WorldWideScience

Sample records for volume oxidation kinetics

  1. Biochemical kinetics in changing volumes.

    Science.gov (United States)

    Pawłowski, Piotr H; Zielenkiewicz, Piotr

    2004-01-01

    The need of taking into account the change of compartment volume when developing chemical kinetics analysis inside the living cell is discussed. Literature models of a single enzymatic Michaelis-Menten process, glycolytic oscillations, and mitotic cyclin oscillations were tested with appropriate theoretical extension in the direction of volume modification allowance. Linear and exponential type of volume increase regimes were compared. Due to the above, in a growing cell damping of the amplitude, phase shift, and time pattern deformation of the metabolic rhythms considered were detected, depending on the volume change character. The performed computer simulations allow us to conclude that evolution of the cell volume can be an essential factor of the chemical kinetics in a growing cell. The phenomenon of additional metabolite oscillations caused by the periodic cell growth and division was theoretically predicted and mathematically described. Also, the hypothesis of the periodized state in the growing cell as the generalization of the steady-state was formulated.

  2. 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.

  3. Oxidation kinetics of aluminum diboride

    Energy Technology Data Exchange (ETDEWEB)

    Whittaker, Michael L., E-mail: michaelwhittaker2016@u.northwestern.edu [Department of Materials Science and Engineering, University of Utah, 122S. Central Campus Drive, Salt Lake City, UT 84112 (United States); Sohn, H.Y. [Department of Metallurgical Engineering, University of Utah, 135S 1460 E, Rm 00412, Salt Lake City, UT 84112 (United States); Cutler, Raymond A. [Ceramatec, Inc., 2425S. 900W., Salt Lake City, UT 84119 (United States)

    2013-11-15

    The oxidation characteristics of aluminum diboride (AlB{sub 2}) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB{sub 2} in the onset of oxidation and final conversion fraction, with AlB{sub 2} beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB{sub 2} and Al+2B in both air and oxygen. AlB{sub 2} exhibited O{sub 2}-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O{sub 2} than in air. Differences in the composition and morphology between oxidized Al+2B and AlB{sub 2} suggested that Al{sub 2}O{sub 3}–B{sub 2}O{sub 3} interactions slowed Al+2B oxidation by converting Al{sub 2}O{sub 3} on aluminum particles into a Al{sub 4}B{sub 2}O{sub 9} shell, while the same Al{sub 4}B{sub 2}O{sub 9} developed a needle-like morphology in AlB{sub 2} that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB{sub 2}, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB{sub 2} in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time

  4. Copolymerization Kinetics of Ethylene Oxide and Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    尹红; 陈志荣

    2002-01-01

    The copolymerization kinetics of ethylene oxide and propylene oxide in an atomizing-circulation reactorunder semi-continuous operation is studied which is of great importance for molecular designation. The kineticparameters are obtained by numerical optimization of the kinetic model.

  5. The kinetics of the hydrogen chloride oxidation

    Directory of Open Access Journals (Sweden)

    Gonzalez Martinez Isai

    2013-01-01

    Full Text Available Hydrogen chloride (HCl oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

  6. Kinetics of yttrium oxide carbochlorination

    Energy Technology Data Exchange (ETDEWEB)

    Gaviria, J.P., E-mail: gaviriaj@cab.cnea.gov.ar [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Fouga, G.G. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Bohe, A.E. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Centro Regional Universitario Bariloche - Universidad Nacional del Comahue (Argentina)

    2011-04-20

    Research highlights: {yields} Chlorination kinetics of Y{sub 2}O{sub 3}-C system was studied by thermogravimetry. {yields} The influence of carbon content, flow rate, sample mass and pCl{sub 2} were evaluated. {yields} Reaction proceeds through three successive stages until the formation of YCl{sub 3}(l). {yields}STAGE I is the formation of YOCl(s) and is under chemical control for T < 700 {sup o}C. {yields}STAGE I follows a nucleation and growth model. Kinetics parameters were obtained. - Abstract: The chlorination kinetics of the Y{sub 2}O{sub 3}-sucrose carbon system was studied by thermogravimetry. This work is a continuation of a previous one in which the reaction stages and the stoichiometry of each reaction have been determined. The influence of carbon content, total flow rate, sample initial mass and chlorine partial pressure was evaluated. The effect of carbon content on the reactive mixture was studied between 6.7 and 70% (carbon mass/total mass). The results showed that the reaction rate of each stage is strongly increased as the carbon content increases and the range of occurrence of the stages depends on the amount of carbon in the solid reactive mixture. The formation reaction of YOCl (STAGE I) is chemically controlled for temperatures lower than 700 {sup o}C with average effective activation energies of 165 {+-} 6 and 152 {+-} 7 kJ/mol for 8.7 and 16.7%C, respectively. The formation of the YOCl follows a nucleation and growth mechanism, with a combination of continuous nucleation and site saturation, and anisotropic growth controlled by diffusion. The kinetics of STAGE I can be expressed by the following global rate equation that includes the variables analyzed: (d{alpha})/(dt) =k{sub 0}Bexp(-(Ea)/(R{sub g}T) )pCl{sub 2}{l_brace}n(1-{alpha})[-ln(1-{alpha})]{r_brace}{sup (n-1)/n} where k{sub 0}B = 1.9 x 10{sup 4}, n = 1.20 for 8.7%C, and k{sub 0}B = 8.4 x 10{sup 3}, n = 1.14 for 16.7%C. STAGES II and III correspond to the YOCl carbochlorination to

  7. Autoxidation kinetics of aqueous nitric oxide

    OpenAIRE

    1993-01-01

    Reports on the kinetics of the autoxidation of aqueous nitric oxide are discussed. It is concluded that the correct rate law is -d[NO]/dt = 4kaq[NO]2 [O2] with kaq = 2 × 106 M-2 · s-1 at 25°C and that a recent report of a rate law zero order in NO is incorrect. © 1993.

  8. Oxidation kinetics of aluminum nitride at different oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Hou Xinmei [Metallurgical and Ecological Engineering School, University of Science and Technology Beijing, Beijing 100083 (China); Chou, K.-C. [Metallurgical and Ecological Engineering School, University of Science and Technology Beijing, Beijing 100083 (China)], E-mail: kcc126@126.com; Zhong Xiangchong [High Temperature Ceramics Institute, Zhengzhou University, Henan Province 450052 (China); Seetharaman, Seshadri [Department of Materials Science and Engineering, Royal Institute of Technology, Stockholm (Sweden)

    2008-10-06

    In the present work, the oxidation kinetics of AlN powder was investigated by using thermogravimetric analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The experiments were carried out both in isothermal as well as non-isothermal modes under two different oxidizing atmospheres. The results showed that the oxidation reaction started at around 1100 K and the rate increased significantly beyond 1273 K forming porous aluminum oxide as the reaction product. The oxidation rate was affected by temperature and oxygen partial pressure. A distinct change in the oxidation mechanism was noticed in the temperature range 1533-1543 K which is attributed to the phase transformation in oxidation product, viz. alumina. Diffusion is the controlling step during the oxidation process. Based on the experimental data, a new model for predicting the oxidation process of AlN powder had been developed, which offered an analytic form expressing the oxidation weight increment as a function of time, temperature and oxygen partial pressure. The application of this new model to this system demonstrated that this model could be used to describe the oxidation behavior of AlN powder.

  9. Coal char oxidation kinetics in air medium

    Directory of Open Access Journals (Sweden)

    Korotkikh Alexander G.

    2017-01-01

    Full Text Available Study of oxidation kinetics for three types of coal char with different carbon content in air is presented. The coal char powders of anthracite, bituminous T-grade coal and 2B-grade lignite with particle size less than 80 μm were tested. The coal char oxidation was researched by isothermal method via simultaneous TG-DSC analyzer Netzsch STA 449 Jupiter F3 in the temperature range of 1000–1200 °C. Measurements were carried out at ambient pressure. Volumetric flow rate of oxidizing medium into analyser chamber was 250 ml/min. Flow consisted of air and argon with volumetric ratio 24/1. Carbon average rate of oxidation reaction at each temperature were defined based on experimental results. Kinetic constants (the frequency factor and activation energy were defined for Arrhenius equation modified with three submodels: volumetric model, shrinking core model and random pore model. The activation energy values for anthracite are 1,6-1,7 times higher than for chars of bituminous coal and lignite.

  10. Modeling Oxidation Kinetics of SiC-Containing Refractory Diborides

    Science.gov (United States)

    2012-01-01

    K. E. Spear, R. E. Tressler, and C. F. Ram- berg, “Passive-Oxidation Kinetics of High - Purity Silicon Carbide from 800 to 1100 C,” J. Am. Ceram. Soc...investigations47–53 in pure oxygen; there is a large scatter in the data. Figure 2 includes data collected on high purity SiC by Ramberg et al.,47 and...mechanism. Data reported for pure SiC in air/oxygen, for ZrB2 containing varying volume fractions of SiC , and for SiC –HfB2 ultra- high temperature

  11. Electroreduction Kinetics for Molten Oxide Slags

    Institute of Scientific and Technical Information of China (English)

    GAO Yun-ming; CHOU Kuo-chih; GUO Xing-min; WANG Wei

    2007-01-01

    The oxygen-ion conductor, the reducing agent, and the molten oxide slag containing electroactive matter were used as constituent of a galvanic cell. Metal was directly electroreduced from molten slag using a short-circuit galvanic cell. The following galvanic cell was assembled in the present experiment: graphite rod, [O]Fe-C saturated|ZrO2(MgO)|Cu(l)+(FeO)(slag), and molybdenum wire. The FeO electroreduction reaction was studied through measuring short circuit current by controlling factors such as temperature, the FeO content in molten slags, and the external circuit resistance. An overall kinetics model was developed to describe the process of FeO electroreduction. It was found that the modeled curves were in good agreement with the experimental values. The new oxide reduction method in the metallurgy with controlled oxygen flow was proposed and the metallurgical theory with controlled oxygen flow was developed.

  12. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-11-10

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

  13. Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation

    Science.gov (United States)

    Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert

    2008-08-01

    The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.

  14. 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.

  15. Fluid volume kinetics of dilutional hyponatremia; a shock syndrome revisited

    Directory of Open Access Journals (Sweden)

    Robert G. Hahn

    2014-02-01

    Full Text Available OBJECTIVE: To evaluate whether the pathophysiology of shock syndromes can be better understood by comparing central hemodynamics with kinetic data on fluid and electrolyte shifts. METHODS: We studied the dilutional hyponatremic shock that developed in response to overhydration with electrolyte-free irrigating fluid - the so-called ‘transurethral resection syndrome' - by comparing cardiac output, arterial pressures, and volume kinetic parameters in 17 pigs that were administered 150 ml/kg of either 1.5% glycine or 5% mannitol by intravenous infusion over 90 minutes. RESULTS: Natriuresis appeared to be the key factor promoting hypovolemic hypotension 15-20 minutes after fluid administration ended. Excessive sodium excretion, due to osmotic diuresis caused by the irrigant solutes, was associated with high estimates of the elimination rate constant (k10 and low or negative estimates of the rate constant describing re-distribution of fluid to the plasma after translocation to the interstitium (k21. These characteristics indicated a high urinary flow rate and the development of peripheral edema at the expense of plasma volume and were correlated with reductions in cardiac output. The same general effects of natriuresis were observed for both irrigating solutions, although the volume of infused 1.5% glycine had a higher tendency to enter the intracellular fluid space. CONCLUSION: Comparisons between hemodynamics and fluid turnover showed a likely sequence of events that led to hypovolemia despite intravenous administration of large amounts of fluid.

  16. 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.

  17. 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.

  18. The kinetics of sulfation of calcium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Sarofim, A.F.; Longwell, J.P.

    1990-01-01

    The rate of sulfation of a CaO surface is rapid at first, limited by the intrinsic kinetics, but slows down with increasing conversion as a consequence of the increased resistance to diffusion through the product layer. The objectives of this study are to determine the intrinsic kinetics and the product layer diffusion pate by minimizing the resistances to gas-phase pore diffusion, and eliminating complications due to pore filling. This is achieved by the use of nonporous CaO. A wide range of particle sizes are used to change the relative importance of the regimes in which the intrinsic kinetics and product layer diffusion control. The assumption of constant product layer diffusivity can then be tested and the variables that determine this diffusivity independently studied. Information on product layer diffusion can also be obtained from studies of porous particles after the pore mouths are all plugged and a uniform surface coating is obtained. This information on diffusion rate and intrinsic reactivity can then be combined with a geometrical model to describe the rate of reaction over the entire range of conversions and is particularly useful in treating the effect of particle size on conversion history.

