kinetic parameters are incorporated into a simple one-dimensional species model to study the relative position of each reaction inside a smoulder front. Computational results show that the species model agrees with experimental observations. This is the first time that the smouldering kinetics of SOM is explained and predicted, thus helping to understanding this important natural and widespread phenomenon.

Oxidation kinetics of a Pb-64 at.% In single-phase alloy

International Nuclear Information System (INIS)

Zhang, M.X.; Chang, Y.A.; Marcotte, V.C.

1991-01-01

The solid-state oxidation kinetics of a Pb-64 at.% IN(50 wt.%) single-phase alloy were studied from room temperature to 150C using AES (Auger Electron Spectroscopy) depth profiling technique. The general oxidation behavior of this alloy is different from that of a Pb-3 at.% In alloy but similar to that of a Pb-30 at.% In alloy. The oxide formed on this alloy is almost pure In oxide (In 2 O 3 ) with the possible existence of some In suboxide near the oxide/alloy interface. At room temperature, oxidation of the alloy follows a direct logarithmic law, and the results can be described by the model proposed previously by Zhang, Chang, and Marcotte. At temperatures higher than 75C, rapid oxidation occurred initially followed by a slower parabolic oxidation at longer time. These data were described quantitatively by the model which assumes the existence of short-circuit diffusion in addition to lattice diffusion in the oxide as proposed by Smeltzer, Haering, and Kirkaldy. The effects of alloy composition in the oxidation kinetics of (pb, In) alloy are also examined by comparing the data for Pb-3, 30, and 64 at.% In alloys

Behaviour of defective CANDU fuel: fuel oxidation kinetic and thermodynamic modelling

International Nuclear Information System (INIS)

Higgs, J.

2005-01-01

The thermal performance of operating CANDU fuel under defect conditions is affected by the ingress of heavy water into the fuel element. A mechanistic model has been developed to predict the extent of fuel oxidation in defective fuel and its affect on fuel thermal performance. A thermodynamic treatment of such oxidized fuel has been performed as a basis for the boundary conditions in the kinetic model. Both the kinetic and thermodynamic models have been benchmarked against recent experimental work. (author)

A new improvement on a chemical kinetic model of primary reference fuel for multi-dimensional CFD simulation

International Nuclear Information System (INIS)

Zhen, Xudong; Wang, Yang; Liu, Daming

2016-01-01

Highlights: • A new optimized chemical kinetic mechanism for PRF is developed. • New mechanism optimization is performed based on the CHEMKIN simulations. • More reactions of C_0–C_1 oxidation are added in the present mechanism. • Good performance is achieved of mechanism by validating various reactors and operating conditions. - Abstract: In the present study, for the multi-dimensional CFD (computational fluid dynamics) combustion simulations of internal combustion engines, a new optimized chemical kinetic reaction mechanism for the oxidation of PRF (primary reference fuel) instead of gasoline has been developed. In order to carry out the in-depth research for combustion phenomenon of internal combustion engines, an optimized reduced PRF mechanism including more intermediate species and radicals was developed. The developed mechanism contains of iso-octane (C_8H_1_8) and n-heptane (C_7H_1_6) surrogates, which contains of 51-species and 193 reactions. Compared with many other mechanisms of PRF, more reactions of C_0–C_1 oxidation (100 reactions) are added in the present mechanism. In order to improve the performances of the model, the developed mechanism focused on the improvement through the prediction of the ignition delay time. The developed mechanism has been validated against various experimental and simulation data including shock tube data, laminar flame speed data and HCCI (homogeneous charge compression ignition) engine data. The results showed that the developed PRF mechanism was agreements with the experimental data and other approved reduced mechanisms, and it could be applied to the multi-dimensional CFD simulations for internal combustion engines.

Reverse Stability Kinetics of Meat Pigment Oxidation in Aqueous Extract from Fresh Beef.

Science.gov (United States)

Frelka, John C; Phinney, David M; Wick, Macdonald P; Heldman, Dennis R

2017-12-01

The use of kinetic models is an evolving approach to describing quality changes in foods during processes, including storage. Previous studies indicate that the oxidation rate of myoglobin is accelerated under frozen storage conditions, a phenomenon termed reverse stability. The goal of this study was to develop a model for meat pigment oxidation to incorporate the phenomenon of reverse stability. In this investigation, the model system was an aqueous extract from beef which was stored under a range of temperatures, both unfrozen and frozen. The kinetic analysis showed that in unfrozen solutions, the temperature dependence of oxidation rate followed Arrhenius kinetics. However, under in frozen solutions the rate of oxidation increased with decreasing temperature until reaching a local maximum around -20 °C. The addition of NaCl to the model system increased oxidation rates at all temperatures, even above the initial freezing temperature. This observation suggests that this reaction is dependent on the ionic strength of the solution as well as temperature. The mechanism of this deviant kinetic behavior is not fully understood, but this study shows that the interplay of temperature and composition on the rate of oxidation of meat pigments is complicated and may involve multiple mechanisms. A better understanding of the kinetics of quality loss in a meat system allows for a re-examination of the current recommendations for frozen storage. The deviant kinetic behavior observed in this study indicates that the relationship between quality loss and temperature in a frozen food is not as simple as once thought. Product-specific recommendations could be implemented in the future that would allow for a decrease in energy consumption without a significant loss of quality. © 2017 Institute of Food Technologists®.

Kinetic investigation of vanadium (V)/(IV) redox couple on electrochemically oxidized graphite electrodes

International Nuclear Information System (INIS)

Wang, Wenjun; Wei, Zengfu; Su, Wei; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

2016-01-01

Highlights: • The VO_2"+/VO"2"+ redox reaction of the electrode could be facilitated to some extent with the increasing anodic corrosion. • A real reaction kinetic equation for the oxidation of VO"2"+ on the electrochemically oxidized electrode has been firstly obtained. • The establishment of the kinetic equation is conducive to predict polarization behaviors of the electrodes in engineering application. - Abstract: The morphology, surface composition, wettability and the kinetic parameters of the electrochemically oxidized graphite electrodes obtained under different anodic polarization conditions have been examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), contact angle measurements, steady-state polarization and cyclic voltammetry (CV) tests, with an attempt to investigate the inherent correlation between the physicochemical properties and the kinetic characteristics for carbon electrodes used in an all-vanadium redox flow battery (VRFB). When the anodic polarization potential raises up to 1.8 V vs. SCE, the anodic corrosion of the graphite might happen and a large number of oxygen-containing functional groups generate. The VO_2"+/VO"2"+ redox reaction can be facilitated and the reaction reversibility tends to become better with the increasing anodic potential, possibly owing to the increased surface oxides and the resulting improved wettability of the electrode. Based on this, a real reaction kinetic equation for the oxidation of VO"2"+ has been obtained on the electrode polarized at 1.8 V vs. SCE and it can be also well used to predict the polarization behavior of the oxidized electrode in vanadium (IV) acidic solutions.

Microfluidic photoinduced chemical oxidation for Ru(bpy)33+ chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation.

Science.gov (United States)

Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A J; Suliman, Fakhr Eldin O

2017-08-05

For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy) 3 2+ CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy) 3 2+ CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N=3 or above for 1μgmL -1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81×10 -10 M compared to most lowest ever reported 6×10 -9 M. Earlier, penicillamine was detected at 0.1μgmL -1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82ngmL -1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under photoinduced

Microfluidic photoinduced chemical oxidation for Ru(bpy)33 + chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation

Science.gov (United States)

Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A. J.; Suliman, Fakhr Eldin O.

2017-08-01

For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy)32 + CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy)32 + CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N = 3 or above for 1 μgmL- 1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81 × 10- 10 M compared to most lowest ever reported 6 × 10- 9 M. Earlier, penicillamine was detected at 0.1 μg mL- 1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82 ng mL- 1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under

Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

African Journals Online (AJOL)

NICOLAAS

The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess .... kinetics experiments were performed at 25.0 ± 0.1 °C and at an ..... thiourea compounds with potent anti-HIV activity.

Simplified kinetic models of methanol oxidation on silver

DEFF Research Database (Denmark)

Andreasen, A.; Lynggaard, H.; Stegelmann, C.

2005-01-01

Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

A kinetic model for chemical neurotransmission

Science.gov (United States)

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

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

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

Science.gov (United States)

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

2011-01-01

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

Zirconium metal-water oxidation kinetics. V. Oxidation of Zircaloy in high pressure steam

International Nuclear Information System (INIS)

Pawel, R.E.; Cathcart, J.V.; Campbell, J.J.; Jury, S.H.

1977-12-01

A series of scoping tests to determine the influence of steam pressure on the isothermal oxidation kinetics of Zircaloy-4 PWR tubing was undertaken. The oxidation experiments were conducted in flowing steam at 3.45, 6.90, and 10.34 MPa (500, 1000, and 1500 psi) at 905 0 C (1661 0 F), and at 3.45 and 6.90 MPa at 1101 0 C (2014 0 F). A comparison of the results of these experiments with those obtained for oxidation in steam at atmospheric pressure under similar conditions indicated that measurable enhancement of the oxidation rate occurred with increasing pressure at 905 0 C, but not at 1100 0 C

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

NARCIS (Netherlands)

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

1976-01-01

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

Zirconium metal-water oxidation kinetics. III. Oxygen diffusion in oxide and alpha Zircaloy phases

International Nuclear Information System (INIS)

Pawel, R.E.

1976-10-01

The reaction of Zircaloy in steam at elevated temperature involves the growth of discrete layers of oxide and oxygen-rich alpha Zircaloy from the parent beta phase. The multiphase, moving boundary diffusion problem involved is encountered in a number of important reaction schemes in addition to that of Zircaloy-oxygen and can be completely (albeitly ideally) characterized through an appropriate model in terms of oxygen diffusion coefficients and equilibrium concentrations for the various phases. Conversely, kinetic data for phase growth and total oxygen consumption rates can be used to compute diffusion coefficients. Equations are developed that express the oxygen diffusion coefficients in the oxide and alpha phases in terms of the reaction rate constants and equilibrium solubility values. These equations were applied to recent experimental kinetic data on the steam oxidation of Zircaloy-4 to determine the effective oxygen diffusion coefficients in these phases over the temperature range 1000--1500 0 C

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

Science.gov (United States)

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

2016-05-01

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

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 1; Oxidation Kinetics

Science.gov (United States)

Raj, S. V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Kinetics of the oxidation of Ba2YCu3O/sub x/ ceramics

International Nuclear Information System (INIS)

O'Bryan, H.M.; Gallagher, P.K.

1988-01-01

The kinetics of the oxidation of dense and porous samples of Ba 2 YCu 3 O/sub x/ ceramic have been determined by gravimetric analysis at 400--700 0 C. At 600 0 C and above, the rate decreases as the thickness of the oxidized layer increases. At 500 0 C and below, the kinetics show a linear relation that indicates that the oxidized layer does not protect the ceramic. Dilatometric, microscopic, and high-temperature x-ray data suggest that fractures in the oxide layer at the lower temperatures are caused by the large volume decrease that accompanies the change in oxygen stoichiometry

Modeling chemical kinetics of avocado oil ethanolysis catalyzed by solid glycerol-enriched calcium oxide

International Nuclear Information System (INIS)

Avhad, M.R.; Sánchez, M.; Bouaid, A.; Martínez, M.; Aracil, J.; Marchetti, J.M.

2016-01-01

Highlights: • Raw materials for biodiesel production can be obtained from the natural resources. • The glycerol-enriched CaO catalyst was tested for the ethanolysis of avocado oil. • CaO synthesized through the thermal treatment of Mytilus Galloprovincialis shells. • The ethanol-adsorption step controlled the overall ethanolysis process. • The physico-chemical properties of avocado oil and FAEEs is presented. - Abstract: The catalytic activity of glycerol-enriched calcium oxide for the alcoholysis reaction between avocado oil and ethanol was investigated. The calcium oxide was derived from Mytilus Galloprovincialis shells. This study systematically examined the influence of temperature, ethanol-to-oil molar ratio, and the catalyst amount on the variation in the concentration of triacylglycerols and biodiesel with reaction time. The interaction between the reaction variables (ethanol-to-oil molar ratio and catalyst amount), their influence on the ethanolysis process, and the optimum variables affecting the process were determined through the response surface methodology. A previously developed mathematical model was applied for the current ethanolysis process, and the model parameters were determined. The ethanolysis reaction occurred between the surface chemisorbed ethoxide ions and oil molecules in the liquid phase, while, the overall process was controlled by the ethanol-adsorption step. The physico-chemical properties of biodiesel, produced using potassium methoxide catalyst, were additionally measured.

Oxidation Kinetics of Cast TiAl3

Science.gov (United States)

Smialek, J. L.; Humphrey, D. L.

1992-01-01

The isothermal oxidation kinetics of the TiAl3 compound over a wide temperature range is documented, and these rates are related to exclusive alpha-Al2O3 scale growth. The specific weight change vs time curves are shown. Two abnormalities are immediately apparent. One is that a rapid initial uptake of oxygen occurs at times less than 5 h, followed by a lower oxidation rate at longer times, for tests at 900 C and below. The other is that the final weight changes for the 700, 800, and 900 C tests are not in the sequence expected with respect to temperature. Isothermal oxidation of drop cast TiAl above 1000 C was found to exhibit parabolic oxidation controlled by protective alpha-Al2O3 scale formation. TiAl is the only phase in the binary Ti-Al system that forms exclusive scales of alpha-Al2O3 in isothermal oxidation. High anomalous rates at short times and at temperatures below 1000 C resulted from the internal oxidation of a second phase of aluminum.

Experimental and Kinetic Modeling Study of Ethyl Levulinate Oxidation in a Jet-Stirred Reactor

KAUST Repository

Wang, Jui-Yang

2017-06-01

A jet-stirred reactor was designed and constructed in the Clean Combustion Research Center (CCRC) at King Abdullah University of Science and Technology (KAUST); was validated with n-heptane, iso-octane oxidation and cyclohexene pyrolysis. Different configurations of the setup have been tested to achieve good agreement with results from the literature. Test results of the reactor indicated that installation of a pumping system at the downstream side in the experimental apparatus was necessary to avoid the reoccurrence of reactions in the sampling probe. Experiments in ethyl levulinate oxidation were conducted in the reactor under several equivalence ratios, from 600 to 1000 K, 1 bar and 2 s residence time. Oxygenated species detected included methyl vinyl ketone, levulinic acid and ethyl acrylate. Ethylene, methane, carbon monoxide, hydrogen, oxygen and carbon dioxide were further quantified with a gas chromatography, coupled with a flame ionization detector and a thermal conductivity detector. The ethyl levulinate chemical kinetic model was first developed by Dr. Stephen Dooley, Trinity College Dublin, and simulated under the same conditions, using the Perfect-Stirred Reactor code in Chemkin software. In comparing the simulation results with experimental data, some discrepancies were noted; predictions of ethylene production were not well matched. The kinetic model was improved by updating several classes of reactions: unimolecular decomposition, H-abstraction, C-C and C-O beta-scissions of fuel radicals. The updated model was then compared again with experimental results and good agreement was achieved, proving that the concerted eliminated reaction is crucial for the kinetic mechanism formulation of ethyl levulinate. In addition, primary reaction pathways and sensitivity analysis were performed to describe the role of molecular structure in combustion (800 and 1000 K for ethyl levulinate oxidation in the jet-stirred reactor).