  19. Wet oxidation kinetics of refractory low molecular mass carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J.

    1999-10-01

    Wet oxidation kinetics of aqueous solutions of formic, acetic, oxalic, and glyoxalic acids was studied in a titanium autoclave at a temperature range of 150--320 C and oxygen partial pressures between 8 and 60 bar. Oxidation reactions obeyed a first-order kinetics with respect to concentration of all substrates. On the basis of acid concentration decay, the activation energy for acetic, oxalic, and glyoxalic acid oxidation was 178, 137, and 97 kJ/mol, respectively; whereas on the total organic carbon (TOC) conversion basis, these values were slightly higher, namely 182, 141, and 104 kJ/mol. The activation energy for formic acid took a unique value of 149 kJ/mol regardless of the type of concentration used. The rate of oxidation was proportional to a square root of oxygen concentration (partial pressure) for acetic, formic, and oxalic acids, whereas it was linearly proportional for glyoxalic acid. When sufficiently high oxygen partial pressure was applied ({ge}22 bar), the individual acid conversion in a mixture of these acids was well predicted by the rate expression derived for that acid. The lumped TOC concentration of mixtures did not obey a first-order kinetic behavior, although underlying TOC kinetics for each individual acid was linear. The oxidation results are also discussed in a view of speculated reaction pathways and the reactor material.

  20. Effect of inhibitors on macroscopical oxidation kinetics of calcium sulfite

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yi; WANG Li-dong; WANG Xiao-ming; LI Qiang-wei; XU Pei-yao

    2005-01-01

    In the presence of inhibitors, the macroscopical oxidation kinetics of calcium sulfite, the main byproduct in wet limestone scrubbing, was studied for the first time by adding different inhibitors and varying pH, concentration of calcium sulfite, oxygen partial pressure, concentration of inhibitors and temperature. The mathematical model about the general oxidation reaction was established,which was controlled by three steps involving dissolution of calcium sulfite, mass transfer of oxygen and chemical reaction in the solution.It was concluded that the general reaction was controlled by mass transfer of oxygen under uncatalyzed conditions, while it was controlled by dissolution of calcium sulfite after adding three kinds of inhibitors. Thus, the theory was provided for investigating the mechanism and oxidation kinetics of sulfite. The beneficial references were also supplied for design of oxidation technics in the wet limestone scrubbing.

  1. 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)

  2. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten;

    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...

  3. 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...

  4. 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

  5. Kinetics of methane oxidation in selected mineral soils

    Science.gov (United States)

    Walkiewicz, A.; Bulak, P.; Brzeziñska, M.; Włodarczyk, T.; Polakowski, C.

    2012-10-01

    The kinetic parameters of methane oxidation in three mineral soils were measured under laboratory conditions. Incubationswere preceded by a 24-day preincubationwith 10%vol. of methane. All soils showed potential to the consumption of added methane. None of the soils, however, consumed atmospheric CH4. Methane oxidation followed the Michaelis-Menten kinetics, with relatively low values of parameters for Eutric Cambisol, while high values for Haplic Podzol, and especially for Mollic Gleysol which showed the highest methanotrophic activity and much lower affinity to methane. The high values of parameters for methane oxidation are typical for organic soils and mineral soils from landfill cover. The possibility of the involvement of nitrifying microorganisms, which inhabit the ammonia-fertilized agricultural soils should be verified.

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

    Science.gov (United States)

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

    2011-07-14

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

  7. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg;

    2016-01-01

    Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen/steam and refor......Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen....../steam and reformate fuels hydrogen/carbon-dioxide and hydrogen/methane/steam. It was found that the kinetics at the fuel electrode were exactly the same in both reformates. The hydrogen/steam fuel displayed slightly faster kinetics than the reformate fuels. Furthermore the gas conversion impedance in the hydrogen...... into a single process as the gas conversion was reduced. The SOC with finer electrode microstructure displayed improved kinetics....

  8. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-20

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  9. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO2 production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  10. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-20

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  11. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO2 production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  12. Kinetics of Fe3O4 formation by air oxidation

    Institute of Scientific and Technical Information of China (English)

    杨喜云; 龚竹青; 刘丰良

    2004-01-01

    The kinetics of Fe3O4 formation by air oxidation of slightly acidic suspension of Fe(OH)2 was studied. The effects of initial concentration of Fe(Ⅱ), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe3O4 formation is composed of two-step reaction, the first step is the formation of Fe(OH)+2 by oxidation of Fe(OH)+ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)+ and Fe(OH)+2. The oxidation reaction is zero-order with respect to the concentration of Fe(Ⅱ) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ·mol-1.

  13. Neptunium_Oxide_Precipitation_Kinetics_AJohnsen

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, A M; Roberts, K E; Prussin, S G

    2012-06-08

    We evaluate the proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation system at elevated temperatures to obtain primary information on the effects of temperature, ionic strength, O{sub 2} and CO{sub 2}. Experiments conducted on unfiltered solutions at 10{sup -4} M NpO{sub 2}{sup +}(aq), neutral pH, and 200 C indicated that solution colloids strongly affect precipitation kinetics. Subsequent experiments on filtered solutions at 200, 212, and 225 C showed consistent and distinctive temperature-dependent behavior at reaction times {le} 800 hours. At longer times, the 200 C experiments showed unexpected dissolution of neptunium solids, but experiments at 212 C and 225 C demonstrated quasi steady-state neptunium concentrations of 3 x 10{sup -6} M and 6 x 10{sup -6} M, respectively. Solids from a representative experiment analyzed by X-ray diffraction were consistent with NpO{sub 2}(cr). A 200 C experiment with a NaCl concentration of 0.05 M showed a dramatic increase in the rate of neptunium loss. A 200 C experiment in an argon atmosphere resulted in nearly complete loss of aqueous neptunium. Previously proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation mechanisms in the literature specified a 1:1 ratio of neptunium loss and H{sup +} production in solution over time. However, all experiments demonstrated ratios of approximately 0.4 to 0.5. Carbonate equilibria can account for only about 40% of this discrepancy, leaving an unexpected deficit in H+ production that suggests that additional chemical processes are occurring.

  14. 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 |

  15. 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.

  16. Oxidation Kinetics of K Basin Fuel (OCRWM)

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    2000-09-25

    Oxidation testing of K Basin-stored N Reactor fuel in dry air, moist air, and moist helium provided reaction rate data for the Spent Nuclear Fuel Project. The tests were performed on small samples from two spent nuclear fuel elements retrieved from the closed canisters of the K West Basin. The spent nuclear fuel samples were tested using a thermogravimetric analysis system modified for moist-gas operation to allow testing in moist environments. The tests were run at constant temperature and water vapor pressure. The moist helium tests used 6.5 H a water vapor, producing seventeen data between 75 C and 210 C. Eight of these data were excluded from primary consideration due to testing anomalies and balance drift issues. Regression analysis of the nine acceptable data provided good assurance that the moist-helium results are consistent with literature data within the temperature range of 25 C to 210 C. Concerns about possible oxygen poisoning from air in-leakage and mass transfer limitations on the test data were reviewed. If oxygen poisoning occurred it was not likely to have biased the data sufficiently to change the basic conclusions of comparability to the literature data. Mass transfer limitations did not appear to have had significant effect on the moist-helium data.

  17. Kinetics of wet oxidation of propionic and 3-hydroxypropionic acids

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. for Catalysis and Chemical Reaction Engineering]|[Univ. of Ljubljana (Slovenia). Dept. of Chemical Engineering

    1999-07-01

    Oxidation of aqueous solutions of 3-hydroxypropionic (3-HPA) and propionic acids (PA) was studied in a titanium high-pressure reactor at 280--310 C using oxygen partial pressures between 10 and 45 bar. Oxidation of both acids was found to obey first-order kinetic with respect to their concentrations as well as to their lumped TOC concentrations. Oxidation rate revealed a half order dependence with respect to oxygen for oxidation of both acids. In the case of 3-HPA oxidation, the activation energy was found to be 135 kJ/mol, and it was 140 kJ/mol when lumped concentration TOC was used. The activation energy for PA oxidation is 150 kJ/mol, and it is slightly higher, 158 kJ/mol, for TOC reduction. Almost complete conversion of 3-HPA was achieved at 300 C after 1 h, whereas 95% conversion of PA acid was obtained at 310 C after 3 h. During oxidation of 3-HPA, 3-oxopropionic and acetic acids were identified as intermediate products. Oxidation of PA yielded acetic and formic acids as intermediates; at oxygen partial pressures above 25 bar and 310 C, the formation of acetic acid was appreciably reduced. In both cases, however, direct oxidation to carbon dioxide and water was found to be the main reaction route.

  18. 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...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute....... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  19. Kinetics of wet oxidation of formic acid and acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. [Univ. of Mumbai (India). Dept. of Chemical Technology

    1997-11-01

    Oxidation of lower molecular weight carboxylic acids such as formic, acetic, glyoxalic, and oxalic acids is often the rate-controlling step during wet oxidation (WO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WO of formic acid was studied in the absence and presence of a cupric sulfate as catalyst in the temperature range 150--240 C and oxygen partial pressure range 0.345--1.380 MPa. Wet oxidation of acetic acid was carried out in the presence of cupric sulfate in the temperature range 215--235 C. Homogeneous copper sulfate was found to be a very good catalyst for oxidation of formic acid and acetic acid.

  20. 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.

  1. Aluminium-oxide wires for superconducting high kinetic inductance circuits

    Science.gov (United States)

    Rotzinger, H.; Skacel, S. T.; Pfirrmann, M.; Voss, J. N.; Münzberg, J.; Probst, S.; Bushev, P.; Weides, M. P.; Ustinov, A. V.; Mooij, J. E.

    2017-02-01

    We investigate thin films of conducting aluminium-oxide, also known as granular aluminium, as a material for superconducting high quality, high kinetic inductance circuits. The films are deposited by an optimised reactive DC magnetron sputter process and characterised using microwave measurement techniques at milli-Kelvin temperatures. We show that, by precise control of the reactive sputter conditions, a high room temperature sheet resistance and therefore high kinetic inductance at low temperatures can be obtained. For a coplanar waveguide resonator with 1.5 kΩ sheet resistance and a kinetic inductance fraction close to unity, we measure a quality factor in the order of 700 000 at 20 mK. Furthermore, we observe a sheet resistance reduction by gentle heat treatment in air. This behaviour is exploited to study the kinetic inductance change using the microwave response of a coplanar wave guide resonator. We find the correlation between the kinetic inductance and the sheet resistance to be in good agreement with theoretical expectations.

  2. 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.

  3. Experimental investigation on oxidation kinetics of germanium by ozone

    Science.gov (United States)

    Wang, Xiaolei; Zhao, Zhiqian; Xiang, Jinjuan; Wang, Wenwu; Zhang, Jing; Zhao, Chao; Ye, Tianchun

    2016-12-01

    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 GeOx 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 O3 molecules but O radicals that go through the GeOx film.

  4. 2-chlorophenol oxidation kinetic by photo-assisted Fenton process

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Experimental data are presented to test and validate a kinetic model for the oxidation of 2-chlorophenol wastewater by photo-assistedFenton process. The data showed that this process had produced good effects under acidic conductions. Up to 90% 2-chlorophenol was removedafter 90-minute reaction time with H2 O2 of 25 % CODcr in while in UV/H2 O2 system only 16.8% 2-chlorophenol was removed after one hourtreatment. The optimal pH in this reaction occurred between pH 3.0 and pH 4.0. The reaction kinetics for photo-assisted Fenton processexperimented in this research was investigated. Kinetic models were proposed for the treatment of 2-chlorophenol wastewater. The reaction wasfound to follow the 2nd order. The equations of reaction kinetics are as follows: - dt/d[RH]= KRH [ RH] [ H2O2 ]0exp(-KH2O2t); -dt/d[CODcr]= KCODCr[CODCr][ H2O2 ]0exp( - K't). The prediction of the models was found to be in a good agreement with experimentalresults, thus confirming the proposed reaction mechanism.

  5. Apparent kinetics of high temperature oxidative decomposition of microalgal biomass.

    Science.gov (United States)

    Ali, Saad Aldin M; Razzak, Shaikh A; Hossain, Mohammad M

    2015-01-01

    The oxidative thermal characteristics of two microalgae species biomass Nannochloropsis oculta and Chlorella vulgaris have been investigated. The apparent kinetic parameters for the microalgal biomass oxidation process are estimated by fitting the experimental data to the nth order rate model. Also, the iso-conversional methods Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) were used to evaluate the apparent activation energy. The results indicate that biomass of different microalgae strains exhibit different thermal behavior and characteristics. In addition, growth parameters and medium composition can affect the biomass productivity and composition. This would have significant impact on the thermal decomposition trend of the biomass. The kinetic modeling of the oxidation reaction with direct model fitting method shows good prediction to the experimental data. The apparent activation energies estimated by KAS and FWO methods for N. oculta were 149.2 and 151.8kJ/mol, respectively, while for C. vulgaris were 214.4 and 213.4kJ/mol, respectively.

  6. Probing the oxidation kinetics of small permalloy particles

    Science.gov (United States)

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

    2017-02-01

    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. Fe2O3/(Ni, Fe)3O4 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 Fe2O3 to (Ni, Fe)3O4 induces diffusion change and affects the diffusion process at the intermediate temperature. Relevant oxidation kinetics and diffusion mechanisms are discussed.

  7. Kinetics of p-xylene liquid-phase catalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Cao, G.; Servida, A. (Univ. di Cagliari (Italy). Dipt. di Ingegneria Chimica e Materiali); Pisu, M. (Sviluppo e Studi Superiori in Sardegna, Cagliari (Italy). Centro di Ricerche); Morbidelli, M. (Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata)

    1994-07-01

    A semibatch gas-liquid reactor model based on a lumped kinetic scheme for the liquid-phase oxidation of p-xylene to p-toluic acid catalyzed by cobalt naphthenate is developed. The model accounts for the complex nature of the involved reaction network, as well as for the interphase and intraphase mass transport processes of both reactants and products. The model reliability is tested by comparison with suitable experimental data obtained in a semibatch oxidation reactor, where the role of the composition of both the gaseous and the liquid feed has been investigated. It is shown that the model describes the reactor behavior in any of the regimes which may prevail depending upon the operating conditions and the depletion of liquid reactants in time.

  8. Kinetics of wet air oxidation (WAO) of alcaloide factory wastewater.

    Science.gov (United States)

    Kunukcu, Y Kaçar

    2005-01-01

    Wet air oxidation (WAO) of Afyon alcaloide factory wastewater, a typical high strength industrial wastewater, was carried out. The process was performed in a specifically designed titanium bubble reactor at temperatures in the range of 140-160 degrees C. The kinetics of WAO of alcaloide factory wastewater was modeled by assuming two distinct steps. The rates of destruction were measured with respect to reduction in COD. The oxidation reaction was found to be first order with respect to COD concentration and also second order with respect to oxygen concentration in both steps. The values of activation energies were found to be in the range of 4.93 x 10(4)-7.85 x 10(4) kJ/kmol.

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

    Science.gov (United States)

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

    2017-07-19

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

  10. Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: Uptake kinetics and condensed-phase products

    Directory of Open Access Journals (Sweden)

    I. J. George

    2007-05-01

    Full Text Available The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-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 = 1.26 (±0.04, 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.

  11. The Kinetics Of Ti-1Al-1Mn Alloy Thermal Oxidation And Charcteristic Of Oxide Layer

    Directory of Open Access Journals (Sweden)

    Klimecka-Tatar D.

    2015-06-01

    Full Text Available The main goal of the study was to carry out the treatment of cyclic oxidation of Ti alloy (Ti-1Al-1Mn in air atmosphere. Based on measurements of mass gain of titanium alloy samples (Ti-1Al-1Mn the kinetic oxidation curves during cyclic annealing were determined. The oxidized surface of the titanium alloy was carefully observed with optical microscopy equipment and the geometrical development, shape and surface morphology were defined. The phase composition of the obtained oxide layers on the Ti-alloy with qualitative analysis of the X-ray were defined. Since titanium alloys are among the most widely used metallic materials in dental prosthetics the corrosion measurements in a solution simulating the environment of the oral cavity were carried out. The results confirmed that the used titanium alloy easily covered with oxides layers, which to some extent inhibit the processes of electrochemical corrosion in artificial saliva solution.

  12. 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

  13. Oxidative degradation study on antimicrobial agent ciprofloxacin by electro-Fenton process: kinetics and oxidation products.

    Science.gov (United States)

    Yahya, Muna Sh; Oturan, Nihal; El Kacemi, Kacem; El Karbane, Miloud; Aravindakumar, C T; Oturan, Mehmet A

    2014-12-01

    Oxidative degradation of the antimicrobial agent ciprofloxacin hydrochloride (CIP) has been investigated using electro-Fenton (EF) treatment with a constant current in the range 60-500 mA. The process generates highly oxidant species OH in situ via electrochemically monitored Fenton reaction. The EF experiments were performed using cells with a carbon felt cathode and Pt anode. Effect of applied current and catalyst concentration on the kinetics of oxidative degradation and mineralization efficiency have been investigated. Degradation of CIP followed pseudo-first order reaction kinetics. The rate constant of the oxidation of CIP by OH has been determined to be (1.01 ± 0.14) × 10(10) M(-1) s(-1) by using competitive kinetics method. An optimum current of 400 mA and a catalyst concentration of Fe(2+) at 0.1mM are found to be optimal for an effective degradation of CIP under our operating conditions. A remarkably high degree of mineralization (>94%) was obtained at 6h of treatment under these conditions. A number of stable intermediate products have been identified using HPLC and LC-MS/MS analyses. Based on the identified reaction intermediates, a plausible reaction pathway was proposed for the mineralization process. The high degree of mineralization obtained in this work highlights the potential application of EF process in the efficient removal of fluoroquinolone based drugs in aqueous medium. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. 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.

  15. Kinetic equation for internal oxidation of Cu-Al alloy cylinders

    Institute of Scientific and Technical Information of China (English)

    Kexing Song; Jiandong Xing; Baohong Tian; Ping Liu; Qiming Dong

    2005-01-01

    The kinetics of internal oxidation of Cu-Al alloy cylinders, containing up to 2.214mol% Al, were investigated in the temperature range of 1023 K to 1273 K, and the depth of internal oxidation was measured in the microscopy. A kinetic equation was derived to describe the internal oxidation of Cu-Al alloy cylinders. For the internal oxidation of Cu-Al alloys employed in the synthesis of alumina dispersion strengthened copper, the kinetic equation can be simplified. The derived equation was checked experimentally by means of oxidation depth measurements and the results show that the derived equation is exact enough to describe the kinetics of internal oxidation of Cu-Al alloy cylinders. Based on this equation and the oxidation depth measurements, the permeability of oxygen in solid copper was obtained. Investigation also shows that there is no evidence for preferential diffusion along grain boundaries in the process of internal oxidation.

  16. Kinetics of oxytetracycline reaction with a hydrous manganese oxide.

    Science.gov (United States)

    Rubert, Kennedy F; Pedersen, Joel A

    2006-12-01

    Tetracycline antibiotics comprise a class of broad spectrum antimicrobial agents finding application in human therapy, animal husbandry, aquaculture, and fruit crop production. To better understand the processes affecting these antibiotics in soils and sediments, the kinetics of oxytetracycline transformation by a hydrous manganese oxide (MnO2) were investigated as a function of reactant concentration, pH, and temperature. Oxytetracycline was rapidly degraded by MnO2. Initial reaction rates exhibited pronounced pH-dependence, increasing as pH decreased. Reaction of oxytetracycline with MnO2 was accompanied by generation of Mn(II) ions, suggesting oxidative transformation of the antibiotic. At pH 5.6, apparent reaction orders for oxytetracycline and MnO2 were 0.7 and 0.8. Reaction order with respect to H+ was 0.6 between pH 4 and 9. Initial reaction rates increased by a factor of approximately 2.4 for 10 degrees C temperature increases; the apparent activation energy (60 kJ x mol(-1)) was consistent with a surface-controlled reaction. Reactivity of tetracycline antibiotics toward MnO2 increased in the following order: rolitetracyline oxytetracycline manganese oxides in soils and sediments are likely to promote appreciable degradation of tetracycline antibiotics, and that reaction rates are strongly dependent on reaction time scale and solution conditions.

  17. 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).

  18. Kinetics of Uranium Extraction from Uranium Tailings by Oxidative Leaching

    Science.gov (United States)

    Zhang, Biao; Li, Mi; Zhang, Xiaowen; Huang, Jing

    2016-07-01

    Extraction of uranium from uranium tailings by oxidative leaching with hydrogen peroxide (H2O2) was studied. The effects of various extraction factors were investigated to optimize the dissolution conditions, as well as to determine the leaching kinetic parameters. The behavior of H2O2 in the leaching process was determined through scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray diffraction analysis of leaching residues. Results suggest that H2O2 can significantly improve uranium extraction by decomposing the complex gangue structures in uranium tailings and by enhancing the reaction rate between uranium phases and the leaching agent. The extraction kinetics expression was changed from 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)-0.14903(S/L)-1.80435( R o)0.20023 e -1670.93/T t ( t ≥ 5) to 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)0.01382(S/L)-1.83275( R o)0.25763 e -1654.59/T t ( t ≥ 5) by the addition of H2O2 in the leaching process. The use of H2O2 in uranium leaching may help in extracting uranium more efficiently and rapidly from low-uranium-containing ores or tailings.

  19. A phenomenological analysis of sintering kinetics from the viewpoint of activated volume

    Directory of Open Access Journals (Sweden)

    Nikolić M.V.

    2005-01-01

    Full Text Available The sintering kinetics of real systems has been viewed as a process of transport of activated volume. Activated volume is a parameter that can be used to describe mass transport during the sintering process. It defines the movement of point defects and dislocations during the sintering process. A phenomenological equation has been defined using this parameter, which can be applied to analyze kinetics of the sintering process. It has been applied to analyze the sintering process of several disperse systems. Values obtained for parameters of the equation have also been analyzed.

  20. Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process.

    Science.gov (United States)

    Lefèvre, Sébastien; Boutin, Olivier; Ferrasse, Jean-Henry; Malleret, Laure; Faucherand, Rémy; Viand, Alain

    2011-08-01

    This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350°C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H(2)O and CO(2). The Arrhenius law data obtained for the phenol disappearance are the following: k=1.8×10(6)±3.9×10(5)M(-1)s(-1) (pre-exponential factor) and E(a)=77±8 kJ mol(-1) (activation energy).

  1. Kinetics of the oxidation of Zn foils in air atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Baca, R; Martinez, J [Centro de Investigacion de Dispositivos Semiconductores, BUAP, Puebla. C.P. 72570 (Mexico); Kryshtab, T [Departamento de Ciencias de Materiales, ESFM - IPN, Mexico D.F (Mexico); Juarez, G; Solache, H; Andraca, J; Garcia, O; Pena-Sierra, R, E-mail: rbaca02006@yahoo.com.mx

    2010-02-15

    The formation kinetics of ZnO thin films grown by oxidation of polycrystalline Zn foils in air atmosphere at temperatures below the melting point is reported. Previous to the oxidation process the Zn foils were polished to produce mirror-like finished surfaces. The growth rate of the ZnO films was monitored by ellipsometric measurements. The growth rate of the ZnO films under 100 nm follows a linear and parabolic behavior in accordance with previously reported studies. The thicknesses of the films strongly influence the appearance of the final produced ZnO surface. The ZnO films surfaces with thicknesses less than 100 nm resulted uniform with low rms roughness. However as the films become thicker the rms roughness increased and a uniform distribution of whiskers was observed. X-ray diffraction and photoluminescence (PL) studies were done on the ZnO films to find out their structural and optical characteristics. PL spectra on the films are composed by two main bands; a weak near-band gap in the ultraviolet region and a strong but well defined green band. A discussion is included on the origins of the observed PL spectra.

  2. 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.

  3. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-02-15

    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

  4. 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.

  5. Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WAN Jia-feng; FENG Yu-jie; CAI Wei-min; YANG Shao-xia; SUN Xiao-jun

    2004-01-01

    Four metal oxide catalysts composed of copper (Cu), stannum (Sn), copper-stannum (Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al2O3) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu-10%Ce/γ-Al2O3 showed the best catalytic activity. This is consistent with the result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 min. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.

  6. Intrinsic kinetics of the oxidation of methane over an industrial copper II oxide catalyst on a gamma-alumina support

    NARCIS (Netherlands)

    Veldsink, J.W.; Veldsink, J.W.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    The kinetic rate of the heterogeneously catalysed methane oxidation reaction was studied at temperatures ranging from 723 to 923 K and atmospheric pressure. A commercially available CuO catalyst supported by thermally stable γ-Al2O3 was used as the catalyst. This kinetic study was carried out in ord

  7. Kinetic Model of Hypophosphite Oxidation on a Nickel Electrode in D2O Solution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Kinetic model of hypophosphite oxidation on a nickel electrode was studied in D2Osolution in order to reach a better understanding of the oxidation mechanism. In the model the electrooxidation of hypophosphite undergo a H abstraction of hypophosphite from the P-H bond to form the phosphorus-centered radical PHO2-, which subsequently is electrochemically reacted with water to form the final product, phosphite. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The process of hypophosphite electrooxidation could be well simulated by this model

  8. Kinetic Equation for Internal Oxidation of Cu-Al Alloy Spheres

    Institute of Scientific and Technical Information of China (English)

    SONG Kexing; GAO Jianxin; XU Xiaofeng; LI Peiquan; TIAN Baohong; GUO Xiuhua

    2007-01-01

    The kinetics of internal oxidation of Cu-Al alloy spheres, containing up to 2.214% mole fraction Al was investigated in the temperature range 1 023 K to 1 273 K, and the depth of internal oxidation was measured in the microscopy. A kinetic equation was derived to describe the internal oxidation of Cu-Al alloy spheres, which was checked experimentally by means of oxidation depth measurements. The results show that the derived equation is exact enough to describe the kinetics of internal oxidation of Cu-Al alloy spheres.Based on this equation and the oxidation depth measurements, the permeability of oxygen in solid copper has been obtained. Investigation also shows that in the process of internal oxidation, there is no evidence for preferential diffusion along grain boundaries.