Kinetic Investigations on Pd(II) Catalyzed Oxidation of Some Amino ...

African Journals Online (AJOL)

Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl-threonine by acidic solution of potassium bromate in the presence of mercuric acetate, as a scavenger have been made in the temperature range of 30–45°C. The rate shows zero order kinetics in bromate [BrO3‾] and order of reaction is one with respect ...

Chemical kinetics and combustion modelling with CFX 4

Energy Technology Data Exchange (ETDEWEB)

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

1998-12-31

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

Chemical kinetics and combustion modelling with CFX 4

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Iron-Mediated Oxidation of Methoxyhydroquinone under Dark Conditions: Kinetic and Mechanistic Insights.

Science.gov (United States)

Yuan, Xiu; Davis, James A; Nico, Peter S

2016-02-16

Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH2Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

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

Science.gov (United States)

Pineda, M.; Stamatakis, M.

2017-07-01

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

Electrochemical oxidation of COD from real textile wastewaters: Kinetic study and energy consumption.

Science.gov (United States)

Zou, Jiaxiu; Peng, Xiaolan; Li, Miao; Xiong, Ying; Wang, Bing; Dong, Faqin; Wang, Bin

2017-03-01

In the present study, the electrochemical oxidation of real wastewaters discharged by textile industry was carried out using a boron-doped diamond (BDD) anode. The effect of operational variables, such as applied current density (20-100 mA·cm -2 ), NaCl concentration added to the real wastewaters (0-3 g·L -1 ), and pH value (2.0-10.0), on the kinetics of COD oxidation and on the energy consumption was carefully investigated. The obtained experimental results could be well matched with a proposed kinetic model, in which the indirect oxidation mediated by electrogenerated strong oxidants would be described through a pseudo-first-order kinetic constant k. Values of k exhibited a linear increase with increasing applied current density and decreasing pH value, and an exponential increase with NaCl concentration. Furthermore, high oxidation kinetics resulted in low specific energy consumption, but this conclusion was not suitable to the results obtained under different applied current density. Under the optimum operational conditions, it only took 3 h to complete remove the COD in the real textile wastewaters and the specific energy consumption could be as low as 11.12 kWh·kg -1  COD. The obtained results, low energy consumption and short electrolysis time, allowed to conclude that the electrochemical oxidation based on BDD anodes would have practical industrial application for the treatment of real textile wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental investigation on oxidation kinetics of germanium by ozone

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiaolei, E-mail: wangxiaolei@ime.ac.cn [Key Laboratory of Microelectronics Devices & Integrated Technology, Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029 (China); Zhao, Zhiqian; Xiang, Jinjuan [Key Laboratory of Microelectronics Devices & Integrated Technology, Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029 (China); Wang, Wenwu, E-mail: wangwenwu@ime.ac.cn [Key Laboratory of Microelectronics Devices & Integrated Technology, Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029 (China); Zhang, Jing, E-mail: zhangj@ncut.edu.cn [Key Laboratory of Microelectronics Devices & Integrated Technology, Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029 (China); Microelectronics Department, North China University of Technology, Beijing 100041 (China); Zhao, Chao; Ye, Tianchun [Key Laboratory of Microelectronics Devices & Integrated Technology, Institute of Microelectronics, Chinese Academy of Sciences, Beijing 100029 (China)

2016-12-30

Highlights: • Kinetics mechanism of Ge surface oxidation by ozone at low temperature is experimentally investigated. • The growth process contains initially linear growth region and following parabolic growth region. • The GeO{sub x} thickness vs. oxidation time plot obeys the well-known Deal-Grove or linear parabolic model. • The linear growth region includes the oxidation of two topmost Ge layers, and the oxidation of third layer and following layers of Ge is diffusion limited. • The activation energies for linear and parabolic regions are 0.04 and 0.55 eV, respectively. - Abstract: Oxidation kinetics of germanium surface by ozone at low temperature (≤400 °C) is experimentally investigated. The growth process contains two regions: initial linear growth region and following parabolic growth region. The GeO{sub x} thickness vs. oxidation time plot obeys the well-known Deal-Grove or linear parabolic model. The linear growth region contains reaction of oxygen atoms with surface bond and back bonds of outmost Ge layer. And the activation energy is experimentally estimated to be 0.06 eV. Such small activation energy indicates that the linear growth region is nearly barrier-less. The parabolic growth region starts when the oxygen atoms diffuse into back bonds of second outmost Ge layers. And the activation energy for this process is found to be 0.54 eV. Furthermore, in the ozone oxidation it is not O{sub 3} molecules but O radicals that go through the GeO{sub x} film.

Steam oxidation of ferritic steels: kinetics and microestructure

Directory of Open Access Journals (Sweden)

Aríztegui, A.

2000-06-01

Full Text Available The ferritic 2.25Cr–1Mo steel has been subjected to isothermal and non-isothermal oxidation treatments in water steam at several temperatures ranging from 550 to 700 °C for up to 56 days. Under isothermal conditions this steel follows a parabolic oxidation kinetics, with an activation energy of 324 kJ mol–1. This value corresponds to an apparent activation energy for the global process, which includes both outward diffusion of Fe cations and inward diffusion of oxygen. The oxidation products present in the oxide scales, which were characterised by X-ray diffraction and SEM, are in total agreement with the Fe-O phase diagram. Thus, magnetite is the most stable oxide at low temperatures and wustite starts to form above 570 °C. Further studies of the effect of cooling rate have shown that wustite formed at 700 °C transforms into magnetite during a slow cooling, whereas a rapid cooling inhibits this transformation to a certain extent. For non-isothermal oxidation treatments consisting of a holding period at 550 °C followed by a single or double 4 hours exposure at 700 °C, the oxidation process seems to occur in sequence, thus presenting an additive effect of the oxidation treatments carried out at each temperature. This effect was observed both, for the type of oxide grown, and for the kinetics of the process. Microscopic observations of the oxide scales formed after the various oxidation treatments revealed that the oxide scales are constituted by sublayers of distinct microstructure and chemical composition changing from their surface to the substrate interface.

Se han realizado tratamientos de oxidación isotermos y no isotermos a un acero ferrítico 2,25Cr–1Mo en vapor de agua, a temperaturas comprendidas entre 550 y 700 °C y tiempos de hasta 56 días. En condiciones isotermas, este acero tiene una cinética de oxidación parabólica, con una energía de activación de 324 kJ mol–1. Este valor corresponde a una energía de

Investigation of Chemical Equilibrium Kinetics by the Electromigration Method

CERN Document Server

Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N

2002-01-01

Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.

Electrochemical, Chemical and Enzymatic Oxidations of Phenothiazines

NARCIS (Netherlands)

Blankert, B.; Hayen, H.; van Leeuwen, S.M.; Karst, U.; Bodoki, E.; Lotrean, S.; Sandulescu, R.; Mora Diaz, N.; Dominguez, O.; Arcos, J.; Kauffmann, J.-M.

2005-01-01

The oxidation of several phenothiazine drugs (phenothiazine, promethazine hydrochloride, promazine hydrochloride, trimeprazine hydrochloride and ethopropazine hydrochloride) has been carried out in aqueous acidic media by electrochemical, chemical and enzymatic methods. The chemical oxidation was

Kinetics and Mechanism of Oxidation of Benzyl Alcohol by Benzimidazolium Fluorochromate

Directory of Open Access Journals (Sweden)

J. Dharmaraja

2008-01-01

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

Kinetics and mechanism of oxidation of tellurium (IV) by periodate in alkaline medium

International Nuclear Information System (INIS)

Srinivas, K.; Vani, P.; Dikshitulu, L.S.A.

1995-01-01

Detailed kinetic study of the oxidation of tellurium (IV) by periodate in alkaline medium has been carried out to compare the mechanisms of oxidation in the acid and alkaline media. It is interesting to note that the rate step involves a two-electron transfer from tellurium (IV) to periodate in alkaline medium although the kinetic pattern is somewhat different from that in the acid medium. 7 refs., 1 tab

Radio-Oxidation in Polyolefins: Non-Stationary Kinetic Conditions

International Nuclear Information System (INIS)

Dely, N.

2006-01-01

In the last fifty years, many authors have been interested in the radio-oxidation processes occurring in polymers. The polymer degradation under ionising radiations in presence of dioxygen is well described by a radical chemistry. The radio-oxidation process occurs in three steps: the first one is the production of radicals P degree by interaction between the polymer and the ionising radiations; then radicals P degree react spontaneously with O 2 solved in the polymer giving a peroxy radical POO degree which attacks the polymer forming a hydroperoxide POOH and a new radical P degree (propagation). The third step corresponds to the termination step, that is bimolecular reactions between radicals. It is generally assumed that the stationary state is rapidly reached and consequently that the oxidation induced during the built-up period of the radical concentration can be neglected. However, to our best knowledge, the temporal evolution of radical concentrations before reaching the steady state regime has never been studied in details. We recently performed a complete study of oxygen consumption under electron irradiation for an EPDM elastomer. An analysis, as function of dose rate and oxygen pressure, and assuming steady state conditions, allowed extracting all the kinetic constants. Starting for these experimental data, we calculated the build-up of the radical concentration by solving numerically the differential equations with help of the Minichem code. We conclude that, in fact, the oxidation induced during the built-up period is negligible. In this paper we show that [P degree] could present a quasi-stationary plateau before reaching its stationary level. Consequently, the full radical time evolution is essentially determined by two characteristic times for reaching the quasi and stationary levels and three concentrations: [P degree] and [POO degree] at the stationary level and [P degree] at the quasi-stationary plateau. We show that realistic approximations can

Dose dependent oxidation kinetics of lipids in fish during irradiation processing

International Nuclear Information System (INIS)

Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T.; Bicer, A.; Pamuk, V.

1997-01-01

Kinetic aspects of the development of lipid oxidation in complex foods as fish in the course of irradiation were analyzed with respect to the associated formation of malonaldehyde (MA) through the reactions modified so as to be consistent with those in complex foods as fish. Air-packed anchovy (Engraulis encrasicholus) samples in polyethylene pouches were irradiated at the doses of 1, 2, 5, 10, 15,20 and 25 kGy at 20 o C in a Cs-137 gamma irradiator of 1.806 kGy/h dose rate. Immediately after each irradiation, MA contents of irradiated and unirradiated samples were determined by thiobarbituric acid test. Based on the MA formation, a kinetic model to simulate the apparent oxidation of lipid in fish as a function of irradiation dose was derived from the rate equations consistent with modified reactions. Kinetic parameters and simulation were related to conditions of lipid oxidation, and associated rancidity state of fish with respect to the doses applied in different irradiation-preservation processes. Numerical values of kinetic parameters based on the MA formation were found as a threshold dose of 0.375 kGy, an apparent yield of 1.871 μmol/kg kGy, and a maximum attainable concentration of 15.853 μmol/kg which may be used for process control and dosimetry. (author)

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

International Nuclear Information System (INIS)

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

2002-01-01

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

Oxidation of L-cystine by chromium(VI) - a kinetic study | Kumar ...

African Journals Online (AJOL)

The kinetics of the title reaction was studied spectrophotometrically in HClO4 medium at 380 nm. The data suggested that the order with respect to cystine is fractional, whereas chromium(VI) follows first order kinetics. The reaction was second order in [H+]. Cysteic acid was found to be the main product of oxidation.

Kinetic models of controllable pore growth of anodic aluminum oxide membrane

Science.gov (United States)

Huang, Yan; Zeng, Hong-yan; Zhao, Ce; Qu, Ye-qing; Zhang, Pin

2012-06-01

An anodized Al2O3 (AAO) membrane with apertures about 72 nm in diameter was prepared by two-step anodic oxidation. The appearance and pore arrangement of the AAO membrane were characterized by energy dispersive x-ray spectroscopy and scanning electron microscopy. It was confirmed that the pores with high pore aspect ratio were parallel, well-ordered, and uniform. The kinetics of pores growth in the AAO membrane was derived, and the kinetic models showed that pores stopped developing when the pressure ( σ) trended to equal the surface tension at the end of anodic oxidation. During pore expansion, the effects of the oxalic acid concentration and expansion time on the pore size were investigated, and the kinetic behaviors were explained with two kinetic models derived in this study. They showed that the pore size increased with extended time ( r= G· t+ G'), but decreased with increased concentration ( r = - K·ln c- K') through the derived mathematic formula. Also, the values of G, G', K, and K' were derived from our experimental data.

Static and kinetic friction characteristics of nanowire on different substrates

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun-Joon [Department of Precision Mechanical Engineering, Kyungpook National University, Sangju 37224 (Korea, Republic of); Nguyen, Gia Hau; Ky, Dinh Le Cao; Tran, Da Khoa [School of Mechanical Engineering, University of Ulsan, Ulsan 44610 (Korea, Republic of); Jeon, Ki-Joon [Department of Environmental Engineering, Inha University, Incheon 22212 (Korea, Republic of); Chung, Koo-Hyun, E-mail: khchung@ulsan.ac.kr [School of Mechanical Engineering, University of Ulsan, Ulsan 44610 (Korea, Republic of)

2016-08-30

Highlights: • Direct measurement of kinetic friction of oxidized Si NW using AFM. • Determination of static friction of oxidized Si NW from most bent state. • Friction characteristics of oxidized Si NW on SiO{sub 2} and graphene. • Estimation of shear stress between cylindrical NW and flat substrate. • No significant dependence of shear stress on NW radius. - Abstract: Friction characteristics of nanowires (NWs), which may be used as building blocks for nano-devices, are crucial, especially for cases where contact sliding occurs during the device operation. In this work, the static and kinetic friction characteristics of oxidized Si NWs deposited on thermally grown SiO{sub 2} and chemical vapor-deposited single layer graphene were investigated using an atomic force microscope (AFM). Kinetic friction between the oxidized Si NWs and the substrates was directly measured by the AFM. Static friction was also obtained from the most bent state of the NWs using the individually determined elastic moduli of the NWs from kinetic friction experiments based on elastic beam theory. Furthermore, the shear stress between the oxidized Si NWs and the substrates was estimated based on adhesive contact theory. It was found that both static and kinetic friction increased as the radius of the NWs increased. The friction of the oxidized Si NWs on the graphene substrate was found to be smaller than that on the SiO{sub 2} substrate, which suggests that chemical vapor-deposited graphene can be used as a lubricant or as a protective layer in nano-devices to reduce friction. The shear stress estimated from the kinetic friction data between the oxidized Si NWs and the SiO{sub 2} substrate ranged from 7.5 to 12.3 MPa while that between the oxidized Si NWs and the graphene substrate ranged from 4.7 to 7.0 MPa. The result also indicated that the dependence of shear stress on the radius of the NWs was not significant. These findings may provide insight into the friction characteristics

Static and kinetic friction characteristics of nanowire on different substrates

International Nuclear Information System (INIS)

Kim, Hyun-Joon; Nguyen, Gia Hau; Ky, Dinh Le Cao; Tran, Da Khoa; Jeon, Ki-Joon; Chung, Koo-Hyun

2016-01-01

Highlights: • Direct measurement of kinetic friction of oxidized Si NW using AFM. • Determination of static friction of oxidized Si NW from most bent state. • Friction characteristics of oxidized Si NW on SiO 2 and graphene. • Estimation of shear stress between cylindrical NW and flat substrate. • No significant dependence of shear stress on NW radius. - Abstract: Friction characteristics of nanowires (NWs), which may be used as building blocks for nano-devices, are crucial, especially for cases where contact sliding occurs during the device operation. In this work, the static and kinetic friction characteristics of oxidized Si NWs deposited on thermally grown SiO 2 and chemical vapor-deposited single layer graphene were investigated using an atomic force microscope (AFM). Kinetic friction between the oxidized Si NWs and the substrates was directly measured by the AFM. Static friction was also obtained from the most bent state of the NWs using the individually determined elastic moduli of the NWs from kinetic friction experiments based on elastic beam theory. Furthermore, the shear stress between the oxidized Si NWs and the substrates was estimated based on adhesive contact theory. It was found that both static and kinetic friction increased as the radius of the NWs increased. The friction of the oxidized Si NWs on the graphene substrate was found to be smaller than that on the SiO 2 substrate, which suggests that chemical vapor-deposited graphene can be used as a lubricant or as a protective layer in nano-devices to reduce friction. The shear stress estimated from the kinetic friction data between the oxidized Si NWs and the SiO 2 substrate ranged from 7.5 to 12.3 MPa while that between the oxidized Si NWs and the graphene substrate ranged from 4.7 to 7.0 MPa. The result also indicated that the dependence of shear stress on the radius of the NWs was not significant. These findings may provide insight into the friction characteristics of NWs.