  9. Influence of flotation cell volume and solids mass on kinetics of sulfide ore flotation

    Directory of Open Access Journals (Sweden)

    Plawski Michal

    2016-01-01

    Full Text Available The paper presents studies on the influence of flotation cell capacity and mass of solids in the suspension on the flotation kinetics of sulfide copper ore. A sample of copper ore that was collected from the Polkowice Mine of KGHM Polska Miedz S.A. in Poland was used in the experiments. It was determined that neither the volume of flotation cell nor the mass of solids had influence on the type of kinetics equation of flotation. Copper-bearing minerals floated according to the second-order equation, while the remaining components according to the first-order equation. The kinetic rate constants and maximum recovery of the studied components decreased with increasing solids mass in the flotation cell, regardless of the capacity of the cell. The best results were obtained for tests using a 1.0 dm3 cell, while the less favorable kinetics results were observed in the test with the smallest cell of 0.75 dm3 volume. The obtained results can be helpful in choosing the most appropriate methodology of upgrading the sulfide copper ore from Poland in order to obtain the best kinetics results.

  10. In situ oxidation remediation technologies: kinetic of hydrogen peroxide decomposition on soil organic matter.

    Science.gov (United States)

    Romero, Arturo; Santos, Aurora; Vicente, Fernando; Rodriguez, Sergio; Lafuente, A Lopez

    2009-10-30

    Rates of hydrogen peroxide decomposition were investigated in soils slurries. The interaction soil-hydrogen peroxide was studied using a slurry system at 20 degrees C and pH 7. To determine the role of soil organic matter (SOM) in the decomposition of hydrogen peroxide, several experiments were carried out with two soils with different SOM content (S1=15.1%, S2=10%). The influence of the oxidant dosage ([H2O2](o) from 10 to 30 g L(-1) and soil weight to liquid phase volume ratio=500 g L(-1)) was investigated using the two calcareous loamy sand soil samples. The results showed a rate dependency on both SOM and hydrogen peroxide concentration being the H2O2 decomposition rate over soil surface described by a second-order kinetic expression r(H2O2) = -dn(H2O2) / W(SOM) dt = kC(H2O2) C(SOM). Thermogravimetric analysis (TGA) was used to evaluate the effect caused by the application of this oxidant on the SOM content. It was found a slightly increase of SOM content after treatment with hydrogen peroxide, probably due to the incorporation of oxygen from the oxidant (hydrogen peroxide).

  11. 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.

  12. Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

    Institute of Scientific and Technical Information of China (English)

    罗伟平; 刘大为; 孙俊; 邓伟; 盛文兵; 刘强; 郭灿城

    2014-01-01

    Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

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

    NARCIS (Netherlands)

    Mahmoodlu, M.G.|info:eu-repo/dai/nl/357287746; Hassanizadeh, S.M.|info:eu-repo/dai/nl/074974424; Hartog, Niels|info:eu-repo/dai/nl/255171307

    2014-01-01

    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

  14. Influence of flotation cell volume and solids mass on kinetics of sulfide ore flotation

    OpenAIRE

    Plawski Michal; Bakalarz Alicja

    2016-01-01

    The paper presents studies on the influence of flotation cell capacity and mass of solids in the suspension on the flotation kinetics of sulfide copper ore. A sample of copper ore that was collected from the Polkowice Mine of KGHM Polska Miedz S.A. in Poland was used in the experiments. It was determined that neither the volume of flotation cell nor the mass of solids had influence on the type of kinetics equation of flotation. Copper-bearing minerals floated according to the second-order equ...

  15. Kinetics and Microstructural Investigation of High-Temperature Oxidation of IN-738LC Super Alloy

    Science.gov (United States)

    Hamidi, S.; Rahimipour, M. R.; Eshraghi, M. J.; Hadavi, S. M. M.; Esfahani, H.

    2017-02-01

    The present study was carried out to investigate the kinetics and the surface chemistry of the oxide layers formed on the IN-738LC super alloy during high-temperature oxidation at 950 °C in air from 1 to 260 h. Oxidation kinetics were studied by mass gain measurement. The oxide layers were characterized by field emission scanning electron microscope, elemental distribution map, energy-dispersive spectroscopy as well as x-ray diffractometry (XRD). The oxidation kinetics followed the parabolic law. The XRD analysis revealed that the oxide scale contained mainly NiO, Ni (Cr, Al)2O4, Al2O3, TiO2 and Cr2O3. The oxide structure, from the top surface down to the substrate, was clarified by elemental map distribution studies as Ni-Ti oxides, Cr-Ti oxides, Cr2O3 oxide band, Ni-Co-Cr-W oxide and finally a blocky Al2O3 region. The oxidation scales were composed of three distinct layers of the outer and mid layers enriched by TiO2 and Cr2O3, NiCr2O4 oxide, respectively, and the innermost layer was composed of Al2O3 and matrix alloy. The depleted gamma prime layer was formed under the oxidation scales due to the impoverishment of Al and Ti which were induced by the formation of Al2O3 and TiO2.

  16. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

    Indian Academy of Sciences (India)

    Garima Goswami; Seema Kothari; Kalyan K Banerji

    2001-02-01

    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 (/) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

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

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

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

  18. Kinetic analysis of nitric oxide reduction using biogas as reburning fuel

    African Journals Online (AJOL)

    STORAGESEVER

    2009-05-18

    May 18, 2009 ... reburnning technology potential to reduce NO pollution. Key word: Biomass, biogas, kinetic analysis, modeling, nitric oxide, reburning. INTRODUCTION .... factor A, the temperature β, and the activation energy E are specified.

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

    KAUST Repository

    Hanson, Ronald K.

    2013-09-01

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

  20. Kinetics analysis of volume phase transition of intelligent neutral thermo-sensitive hydrogels

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    In this work,utilizing the first law of thermodynamics and the Flory mean-field theory,the kinetic deformation studies concerning the volume phase transition of the neutral thermo-sensitive hydrogels were performed analytically.The hydrogel was assumed as a biphasic mixture medium in the framework of the continuum mixture theory.From the energy conservation of the thermodynamics system of the hydrogel,the governing equations for the kinetics of the nonlinear large deforma-tion were derived.The explicit analytical expressions of the effective stress tensor and the chemical potential of the fluid of the thermo-sensitive hydrogel PNIPA were also obtained from the Helmholtz free energy,which can model the steady-static volume phase transition quantitatively.

  1. Kinetics analysis of volume phase transition of intelligent neutral thermo-sensitive hydrogels

    Institute of Scientific and Technical Information of China (English)

    WANG XiaoGui; LI YiQuan

    2008-01-01

    In this work, utilizing the first law of thermodynamics and the FIory mean-field theory, the kinetic deformation studies concerning the volume phase transition of the neutral thermo-sensitive hydrogels were performed analytically. The hydrogel was assumed as a biphasic mixture medium in the framework of the continuum mixture theory. From the energy conservation of the thermodynamics system of the hydrogel, the governing equations for the kinetics of the nonlinear large deforma-tion were derived. The explicit analytical expressions of the effective stress tensor and the chemical potential of the fluid of the thermo-sensitive hydrogel PNIPA were also obtained from the Helmholtz free energy, which can model the steady-static volume phase transition quantitatively.

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

    Science.gov (United States)

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

    2016-01-01

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

  3. 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.

  4. Characterizing the kinetics of volume recovery in glasses by instantaneous temperature-jump experiments

    Energy Technology Data Exchange (ETDEWEB)

    Lagasse, R.R. (Sandia National Labs., Albuquerque, NM); Cohen, R.E.; Letton, A.

    1982-03-01

    This article proposes a temperature-jump (T-jump) approach for characterizing the kinetics of volume recovery in glassy materials. The kinetic characterization is based on the Kovacs-Aklonis model. This incorporates a retardation-time spectrum which shifts according to both the temperature and the instantaneous volume. The proposed experiments involve measuring the change in recovery rate caused by an abrupt temperature jump. Although an analogous procedure has been used to determine the activation energy for linear viscoelastic creep, the analysis for volume recovery is complicated by its inherent nonlinearity. Nevertheless, accounting for the nonlinearity by a reduction of the time scale permits the T-jump results to be analyzed. In particular, the T-jump approach can be used to: (i) test a particular functional form for the shift factor; and (ii) determine the previously unmeasurable parameter x, which defines the relative importance of the temperature dependence and the volume dependence in this function. In addition, numerical simulations indicate that the proposed method can be implemented in the laboratory. 7 figures.

  5. Oxidation Kinetics and Strength Degradation of Carbon Fibers in a Cracked Ceramic Matrix Composite

    Science.gov (United States)

    Halbig, Michael C.

    2003-01-01

    Experimental results and oxidation modeling will be presented to discuss carbon fiber susceptibility to oxidation, the oxidation kinetics regimes and composite strength degradation and failure due to oxidation. Thermogravimetric Analysis (TGA) was used to study the oxidation rates of carbon fiber and of a pyro-carbon interphase. The analysis was used to separately obtain activation energies for the carbon constituents within a C/SiC composite. TGA was also conducted on C/SiC composite material to study carbon oxidation and crack closure as a function of temperature. In order to more closely match applications conditions C/SiC tensile coupons were also tested under stressed oxidation conditions. The stressed oxidation tests show that C/SiC is much more susceptible to oxidation when the material is under an applied load where the cracks are open and allow for oxygen ingress. The results help correlate carbon oxidation with composite strength reduction and failure.

  6. Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: obs = + [H+]. The oxidation of -deuterioformic acid exhibits a substantial primary kinetic isotope effect (H/D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed

  7. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    acer

    spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were ... presence alcohols and ketones while the GC/MS shows the presence of cyclohexanol (2.46%), .... Result of the GC/MS analysis: Summary of.

  8. Effect of excluded volume on 2D discrete stochastic chemical kinetics

    Science.gov (United States)

    Lampoudi, Sotiria; Gillespie, Dan T.; Petzold, Linda R.

    2009-06-01

    The stochastic simulation algorithm (SSA) is widely used in the discrete stochastic simulation of chemical kinetics. The propensity functions which play a central role in this algorithm have been derived under the point-molecule assumption, i.e., that the total volume of the molecules is negligible compared to the volume of the container. It has been shown analytically that for a one-dimensional system and the A + A reaction, when the point-molecule assumption is relaxed, the propensity function need only be adjusted by replacing the total volume of the system with the free volume of the system. In this paper we investigate via numerical simulations the impact of relaxing the point-molecule assumption in two dimensions. We find that the distribution of times to the first collision is close to exponential in most cases, so that the formalism of the propensity function is still applicable. In addition, we find that the area excluded by the molecules in two dimensions is usually higher than their close-packed area, requiring a larger correction to the propensity function than just the replacement of the total volume by the free volume.

  9. Oxidation kinetics of nanoscale copper films studied by terahertz transmission spectroscopy

    NARCIS (Netherlands)

    Ramanandan, G.K.P.; Ramakrishnan, G.; Planken, P.C.M.

    2012-01-01

    Terahertz (THz) transmission spectroscopy is used to measure the oxidation kinetics of copper thin films evaporated on silicon substrates. The transmission of broadband THz pulses from 1 to 7 THz through the copper film is measured while it gets oxidized at an elevated temperature in ambient air. Th

  10. Water-Promoted Kinetic Separation of trans- and cis-Limonene Oxides

    Institute of Scientific and Technical Information of China (English)

    徐招兵; 渠瑾

    2012-01-01

    The efficient hydrolytic kinetic separation of trans/cis-(R)-(+)-limonene oxides was realized in a 1 : 1 mixed solvent of water and 1,4-dioxane without additional catalyst. Optically pure trans-(R)-(+)-limonene oxide was recovered in high yield (77%).

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

    DEFF Research Database (Denmark)

    Nielsen, A.H.; Vollertsen, Jes; Hvitved-jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...

  12. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.; Graaff, M. de; Bosch, P.L. van den; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.W.M.

    2013-01-01

    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 concl

  13. Comparative kinetic analysis of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol.

    Science.gov (United States)

    Rokhina, Ekaterina V; Repo, Eveliina; Virkutyte, Jurate

    2010-03-01

    The kinetic study of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol in water was performed to qualitatively assess the effect of ultrasound on the process kinetics. Various kinetic parameters such as the apparent kinetic rate constants, the surface utilization coefficient and activation energy of phenol oxidation over RuI(3) catalyst were investigated. Comparative analysis revealed that the use of ultrasound irradiation reduced the energy barrier of the reaction but had no impact on the reaction pathway. The activation energy for the oxidation of phenol over RuI(3) catalyst in the presence of ultrasound was found to be 13kJmol(-1), which was four times smaller in comparison to the silent oxidation process (57kJmol(-1)). Finally, 'figures-of-merit' was utilized to assess different experimental strategies such as sonolysis alone, H(2)O(2)-enhanced sonolysis and sono-catalytic oxidation of phenol in order to estimate the electric energy consumption based on the kinetic rate constants of the oxidation process.

  14. Kinetic features and industrial prospects of the selective oxidative cracking of light alkanes

    Science.gov (United States)

    Arutyunov, V. S.; Savchenko, V. I.; Sedov, I. V.; Nikitin, A. V.; Magomedov, R. N.; Proshina, A. Yu

    2017-01-01

    The results of kinetic investigations of selective oxidative cracking of light alkanes are analyzed and integrated. This process attracts researchers' attention owing to possible opportunities for designing new industrial processes based on light hydrocarbon feed. Particular attention is paid to ethane for which comprehensive and adequate models of oxidative conversion suitable for detailed analysis of the process kinetics have already been developed. The prospects for the practical application of methane homologues present in natural and associated gases in the selective oxidative cracking are discussed. The bibliography includes 85 references.

  15. Kinetics of wet air oxidation of glyoxalic acid and oxalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. (Univ. of Bombay (India). Dept. of Chemical Technology)

    1994-12-01

    Oxidation of lower molecular weight monobasic and dibasic acids such as formic acid, acetic acid, glyoxalic acid, and oxalic acid is often the rate-controlling step during wet air oxidation (WAO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WAO of glyoxalic acid and oxalic acid was studied in absence and presence of a cupric sulfate catalyst in the temperature range of 120--245 C and oxygen partial pressure of 0.345--1.380 MPa. The wet oxidation of oxalic acid was found to require more severe conditions as compared to glyoxalic acid. The reaction mechanism and kinetic model have been discussed.

  16. Kinetic study of formic acid oxidation on carbon supported Pd electrocatalyst

    Science.gov (United States)

    Wang, Yujiao; Wu, Bing; Gao, Ying; Tang, Yawen; Lu, Tianhong; Xing, Wei; Liu, Changpeng

    The oxidation of formic acid at the Pd/C catalyst electrode is a completely irreversible kinetic process with the reaction order of 1.0. The oxidation rate of formic acid is increased with increasing the concentration of formic acid and is decreased with increasing H + concentration. The apparent negative reaction order with respect to H + is about -0.18 or -0.04 in H 2SO 4 or HClO 4 solution respectively, because bisulfate anions would inhibit formic acid oxidation at some extent. The kinetic parameters, charge transfer coefficient and the diffusion coefficient of formic acid were obtained under the quasi steady-state conditions.

  17. Reaction Kinetics for Heterogeneous Oxidation of Mn(Ⅲ)—Toluene

    Institute of Scientific and Technical Information of China (English)

    张彰; 朱宪

    2002-01-01

    The reaction kinetics of the heterogeneous oxidation oftoluene with Mn3+ was studied by considering the effects of disproportionation of Mn3+ in reaction system,a “parallel”modulus was set up.And then the concentration of Mn3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn.the rate constant,order and pseudo-activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded.In addition,the reaction mechanism was analyzed.It shows that the results are completely consistent with modulus.

  18. [Changes in Kinetics of Chemiluminescence of Plasma as a Measure of Systemic Oxidative Stress in Humans].

    Science.gov (United States)

    Sozarukova, M M; Polimova, A M; Proskurnina, E V; Vladimirov, Yu A

    2016-01-01

    Oxidative stress is a pathogenetic factor of many diseases. The control of its level is important for early diagnosis and therapy adjustment. In this work, antioxidant status was estimated in blood plasma. In the system of 2,2'-azo-bis(2-amidinopropane)dihydrochloride-luminol a set of chemiluminescence kinetic curve parameters is proposed for oxidative stress level estimation (the latent period τ(lat) and the increasing of analytical signal ΔI(CL)). Uric acid and albumin were shown as the main components that responsible for changes in chemiluminescence kinetic curve of plasma. Serum albumin undergoes oxidative modification in dose-depend manner under the action of UV irradiation, it causes the enhancement of antioxidant properties. Changes in plasma chemiluminescence kinetics are proposed as a measure of oxidative stress in human body.

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

    DEFF Research Database (Denmark)

    Nielsen, A.H.; Vollertsen, Jes; Hvitved-jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...... parameters determined in a triplicate experiment. The kinetic parameters determined in 25 experiments on wastewater samples from a single site exhibited good constancy with a variation of the same order of magnitude as the precision of the method. It was found that the stoichiometry of the reaction could...... be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m...

  20. High-temperature steam oxidation kinetics of the E110G cladding alloy

    Science.gov (United States)

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

    2016-07-01

    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.

  1. Kinetics study on photochemical oxidation of polyacrylamide by ozone combined with hydrogen peroxide and ultraviolet radiation

    Institute of Scientific and Technical Information of China (English)

    REN Guang-meng; SUN De-zhi; CHUNG Jong Shik

    2006-01-01

    An investigation on the process of ozone combined with hydrogen peroxide and ultraviolet radiation has been carried out in order to establish the kinetics for photochemical oxidation of polyacrylamide (PAM) in aqueous solution. Effects of operating parameters, including initial PAM concentration, dosages of ozone and hydrogen peroxide, UV radiation and pH value on the photochemical oxidation of PAM, have been studied. There was an increase in photochemical oxidation rate of PAM with increasing of dosages of O3, H2O2 and ultraviolet radiation. Upon increasing of the initial PAM concentration, the photochemical oxidation rate of PAM decreased. Slight effect of pH value on the photochemical oxidation rate of PAM was observed in the experiments. The kinetics equation for the photochemical oxidation of PAM by the system has been established.

  2. Iron oxidation kinetics study by using infrared spectral emissivity measurements below 570deg. C

    Energy Technology Data Exchange (ETDEWEB)

    Campo, Leire del [Departamento de Fisica de la Materia Condensada, Facultad de Ciencia y Tecnologi' a, Universidad del Pai' s Vasco, Barrio Sarriena s/n, 48940 Leioa, Bizkaia (Spain); Perez-Saez, Raul B. [Departamento de Fisica de la Materia Condensada, Facultad de Ciencia y Tecnologi' a, Universidad del Pai' s Vasco, Barrio Sarriena s/n, 48940 Leioa, Bizkaia (Spain); Instituto de Sintesis y Estudio de Materiales, Universidad del Pais Vasco, Apdo. 644, 48080 Bilbao (Spain)], E-mail: raul.perez@ehu.es; Tello, Manuel J. [Departamento de Fisica de la Materia Condensada, Facultad de Ciencia y Tecnologi' a, Universidad del Pai' s Vasco, Barrio Sarriena s/n, 48940 Leioa, Bizkaia (Spain); Instituto de Sintesis y Estudio de Materiales, Universidad del Pais Vasco, Apdo. 644, 48080 Bilbao (Spain)

    2008-01-15

    The oxidation kinetics of iron below 570deg. C is investigated through the dependence of the spectral emissivity on the surface oxidation state. Using the theory of radiative effects of thin films, the oxide scale thickness is obtained as a function of time. A parabolic growth has been observed in all the cases, and applying Wagner's theory, the oxidation parabolic rate constants have been calculated at four temperatures. The temperature dependence of these results has additionally been used to obtain the activation energy of the oxidation process in iron. The parabolic rate constants and activation energy values are in good agreement with the theoretical predictions, and this suggests that the lattice diffusion mechanisms for the high temperature magnetite growth also occur until 400deg. C. The experimental results are also useful to test the applicability of emissivity measurements for in situ oxidation kinetics studies in the spectral range where the scales are optically thin.

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

    Science.gov (United States)

    Zalkind, S.; Rafailov, G.; Halevy, I.; Livneh, T.; Rubin, A.; Maimon, H.; Schweke, D.

    2017-03-01

    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 UO2(111) is the prominent one. As the oxide thickens, the growth rate of UO2(220) plane increases and both planes grow concurrently. The activation energies obtained for the oxide growth are Qparabolic = 17.5 kcal/mol and Qlinear = 19 kcal/mol. Enhanced oxidation around uranium carbide (UC) inclusions is clearly observed by scanning electron microscopy (SEM).

  4. Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate

    Indian Academy of Sciences (India)

    Poonam Gupta; Seema Kothari

    2001-04-01

    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 isotope effect. Addition of benzyltrimethylammonium chloride enhances the rate. It is proposed that the reactive oxidizing species is [(PhCH2Me3N)+ (IZn2Cl6)−]. Suitablemechanisms have been proposed.

  5. 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.

  6. Less Stress : Oxidative stress and glutathione kinetics in preterm infants

    NARCIS (Netherlands)

    D. Rook (Denise)

    2013-01-01

    textabstractDue to immature antioxidant defenses, preterm infants are at susceptible to oxidative stress, which is associated with bronchopulmonary dysplasia, retinopathy of prematurity and periventricular leukomalacia. The general aim of this thesis was to study oxidative stress in preterm infants

  7. Less Stress : Oxidative stress and glutathione kinetics in preterm infants

    NARCIS (Netherlands)

    D. Rook (Denise)

    2013-01-01

    textabstractDue to immature antioxidant defenses, preterm infants are at susceptible to oxidative stress, which is associated with bronchopulmonary dysplasia, retinopathy of prematurity and periventricular leukomalacia. The general aim of this thesis was to study oxidative stress in preterm infants

  8. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Introduction The Solid Oxide Fuel Cell (SOFC), which converts hydrogen as well as hydrocarbon fuels directly into electricity, has demonstrated almost comparable performance when operated reversely as Solid Oxide Electrolyser Cell (SOEC) for electrical energy storage as fuels. In both application...

  9. Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm

    Institute of Scientific and Technical Information of China (English)

    刘平乐; 邹丽珊; 罗和安; 王良芥; 郑金华

    2004-01-01

    A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed. This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data. Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

  10. Effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Chlorine content and position of chlorinated phenols have many significant effects on the reactivity of oxido-reduction. The effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate were evaluated through different kinetics studies. Since chlorine was an electron withdrawing atom, the substitution of chlorine on the aromatic ring decreased the oxidation rate constant by σ-electron withdrawing conductive effect; at the same time, the substitution of chlorine at ortho or para position on the aromatic ring increased the oxidation rate constant by π-electron donating conjugative effect, and the conjugative effect could counteract the negative impact of the conductive effect to some extent. On the other hand, the substitution of chlorine at ortho position on the aromatic ring decreased the oxidation rate constant by steric hindrance effect. The oxidation rate constants of phenol and chlorinated phenols studied decreased as follow order: 4-chlorophenol>2,4-dichlorophenol>phenol>2,6-dichlorophenol.

  11. 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 sputter cleaned + annealed epsilon-Fe2N1-x was observed to be lower than of sputter cleaned epsilon-Fe2N1-x, but upon prolonged oxidation sputter cleaned + annealed epsilon-Fe2N1-x attained a higher oxidation rate than sputter cleaned epsilon-Fe2N1-x. The oxidation kinetics was interpreted using the model...

  12. Assessing Effects of Oxidizer Characteristics on Composite Reaction Kinetics

    Science.gov (United States)

    2013-12-01

    these 2 reactants react to form the products shown. For a complete reaction it was necessary to have two oxygen molecules for each methane molecule. A...properties such as high density (13.31 g cm-3) and large neutron capture cross section such that Hf and HfH2 are widely used for nuclear reactor and...volume can be calculated. In this case, plastic work per volume is = = 2 (−) , where Y is the yield strength of the plate

  13. Kinetics and mechanism of oxidation of chloramphenicol by 1-chlorobenzotriazole in acidic medium

    Indian Academy of Sciences (India)

    R C Hiremath; R V Jagadeesh; Puttaswamy; S M Mayanna

    2005-07-01

    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 respect to [CAP]o. The fractional-order dependence of rate on [H+] suggests complex formation between CBT and H+. It fails to induce polymerization of acrylonitrile under the experimental conditions employed. Activation parameters are evaluated. The observed solvent isotope effect indicates the absence of hydride transfer during oxidation. Effects of dielectric constant and ionic strength of the medium on the reaction rate have been studied. Oxidation products are identified. A suitable reaction scheme is proposed and an appropriate rate law is deduced to account for the observed kinetic data.

  14. Electrode Kinetics and Gas Conversion in Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude

    for operation in the different fuels, operation temperature and operation modes it is important to understand the kinetics of the SOC electrodes. This thesis was aimed at understanding the kinetics of the SOC under different operation conditions of temperature, polarization, and fuel mixture. For investigations...... conditions of temperature and current density nano particles were also found on Ni particles, identified as ZrO2 and attributed the major cause of fuel electrode ageing. In cyclic operation these enhancing conditions were not maintained long-enough for severe nickel precipitation. It is known...... compared well with those reported in literature and their evolution with temperature was similar to that reported in literature based on porous Ni/YSZ fuel electrodes. From the two investigated oxygen electrodes, the higher performing (La0.6Sr0.4)0.99CoO3/Ce0.9Gd0.1O1.95 (LSC/CGO) oxygen electrode showed...