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

KAUST Repository

Nagaraju, Doddahalli H.

2014-12-01

Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.

Comparison of NBG-18, NBG-17, IG-110 and IG-11 oxidation kinetics in air

Science.gov (United States)

Lee, Jo Jo; Ghosh, Tushar K.; Loyalka, Sudarshan K.

2018-03-01

The oxidation rates of several nuclear-grade graphites, NBG-18, NBG-17, IG-110 and IG-11, were measured in air using thermogravimetry. Kinetic parameters and oxidation behavior for each grade were compared by coke type, filler grain size and microstructure. The thickness of the oxidized layer for each grade was determined by layer peeling and direct density measurements. The results for NBG-17 and IG-11 were compared with those available in the literature and our recently reported results for NBG-18 and IG-110 oxidation in air. The finer-grained graphites IG-110 and IG-11 were more oxidized than medium-grained NBG-18 and NBG-17 because of deeper oxidant penetration, higher porosity and higher probability of available active sites. Variation in experimental conditions also had a marked effect on the reported kinetic parameters by several studies. Kinetic parameters such as activation energy and transition temperature were sensitive to air flow rates as well as sample size and geometry.

Development of Kinetics for Soot Oxidation at High Pressures Under Fuel-Lean Conditions

Energy Technology Data Exchange (ETDEWEB)

Lighty, JoAnn [Univ. of Utah, Salt Lake City, UT (United States); Vander Wal, Randy [Pennsylvania State Univ., University Park, PA (United States)

2014-04-21

The focus of the proposed research was to develop kinetic models for soot oxidation with the hope of developing a validated, predictive, multi-­scale, combustion model to optimize the design and operation of evolving fuels in advanced engines for transportation applications. The work focused on the relatively unstudied area of the fundamental mechanism for soot oxidation. The objectives include understanding of the kinetics of soot oxidation by O2 under high pressure which require: 1) development of intrinsic kinetics for the surface oxidation, which takes into account the dependence of reactivity upon nanostructure and 2) evolution of nanostructure and its impact upon oxidation rate and 3) inclusion of internal surface area development and possible fragmentation resulting from pore development and /or surface oxidation. These objectives were explored for a variety of pure fuel components and surrogate fuels. This project was a joint effort between the University of Utah (UU) and Pennsylvania State University (Penn State). The work at the UU focuses on experimental studies using a two-­stage burner and a high- pressure thermogravimetric analyzer (TGA). Penn State provided HRTEM images and guidance in the fringe analysis algorithms and parameter quantification for the images. This report focuses on completion done under supplemental funding.

Kinetic study of diesel soot oxidation: application to simulation of diesel particulate filter regeneration; Etude cinetique de la combustion des suies diesel: application a la modelisation de la regeneration du filtre a particule

Energy Technology Data Exchange (ETDEWEB)

Huguet, Ch.

2005-11-15

Because of their toxicity, soot are considered as the most important pollutant from Diesel engines. The Diesel Particulate Filter (DPF) is widely deployed in Europe to address the significant reductions in particulate emissions required by increasingly stringent emission standards, both for heavy duty vehicles and passenger cars. Such a DPF filtrates above 99% of soot emissions and must be regularly regenerated. The use of additive allows to decrease the soot oxidation temperature to values which can be reached by appropriate engine tuning. The soot addition is a dominant parameter for the development of regeneration strategies. Its influence must be correctly represented by models. This Ph-D was performed at IFP in collaboration with ADEME and was supported by the LCSR at Orleans. The aim of the present research is to develop a kinetic mechanism characteristic of Diesel soot oxidation, which can be integrated into a DPF regeneration model and used for engine control. The oxidation study was based on soot characterisation and reaction kinetics investigations. The samples of Diesel soot were collected, without and with Cerium/Iron additive, by using two engines points representative of two normalized European cycles (ECE and EUDC). Thermal and composition analyses with techniques such as XPS, XRD or TEM were used to determine their physical and chemical properties. Their oxidation kinetics was experimentally studied on a synthetic gas bench (SGB) with a fixed bed reactor. Different tests were performed: temperature-programmed oxidation (TPO), Isothermal oxidation (IO), and sequential oxidation. The results allowed to correlate Diesel soot physical and chemical properties with their oxidation rate. A kinetic model was developed, which is based on global carbon consummation law and distinguishes the oxidation of different soot components. The simulation results agree very well with the experimental results of Diesel soot oxidation. (author)

Bayesian inference of chemical kinetic models from proposed reactions

KAUST Repository

Galagali, Nikhil; Marzouk, Youssef M.

2015-01-01

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

Clad-coolant chemical interaction

International Nuclear Information System (INIS)

Iglesias, F.C.; Lewis, B.J.; Desgranges, C.; Toffolon, C.

2015-01-01

This paper provides an overview of the kinetics for zircaloy clad oxidation behaviour in steam and air during reactor accident conditions. The generation of chemical heat from metal/water reaction is considered. Low-temperature oxidation of zircaloy due to water-side corrosion is further described. (authors)

Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

Science.gov (United States)

Meagher, Nancy E.; Bates, Kami R.

2000-01-01

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

Evaluation of thermodynamic and kinetic stability of P-type transparent conducting oxide, SrCu2O2 under various oxygen partial pressures

International Nuclear Information System (INIS)

Sugimoto, Takayuki; Yanagawa, Atsumi; Hashimoto, Takuya

2012-01-01

Highlights: ▶ Thermodynamic and kinetic stabilities of SrCu 2 O 2 under various P(O 2 ) was estimated. ▶ The reaction rate for decomposition decreased with decreasing temperature and P(O 2 ). ▶ The activation energy for decomposition of SrCu 2 O 2 was estimated to be 66 kJ/mol. ▶ SrCu 2 O 2 showed less stability than those of other transparent p-type semiconductors. - Abstract: Kinetic stability of transparent p-type conducting oxide, SrCu 2 O 2 , has been evaluated by using X-ray diffraction measurement and thermogravimetry. It was revealed that SrCu 2 O 2 decomposed to mixture of CuO and Sr 14 Cu 24 O 41 in air at temperatures above 300 °C. The decomposition reaction rate can be successfully explained by kinetic model assuming first-order chemical reaction. The rate constant can be suppressed with decreasing temperature and oxygen partial pressure. The activation energy for decomposition reaction of SrCu 2 O 2 calculated from Arrhenius plot was 66 kJ/mol, which was lower than those of other transparent p-type semiconductors such as CuAlO 2 and CuGaO 2 . The low decomposition temperature and activation energy for decomposition indicate that chemical stability of SrCu 2 O 2 is far lower than those of other p-type conducting oxides.

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

Science.gov (United States)

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

2016-06-01

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

Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

Energy Technology Data Exchange (ETDEWEB)

Contescu, Cristian I [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burchell, Timothy D [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert [Univ. of Tennessee, Knoxville, TN (United States)

2015-05-01

This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetime of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.

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.

Kinetics and mechanism of the oxidation of formic and oxalic acids ...

Indian Academy of Sciences (India)

The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic ...

Propylene oxidation on catalytic Pt-Cu/y alumina. (Part II) chemical Kinetics of catalysts of Pt-Cu/y-alumina in the propylene oxidation

International Nuclear Information System (INIS)

Carballo, Luis M; Zea, Hugo R

1999-01-01

In this work is treated the effect of the composition of catalysts of Pt-Cu/y - alumina on the specific superficial activity corresponding to the total oxidation of propylene. Although the catalyst activity of the Cu in the operation conditions went practically null the specific activity of the catalytic Pt-Cu it incremented with the increase of the contained proportion of Cu in the catalyst. The total global speed by gram of catalyst was also increased with the introduction of Cu, but only to medium and high concentrations of propylene. The specific superficial activity was bigger for the sinterizated catalyst, for a given composition of the bimetallic catalyst, compared with that of the fresh catalyst (non-sinterizated). To explain, the catalytic behavior of the propylene oxidation, on the catalysts here studied, it is postulated that the propylene molecule it absorb with less force on the faces than in the corners or borders of the crystals of the catalyst and that the connection of adsorption on a place of given Pt is affected by the atoms of neighboring Cu on the surface causing changes in the mobility of the absorbed species. The kinetic results reveal a complex dependence between the reaction speed and the concentration of the propylene. In low concentrations of propylene the reaction speed was increased until to reach a maximum, and then to continue with a marked decreasing; and to concentrations. In bigger propylene concentrations, the reaction kinetics is presented as zero order with regard to the propylene, for some given concentrations of oxygen

Progress in Chemical Kinetic Modeling for Surrogate Fuels

Energy Technology Data Exchange (ETDEWEB)

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

2008-06-06

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

Kinetics and mechanism of furfural oxidation by ions of heterovalent metals

Energy Technology Data Exchange (ETDEWEB)

Krupenskij, V.I. (Ukhtinskij Industrial' nyj Inst. (USSR))

1983-01-01

Real constants of rate of furfural oxidation by Cu/sup 2 +/, Fe/sup 3 +/, Ce/sup 4 +/, Ag/sup +/, Hg/sup 2 +//sub 2/ ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested.

Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation

International Nuclear Information System (INIS)

Moradmand Jalali, Hamed; Bashiri, Hadis; Rasa, Hossein

2015-01-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO 2 , ZnO and ZrO 2 ) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO 2 (rutile and anatase), ZnO and ZrO 2 . • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained

Oxidative kinetic resolution of racemic alcohols catalyzed by chiral ferrocenyloxazolinylphosphine-ruthenium complexes.

Science.gov (United States)

Nishibayashi, Yoshiaki; Yamauchi, Akiyoshi; Onodera, Gen; Uemura, Sakae

2003-07-25

Oxidative kinetic resolution of racemic secondary alcohols by using acetone as a hydrogen acceptor in the presence of a catalytic amount of [RuCl(2)(PPh(3))(ferrocenyloxazolinylphosphine)] (2) proceeds effectively to recover the corresponding alcohols in high yields with an excellent enantioselectivity. When 1-indanol is employed as a racemic alcohol, the oxidation proceeds quite smoothly even in the presence of 0.0025 mol % of the catalyst 2 to give an optically active 1-indanol in good yield with high enantioselectivity (up to 94% ee), where turnover frequency (TOF) exceeds 80,000 h(-1). From a practical viewpoint, the kinetic resolution is investigated in a large scale, optically pure (S)-1-indanol (75 g, 56% yield, >99% ee) being obtained from racemic 1-indanol (134 g) by employing this kinetic resolution method twice.

Oxidation of nonylphenol and octylphenol by manganese dioxide: Kinetics and pathways

International Nuclear Information System (INIS)

Lu, Zhijiang; Gan, Jay

2013-01-01

Due to their potent estrogenicity and ubiquitous occurrence, non-ionic surfactant metabolites nonylphenol (NP) and octylphenol (OP) are of significant concern. Abiotic chemical oxidation by naturally abundant metal oxides may be an important route of their environmental attenuation, but is poorly understood. We investigated the reaction kinetics and pathways of NP and OP with MnO 2 . At pH 5.5 and 100 mg/L δ-MnO 2 , 92, 84 and 76% of 4-n-NP, 4-tert-OP and technical nonylphenol (tNP) was transformed in 90 min, respectively. A further experiment using a Mn-containing soil and Mn-removed soil confirmed that soil MnO 2 caused NP removal. Multiple reaction products, including hydroquinone, hydroxylated products, dimers and trimers were identified through fragmentation analysis by GC–MS/MS and UPLC–MS/MS, allowing the construction of tentative pathways. This study suggested that abiotic oxidation by MnO 2 may contribute to the dissipation of tNP, 4-n-NP, 4-tert-OP and their analogues in the natural environment. Highlights: •The oxidation of nonylphenol and octylphenol by manganese dioxide was efficient and pH dependent. •The importance of soil MnO 2 was further confirmed by experiment using Mn-containing soil. •The reaction in environment is substantially slower than with synthetic MnO 2 . •The oxidation was inhibited by metal ions and enhanced by humic acids. •Reaction pathway is proposed based on reaction intermediates identified. -- Naturally occurring MnO 2 may contribute significantly to the attenuation of nonylphenol and octylphenol in soil, water and sediment

A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

Science.gov (United States)

Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

2015-12-15

Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetics and mechanism of oxidation of super-reduced cobalamin and cobinamide species by thiosulfate, sulfite and dithionite.

Science.gov (United States)

Dereven'kov, Ilia A; Salnikov, Denis S; Makarov, Sergei V; Boss, Gerry R; Koifman, Oskar I

2013-11-21

We studied the kinetics of reactions of cob(I)alamin and cob(I)inamide with thiosulfate, sulfite, and dithionite by UV-Visible (UV-Vis) and stopped-flow spectroscopy. We found that the two Co(I) species were oxidized by these sulfur-containing compounds to Co(II) forms: oxidation by excess thiosulfate leads to penta-coordinate complexes and oxidation by excess sulfite or dithionite leads to hexa-coordinate Co(II)-SO2(-) complexes. The net scheme involves transfer of three electrons in the case of oxidation by thiosulfate and one electron for oxidation by sulfite and dithionite. On the basis of kinetic data, the nature of the reactive oxidants was suggested, i.e., HS2O3(-) (for oxidation by thiosulfate), S2O5(2-), HSO3(-), and aquated SO2 (for oxidation by sulfite), and S2O4(2-) and SO2(-) (for oxidation by dithionite). No difference was observed in kinetics with cob(i)alamin or cob(i)inamide as reductants.

Chemical Kinetic Models for Advanced Engine Combustion

Energy Technology Data Exchange (ETDEWEB)

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

2014-10-22

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

Characteristics of SME biodiesel-fueled diesel particle emissions and the kinetics of oxidation.

Science.gov (United States)

Jung, Heejung; Kittelson, David B; Zachariah, Michael R

2006-08-15

Biodiesel is one of the most promising alternative diesel fuels. As diesel emission regulations have become more stringent, the diesel particulate filter (DPF) has become an essential part of the aftertreatment system. Knowledge of kinetics of exhaust particle oxidation for alternative diesel fuels is useful in estimating the change in regeneration behavior of a DPF with such fuels. This study examines the characteristics of diesel particulate emissions as well as kinetics of particle oxidation using a 1996 John Deere T04045TF250 off-highway engine and 100% soy methyl ester (SME) biodiesel (B100) as fuel. Compared to standard D2 fuel, this B100 reduced particle size, number, and volume in the accumulation mode where most of the particle mass is found. At 75% load, number decreased by 38%, DGN decreased from 80 to 62 nm, and volume decreased by 82%. Part of this decrease is likely associated with the fact that the particles were more easily oxidized. Arrhenius parameters for the biodiesel fuel showed a 2-3times greater frequency factor and approximately 6 times higher oxidation rate compared to regular diesel fuel in the range of 700-825 degrees C. The faster oxidation kinetics should facilitate regeneration when used with a DPF.

Oxidation kinetics of CVD silicon carbide and silicon nitride

Science.gov (United States)

Fox, Dennis S.

1992-01-01

The long-term oxidation behavior of pure, monolithic CVD SiC and Si3N4 is studied, and the isothermal oxidation kinetics of these two materials are obtained for the case of 100 hrs at 1200-1500 C in flowing oxygen. Estimates are made of lifetimes at the various temperatures investigated. Parabolic rate constants for SiC are within an order of magnitude of shorter exposure time values reported in the literature. The resulting silica scales are in the form of cristobalite, with cracks visible after exposure. The oxidation protection afforded by silica for these materials is adequate for long service times under isothermal conditions in 1-atm dry oxygen.

Oxidation of trimethoprim by ferrate(VI): kinetics, products, and antibacterial activity.

Science.gov (United States)

Anquandah, George A K; Sharma, Virender K; Knight, D Andrew; Batchu, Sudha Rani; Gardinali, Piero R

2011-12-15

Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid-base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of TMP in the secondary effluent by Fe(VI) was achieved.

Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

Science.gov (United States)

Lashina, Elena A; Kaichev, Vasily V; Saraev, Andrey A; Vinokurov, Zakhar S; Chumakova, Nataliya A; Chumakov, Gennadii A; Bukhtiyarov, Valerii I

2017-09-21

The self-sustained kinetic oscillations in the oxidation of CH 4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO 2 , H 2 , and H 2 O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.

Kinetics of Oxidation of Metochlopramide withChloramine-T in HClO4 Medium

Directory of Open Access Journals (Sweden)

K. M. Meenakshi

2009-01-01

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

Probing the oxidation kinetics of small permalloy particles

International Nuclear Information System (INIS)

Dong, Xiaolei; Song, Xiao; Yin, Shiliu; Shirolkar, Mandar M.; Li, Ming; Wang, Haiqian

2017-01-01

The oxidation of permalloys is important to apply in a wide range. The oxidation and diffusion mechanisms of small permalloy particles with different Fe content are studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. Fe 2 O 3 /(Ni, Fe) 3 O 4 plays a key role in the morphology evolution and diffusion mechanisms of small NiFe particles upon oxidation. The activation energies of grain boundary diffusion for the NiFe alloys increase from 141 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to ~50 wt%. We have developed a diffusion process resolved temperature programed oxidation (PR-TPO) analysis method. Three diffusion mechanisms have been recognized by using this method: In addition to the grain boundary diffusion and lattice diffusion, our TGA analysis suggests that the phase conversion from Fe 2 O 3 to (Ni, Fe) 3 O 4 induces diffusion change and affects the diffusion process at the intermediate temperature. Relevant oxidation kinetics and diffusion mechanisms are discussed. - Graphical abstract: The oxidation mechanisms of small Permalloy particles with different Fe content is studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. The activation energies of grain boundary diffusion for the NiFe alloys increases from 140 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to 50 wt% as determined by TGA. We have developed a diffusion process resolved temperature programed oxidation (DPR-TPO) analysis method, and three diffusion mechanisms have been recognized by using this method: In addition to the well-known grain boundary diffusion and lattice diffusion, we found that the phase conversion from Fe 2 O 3 to (Ni, Fe) 3 O 4 will induce diffusion changes and affect the diffusion process at the intermediate temperature. The diffusion processes can be characterized by the corresponding characteristic peak temperatures in temperature programmed oxidation (TPO) analysis. This work not only

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

International Nuclear Information System (INIS)

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

1995-01-01

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

On kinetics and mechanism of' furfural oxidation by ions of heterovalent metals

International Nuclear Information System (INIS)

Krupenskij, V.I.

1983-01-01

Real constants of rate of furfural oxidation by Cu 2+ , Fe 3+ , Ce 4+ , Ag + , Hg 2+ 2 ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

DEFF Research Database (Denmark)

Lopez, Jorge Gimenez; Rasmussen, Christian Lund; Alzueta, Maria

2009-01-01

of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH2O and HCO, is the dominant product. The experiments, involving C2H4/O-2 mixtures diluted in N-2, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying......A detailed chemical kinetic model for oxidation of C2H4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C2H3 + O-2 reaction was used to obtain rate coefficients over a wide range...

Zirconium metal-water oxidation kinetics. I. Thermometry

International Nuclear Information System (INIS)

Cathcart, J.V.; McElroy, D.L.; Pawel, R.E.; Perkins, R.A.; Williams, R.K.; Yurek, G.J.

1976-02-01

A description is given of the thermometry techniques used in the Zirconium Metal--Water Oxidation Kinetics Program. Temperature measurements in the range 900 to 1500 0 C are made in three experimental systems: two oxidation apparatuses and the annealing furnace used in a corollary study of the diffusion of oxygen in β-Zircaloy. Carefully calibrated Pt vs Pt--10 percent Rh thermocouples are employed in all three apparatuses, while a Pt--6 percent Rh vs Pt-- 30 percent Rh thermocouple and an optical pyrometer are used in addition in the annealing furnace. Features of the experimental systems pertaining to thermocouple installation, temperature control, emf measurements, etc. are described, and potential temperature-measurement error sources are discussed in detail. The accuracy of the temperature measurements is analyzed

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

African Journals Online (AJOL)

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

Kinetic modeling of low density lipoprotein oxidation in arterial wall and its application in atherosclerotic lesions prediction.

Science.gov (United States)

Karimi, Safoora; Dadvar, Mitra; Modarress, Hamid; Dabir, Bahram

2013-01-01

Oxidation of low-density lipoprotein (LDL) is one of the major factors in atherogenic process. Trapped oxidized LDL (Ox-LDL) in the subendothelial matrix is taken up by macrophage and leads to foam cell generation creating the first step in atherosclerosis development. Many researchers have studied LDL oxidation using in vitro cell-induced LDL oxidation model. The present study provides a kinetic model for LDL oxidation in intima layer that can be used in modeling of atherosclerotic lesions development. This is accomplished by considering lipid peroxidation kinetic in LDL through a system of elementary reactions. In comparison, characteristics of our proposed kinetic model are consistent with the results of previous experimental models from other researches. Furthermore, our proposed LDL oxidation model is added to the mass transfer equation in order to predict the LDL concentration distribution in intima layer which is usually difficult to measure experimentally. According to the results, LDL oxidation kinetic constant is an important parameter that affects LDL concentration in intima layer so that existence of antioxidants that is responsible for the reduction of initiating rates and prevention of radical formations, have increased the concentration of LDL in intima by reducing the LDL oxidation rate. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Statistical model for grain boundary and grain volume oxidation kinetics in UO2 spent fuel

International Nuclear Information System (INIS)

Stout, R.B.; Shaw, H.F.; Einziger, R.E.

1989-09-01

This paper addresses statistical characteristics for the simplest case of grain boundary/grain volume oxidation kinetics of UO 2 to U 3 O 7 for a fragment of a spent fuel pellet. It also presents a limited discussion of future extensions to this simple case to represent the more complex cases of oxidation kinetics in spent fuels. 17 refs., 1 fig

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].

Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation

Energy Technology Data Exchange (ETDEWEB)

Moradmand Jalali, Hamed; Bashiri, Hadis, E-mail: hbashiri@kashanu.ac.ir; Rasa, Hossein

2015-05-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO{sub 2}, ZnO and ZrO{sub 2}) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO{sub 2} (rutile and anatase), ZnO and ZrO{sub 2}. • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained.

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

Energy Technology Data Exchange (ETDEWEB)

Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)

2014-12-15

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

International Nuclear Information System (INIS)

Nagaraju, D.H.; Devaraj, S.; Balaya, P.

2014-01-01

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd 2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl 2 . X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells

An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics

Science.gov (United States)

Masubuchi, Tsugunosuke; Eckhard, Jan F.; Lange, Kathrin; Visser, Bradley; Tschurl, Martin; Heiz, Ulrich

2018-02-01

A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

[Oxidation behavior and kinetics of representative VOCs emitted from petrochemical industry over CuCeOx composite oxides].

Science.gov (United States)

Chen, Chang-Wei; Yu, Yan-Ke; Chen, Jin-Sheng; He, Chi

2013-12-01

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

Non-equilibrium reaction rates in chemical kinetic equations

Science.gov (United States)

Gorbachev, Yuriy

2018-05-01

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

On the theory of time dilation in chemical kinetics

Science.gov (United States)

Baig, Mirza Wasif

2017-10-01

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

Study of liquid phase formation kinetics due to solid/solid chemical interaction and its model. Application to the Zircaloy/Inconel

International Nuclear Information System (INIS)

Garcia, E.A.; Denis, A.

1990-01-01

A description is made of the chemical interaction between Inconel spacing grids and the Zircaloy of the sheaths. Experiments performed at 1000, 1100 and 1200 deg C with base Zircaloy and with a previously formed layer of ZrO 2 , show that the kinetics is parabolic. The difference between both types of experiments is that the oxide layer delays the initiation of the Inconel-Zry interaction. A model is presented, for the description of the solid/solid interaction, which leads to the formation of eutectic that is liquid at the experiment temperature. Also a model, which represents the oxide layer dissolution and predicts the instant in which it disappears completely, is presented. (Author) [es

Infrared absorption spectroscopy and chemical kinetics of free radicals

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

Science.gov (United States)

Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

2011-01-01

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

The oxidation kinetics for sublimates formed during niobium electron-beam remelting

International Nuclear Information System (INIS)

Chumarev, V.M.; Gulyaeva, R.I.; Mar'evich, V.P.; Upolovnikova, A.G.; Udoeva, L.Yu.

2003-01-01

The oxidation of sublimates of Nb-Al electron beam remelting is investigated under conditions of isothermal and continuous heating in the air. It is stated that basic oxidation products are niobium and aluminium oxides, as well as aluminium niobates of variable composition of Al 2 O 3 · mNb 2 O 5 . The more aluminium enriched sublimates possess an increased resistance to oxidation. Formed in sublimates NbAl 3 intermetallic compound features the highest heat resistance. Oxidation parameters are determined by the method of nonisothermic kinetics. It is noted that the running processes exhibit a multistage nature and are limited by internal diffusion [ru

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

Energy Technology Data Exchange (ETDEWEB)

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

On the effect of pre-oxidation on the nitriding kinetics

DEFF Research Database (Denmark)

Friehling, Peter Bernhard; Somers, Marcel A. J.

2000-01-01

The oxidation of ferritic surfaces prior to gaseous nitriding has been reported to lead to improved uniformity of the compound layer thickness and enhanced nitriding kinetics. The present work considers the nucleation and growth of a model compound layer on pure iron and, using previous...... experimental and theoretical work reported in the literature, puts forward two hypotheses to explain the effects of pre-oxidation on compound layer formation. It is proposed that the nucleation of iron nitrides is enhanced by the presence of an iron-oxide layer and that the growth of an iron-nitride layer...... proceeds faster after pre-oxidation, due to a higher nitrogen content in the part of the compound layer closest to the surface....

The modelling of direct chemical kinetic effects in turbulent flames

Energy Technology Data Exchange (ETDEWEB)

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

2000-06-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Lilleberg, Bjorn

2011-07-01

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

Science.gov (United States)

Kashiwagi, Takashi; Nambu, Hidesaburo

1992-01-01

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

Kinetic Study of Hydroxyl and Sulfate Radical-Mediated Oxidation of Pharmaceuticals in Wastewater Effluents.

Science.gov (United States)

Lian, Lushi; Yao, Bo; Hou, Shaodong; Fang, Jingyun; Yan, Shuwen; Song, Weihua

2017-03-07

Advanced oxidation processes (AOPs), such as hydroxyl radical (HO • )- and sulfate radical (SO 4 •- )-mediated oxidation, are alternatives for the attenuation of pharmaceuticals and personal care products (PPCPs) in wastewater effluents. However, the kinetics of these reactions needs to be investigated. In this study, kinetic models for 15 PPCPs were built to predict the degradation of PPCPs in both HO • - and SO 4 •- -mediated oxidation. In the UV/H 2 O 2 process, a simplified kinetic model involving only steady state concentrations of HO • and its biomolecular reaction rate constants is suitable for predicting the removal of PPCPs, indicating the dominant role of HO • in the removal of PPCPs. In the UV/K 2 S 2 O 8 process, the calculated steady state concentrations of CO 3 •- and bromine radicals (Br • , Br 2 •- and BrCl •- ) were 600-fold and 1-2 orders of magnitude higher than the concentrations of SO 4 •- , respectively. The kinetic model, involving both SO 4 •- and CO 3 •- as reactive species, was more accurate for predicting the removal of the 9 PPCPs, except for salbutamol and nitroimidazoles. The steric and ionic effects of organic matter toward SO 4 •- could lead to overestimations of the removal efficiencies of the SO 4 •- -mediated oxidation of nitroimidazoles in wastewater effluents.

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

KAUST Repository

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

2017-01-01

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

Kinetics and mechanism of oxidation of aliphatic primary alcohols by ...