  15. Pyrolysis and Oxidation Kinetics of Anisole and Phenol

    Science.gov (United States)

    1997-06-01

    opportunity later on to serve as Rob’s teaching assistant. I chose to work with Profs. Irv Glassman and Ken Brezinsky because of their obvious enthusiasm...solvents. In general, the thermochemistry for H abstraction by C6H50- is similar to the thermochemistry for the same H abstraction by H02. However, the...1965). Effects of resonance and structure on the thermochemistry of organic’peroxy radicals and the kinetics of combustion reactions. J. Am. Chem

  16. Kinetic of benzotriazole oxidation by ozone and hydroxyl radical.

    Science.gov (United States)

    Vel Leitner, Nathalie Karpel; Roshani, Babak

    2010-03-01

    Ozonation experiments were performed in batch reactors in order to determine the rate constants for the reaction of molecular ozone and OH radicals with benzotriazole (BT) at different pHs. The first group of ozonation experiments was carried out for the determination of the rate constant for the direct reactions between ozone and BT. Two different kinetic models were used for the determination of kinetic rate constants: (i) the log-reduction of BT with ozone in excess, (ii) the competition kinetic model. The second-order rate constants for BT with molecular ozone were determined to be 36.4+/-3.8M(-1) s(-1) and 18.4+/-0.8M(-1) s(-1) at pH 2 from the two methods respectively. With the competition method, the value at pH 5 was found to be 22.0+/-2.0M(-1) s(-1). In a following stage, the reaction of BT with OH radicals was investigated at pH values ranging from 2 to 10.2. Using a method involving two probe compounds during the ozonation, the second-order rate constants of the BT reaction with hydroxyl radicals were determined. The rate constants were found to vary from 6.2x10(9)M(-1) s(-1) at pH 10.2 to 1.7x10(10)M(-1) s(-1) at pH 2.

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

    Science.gov (United States)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

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

  18. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670-773 K

  19. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

  20. Kinetic aspects of the formation of aluminium oxide by use of a microwave-induced plasma.

    Science.gov (United States)

    Quade, A; Steffen, H; Hippler, R; Wulff, H

    2002-10-01

    The oxidation of thin aluminium layers in a microwave plasma has been investigated to determine the kinetics of oxide growth. Thin Al-coatings were oxidized by means of a variety of gas mixtures, characterized by different partial pressures of oxygen, in microwave-induced plasmas of different power. To study the whole kinetic process the Al-metal and the oxide formed were investigated by means of a combination of grazing incidence X-ray reflectometry (GIXR) and grazing incidence X-ray diffractometry (GIXRD). XPS and FTIR spectroscopy confirmed the formation of stoichiometric Al(2)O(3). The alumina formed is X-ray amorphous. Quantitative description of oxide formation was achieved indirectly by determination of the decrease in the integrated intensity of the Al(111)-peak and the total thickness of the whole coating. These values enabled calculation of kinetic data. It was found that oxide growth was a combination of two simultaneous processes - diffusion and sputter processes. The diffusion coefficient D (cm(2) s(-1)) and the sputter rate S (nm s(-1)) were determined. The effect of the composition of the gas mixture, microwave power, and concentration of activated oxygen species on the oxidation process will be discussed. For calculation of the activation energy, E(A), of this plasma-enhanced diffusion process the temperature-dependence of D was investigated.

  1. Volume of visual field assessed with kinetic perimetry and its application to static perimetry

    Directory of Open Access Journals (Sweden)

    Christoforidis JB

    2011-04-01

    Full Text Available John B ChristoforidisCollege of Medicine, The Ohio State University, Columbus, OH, USABackground: The purpose of this study was to quantify the volume of the kinetic visual field with a single unit that accounts for visual field area and differential luminance sensitivity.Methods: Kinetic visual field perimetry was performed with a Goldmann perimeter using I4e, I3e, I2e, and I1e targets. The visual fields of 25 normal volunteers (17 women, eight men of mean age 33.9 ± 10.1 (range 17–64 years were obtained and digitized. Isopter areas were measured with a method devised to correct cartographic distortion due to polar projection inherent in perimetry and are expressed in steradians. The third dimension of each isopter represents sensitivity to target luminance and was calculated as log (target luminance-1. If luminance is expressed in cd/m2, the values for the third dimension are 0.5 for I4e, 1.0 for I3e, 1.5 for I2e, and 2.0 for I1e. The resulting unit is a steradian (log 103 (cd/m2-1 which is referred to as a Goldmann. In addition, the visual fields of four patients with representative visual defect patterns were examined and compared with normal subjects.Results: Mean isopter areas for normal subjects were 3.092 ± 0.242 steradians for I4e, 2.349 ± 0.280 steradians for I3e, 1.242 ± 0.263 steradians for I2e, and 0.251 ± 0.114 steradians for the I1e target. Isopter volumes were 1.546 ± 0.121 Goldmanns for the I4e target, 1.174 ± 0.140 Goldmanns for I3e, 0.621 ± 0.131 Goldmanns for I2e, and 0.126 ± 0.057 Goldmanns for I1e. The total mean visual field volume in our study for the I target was 3.467 ± 0.371 Goldmanns.Conclusion: The volume of the island of vision may be used to quantify a visual field with a single value which contains information about both visual field extension and differential luminance sensitivity. This technique may be used to assess the progression or stability of visual field defects over time. A similar method may

  2. On the kinetics of the initial oxidation of iron and iron nitride

    DEFF Research Database (Denmark)

    Graat, P.C.J.; Somers, Marcel A.J.; Mittemeijer, E.J.

    2002-01-01

    The initial oxidation of alfa-Fe and epsilon Fe2N1-x was investigated. Prior to oxidation the sample surfaces were either sputter cleaned with Ar+ ions or sputter cleaned followed by annealing. It was shown that the sputter cleaning pretreatment of epsilon Fe2N1-x led to a reduction of the N......), ellipsometry and high-resolution transmission electron microscopy (HREM). The oxidation kinetics, as determined with ellipsometry, were described theoretically with the model due to Fromhold and Cook, adopting time-dependent work functions of the metal-oxide and oxide-oxygen interfaces. The calculated...... the oxide film. For sputter-cleaned + annealed epsilon Fe2N1-x this lead to a nitrogen concentration larger than the maximum solubility of nitrogen in epsilon Fe2N1-x. The excess nitrogen at the metal-oxide interface, which is negatively charged as was indicated by the corresponding XPS N 1s peak, lead...

  3. Kinetics and Mechanism of the Oxidation of Menthol by Potassium Bromate in Acidic Solution

    Directory of Open Access Journals (Sweden)

    Ravikant na

    2014-06-01

    Full Text Available No suitable method is available for the estimation of menthol, hence in all kinetic results reported in this chapter, menthol was in excess over potassium bromate and the stoichiometry was also determined under the experimental conditions where menthol (substrate was in excess over potassium bromate (oxidant. Present study was focused on the analysis of kinetics and mechanism of oxidation of neomenthol by potassium bromate in acidic medium. For oxidizing neomenthol, potassium bromate stock solution (5.0×10─2 mol. dm─3 was prepared by dissolving exactly weighed quantity of potassium bromate in doubly distilled water. The suitable reaction mixtures were prepared and left at 313 K for over 24 hours to ensure complete oxidation of neomenthol. The unreacted potassium bromate was determined iodometrically and the results indicate that one mole of potassium bromate is consumed for every three moles of neomenthol and leads to the formation of menthone (ketone.

  4. 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.

  5. Kinetics studies of oxidation of niacinamide by alkaline potassium permanganate

    Directory of Open Access Journals (Sweden)

    Sandipsingh Gour

    2012-04-01

    Full Text Available The oxidation of niacinamide in alkaline media is carried out using potassium permanganate as a oxiding agent. The reaction was monitored using UV-Visible spectrophotometer at 525 nm. It was found to be zero order with respect to oxidant,, fractional order with respect to hydrogen ion concentration and first order with respect to substrate. The thermodynamic parameters(were determinied . The average (?G# was found to be 87.60 KJ/mol. The values ?S# was found to be -0.2132 KJ/mole and energy of activation was found to be 23.95 KJ/mole. A suitable mechanism is proposed based on the experimental conditions.

  6. 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

  7. 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

  8. Kinetics and mechanism of the oxidation process of two-component Fe-Al alloys

    Science.gov (United States)

    Przewlocka, H.; Siedlecka, J.

    1982-01-01

    The oxidation process of two-component Fe-Al alloys containing up to 7.2% Al and from 18 to 30% Al was studied. Kinetic measurements were conducted using the isothermal gravimetric method in the range of 1073-1223 K and 1073-1373 K for 50 hours. The methods used in studies of the mechanism of oxidation included: X-ray microanalysis, X-ray structural analysis, metallographic analysis and marker tests.

  9. Eco-friendly kinetic separation of trans-limonene and carvomenthene oxides

    Indian Academy of Sciences (India)

    S Chandrappa Santosh Kumar; Javagal Rangaswamy Manjunatha; Pullabhatla Srinivas; Bheemanakere Kemapaiah Bettadaiah

    2014-05-01

    Kinetic separation of trans-limonene oxide and trans-carvomenthene oxide was achieved in high yield by selective ring opening of their cis-epoxides in the presence of InCl3 catalyst in water. Catalytic activity of InCl3 was conserved up to 10 cycles. Nucleophilic addition of methanol in presence of InCl3 was also selective as cis-epoxides preferentially reacted leaving behind trans-epoxides, which were separated by fractional distillation.

  10. 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

    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...

  11. Kinetic and geometric aspects of solid oxide fuel cell electrodes

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Skaarup, Steen

    1996-01-01

    The paper gives an overview of the main factors controlling the performance of the solid oxide fuel cell (SOFC) electrodes, emphasizing the most widely chosen anodes and cathodes, Ni-YSZ and LSM-YSZ. They are often applied as composites (mixtures) of the electron conducting electrode material...

  12. Kinetics of ruthenium(III) catalyzed and uncatalyzed oxidation of monoethanolamine by N-bromosuccinimide

    Science.gov (United States)

    Venkata Nadh, R.; Syama Sundar, B.; Radhakrishnamurti, P. S.

    2016-09-01

    Kinetics of uncatalyzed and ruthenium(III) catalyzed oxidation of monoethanolamine by N-bromosuccinimide (NBS) has been studied in an aqueous acetic acid medium in the presence of sodium acetate and perchloric acid, respectively. In the uncatalyzed oxidation the kinetic orders are: the first order in NBS, a fractional order in the substrate. The rate of the reaction increased with an increase in the sodium acetate concentration and decreased with an increase in the perchloric acid concentration. This indicates that free amine molecules are the reactive species. Addition of halide ions results in a decrease in the kinetic rate, which is noteworthy. Both in absence and presence of a catalyst, a decrease in the dielectric constant of the medium decreases the kinetic rate pointing out that these are dipole—dipole reactions. A relatively higher oxidation state of ruthenium i.e., Ru(V) was found to be the active species in Ru(III) catalyzed reactions. A suitable mechanism consistent with the observations has been proposed and a rate law has been derived to explain the kinetic orders.

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

    Science.gov (United States)

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

    2016-12-01

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

  14. 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.

  15. Kinetic stabilization against the oxidation reaction induced by a silaalkane cage in a thiophene-bridged molecular gyroscope.

    Science.gov (United States)

    Setaka, Wataru; Ohmizu, Soichiro; Kira, Mitsuo

    2014-02-01

    Macrocage molecules with a bridged rotor have been synthesized as molecular gyroscopes. The kinetics of the oxidation reaction of the thiophene-bridged molecular gyroscope, whose thiophene ring was bridged inside a silaalkane cage, was investigated. A remarkable kinetic stabilization against the oxidation of the thiophene moiety induced by the molecular cage framework was observed.

  16. Effects of alloy heat treatment on oxidation kinetics and scale morphology for Crofer 22 APU

    Science.gov (United States)

    Magdefrau, Neal J.; Chen, Lei; Sun, Ellen Y.; Aindow, Mark

    2013-11-01

    The effect of alloy heat treatment on the oxidation kinetics and oxide scale microstructure of Crofer 22 APU has been studied. Parabolic oxidation rate constants were measured for the as-received alloy and after pre-oxidation heat treatment in argon at 1050 °C for 1 and 4 h. The oxide scale microstructure was investigated using scanning electron microscopy, focused ion beam milling and transmission electron microscopy. It was found that the alloy forms a two-layer scale with a continuous chromia layer and a discontinuous MnCr2O4 overlayer. Two forms of internal oxides were also formed: subscale pockets of spinel and isolated TiOx precipitates in the underlying alloy. The pre-oxidation heat treatment had a profound effect on the grain size and morphology of the Cr2O3 and MnCr2O4 layers in the scale. The heat-treated samples exhibit a 3.5× lower parabolic oxidation rate constant than the as-received Crofer 22 APU. This improvement in oxidation resistance is attributed to the dramatic differences in the morphology of the oxide scale that forms during the earliest stages of oxidation (<5 h). The implications of these findings for oxidation mechanisms and long-term SOFC performance are discussed.

  17. Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method

    Science.gov (United States)

    Sun, Yi; Shen, Xiao-yi; Zhai, Yu-chun

    2015-05-01

    Thermodynamic analyses and kinetic studies were performed on zinc oxide ore treatment by (NH4)2SO4 roasting technology. The results show that it is theoretically feasible to realize a roasting reaction between the zinc oxide ore and (NH4)2SO4 in a temperature range of 573-723 K. The effects of reaction temperature and particle size on the extraction rate of zinc were also examined. It is found that a surface chemical reaction is the rate-controlling step in roasting kinetics. The calculated activation energy of this process is about 45.57 kJ/mol, and the kinetic model can be expressed as follows: 1 - (1 - α)1/3 = 30.85 exp(-45.57/ RT)· t. An extraction ratio of zinc as high as 92% could be achieved under the optimum conditions.

  18. 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.