Indian Academy of Sciences (India)

Unknown

Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate. SONU SARASWAT, VINITA SHARMA and K K BANERJI*. Department of Chemistry, JNV University, Jodhpur 342 005, India e-mail: banerjikk@rediffmail.com. MS received 4 December 2001; revised 2 November 2002.

Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

Science.gov (United States)

Ebisuzaki, Y.; Sanborn, W. B.

1985-01-01

Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Review of zircaloy oxidation

Energy Technology Data Exchange (ETDEWEB)

Iglesias, F.C. [Royal Military College of Canada, Kingston, Ontario (Canada); Lewis, B.J. [Univ. of Ontario Inst. of Technology, Faculty of Energy Systems and Nuclear Science, Oshawa, Ontario (Canada)

2013-07-01

This paper provides an overview of the kinetics for Zircaloy clad oxidation behaviour in steam and air during reactor accident conditions. The generation of chemical heat from metal/water reaction is considered. The effect of internal clad oxidation due to Zircaloy/UO{sub 2} interaction is also discussed. Low-temperature oxidation of Zircaloy due to water-side corrosion is further described. (author)

Oxidation kinetics of a continuous carbon phase in a nonreactive matrix

Science.gov (United States)

Eckel, Andrew J.; Cawley, James D.; Parthasarathy, Triplicane A.

1995-01-01

Analytical solutions of and experimental results on the oxidation kinetics of carbon in a pore are presented. Reaction rate, reaction sequence, oxidant partial pressure, total system pressure, pore/crack dimensions, and temperature are analyzed with respect to the influence of each on an overall linear-parabolic rate relationship. Direct measurement of carbon recession is performed using two microcomposite model systems oxidized in the temperature range of 700 to 1200 C, and for times to 35 h. Experimental results are evaluated using the derived analytical solutions. Implications on the oxidation resistance of continuous-fiber-reinforced ceramic-matrix composites containing a carbon constituent are discussed.

CHEMSIMUL: A simulator for chemical kinetics

International Nuclear Information System (INIS)

Kirkegaard, P.; Bjergbakke, E.

1999-01-01

CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving the resulting coupled nonlinear ordinary differential equations. An overview of the program system is given, and its use is illustrated by examples. A number of special features are described, in particular a method for verifying the mass balance. Moreover, the document contains a complete User's Guide for running CHEMSIMUL on a PC or another computer. Finally, the mathematical implementation is discussed. (au)

Investigation of effect of air flow rate on Zircaloy-4 oxidation kinetics and breakaway phenomenon in air at 850 .deg. C

International Nuclear Information System (INIS)

Maeng, Yunhwan; Lee, Jaeyoung; Park, Sanggil

2016-01-01

This paper analyzed an effect of flow rate on oxidation kinetics of Zircaloy-4 in air at 850 .deg. C. In case of the oxidation of Zircaloy-4 in air at 850 .deg. C, acceleration of oxidation kinetics from parabolic to linear (breakaway phenomenon) occurs. Oxidation and breakaway kinetics of the Zircaloy-4 in air was experimentally studied by changing a flow rate of argon/air mixture. Tests were conducted at 850 .deg. C under constant ratio of argon and air. The effects of flow rate on the oxidation and breakaway kinetics was observed. This paper is based on a revised and considerably extended presentation given at the 21 st International Quench Workshop. The effects of flow conditions on the oxidation kinetics of Zircaloy-4 samples were explained with residence time and percent flow efficiency. In addition, several issues were observed from this study, interdiffusion at breakaway and deformation of oxide structure by breakaway phenomenon

Oxidative conversion of propane over lithium-promoted magnesia catalyst. I. Kinetics and mechanism

NARCIS (Netherlands)

Leveles, L.; Seshan, Kulathuiyer; Lercher, J.A.; Lefferts, Leonardus

2003-01-01

Oxidative conversion of lower alkanes over lithium-promoted magnesia catalysts offers a viable alternative for propene and ethene production. The catalytic performance of propane oxidative dehydrogenation and cracking shows yields up to 50% of olefin (propene and ethene). The reaction kinetics were

Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

Directory of Open Access Journals (Sweden)

Effendy Mohammad

2016-01-01

Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

International Nuclear Information System (INIS)

Sharma, J.N.; Bhattacharya, K.; Swami, R.G.; Tangri, S.K.; Mukherjee, T.K.

1996-01-01

The dissolution of UO 2 in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol -1 . This relatively high activation energy value indicates a chemically controlled behavior of UO 2 dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity. (author). 18 refs., 6 figs

Anaerobic digestion of amine-oxide-based surfactants: biodegradation kinetics and inhibitory effects.

Science.gov (United States)

Ríos, Francisco; Lechuga, Manuela; Fernández-Arteaga, Alejandro; Jurado, Encarnación; Fernández-Serrano, Mercedes

2017-08-01

Recently, anaerobic degradation has become a prevalent alternative for the treatment of wastewater and activated sludge. Consequently, the anaerobic biodegradability of recalcitrant compounds such as some surfactants require a thorough study to avoid their presence in the environment. In this work, the anaerobic biodegradation of amine-oxide-based surfactants, which are toxic to several organisms, was studied by measuring of the biogas production in digested sludge. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R 12 ), Myristamine oxide (AO-R 14 ) and Cocamidopropylamine oxide (AO-cocoamido). Results show that AO-R 12 and AO-R 14 inhibit biogas production, inhibition percentages were around 90%. AO-cocoamido did not cause inhibition and it was biodegraded until reaching a percentage of 60.8%. Otherwise, we fitted the production of biogas to two kinetic models, to a pseudo first-order model and to a logistic model. Production of biogas during the anaerobic biodegradation of AO-cocoamido was pretty good adjusted to the logistics model. Kinetic parameters were also determined. This modelling is useful to predict their behaviour in wastewater treatment plants and under anaerobic conditions in the environment.

Chemical interactions between as-received and pre-oxidized Zircaloy-4 and Inconel-718 at high temperatures

International Nuclear Information System (INIS)

Hofmann, P.; Markiewicz, M.

1994-06-01

Isothermal reaction experiments were performed in the temperature range of 1000 - 1300 C in order to determine the chemical interactions between Zircaloy-4 fuel rod cladding and Inconel-718 spacer grids of Pressurized Water Reactors (PWR) under severe accident conditions. It was not possible to apply even higher temperatures since fast and complete liquefaction of the components occurred as a result of eutectic interactions during heatup. The liquid reaction products formed enhance and accelerate the degradation of the material couples and the fuel elements, respectively. Only small amounts of Inconel are necessary to liquefy large amounts of Zircaloy. Thin oxide layers on the Zircaloy surface delay the beginning of the chemical interactions with Inconel but cannot prevent them. In this work the reaction kinetics have been determined for the system: as-received and pre-oxidized Zircaloy-4/Inconel 718. The interactions can be described by parabolic rate laws; the Arrhenius equations for the various interactions are given. (orig.) [de

Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

International Nuclear Information System (INIS)

Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

2012-01-01

Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N 2 -saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO 2 system by changing the reaction atmospheres.

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

Science.gov (United States)

Fox, P.M.; Davis, J.A.; Luther, G. W.

2009-01-01

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

International Nuclear Information System (INIS)

Rau, M.S.; Gennero de Chialvo, M.R.; Chialvo, A.C.

2010-01-01

The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H 2 SO 4 solution at different rotation rates (ω). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on ω 1/2 . On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

Science.gov (United States)

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

The initial oxidation of epsilon-Fesub2Nsub1-x: growth kinetics

DEFF Research Database (Denmark)

Graat, Peter C.J.; Somers, Marcel A. J.; Mittemeijer, Eric J.

1999-01-01

The oxidation kinetics of epsilon-Fe2N1-x, subjected either to a sputter cleaning pretreatment or a sputter cleaning and an additional annealing pretreatment, at P-O2 = 1 x 10(-4) Pa and at temperatures ranging from 300 to 500 K, was investigated with ellipsometry. The initial oxidation rate of s...

Kinetics and mechanism of the oxidation of organic sulphides by 2,2 ...

Indian Academy of Sciences (India)

Unknown

In the present article, we report the kinetics of oxidation of thirty-four organic sulphides by BPCC in ..... t-Butyl alcohol. 24⋅0. Acetone. 40⋅7 .... different sensitivity to the electronic demand for the phenomenon being studied. It has the ... 144. Table 5. Temperature dependence for the reaction constants for the oxidation of.

Experimental kinetic study and modeling of calcium oxide carbonation

International Nuclear Information System (INIS)

Rouchon, L.

2012-01-01

Anthropogenic carbon dioxide (CO 2 ) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO 2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO 2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO 2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/de-carbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO 2 , so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO 2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO 2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO 3 which causes a change in the

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

Science.gov (United States)

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Perturbation of parabolic kinetics resulting from the accumulation of stress in protective oxide layers

International Nuclear Information System (INIS)

Evans, H.E.; Norfolk, D.J.; Swan, T.

1978-01-01

A frequent observation in metal oxidation is the development of subparabolic kinetics, variously described as cubic or quartic. Although a number of detailed mechanisms have been proposed to account for this effect, none seem generally applicable. A model is presented of the oxidation process which is divorced from such restrictions. It is argued that deviations from parabolic behavior occur as a result of the concurrent development of stresses within the oxide. It is shown that the presence of stress fields can influence significantly the rate of transport of vacancy defects within the oxide such that tensile stresses produce positive deviations and compressive stresses, negative deviations from parabolic behavior. The model is applied in detail to Zircaloy-2 oxidation at 773 0 K. It is predicted that the kinetics should be insensitive to the oxygen potential of the environment and this has been confirmed by previous experimental work. 31 refs

Kinetics of oxidation of nickel(II) aza macrocycles by ...

Indian Academy of Sciences (India)

The kinetics of the oxidation of nickel (II) hexaaza and nickel (II) pentaaza macrocycles by the peroxydisulphate anion, S2O8 2-, were studied in aqueous media. Effect of H on reaction rate was also studied. The rate increases with increase of S2OO8 2- concentration. Rates are almost independent of acid between H 4 ...

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

International Nuclear Information System (INIS)

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

1998-01-01

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

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study.

Science.gov (United States)

Yuan, Jia; Long, Xinping; Zhang, Chaoyang

2016-12-01

N-Oxidization is an important strategy for enhancing the density and energy of energetic materials. Nevertheless, the influence of N + -O - introduction on molecular stability remains relatively unknown. Thus, the present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations. The introduction of N + -O - weakens molecular stability in most cases because the process elongates chemical bonds, decreases ring aromaticity, narrows the gaps between the highest occupied and lowest unoccupied molecular orbitals, and increases the photochemical reactivity. Besides, the easy H transfer to the neighboring O atom, which forms a N-OH isomer in azoles, renders the stabilization by N-oxide introduction ineffective. However, N-oxide introduction can enhance the molecular stability of 1,2,3,4-tetrazine-1,3-dioxide and tetrazino-tetrazine 1,3,6,8-tetraoxide by promoting σ-π separation and relieving lone-pair repulsion. Moreover, the alternate arrangement of positive and negative charges is another factor stabilizing the 1,2,3,4-tetrazine ring by 1,3-dioxidation. Finally, we assess the accessibility of N-oxidized azoles and azines by regarding N 2 O and H 2 O 2 as oxidizers. We find that all the oxidations were exothermic, thermodynamically spontaneous, and kinetically feasible. After an overall evaluation, we propose 19 N-oxides as basic structures for high-energy materials with considerable stability.

A first principles study of the oxidation energetics and kinetics of realgar

Science.gov (United States)

Renock, Devon; Becker, Udo

2010-08-01

Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As 4S 4 clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As 4S 4 clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic 3O to diamagnetic 1O spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O 2 dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As 4S 4, q.m. calculations reveal that 3O transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the 3O adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O 2 dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O 2 alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH -. First-principles, periodic calculations of the

Oxidation kinetics and mechanisms of carbon/carbon composites and their components in water vapour at high temperatures

International Nuclear Information System (INIS)

Qin, Fei; Peng, Li-na; He, Guo-qiang; Li, Jiang; Yan, Yong

2015-01-01

Highlights: • 4D-C/C composite was fabricated using carbon fibre and coal tar pitch. • The rate of mass loss and oxidation kinetics parameters of fibres-H 2 O and matrix-H 2 O are obtained. • The rate of mass loss and oxidation kinetics parameters of C/C–H 2 O are obtained. • Oxidation rate of the fibre bundle is greater than the oxidation rate of the matrix. - Abstract: Thermogravimetric analysis and scanning electron microscopy were used to study the oxidation kinetics of four-direction carbon/carbon composites and their components (fibres and matrices) in a H 2 O–Ar atmosphere at high temperatures. The oxidation processes were restricted to reaction-limited oxidation. The rate of mass loss was estimated for the four-direction carbon/carbon composites and their components at high temperature. The pressure exponent for the reaction of the carbon/carbon composites with H 2 O was 0.59, and the pre-exponential factor and activation energy for the reactions of H 2 O with the carbon/carbon composites, carbon fibres and matrices were determined

The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

Science.gov (United States)

Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn

2017-02-01

The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

Study of the oxidation kinetics of the nickel-molybdenum alloy

International Nuclear Information System (INIS)

Gouillon, Marie-Josephe

1974-01-01

This research thesis reports the study of the oxidation of a nickel-molybdenum alloy in the high-nickel-content part of this alloy. After a bibliographical study on the both metals, the author proposes a physical model based on observed phenomena and based on experimental results. Based on a thermodynamic study, the author compares the stability of the different oxides which may be formed, and reports a prediction of oxides obtained on the alloy during oxidation. Qualitative and quantitative studies have been performed by scanning electron microscopy coupled with electronic microprobe analysis to investigate morphological characteristics on oxidation films. A kinetic study by thermogravimetry shows a decrease of the alloy oxidation rate with respect to that of pure nickel at temperatures lower than 800 degrees C. This result is interpreted by the intervention of two opposed diffusion phenomena which act against each other [fr

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

Science.gov (United States)

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

2018-03-01

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

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

NARCIS (Netherlands)

Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

2015-01-01

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO2 films were found to show Arrhenius behaviour. However, a

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

African Journals Online (AJOL)

NICOLAAS

Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue-R dye by Hypochlorite and Role of Acid there in. Srinivasu Nadupalli, Venkata D.B.C. Dasireddy, Neil A. Koorbanally and Sreekantha B. Jonnalagadda*. School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private.

Kinetics of tetravalent plutonium oxidation by cerium (4)

Energy Technology Data Exchange (ETDEWEB)

Nikitina, G P; Shumakov, V G; Egorova, V P

1975-01-01

Stoichiometry and kinetics of the Pu(4) + Ce(4) reaction is studied by spectrophotometric method at 5-30 deg C in nitric acid solutions (..mu..=(HNO/sub 3/)+(NaNO/sub 3/) = 1.0 - 5.7; (Ce(4)) = 5.10/sup -5/ - 1.2.10/sup -3/ g-ion/1, (Pu(4)) =1.10/sup -5/ - 8.5.10/sup -4/ g-ion/1. Oxidation of one Pu(4) ion to a hexavalent state requires two Ce(4) ions. The plutonium oxidation is not complicated by by-processes. Reverse Ce(3) + PuO/sub 2//sup +/ reaction does not contribute essentially to the process at (Ce(3)) 2.6.10/sup -2/ g-ion/1. The reaction rate obeys the kinetic equation - d(Pu(4))/dt = ksub(eff)(Pu(4))(Ce(4))/a sub(+-HNO/sub 3/). The thermodynamical activation parameters are found for solutions at the varied nitric acid concentrations:..delta..Gsup(not equal) = 17.0+-0.2 and ..delta..Hsup(not equal) = 21.8+-2 kcal/mole(..mu..=1.0); ..delta..Gsup(not equal) = 19.1+-0.1 and ..delta..Hsup(not equal) = 23.1+-1 kcal/mole(..mu..=4.9). The reaction mechanism is discussed in terms of the theory of absolute reaction rates and the model of long-range charge transfer.

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

Science.gov (United States)

Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

2014-09-01

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

Graphite Oxidation Simulation in HTR Accident Conditions

Energy Technology Data Exchange (ETDEWEB)

El-Genk, Mohamed

2012-10-19

Massive air and water ingress, following a pipe break or leak in steam-generator tubes, is a design-basis accident for high-temperature reactors (HTRs). Analysis of these accidents in both prismatic and pebble bed HTRs requires state-of-the-art capability for predictions of: 1) oxidation kinetics, 2) air helium gas mixture stratification and diffusion into the core following the depressurization, 3) transport of multi-species gas mixture, and 4) graphite corrosion. This project will develop a multi-dimensional, comprehensive oxidation kinetics model of graphite in HTRs, with diverse capabilities for handling different flow regimes. The chemical kinetics/multi-species transport model for graphite burning and oxidation will account for temperature-related changes in the properties of graphite, oxidants (O2, H2O, CO), reaction products (CO, CO2, H2, CH4) and other gases in the mixture (He and N2). The model will treat the oxidation and corrosion of graphite in geometries representative of HTR core component at temperatures of 900°C or higher. The developed chemical reaction kinetics model will be user-friendly for coupling to full core analysis codes such as MELCOR and RELAP, as well as computational fluid dynamics (CFD) codes such as CD-adapco. The research team will solve governing equations for the multi-dimensional flow and the chemical reactions and kinetics using Simulink, an extension of the MATLAB solver, and will validate and benchmark the model's predictions using reported experimental data. Researchers will develop an interface to couple the validated model to a commercially available CFD fluid flow and thermal-hydraulic model of the reactor , and will perform a simulation of a pipe break in a prismatic core HTR, with the potential for future application to a pebble-bed type HTR.

Influence of organic substrates on the kinetics of bacterial As(III) oxidation

Science.gov (United States)

Lescure, T.; Joulian, C.; Bauda, P.; Hénault, C.; Battaglia-Brunet, F.

2012-04-01

Soil microflora plays a major role on the behavior of metals and metalloids. Arsenic speciation, in particular, is related to the activity of bacteria able to oxidize, reduce or methylate this element, and determines mobility, bioavailability and toxicity of As. Arsenite (AsIII) is more toxic and more mobile than arsenate (AsV). Bacterial As(III)-oxidation tends to reduce the toxicity of arsenic in soils and the risk of transfer toward underlying aquifers, that would affect the quality of water resources. Previous results suggest that organic matter may affect kinetics or efficiency of bacterial As(III)-oxidation in presence of oxygen, thus in conventional physico-chemical conditions of a surface soil. Different hypothesis can be proposed to explain the influence of organic matter on As(III) oxidation. Arsenic is a potential energy source for bacteria. The presence of easily biodegradable organic matter may inhibit the As(III) oxidation process because bacteria would first metabolize these more energetic substrates. A second hypothesis would be that, in presence of organic matter, the Ars system involved in bacterial resistance to arsenic would be more active and would compete with the Aio system of arsenite oxidation, decreasing the global As(III) oxidation rate. In addition, organic matter influences the solubility of iron oxides which often act as the main pitfalls of arsenic in soils. The concentration and nature of organic matter could therefore have a significant influence on the bioavailability of arsenic and hence on its environmental impact. The influence of organic matter on biological As(III) oxidation has not yet been determined in natural soils. In this context, soil amendment with organic matter during operations of phytostabilization or, considering diffuse pollutions, through agricultural practices, may affect the mobility and bio-availability of the toxic metalloid. The objective of the present project is to quantify the influence of organic matter

Simulation; an everyday tool for research in chemical kinetics

International Nuclear Information System (INIS)

Nakhle, M.; Roux, P.; Thomas de Montpreville, C.

1985-08-01

In order to make apparent the facilities offered by the NEPTUNIX package in solving some complex problems in chemical kinetics, the paper deals with its application to a particular example taken from material science: assistance to the validation of mechanisms governing colloids growth in a fluorite crystal when it is irradiated by an electron beam

Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

Science.gov (United States)

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

2016-05-26

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

Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

International Nuclear Information System (INIS)

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

2010-01-01

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

Influence of radiational oxidation on the kinetics of electrization of polypropylene by electron irradiation

International Nuclear Information System (INIS)

Rozno, A.G.; Romanov, A.V.; Sukhov, N.L.; Gromov, V.V.; Ershov, B.G.

1992-01-01

Kinetics of volumetric electric charge and accumulation of paramagnetic centres (PMC) in polypropylene (PP) of two crystal modifications, subjected to radiational oxidation were studied. A correlation between volumetric charge and PMC in radiationally oxidation PP was detected. Considerable influence of crystal phase on the processes of charging and radiational oxidation was revealed

Oxidation kinetics and soot formation

Science.gov (United States)

Glassman, I.; Brezinsky, K.

1983-01-01

The research objective is to clarify the role of aromaticity in the soot nucleation process by determining the relative importance of phenyl radical/molecular oxygen and benzene/atomic oxygen reactions in the complex combustion of aromatic compounds. Three sets of chemical flow reactor experiments have been designed to determine the relative importance of the phenyl radical/molecular oxygen and benzene/atomic oxygen reactions. The essential elements of these experiments are 1) the use of cresols and anisole formed during the high temperature oxidation of toluene as chemical reaction indicators; 2) the in situ photolysis of molecular oxygen to provide an oxygen atom perturbation in the reacting aromatic system; and 3) the high temperature pyrolysis of phenol, the cresols and possibly anisole.

Kinetics of oxidation of the alloy-MR-47VP with nitrogen dioxide

International Nuclear Information System (INIS)

Vasil'eva, A.G.; Rakova, N.N.; Vladimirskaya, I.N.; Kabanova, O.V.; Miklyaev, A.D.

1978-01-01

The kinetic dependences of oxidation of MR-47VP grade molybdenum-rhenium alloy with nitrogen dioxide have been examined within the temperature range of 350 to 550 deg C. It has been shown that the processes take place in the transition region. The specific oxidation rate of the alloy with the nitrogen dioxide is but small, and it is comparable as to its value with the specific rate of its oxidation in oxygen under identical conditions

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

International Nuclear Information System (INIS)

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

1992-01-01

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

Adsorption mechanism and kinetics of azo dye chemicals on oxide nanotubes: a case study using porous CeO_2 nanotubes

International Nuclear Information System (INIS)

Wu, Junshu; Wang, Jinshu; Du, Yucheng; Li, Hongyi; Jia, Xinjian

2016-01-01

Metal oxide nanotubes are believed to be promising materials with adsorption functionality for water purification due to their synergistic effect of the overall microscale morphology for easy separation and nanoscale surface characters providing enough surface active absorption sites. This work shows the synthesis of uniform hierarchical porous CeO_2 nanotubes via nanowire-directed templating method and describes the adsorption behavior of CeO_2 nanotubes for a typical azo dye Congo red which has resistance to oxidation and decoloration in natural conditions. Fourier transform infrared spectroscopy spectra provided the evidence that Congo red was successfully coated on the surface of CeO_2 nanotubes by both bidentate-type bridge link of Ce"4"+ cations from sulfonate SO_3"− groups and the electrostatic attraction between the protonated surface generated by oxygen vacancies and dissociated sulfonate groups. The adsorption kinetic data fitted well to the pseudo-second-order kinetic equation, whereas the Langmuir isotherm equation exhibited better correlation with the experimental data. The calculated maximum adsorption capacity from the isothermal model was 362.32 mg/g. In addition, the prepared CeO_2 nanotubes exhibited good recyclability and reusability as highly efficient adsorbents for Congo red removal after regeneration. These favorable performances enable the obtained CeO_2 nanotubes to be promising materials for dye removal from aqueous solution.Graphical AbstractCeO_2 nanotubes composed of crystallized nanoparticles exhibit well adsorption ability for a typical azo dye Congo red.

Thermoactivated persulfate oxidation of pesticide chlorpyrifos in aquatic system: kinetic and mechanistic investigations.

Science.gov (United States)

Zhou, Lei; Zhang, Ya; Ying, Rongrong; Wang, Guoqing; Long, Tao; Li, Jianhua; Lin, Yusuo

2017-04-01

The widespread occurrence of organophosphorus pesticides (OPPs) in the environment poses risks to both ecologic system as well as human health. This study investigated the oxidation kinetics of chlorpyrifos (CP), one of the typical OPPs, by thermoactivated persulfate (PS) oxidation process, and evaluated the influence of key kinetic factors, such as PS concentrations, pH, temperature, bicarbonate, and chloride ions. The reaction pathways and mechanisms were also proposed based on products identification by LC-MS techniques. Our results revealed that increasing initial PS concentration and temperature favored the decomposition of CP, whereas the oxidation efficiency was not affected by pH change ranging from 3 to 11. Bicarbonate was found to play a detrimental role on CP removal rates, while chloride showed no effect. The oxidation pathways including initial oxidation of P=S bond to P=O, dechlorination, dealkylation, and the dechlorination-hydroxylation were proposed, and the detailed underlying mechanisms were also discussed. Molecular orbital (MO) calculations indicated that P=S bond was the most favored oxidation site of the molecule. The toxicity of reaction solution was believed to increase due to the formation of products with P=O structures. This work demonstrates that OPPs can readily react with SO 4 ·- and provides important information for further research on the oxidation of these contaminants.

Kinetics and Mechanistic Study of Permanganate Oxidation of Fluorenone Hydrazone in Alkaline Medium

Directory of Open Access Journals (Sweden)

Ahmed Fawzy

2016-01-01

Full Text Available The oxidation kinetics of fluorenone hydrazone (FH using potassium permanganate in alkaline medium were measured at a constant ionic strength of 0.1 mol dm−3 and at 25°C using UV/VIS spectrophotometer. A first-order kinetics has been monitored in the reaction of FH with respect to [permanganate]. Less-than-unit order dependence of the reaction on [FH] and [OH−] was revealed. No pronounced effect on the reaction rate by increasing ionic strength was recorded. Intervention of free radicals was observed in the reaction. The reaction mechanism describing the kinetic results was illustrated which involves formation of 1 : 1 intermediate complex between fluorenone hydrazones and the active species of permanganate. 9H-Fluorenone as the corresponding ketone was found to be the final oxidation product of fluorenone hydrazone as confirmed by GC/MS analysis and FT-IR spectroscopy. The expression rate law for the oxidation reaction was deduced. The reaction constants and mechanism have been evaluated. The activation parameters associated with the rate-limiting step of the reaction, along with the thermodynamic quantities of the equilibrium constants, have been calculated and discussed.

The kinetic study of oxidation of iodine by hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Cantrel, L [Institut de Protection et de Surete Nucleaire, IPNS, CEN Cadarache, Saint Paul lez Durance (France); Chopin, J [Laboratoire d` Electrochimie Inorganique, ENSSPICAM, Marseille (France)

1996-12-01

Iodine chemistry is one of the most important subjects of research in the field of reactor safety because this element can form volatile species which represent a biological hazard for environment. As the iodine and the peroxide are both present in the sump of the containment in the event of a severe accident on a light water nuclear reactor, it can be important to improve the knowledge on the reaction of oxidation of iodine by hydrogen peroxide. The kinetics of iodine by hydrogen peroxide has been studied in acid solution using two different analytical methods. The first is a UV/Vis spectrophotometer which records the transmitted intensity at 460 nm as a function of time to follow the decrease of iodine concentration, the second is an amperometric method which permits to record the increase of iodine+1 with time thanks to the current of reduction of iodine+1 to molecular iodine. The iodine was generated by Dushman reaction and the series of investigations were made at 40{sup o}C in a continuous stirring tank reactor. The influence of the initial concentrations of iodine, iodate, hydrogen peroxide, H{sup +} ions has been determined. The kinetics curves comprise two distinct chemical phases both for molecular iodine and for iodine+1. The relative importance of the two processes is connected to the initial concentrations of [I{sub 2}], [IO{sub 3}{sup -}], [H{sub 2}O{sub 2}] and [H{sup +}]. A rate law has been determined for the two steps for molecular iodine. (author) figs., tabs., 22 refs.

The kinetic study of oxidation of iodine by hydrogen peroxide

International Nuclear Information System (INIS)

Cantrel, L.; Chopin, J.

1996-01-01

Iodine chemistry is one of the most important subjects of research in the field of reactor safety because this element can form volatile species which represent a biological hazard for environment. As the iodine and the peroxide are both present in the sump of the containment in the event of a severe accident on a light water nuclear reactor, it can be important to improve the knowledge on the reaction of oxidation of iodine by hydrogen peroxide. The kinetics of iodine by hydrogen peroxide has been studied in acid solution using two different analytical methods. The first is a UV/Vis spectrophotometer which records the transmitted intensity at 460 nm as a function of time to follow the decrease of iodine concentration, the second is an amperometric method which permits to record the increase of iodine+1 with time thanks to the current of reduction of iodine+1 to molecular iodine. The iodine was generated by Dushman reaction and the series of investigations were made at 40 o C in a continuous stirring tank reactor. The influence of the initial concentrations of iodine, iodate, hydrogen peroxide, H + ions has been determined. The kinetics curves comprise two distinct chemical phases both for molecular iodine and for iodine+1. The relative importance of the two processes is connected to the initial concentrations of [I 2 ], [IO 3 - ], [H 2 O 2 ] and [H + ]. A rate law has been determined for the two steps for molecular iodine. (author) figs., tabs., 22 refs

On chemical activity of heavy metal oxides

International Nuclear Information System (INIS)

Mechev, V.V.

1994-01-01

Interaction of solid oxides of heavy nonferrous metals with sulfur and carbon is investigated. The results are discussed. Direct dependence of chemical activity of oxides on disordering of their crystal lattice at heating is established. Beginning of interaction in the systems studied is accompanied by change of oxide conductivity type

Fat oxidation, hormonal and plasma metabolite kinetics during a submaximal incremental test in lean and obese adults.