  19. Uptake and release kinetics of lysozyme in and from an oxidized starch polymer microgel

    NARCIS (Netherlands)

    Li, Y.; Zhang, Z.; Leeuwen, van H.P.; Cohen Stuart, M.A.; Norde, W.; Kleijn, J.M.

    2011-01-01

    The kinetics of uptake and release of fluorescently labeled lysozyme by/from spherical oxidized starch polymer microgel particles (diameter 10–20 µm) was investigated using confocal laser scanning microscopy. Both the protein and the microgel have a pH dependent charge; in the pH range 3–9, the prot

  20. Uptake and release kinetics of lysozyme in and from an oxidized starch polymer microgel

    NARCIS (Netherlands)

    Li, Yuan; Zhang, Zeshi; van Leeuwen, Herman P.; Stuart, Martien A. Cohen; Norde, Willem; Kleijn, J. Mieke

    2011-01-01

    The kinetics of uptake and release of fluorescently labeled lysozyme by/from spherical oxidized starch polymer microgel particles (diameter 10-20 mu m) was investigated using confocal laser scanning microscopy. Both the protein and the microgel have a pH dependent charge; in the pH range 3-9, the pr

  1. Ferrate promoted oxidative cleavage of sulfonamides: Kinetics and product formation under acidic conditions

    Science.gov (United States)

    Sulfonamide-based antibiotics are often detected in surface waters and secondary wastewater effluents and pose an eminent threat for the development of antibiotic resistance bacteria and genes in aquatic environment. This paper presents the kinetics and stoichiometry of the oxid...

  2. Kinetics of the chemical oxidation of polysulfide anions in aqueos solution

    NARCIS (Netherlands)

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

    2005-01-01

    The kinetic properties of the chemical oxidation of aqueous polysulfide solutions have been studied in phosphate-buffered systems at pH 7¿12, at temperatures between 20 and 40 °C, and ionic strength between 0.05 and 0.50 M. Polysulfide solutions were mixed with a buffer solution of known dissolved

  3. 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

    2017-02-13

    Advanced oxidation processes (AOPs), such as hydroxyl radical (HO(•))- and sulfate radical (SO4(•-))-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 SO4(•-)-mediated oxidation. In the UV/H2O2 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/K2S2O8 process, the calculated steady state concentrations of CO3(•-) and bromine radicals (Br(•), Br2(•-) and BrCl(•-)) were 600-fold and 1-2 orders of magnitude higher than the concentrations of SO4(•-), respectively. The kinetic model, involving both SO4(•-) and CO3(•-) 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 SO4(•-) could lead to overestimations of the removal efficiencies of the SO4(•-)-mediated oxidation of nitroimidazoles in wastewater effluents.

  4. 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.

  5. Experimental and Kinetic Modeling Study of C2H2Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Tihic; Hashemi, Hamid

    2016-01-01

    A detailed chemical kinetic model for oxidation of acetylene at intermediate temperatures and high pressure has been developed and evaluated experimentally. The rate coefficients for the reactions of C2H2 with HO2 and O2 were investigated, based on the recent analysis of the potential energy...

  6. 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.

  7. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; Sint Annaland, van M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal product

  8. 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 measure...

  9. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; van Sint Annaland, M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal

  10. Kinetic Aspects of the Direct Electrochemical Oxidation of p-Xylene ...

    African Journals Online (AJOL)

    2004-01-26

    Jan 26, 2004 ... The kinetics of the electrochemical oxidation of p-xylene (A) in ... production of polyester fibres. ... This compound was prepared by treating 4-methylbenzal- ... with water cooling and equipped with a silica gel drying tube ..... 22 E.Kreyszig, Advanced Engineering Mathematics, 8th edn., John Wiley &. Sons ...

  11. Uptake and release kinetics of lysozyme in and from an oxidized starch polymer microgel

    NARCIS (Netherlands)

    Li, Y.; Zhang, Z.; Leeuwen, van H.P.; Cohen Stuart, M.A.; Norde, W.; Kleijn, J.M.

    2011-01-01

    The kinetics of uptake and release of fluorescently labeled lysozyme by/from spherical oxidized starch polymer microgel particles (diameter 10–20 µm) was investigated using confocal laser scanning microscopy. Both the protein and the microgel have a pH dependent charge; in the pH range 3–9, the prot

  12. Uptake and release kinetics of lysozyme in and from an oxidized starch polymer microgel

    NARCIS (Netherlands)

    Li, Yuan; Zhang, Zeshi; van Leeuwen, Herman P.; Stuart, Martien A. Cohen; Norde, Willem; Kleijn, J. Mieke

    2011-01-01

    The kinetics of uptake and release of fluorescently labeled lysozyme by/from spherical oxidized starch polymer microgel particles (diameter 10-20 mu m) was investigated using confocal laser scanning microscopy. Both the protein and the microgel have a pH dependent charge; in the pH range 3-9, the pr

  13. Kinetic solvent effects on 1,3-dipolar cycloadditions of benzonitrile oxide

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    2005-01-01

    The kinetics of 1,3-dipolar cycloadditions of benzonitrile oxide with a series of N-substituted maleimides and with cyclopentene are reported for water, a wide range of organic solvents and binary solvent mixtures. The results indicate the importance of both solvent polarity and specific hydrogen-bo

  14. Ferrate promoted oxidative cleavage of sulfonamides: Kinetics and product formation under acidic conditions

    Science.gov (United States)

    Sulfonamide-based antibiotics are often detected in surface waters and secondary wastewater effluents and pose an eminent threat for the development of antibiotic resistance bacteria and genes in aquatic environment. This paper presents the kinetics and stoichiometry of the oxid...

  15. Kinetics and mechanism of the oxidation of some -hydroxy acids by hexamethylenetetramine-bromine

    Indian Academy of Sciences (India)

    Dimple Garg; Seema Kothari

    2004-11-01

    The oxidation of lactic acid, mandelic acid and ten monosubstituted mandelic acids by hexamethylenetetramine-bromine (HABR) in glacial acetic acid, leads to the formation of the corresponding oxoacid. The reaction is first order with respect to each of the hydroxy acids and HABR. It is proposed that HABR itself is the reactive oxidizing species. The oxidation of -deuteriomandelic acid exhibits the presence of a substantial kinetic isotope effect (/ = 5.91 at 298 K). The rates of oxidation of the substituted mandelic acids show excellent correlation with Brown’s + values. The reaction constants are negative. The oxidation exhibits an extensive cross conjugation between the electron-donating substituent and the reaction centre in the transition state. A mechanism involving transfer of a hydride ion from the acid to the oxidant is postulated.

  16. Study of oxide and α-Zr(O) growth kinetics from high temperature steam oxidation of Zircaloy-4 cladding

    Science.gov (United States)

    Sawarn, Tapan K.; Banerjee, Suparna; Samanta, Akanksha; Rath, B. N.; Kumar, Sunil

    2015-12-01

    Oxidation kinetics of Zircaloy-4 cladding of fuel pins of Indian pressurized heavy water reactors (IPHWRs) under a simulated loss of coolant accident (LOCA) condition was investigated. The kinetic rate constants for the oxide and oxygen stabilized α-Zr phase growth were established from the isothermal metal-steam reaction at high temperatures (900-1200 °C) with soaking periods in the range of 60-900 s. Oxide and α-Zr(O) layer thickness were measured to derive the respective growth rates. The observed rates obeyed a parabolic law and Arrhenius expressions of rate constants were established. Percentage equivalent clad reacted (%ECR) was calculated using Baker-Just equation. Hydrogen estimation was carried out on the oxidized samples using inert gas fusion technique. The hydrogen pick up was found to be in the range 10-30 ppm. The measured values of oxide and α-Zr(O) layer thickness were compared with the results obtained using OXYCON, an indigenously developed model. The model predicts the oxide growth reasonably well but under predicts the α-Zr(O) growth significantly at thickness values higher than 80 μm.

  17. Self-limited kinetics of electron doping in correlated oxides

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jikun, E-mail: jikunchen@seas.harvard.edu; Zhou, You; Jiang, Jun; Shi, Jian; Ramanathan, Shriram [School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 (United States); Middey, Srimanta; Chakhalian, Jak [Department of Physics, University of Arkansas, Fayetteville, Arkansas 72701 (United States); Chen, Nuofu [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Source, North China Electric Power University, Beijing 102206 (China); Chen, Lidong; Shi, Xun [CAS Key Laboratory of Materials for Energy Conversion, Shanghai institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Döbeli, Max [Laboratory of Ion Beam Physics, ETH Zurich, Zurich 8093 (Switzerland)

    2015-07-20

    Electron doping by hydrogenation can reversibly modify the electrical properties of complex oxides. We show that in order to realize large, fast, and reversible response to hydrogen, it is important to consider both the electron configuration on the transition metal 3d orbitals, as well as the thermodynamic stability in nickelates. Specifically, large doping-induced resistivity modulations ranging several orders of magnitude change are only observed for rare earth nickelates with small ionic radii on the A-site, in which case both electron correlation effects and the meta-stability of Ni{sup 3+} are important considerations. Charge doping via metastable incorporation of ionic dopants is of relevance to correlated oxide-based devices where advancing approaches to modify the ground state electronic properties is an important problem.

  18. Self-limited kinetics of electron doping in correlated oxides

    Science.gov (United States)

    Chen, Jikun; Zhou, You; Middey, Srimanta; Jiang, Jun; Chen, Nuofu; Chen, Lidong; Shi, Xun; Döbeli, Max; Shi, Jian; Chakhalian, Jak; Ramanathan, Shriram

    2015-07-01

    Electron doping by hydrogenation can reversibly modify the electrical properties of complex oxides. We show that in order to realize large, fast, and reversible response to hydrogen, it is important to consider both the electron configuration on the transition metal 3d orbitals, as well as the thermodynamic stability in nickelates. Specifically, large doping-induced resistivity modulations ranging several orders of magnitude change are only observed for rare earth nickelates with small ionic radii on the A-site, in which case both electron correlation effects and the meta-stability of Ni3+ are important considerations. Charge doping via metastable incorporation of ionic dopants is of relevance to correlated oxide-based devices where advancing approaches to modify the ground state electronic properties is an important problem.

  19. Iron oxidation kinetics for H-2 and CO production via chemical looping

    Energy Technology Data Exchange (ETDEWEB)

    Stehle, RC; Bobek, MM; Hahn, DW

    2015-01-30

    Solar driven production of fuels by means of an intermediate reactive metal for species splitting has provided a practical and potentially efficient pathway for disassociating molecules at significantly lower thermal energies. The fuels of interest are of or derive from the separation of oxygen from H2O and CO2 to form hydrogen and carbon monoxide, respectively. The following study focuses on iron oxidation through water and CO2 splitting to explore the fundamental reaction kinetics and kinetic rates that are relevant to these processes. In order to properly characterize the reactive metal potential and to optimize a scaled-up solar reactor system, a monolith-based laboratory reactor was implemented to investigate reaction temperatures over a range from 990 to 1400 K. The presence of a single, solid monolith as a reacting surface allowed for a limitation in mass transport effects in order to monitor kinetically driven reaction steps. The formation of oxide layers on the iron monoliths followed Cabrera-Mott models for oxidation of metals with kinetic rates being measured using real-time mass spectrometry to calculate kinetic constants and estimate oxide layer thicknesses. Activation energies of 47.3 kJ/mol and 32.8 kJ/mol were found for water-splitting and CO2 splitting, respectively, and the conclusions of the independent oxidation reactions where applied to experimental results for syngas (H-2-CO) production to explore ideal process characteristics. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  20. Kinetics of oxidation of nickel(II) aza macrocycles by peroxydisulphate in aqueous media

    Indian Academy of Sciences (India)

    J Lalitham; V R Vijayaraghavan

    2000-10-01

    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 and 2, giving overall a relatively simple second-order rate law followed by oxidation within the ion pair solvent shell. Using rate = +1/2 d[Ni(L)3+]/dt = k[Ni(L)2+][S2O8 2-], oxidation rate constants were determined.

  1. Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

    Science.gov (United States)

    Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

    2016-02-01

    Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

  2. Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects.

    Science.gov (United States)

    Drees, Markus; Strassner, Thomas

    2006-03-03

    The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.

  3. 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.

  4. Kinetics of oxidation of total sulfite in the ammonia-based wet flue gas desulfurization process

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Y.; Zhong, Q.; Fan, X.Y.; Wang, X.R. [Nanjing University of Science & Technology, Nanjing (China). School of Chemical Engineering

    2010-10-15

    Using bubbling apparatus, the kinetics of oxidation of total sulfite in ammonia-based wet flue gas desulfurization (FGD) process was investigated by varying concentrations of SO{sub 3}{sup 2-} and SO{sub 4}{sup 2-}, pH, temperatures and air flow. The concentration range of sulfite is 0.0044-0.026 gmol L{sup -1} and that of sulfate is 0.5-2 gmol L{sup -1}. Experiments were conducted at pH level of 4.5-6.5 and air flow ranging from 50 to 200 L h{sup -1}. In the temperature range of 303.15-333.15K, the reaction was found to be -0.5 order with respect to sulfite. The experimental findings also showed that the bisulfite could be oxidized easier than sulfite. Thus, keeping the pH level of the solution low is conducive to the oxidation of total sulfite. The apparent activation energy for the overall oxidation was calculated to be 28.0 kJ mol{sup -1}. A kinetic model has been derived according to the experimental results. The developed kinetic model, including the operating parameters SO{sub 3}2- concentration, SO{sub 4}{sup 2-} concentration, pH, temperature and air flow, can be applied to simulate the oxidation of total sulfite. This model would be useful for the design of the ammonia-based wet FGD system.