Science.gov (United States)

Lanzi, Stefano; Codecasa, Franco; Cornacchia, Mauro; Maestrini, Sabrina; Salvadori, Alberto; Brunani, Amelia; Malatesta, Davide

2014-01-01

This study aimed to compare fat oxidation, hormonal and plasma metabolite kinetics during exercise in lean (L) and obese (O) men. Sixteen L and 16 O men [Body Mass Index (BMI): 22.9 ± 0.3 and 39.0 ± 1.4 kg · m(-2)] performed a submaximal incremental test (Incr) on a cycle-ergometer. Fat oxidation rates (FORs) were determined using indirect calorimetry. A sinusoidal model, including 3 independent variables (dilatation, symmetry, translation), was used to describe fat oxidation kinetics and determine the intensity (Fat(max)) eliciting maximal fat oxidation. Blood samples were drawn for the hormonal and plasma metabolite determination at each step of Incr. FORs (mg · FFM(-1) · min(-1)) were significantly higher from 20 to 30% of peak oxygen uptake (VO2peak) in O than in L and from 65 to 85% VO2peak in L than in O (p ≤ 0.05). FORs were similar in O and in L from 35 to 60% VO2peak. Fat max was 17% significantly lower in O than in L (poxidation kinetics were characterized by similar translation, significantly lower dilatation and left-shift symmetry in O compared with L (poxidation at high exercise intensities suggest that the difference in the fat oxidation kinetics is likely linked to impaired muscular capacity to oxidize NEFA in O. These results may have important implications for the appropriate exercise intensity prescription in training programs designed to optimize fat oxidation in O.

Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

Science.gov (United States)

Fox, D. S.

1994-01-01

Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

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...

Effect of a 1-hour single bout of moderate-intensity exercise on fat oxidation kinetics.

Science.gov (United States)

Chenevière, Xavier; Borrani, Fabio; Ebenegger, Vincent; Gojanovic, Boris; Malatesta, Davide

2009-12-01

The present study aimed to examine the effects of a prior 1-hour continuous exercise bout (CONT) at an intensity (Fat(max)) that elicits the maximal fat oxidation (MFO) on the fat oxidation kinetics during a subsequent submaximal incremental test (IncrC). Twenty moderately trained subjects (9 men and 11 women) performed a graded test on a treadmill (Incr), with 3-minute stages and 1-km.h(-1) increments. Fat oxidation was measured using indirect calorimetry and plotted as a function of exercise intensity. A mathematical model (SIN) including 3 independent variables (dilatation, symmetry, and translation) was used to characterize the shape of fat oxidation kinetics and to determine Fat(max) and MFO. On a second visit, the subjects performed CONT at Fat(max) followed by IncrC. After CONT performed at 57% +/- 3% (means +/- SE) maximal oxygen uptake (Vo(2max)), the respiratory exchange ratio during IncrC was lower at every stage compared with Incr (P rates from 35% to 70% Vo(2max) (P .05), whereas symmetry tended to be greater in IncrC (P = .096). This study showed that the prior 1-hour continuous moderate-intensity exercise bout increased Fat(max), MFO, and fat oxidation rates over a wide range of intensities during the postexercise incremental test. Moreover, the shape of the postexercise fat oxidation kinetics tended to have a rightward asymmetry.

Kinetics of carbon monoxide oxidation over modified supported CuO catalysts

Energy Technology Data Exchange (ETDEWEB)

Loc, Luu Cam; Tri, Nguyen; Cuong, Hoang Tien; Thoang, Ho Si [Vietnam Academy of Science and Technology (VAST), Ho Chi Minh City (Viet Nam). Inst. of Chemical Technology; Agafonov, Yu.A.; Gaidai, N.A.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

2013-11-01

The following supported on {gamma}-Al{sub 2}O{sub 3} catalysts: 10(wt.)%CuO (CuAl), 10%CuO+10%Cr{sub 2}O{sub 3} (CuCrAl) and 10%CuO+20%CeO{sub 2} (CuCeAl) were under the investigation. Physico-chemical characteristics of the catalysts were determined by the methods of BET, X-ray Diffraction (XRD), and Temperature-Programmed Reduction (TPR). A strong interaction of copper with support in CuAl resulted in the formation of low active copper aluminates. The bi-oxide CuCrAl was more active than CuAl owing to the formation of high catalytically active spinel CuCr{sub 2}O{sub 4}. The fact of very high activity of the sample CuCeAl can be explained by the presence of the catalytically active form of CuO-CeO{sub 2}-Al{sub 2}O{sub 3}. The kinetics of CO total oxidation was studied in a gradientless flow-circulating system at the temperature range between 200 C and 270 C. The values of initial partial pressures of carbon monoxide (P{sup o}{sub CO}), oxygen (P{sup o}{sub O2}), and specially added carbon dioxide (P{sup o}{sub CO{sub 2}}) were varied in ranges (hPa): 10 / 45; 33 / 100, and 0 / 30, respectively. (orig.)

Nitrogen metabolism and kinetics of ammonia-oxidizing archaea.

Science.gov (United States)

Martens-Habbena, Willm; Stahl, David A

2011-01-01

The discovery of ammonia-oxidizing mesophilic and thermophilic Group I archaea changed the century-old paradigm that aerobic ammonia oxidation is solely mediated by two small clades of Beta- and Gammaproteobacteria. Group I archaea are extremely diverse and ubiquitous in marine and terrestrial environments, accounting for 20-30% of the microbial plankton in the global oceans. Recent studies indicated that many of these organisms carry putative ammonia monooxygenase genes and are more abundant than ammonia-oxidizing bacteria in most natural environments suggesting a potentially significant role in the nitrogen cycle. The isolation of Nitrosopumilus maritimus strain SCM1 provided the first direct evidence that Group I archaea indeed gain energy from ammonia oxidation. To characterize the physiology of this archaeal nitrifier, we developed a respirometry setup particularly suited for activity measurements in dilute microbial cultures with extremely low oxygen uptake rates. Here, we describe the setup and review the kinetic experiments conducted with N. maritimus and other nitrifying microorganisms. These experiments demonstrated that N. maritimus is adapted to grow on ammonia concentrations found in oligotrophic open ocean environments, far below the survival threshold of ammonia-oxidizing bacteria. The described setup and experimental procedures should facilitate physiological studies on other nitrifying archaea and oligotrophic microorganisms in general. Copyright © 2011 Elsevier Inc. All rights reserved.

Kinetics and mechanism of the oxidation of some diols by ...

Indian Academy of Sciences (India)

Abstract. The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (v/v) acetic acid–water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give.

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

DEFF Research Database (Denmark)

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

2007-01-01

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

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

Science.gov (United States)

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

2014-01-01

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

Modeling of Scale-Dependent Bacterial Growth by Chemical Kinetics Approach

Directory of Open Access Journals (Sweden)

Haydee Martínez

2014-01-01

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

Kinetics and mechanism of oxidation of glycine by iron(III)

Indian Academy of Sciences (India)

Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H+] decreases the rate. Hence it can be inferred that the ...

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation, chemical and advanced oxidation processes.

Science.gov (United States)

Bagal, Manisha V; Gogate, Parag R

2013-09-01

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3-6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3-11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H2O2), ferrous activated persulfate (HC/Na2S2O8/FeSO4) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO4/H2O2), advanced Fenton (HC/Fe/H2O2) and Fenton-like process (HC/CuO/H2O2) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes. Copyright © 2013 Elsevier B.V. All rights reserved.

Enzyme catalyzed oxidative gelation of sugar beet pectin: Kinetics and rheology

DEFF Research Database (Denmark)

Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

2012-01-01

Sugar beet pectin (SBP) is a marginally utilized co-processing product from sugar production from sugar beets. In this study, the kinetics of oxidative gelation of SBP, taking place via enzyme catalyzed cross-linking of ferulic acid moieties (FA), was studied using small angle oscillatory...

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

International Nuclear Information System (INIS)

Markin, Craig J.; Spyracopoulos, Leo

2012-01-01

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

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

Science.gov (United States)

Markin, Craig J; Spyracopoulos, Leo

2012-12-01

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

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies.

Science.gov (United States)

Karthikeyan, S; Ezhil Priya, M; Boopathy, R; Velan, M; Mandal, A B; Sekaran, G

2012-06-01

BACKGROUND, AIM, SCOPE: Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst. Ferrous sulfate (FeSO(4)·7H(2)O), sulfuric acid (36 N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50 cm and diameter 6 cm, were fabricated with PVC while one reactor was packed with MAC of mass 150 g and other without MAC served as control. The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89 kJ/mol, respectively. The thermodynamic parameters ΔG, ΔH, and ΔS were calculated for the oxidation processes using Van't Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV-visible spectroscopy, and cyclic voltammetry. The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time-4 h, and H(2)O(2)/FeSO(4)·7H(2)O in the molar ratio of 2:1.

Poly (3, 4-ethylendioxithiophene) (PEDOT) oxidation: activation energy and conformational energy

International Nuclear Information System (INIS)

Otero, T F; Romero, M C

2008-01-01

The oxidation kinetics of films of the conducting polymer PEDOT-C1O4 after electrochemical reduction by polarization at increasing cathodic potential was studied by potential steps. The response i/t presents a maximum at intermediate oxidation times. At the maximum the reaction occurs under chemical kinetic control following the expected current variations from the Chemical and Electrochemical Kinetics, when reactant concentrations or temperatures are changed. The obtained activation energy of the oxidation present two ranges as a function of the cathodic potential of prepolarization: constant values after prepolarization at low cathodic potentials and a lineal variation after prepolarization at increasing high cathodic potentials. According with the conformational relaxation model during electrochemical reduction the polymer shrinks, closes and packs the conformational structure. The activation energy for the subsequent oxidation includes two terms: the constant chemical activation energy and the conformational energy required to relax the packed polymeric structure. The conformational energy only appears after prepolarization at more cathodic potentials than the closing potential where more packed conformations were obtained. The conformational activation energy accounts the energetic requirements to relax and unfold the polymeric chains generating the required free volume to lodge balancing counterions; meanwhile the chemical activation energy accounts the energetic requirements for the electrochemical reaction to occur.

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

KAUST Repository

Kuti, Olawole

2013-10-14

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

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

KAUST Repository

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

2013-01-01

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

Ammonia oxidation kinetics and temperature sensitivity of a natural marine community dominated by Archaea

Science.gov (United States)

Horak, Rachel E A; Qin, Wei; Schauer, Andy J; Armbrust, E Virginia; Ingalls, Anitra E; Moffett, James W; Stahl, David A; Devol, Allan H

2013-01-01

Archaeal ammonia oxidizers (AOAs) are increasingly recognized as prominent members of natural microbial assemblages. Evidence that links the presence of AOA with in situ ammonia oxidation activity is limited, and the abiotic factors that regulate the distribution of AOA natural assemblages are not well defined. We used quantitative PCR to enumerate amoA (encodes α-subunit of ammonia monooxygenase) abundances; AOA amoA gene copies greatly outnumbered ammonia-oxidizing bacteria and amoA transcripts were derived primarily from AOA throughout the water column of Hood Canal, Puget Sound, WA, USA. We generated a Michaelis–Menten kinetics curve for ammonia oxidation by the natural community and found that the measured Km of 98±14 nmol l−1 was close to that for cultivated AOA representative Nitrosopumilus maritimus SCM1. Temperature did not have a significant effect on ammonia oxidation rates for incubation temperatures ranging from 8 to 20 °C, which is within the temperature range for depths of measurable ammonia oxidation at the site. This study provides substantial evidence, through both amoA gene copies and transcript abundances and the kinetics response, that AOA are the dominant active ammonia oxidizers in this marine environment. We propose that future ammonia oxidation experiments use a Km for the natural community to better constrain ammonia oxidation rates determined with the commonly used 15NH4+ dilution technique. PMID:23657360

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

Data.gov (United States)

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

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

Data.gov (United States)

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

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. Seema Kothari. Articles written in Journal of Chemical Sciences. Volume 113 Issue 1 February 2001 pp 43-54 Organic. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide · Garima Goswami Seema Kothari Kalyan K Banerji.

Kinetics that govern the release of tritium from neutron-irradiated lithium oxide

International Nuclear Information System (INIS)

Bertone, P.C.

1986-01-01

The Lithium Blanket Module (LBM) program being conducted at the Princeton Plasma Physics Laboratory requires that tritium concentrations as low as 0.1 nCi/g, bred in both LBM lithium oxide pellets and gram-size lithium samples, be measured with an uncertainty not exceeding +/-6%. This thesis reports two satisfactory methods of assaying LBM pellets and one satisfactory method of assaying lithium samples. Results of a fundamental kinetic investigation are also reported. The thermally driven release of tritium from neutron-irradiated lithium oxide pellets is studied between the temperatures of 300 and 400 0 C. The observed release clearly obeys first-order kinetics, and the governing activation energy appears to be 28.4 kcal/mole. Finally, a model is presented that may explain the thermally driven release of tritium from a lithium oxide crystal and assemblies thereof. It predicts that under most circumstances the release is controlled by either the diffusion of a tritiated species through the crystal, or by the desorption of tritiated water from it

Oxidation kinetics of zircaloy-4 in the temperature range correspondent to alpha phase

International Nuclear Information System (INIS)

Medeiros, L.F.

1975-12-01

Oxidation kinetics of Zry-4 in the alpha phase is isothermally studied in the temperature range from 600 0 C to 800 0 C, by continuous and discontinuous gravimetric methods. The total mass gain during the oxidation takes place by two distinct ways: oxide formation and solid solution formation. The first one has been studied by microscopy: the latter by microhardness. The oxygen diffusion coefficients in the zirconium are experimentally determined by microhardness measurements and are compared with those obtained by the oxide layer thickness and by oxygen mass in the oxide. The oxygen diffusion coefficients in the oxide are obtained too by oxide layer thickness and by oxygen diffusivities in the alpha phase and compared with literature. (author)

Design of a high-pressure single pulse shock tube for chemical kinetic investigations

International Nuclear Information System (INIS)

Tranter, R. S.; Brezinsky, K.; Fulle, D.

2001-01-01

A single pulse shock tube has been designed and constructed in order to achieve extremely high pressures and temperatures to facilitate gas-phase chemical kinetic experiments. Postshock pressures of greater than 1000 atmospheres have been obtained. Temperatures greater than 1400 K have been achieved and, in principle, temperatures greater than 2000 K are easily attainable. These high temperatures and pressures permit the investigation of hydrocarbon species pyrolysis and oxidation reactions. Since these reactions occur on the time scale of 0.5--2 ms the shock tube has been constructed with an adjustable length driven section that permits variation of reaction viewing times. For any given reaction viewing time, samples can be withdrawn through a specially constructed automated sampling apparatus for subsequent species analysis with gas chromatography and mass spectrometry. The details of the design and construction that have permitted the successful generation of very high-pressure shocks in this unique apparatus are described. Additional information is provided concerning the diaphragms used in the high-pressure shock tube

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Is automated kinetic measurement superior to end-point for advanced oxidation protein product?

Science.gov (United States)

Oguz, Osman; Inal, Berrin Bercik; Emre, Turker; Ozcan, Oguzhan; Altunoglu, Esma; Oguz, Gokce; Topkaya, Cigdem; Guvenen, Guvenc

2014-01-01

Advanced oxidation protein product (AOPP) was first described as an oxidative protein marker in chronic uremic patients and measured with a semi-automatic end-point method. Subsequently, the kinetic method was introduced for AOPP assay. We aimed to compare these two methods by adapting them to a chemistry analyzer and to investigate the correlation between AOPP and fibrinogen, the key molecule responsible for human plasma AOPP reactivity, microalbumin, and HbA1c in patients with type II diabetes mellitus (DM II). The effects of EDTA and citrate-anticogulated tubes on these two methods were incorporated into the study. This study included 93 DM II patients (36 women, 57 men) with HbA1c levels > or = 7%, who were admitted to the diabetes and nephrology clinics. The samples were collected in EDTA and in citrate-anticoagulated tubes. Both methods were adapted to a chemistry analyzer and the samples were studied in parallel. In both types of samples, we found a moderate correlation between the kinetic and the endpoint methods (r = 0.611 for citrate-anticoagulated, r = 0.636 for EDTA-anticoagulated, p = 0.0001 for both). We found a moderate correlation between fibrinogen-AOPP and microalbumin-AOPP levels only in the kinetic method (r = 0.644 and 0.520 for citrate-anticoagulated; r = 0.581 and 0.490 for EDTA-anticoagulated, p = 0.0001). We conclude that adaptation of the end-point method to automation is more difficult and it has higher between-run CV% while application of the kinetic method is easier and it may be used in oxidative stress studies.

Measurement of Antioxidant Effects on the Auto-oxidation Kinetics of Methyl Oleate – Methyl Laurate Blend as a Surrogate Biodiesel System

Directory of Open Access Journals (Sweden)

Tjokorde Walmiki Samadhi

2017-05-01

Full Text Available This research investigates the feasibility of methyl oleate-methyl laurate blend as a surrogate biodiesel system which represents jatropha-coconut oil biodiesel, a potentially suitable formulation for tropical climate, to quantify the efficacy of antioxidant additives in terms of their kinetic parameters. This blend was tested by the Rancimat EN14112 standard method. The Rancimat tests results were used to determine the primary oxidation induction period (OIP and first-order rate constants and activation energies. Addition of BHT and EcotiveTM antioxidants reduces the rate constants (k, h-1 between 15 to 90% in the 50-200 ppm dose range, with EcotiveTM producing significantly lower k values. Higher dose reduces the rate constant, while oleate/laurate ratio produces no significant impact. Antioxidants increase the oxidation activation energy (Ea, kJ/mol by 180 to almost 400% relative to the non-antioxidant value of 27.0 kJ/mol. EcotiveTM exhibits lower Ea, implying that its higher efficacy stems from a better steric hindrance as apparent from its higher pre-exponential factors. The ability to quantify oxidation kinetic parameters is indicative of the usefulness of methyl oleate-laurate pure FAME blend as a biodiesel surrogate offering better measurement accuracy due to the absence of pre-existing antioxidants in the test samples. Copyright © 2017 BCREC GROUP. All rights reserved Received: 6th July 2016; Revised: 7th December 2016; Accepted: 30th January 2017 How to Cite: Samadhi, T.W., Hirotsu, T., Goto, S. (2017. Measurement of Antioxidant Effects on the Auto-oxidation Kinetics of Methyl Oleate-Methyl Laurate Blend as a Surrogate Biodiesel System. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 157-166 (doi:10.9767/bcrec.12.2.861.157-166 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.861.157-166

Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation.

Science.gov (United States)

Moradmand Jalali, Hamed; Bashiri, Hadis; Rasa, Hossein

2015-05-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO2, ZnO and ZrO2) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxidation kinetics of zirconium nitride. I. Planar symmetry

International Nuclear Information System (INIS)

Desmaison, Jean; Billy, Michel

1976-01-01

The oxidation behavior of ZrNsub(0.93) plates was investigated at temperatures in the range 625-800 deg C in oxygen over the pressure range 10-730 torr. The reaction product consists of monoclinic zirconia accompanied with trace amounts of cubic or tetragonal zirconia. Although the kinetic results are well interpreted by a Prout and Tompkins type model. The morphological observations suggest a transformation governed by a phase boundary reaction, this being confirmed by the oxygen pressure dependence on the rate law [fr

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

Science.gov (United States)

Otero, Toribio F

2017-01-18

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

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.

A tool model for predicting atmospheric kinetics with sensitivity analysis

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

A package( a tool model) for program of predicting atmospheric chemical kinetics with sensitivity analysis is presented. The new direct method of calculating the first order sensitivity coefficients using sparse matrix technology to chemical kinetics is included in the tool model, it is only necessary to triangularize the matrix related to the Jacobian matrix of the model equation. The Gear type procedure is used to integrate amodel equation and its coupled auxiliary sensitivity coefficient equations. The FORTRAN subroutines of the model equation, the sensitivity coefficient equations, and their Jacobian analytical expressions are generated automatically from a chemical mechanism. The kinetic representation for the model equation and its sensitivity coefficient equations, and their Jacobian matrix is presented. Various FORTRAN subroutines in packages, such as SLODE, modified MA28, Gear package, with which the program runs in conjunction are recommended.The photo-oxidation of dimethyl disulfide is used for illustration.

Thermodynamic and kinetic control on anaerobic oxidation of methane in marine sediments

DEFF Research Database (Denmark)

Knab, Nina J.; Dale, Andrew W.; Lettmann, Karsten

2008-01-01

The free energy yield of microbial respiration reactions in anaerobic marine sediments must be sufficient to be conserved as biologically usable energy in the form of ATP. Anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SRR) has a very low standard free energy yield of ΔG  = -33...... yield was rarely less than -20 kJ mol-1 and was mostly rather constant throughout this zone. The kinetic drive was highest at the lower part of the SMTZ, matching the occurrence of maximum AOM rates. The results show that the location of maximum AOM rates is determined by a combination of thermodynamic...... and kinetic drive, whereas the rate activity mainly depends on kinetic regulation....

Kinetics and mechanisms of the oxidation of cobalt at 600-8000C

International Nuclear Information System (INIS)

Hsu, H.S.; Yurek, G.J.

1982-01-01

Two-phase layered scales comprising CoO and Co 3 O 4 formed on cobalt during oxidation at 600 0 , 700 0 , and 800 0 C and at oxygen partial pressures in the range 0.001-1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, nonparabolic stage of oxidation. The monoxide consisted of relatively large grains (10μ) and the spinel comprised small grains (3μ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinal layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co 3 O 4

Kinetic Studies on the Selective Oxidation of Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis

Directory of Open Access Journals (Sweden)

K. Bijudas

2014-07-01

Full Text Available Kinetic studies on the oxidation of benzyl alcohol and substituted benzyl alcohols in benzene as the reaction medium have been studied by using potassium dichromate under phase transfer catalysis (PTC. The phase transfer catalysts (PT catalysts used were tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB.  Benzyl alcohols were selectively oxidised to corresponding benzaldehydes in good yield (above 90%.  The order of reactivity among the studied benzyl alcohols is p - OCH3 > p - CH3 > - H > p - Cl.  Plots of log k2 versus Hammett's substituent constant (s has been found to be curve shaped and this suggests that there should be a continuous change in transition state with changes in substituent present in the substrate from electron donating to electron withdrawing. A suitable mechanism has been suggested in which the rate determining step involves both C - H bond cleavage and C - O bond formations in concerted manner. © 2014 BCREC UNDIP. All rights reserved.Received: 16th March 2014; Revised: 18th May 2014; Accepted: 18th May 2014[How to Cite: Bijudas, K., Bashpa, P., Nair, T.D.R. (2014. Kinetic Studies on the Selective Oxidation of Benzyl Alcohol and Substituted Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-147. (doi:10.9767/bcrec.9.2.6476.142-147][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6476.142-147] 

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

... Courses · Symposia · Live Streaming. Home; Journals; Journal of Chemical Sciences. V R Vijayaraghavan. Articles written in Journal of Chemical Sciences. Volume 112 Issue 5 October 2000 pp 507-514 Inorganic and Analytical. Kinetics of oxidation of nickel(II) aza macrocycles by peroxydisulphate in aqueous media.

Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

International Nuclear Information System (INIS)

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

2011-01-01

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

Application of Detailed Chemical Kinetics to Combustion Instability Modeling

Science.gov (United States)

2016-01-04

Clearance Number 15692 Clearance Date 12/3/2015 14. ABSTRACT A comparison of a single step global reaction and the detailed GRI -Mech 1.2 for combustion...comparison of a single step global reaction and the detailed GRI -Mech 1.2 for com- bustion instability modeling in a methane-fueled longitudinal-mode...methane as the fuel. We use the GRI -Mech 1.2 kinetics mechanism for methane oxidation.11 The GRI -Mech 1.2 was chosen over 2.11 because the only

Kinetics of lactate turnover and oxidation in man

International Nuclear Information System (INIS)

Searle, G.L.; Shames, D.; Cavalieri, R.R.; DeGrazia, J.; Zarcone, V.; Porte, D. Jr.; Bagdade, J.D.

1975-01-01

The turnover and oxidation of lactic acid have been studied in man by means of 14 C-lactic acid, 14 C-glucose, and 14 C-alanine. The use of these labels in separate studies has enabled us to describe a complete scheme for the kinetics of lactic acid in man. We have determined that lactate arises from a minimum of two sources in overnight fasted man. 66% of lactate at this time arises from the metabolism of glucose while approximately 15% is derived from alanine. These sources and others unidentified supply lactate to the body pool at a rate of approximately 95 mg per kg per h. The disposal of this quantity of lactate is achieved through a minimum of three routes. Approximately 57% of the lactate turnover is oxidized to carbon dioxide, 15% is reduced to glucose, and approximately 25% is converted to alanine. The quantitative changes in the kinetics of this system that are brought on by fasting add an interesting dimension to the system. In agreement with the concepts of fuel economy in fasting the contribution of glucose carbon to lactic acid falls and, in turn, the contribution of lactate carbon to body glucose rises. The study of additional permutations of this system suggest that lactate, with pyruvate, is in the main stream of the intermediary metabolism of the body. The authors suggest that the study of this system offers promise of a fuller understanding of the derangements of metabolic disease. (author)

The influence of the texture and microstructure of a Zr-2.5Nb substrate upon the oxidation kinetics

International Nuclear Information System (INIS)

Lin, J.; Cao Xiaohui; Szpunar, J.A.

2002-01-01

The thin oxide layer growing on the zirconium alloy is dense and adherent and therefore is protective against further oxidation and hydrogen ingress, which is deleterious to zirconium pressure tube used in nuclear power stations because it facilitates formation of zirconium hydrides. Heat treatment and other surface modification methods were applied to zirconium alloys and the texture was investigated. Thermogravimetric analytic (TGA) was used for oxidation kinetics studies. The oxidation kinetics data show the variation of the oxidation rate due to the difference of texture and microstructure and the oxidation resistance is improved after the substrate is cold worked and heat treated. After cold work and heat treatment, the texture of substrate changes from (11-20)[1-100] to (11-23)[1-100]. (orig.)

Thermal properties of graphite oxide, thermally reduced graphene and chemically reduced graphene

Science.gov (United States)

Jankovský, Ondřej; Sedmidubský, David; Lojka, Michal; Sofer, Zdeněk

2017-07-01

We compared thermal behavior and other properties of graphite oxide, thermally reduced graphene and chemically reduced graphene. Graphite was oxidized according to the Hofmann method using potassium chlorate as oxidizing agent in strongly acidic environment. In the next step, the formed graphite oxide was chemically or thermally reduced yielding graphene. The mechanism of thermal reduction was studied using STA-MS. Graphite oxide and both thermally and chemically reduced graphenes were analysed by SEM, EDS, elemental combustion analysis, XPS, Raman spectroscopy, XRD and BET. These findings will help for the large scale production of graphene with appropriate chemical composition.

Kinetic study of methanol oxidation on Pt2Ru3/C catalyst in the alkaline media

Directory of Open Access Journals (Sweden)

A. V. TRIPKOVIC

2007-11-01

Full Text Available The interaction of acridine orange (AO with double-stranded (ds The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

Kinetic Resolution of sec-Thiols via Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase

NARCIS (Netherlands)

Pickl, Mathias; Swoboda, Alexander; Romero, Elvira; Winkler, Christoph; Binda, Claudia; Mattevi, Andrea; Faber, Kurt; Fraaije, Marco

2018-01-01

Various flavoprotein oxidases were recently shown to oxidize prim-thiols. Here we extend this reactivity towards sec-thiols via structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of rac-sec-thiols

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

Science.gov (United States)

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

1980-01-01

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

Factors determining the activity of catalysts of various chemical types in the oxidation of hydrogen. I. Oxidation and isotope exchange of hydrogen on cobalt monoxide-oxide

International Nuclear Information System (INIS)

Polgikh, L.Y.; Golodets, G.I.; Il'chenko, N.I.

1985-01-01

On the basis of data on the kinetics of the reaction 2H 2 + O 2 = 2H 2 O isotope exchange H 2 + D 2 = 2HD under the conditions of oxidative catalysis, and the kinetic isotope effect, a mechanism is proposed for the oxidation of hydrogen on cobalt monoxide-oxide. At low temperatures the reaction proceeds according to a mechanism of alternating reduction-reoxidation of the surface with the participation of hydrogen adsorbed in molecular form; at increased temperature and low P 02 /P /SUB H2/ ratios, a significant contribution to the observed rate is made by a mechanism including dissociative chemisorption of hydrogen

Kinetics and mechanism of the oxidation of some vicinal and non ...

Indian Academy of Sciences (India)

Kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers, by tetrabutylammonium tribromide (TBATB) has been studied. The vicinal diols yield products arising out of glycol-bond fission, while the non-vicinal diols produce the hydroxycarbonyl compounds. The reaction is first-order with ...

Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

Energy Technology Data Exchange (ETDEWEB)

Hubler, T.L. [Pacific Northwest National Lab., Richland, WA (United States)

1997-10-01

The goal of this task is to develop modified resorcinol-formaldehyde (R-F) resin to improve the chemical/oxidative stability of the resin. R-F resin is a regenerable organic ion-exchange resin that is selective for cesium ion in highly alkaline, high ionic-strength solutions. R-F resin tends to undergo chemical degradation, reducing its ability to remove cesium ion from waste solutions; the mechanistic details of these decomposition reactions are currently unknown. The approach used for this task is chemical modification of the resin structure, particularly the resorcinol ring unit of the polymer resin. This approach is based on prior characterization studies conducted at Pacific Northwest National Laboratory (PNNL) that indicated the facile chemical degradation of the resin is oxidation of the resorcinol ring to the para-quinone structure, with subsequent loss of ion-exchange sites for cesium ion. R-F resin represents an important alternative to current radiocesium remediation technology for tank wastes at both the Hanford and Savannah River sites, particularly if regenerable resins are needed.

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