  5. Kinetic studies of sulfide mineral oxidation and xanthate adsorption

    Science.gov (United States)

    Mendiratta, Neeraj K.

    2000-10-01

    Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel

  6. Kinetics and Mechanisms of Ciprofloxacin Oxidation on Hematite Surfaces.

    Science.gov (United States)

    Martin, Sébastien; Shchukarev, Andrey; Hanna, Khalil; Boily, Jean-François

    2015-10-20

    Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment.

  7. Kinetics and mechanism of oxidation of aliphatic alcohols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Manju Baghmar; Pradeep K Sharma

    2001-04-01

    Oxidation of nine primary aliphatic alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the polymerization of acrylonitrile. Tetrabutylammonium chloride has no effect on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The oxidation of [1,1-2H2]ethanol exhibits a substantial kinetic isotope effect. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The reaction is susceptible to both polar and steric effects of substituents. A mechanism involving transfer of a hydride ion in the ratedetermining step has been proposed.

  8. Bond energies in polyunsaturated acids and kinetics of co-oxidation of protiated and deuterated acids

    Science.gov (United States)

    Andrianova, Z. S.; Breslavskaya, N. N.; Pliss, E. M.; Buchachenko, A. L.

    2016-10-01

    A computational program specially designed to analyze co-oxidation of substances in mixtures is suggested. The rigorous kinetic scheme of 32 reactions describing co-oxidation of isotope differing polyunsaturated fatty acids was computed to enlighten experimentally detected enormously large H/D isotope effects. The latter were shown to depend on the kinetic chain length and exhibit two extreme regimes of short and long chains which characterize isotope effects on the initiation and propagation chain reactions of hydrogen (deuterium) atom abstraction. No protective effect of deuterated polyunsaturated acids on the oxidation of protiated acids was detected. Protective effect of the deuterated compounds on the biologically important processes seems to be induced by the low yield of products formed in the chain termination reactions due to the low rate of initiation by deuterated compounds.

  9. Oxidation kinetic analysis of a mixed uranium dicarbide and graphite compound

    Energy Technology Data Exchange (ETDEWEB)

    Marchand, M., E-mail: mickael.marchand@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Fiquet, O., E-mail: olivier.fiquet@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Brothier, M. [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France)

    2013-06-15

    Highlights: ► Experimental study of uranium carbides and graphite powder oxidations. ► Single rate limiting step identification by extensive kinetic analysis. ► Pseudo-steady-state validation during chemical conversion. ► Combination of TGA, TDA, XRD and gas phase chromatography results. -- Abstract: The oxidation of a mixed uranium dicarbide and graphite powder has been investigated by simultaneous thermal gravimetric (TGA) and differential thermal (DTA) analyses coupled with gas phase chromatography. For isothermal oxidation conditions with temperatures below 330 °C, only the UC{sub 2} chemical phase is progressively oxidised into U{sub 3}O{sub 8} oxides. Parabolic weight gain curves as a function of oxidation over time were obtained. A detailed kinetic study is proposed to establish a pseudo-steady-state during the oxidation process. Using an experimental method based on the sudden temperature increases, a single rate-limiting step has been validated and then modelled by a 3D diffusion law. An apparent activation energy calculated from the Arrhenius representation has been evaluated at −35 kJ/mol, thus describing the diffusion of oxygen through the oxide layer.

  10. 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 SO4(·-) and provides important information for further research on the oxidation of these contaminants.

  11. Oxidation kinetics of Ni metallic films: Formation of NiO-based resistive switching structures

    Energy Technology Data Exchange (ETDEWEB)

    Courtade, L.; Turquat, Ch. [L2MP, Laboratoire Materiaux et Microelectronique de Provence, UMR CNRS 6137, Universite du Sud Toulon Var, BP 20132, F-83957 La Garde Cedex (France); Muller, Ch. [L2MP, Laboratoire Materiaux et Microelectronique de Provence, UMR CNRS 6137, Universite du Sud Toulon Var, BP 20132, F-83957 La Garde Cedex (France)], E-mail: christophe.muller@l2mp.fr; Lisoni, J.G.; Goux, L.; Wouters, D.J. [IMEC, Interuniversity MicroElectronics Center, Kapeldreef 75, B-3001 Leuven (Belgium); Goguenheim, D. [L2MP, Laboratoire Materiaux et Microelectronique de Provence, UMR CNRS 6137, ISEN-Toulon, Maison des Technologies, Place Georges Pompidou, F-83000 Toulon (France); Roussel, P. [UCCS, Unite de Catalyse et Chimie du Solide, UMR CNRS 8181, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq (France); Ortega, L. [Laboratoire de Cristallographie, UPR CNRS 5031, BP 166, F-38042 Grenoble Cedex 9 (France)

    2008-04-30

    Resistive switching controlled by external voltage has been reported in many Metal/Resistive oxide/Metal (MRM) structures in which the resistive oxide was simple transition metal oxide thin films such as NiO or TiO{sub 2} deposited by reactive sputtering. In this paper, we have explored the possibility to form NiO-based MRM structures from the partial oxidation of a blanket Ni metallic film using a Rapid Thermal Annealing route, the remaining Ni layer being used as bottom electrode. X-ray diffraction was used to apprehend the Ni oxidation kinetics while transmission electron microscopy enabled investigating local microstructure and film interfaces. These analyses have especially emphasized the predominant role of the as-deposited Ni metallic film microstructure (size and orientation of crystallites) on (i) oxidation kinetics, (ii) NiO film microstructural characteristics (crystallite size, texture and interface roughness) and (iii) subsequent electrical behavior. On this latter point, the as-grown NiO films were initially in the low resistance ON state without the electro-forming step usually required for sputtered films. Above the threshold voltage varying from 2 to 5 V depending on oxidation conditions, the Pt/NiO/Ni MRM structures irreversibly switched into the high resistance OFF state. This irreversibility is thought to originate in the microstructure of the NiO films that would cause the difficulty to re-form conductive paths.

  12. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  13. 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.

  14. Dose dependent oxidation kinetics of lipids in fish during irradiation processing

    Energy Technology Data Exchange (ETDEWEB)

    Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T. [Turkish Atomic Energy Authority, Ankara (Turkey). Lalahan Nuclear Research Inst.; Bicer, A.; Pamuk, V. [Gazi University, Ankara (Turkey). Dept. of Chemical Engineering

    1997-10-01

    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{sup 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 {mu}mol/kg kGy, and a maximum attainable concentration of 15.853 {mu}mol/kg which may be used for process control and dosimetry. (author).

  15. Kinetics of oxidative coupling of methane: Bridging the gap between comprehension and description

    Institute of Scientific and Technical Information of China (English)

    M. Yu. Sinev; Z.T. Fattakhova; V.I. Lomonosov; Yu. A. Gordienko

    2009-01-01

    The development of notions about the mechanism of the oxidative coupling of methane (OCM) over oxide catalysts and corresponding progress in its kinetic description are reviewed and discussed. The latter becomes essential at the stage of scaling up and optimization of the process in pilot and industrial reactors. It is demonstrated that the main achievements in the development of kinetic models can be reached by combining the approaches conventionally used in homo-geneous gas-phase kinetics and in heterogeneous catalysis. In partic-ular,some important features of the OCM process can be described if several elementary reactions of free radical species (formation and transformation) with surface active sites are included into the detailed scheme of methane oxidation in gas. However,some important fea-tures,such as a non-additive character of the reciprocal influence of methane and ethane in the case of their simultaneous presence in the reaction mixture,cannot yet be described and comprehended in the framework of schemes developed so far. Possible ways towards an advanced kinetic model,accounting the main principles of catalyst functioning (redox nature of active sites) and pathways of product formation (via free radicals) are traced.

  16. Kinetics of Oxidation of 3-Benzoylpropionic Acid by N-Chlorobenzamide in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2011-01-01

    Full Text Available The kinetics of oxidation of 3-benzoylpropionic acid (KA by N-chlorobenzamide (NCB in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order dependence each in [KA], [NCB] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of benzamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. Hypochlorous acidium ion (H2O+Cl, has been postulated as the reactive oxidizing species. A mechanism consistent with observed results have been proposed and the related rate law deduced. The activation parameters have been computed with respect to slow step of the mechanism.

  17. Kinetics and mechanism of the oxidation of substituted benzylamines by cetyltrimethylammonium permanganate

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; László Kótai; Kalyan K Banerji

    2003-04-01

    Oxidation of meta- and para-substituted benzylamines by cetyltrimethylammonium permanganate (CTAP) to the corresponding aldimines is first order with respect to both the amine and CTAP. Oxidation of deuteriated benzylamine (PhCD2NH2) exhibited the presence of a substantial kinetic isotope effect (/ = 5.60 at 293 K). This confirmed the cleavage of an -C-H bond in the ratedetermining step. Correlation analyses of the rates of oxidation of 19 monosubstituted benzylamines were performed with various single and multiparametric equations. The rates of the oxidation showed excellent correlations in terms of Yukawa-Tsuno and Brown’s equations. The polar reaction constants are negative. The oxidation exhibited an extensive cross-conjugation, in the transition state, between the electron-donating substituents and the reaction centre. A mechanism involving a hydride-ion transfer from the amine to CTAP in the rate-determining step has been proposed.

  18. Chemical Oxidative Polymerization of 2-Aminothiazole in Aqueous Solution: Synthesis, Characterization and Kinetics Study

    Directory of Open Access Journals (Sweden)

    Hua Zou

    2016-11-01

    Full Text Available The chemical oxidative polymerization of 2-aminothiazole (AT was studied in aqueous solution using copper chloride (CuCl2 as an oxidant. The effect of varying the reaction temperature, reaction time and oxidant/monomer molar ratio on the polymer yield was investigated. The resulting poly(2-aminothiazoles (PATs were characterized by FTIR, 1H NMR, UV-vis, gel permeation chromatography, scanning electron microscopy, thermogravimetric analysis and four-point probe electrical conductivity measurements. Compared with a previous study, PATs with higher yield (81% and better thermal stability could be synthesized. The chemical oxidative polymerization kinetics of AT were studied for the first time. The orders of the polymerization reaction with respect to monomer concentration and oxidant concentration were found to be 1.14 and 0.97, respectively, and the apparent activation energy of the polymerization reaction was determined to be 21.57 kJ/mol.

  19. Chemical kinetic mechanism for the oxidation of paraffinic hydrocarbons needed for primary reference fuels

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-03-01

    A detailed chemical kinetic reaction mechanism is described which simulates the oxidation of the primary reference fuels n-heptane and iso-octane. The high temperature subset of these mechanisms is identified, and the extensions to deal with low temperature conditions are also explained. The algorithms used to assign reaction rates to elementary steps in the reaction mechanism are described, and the means of identifying the different chemical species and the relevant reactions are outlined. Finally, we show how interested kinetic modeling researchers can obtain copies of this reaction mechanism.

  20. Oxidation of phenyl alanine by pyridinium chlorochromate in acidic DMF–water medium: A kinetic study

    Directory of Open Access Journals (Sweden)

    B.L. Hiran

    2016-11-01

    Full Text Available The kinetics of oxidation of phenyl alanine by pyridinium chlorochromate in DMF–water (70:30% mixture in presence of perchloric acid leads to the formation of corresponding aldehyde. The reaction is of first order each in [PCC], [HClO4] and [AA]. Michaelis–Menten type kinetics was observed with phenyl alanine. The reaction rates were determined at different temperatures [25, 30, 35, 40, 45, 50 °C] and the activation parameters were calculated. The reaction does not induce polymerization of acrylonitrile. With an increase in the amount of DMF in its aqueous mixture, the rate increases. A suitable mechanism for the reaction was postulated.

  1. Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

    KAUST Repository

    Eldeeb, Mazen A.

    2016-08-30

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

  2. Kinetics of oxygenated product formation during the heterogeneous oxidation of organic aerosol

    Science.gov (United States)

    Kolesar, K. R.; Cappa, C. D.; Wilson, K. R.

    2014-12-01

    Oxidation of organic aerosols can lead to changes in their atmospheric lifetime, optical properties and health effects. Whereas much is known about the rates of reaction and subsequent branching ratios of gas-phase organic species, much less is known about their condensed phase counterparts. The determination of the kinetics and abundances of the oxidation products associated with condensed phase reactions is needed to understand the oxidation reaction pathways and their branching ratios. The Vacuum Ultraviolet Aerosol Mass Spectrometer (VUV-AMS) at the Chemical Dynamics Beamline at Lawrence Berkeley National Laboratory has been useful in determining the reaction rate constants for a number of condensed phase organic compounds with oxidants such as OH and O3. The relatively soft ionization in the VUV-AMS leads to substantially less fragmentation than other AMS instruments that use electron impact ionization, and therefore preserves a greater amount of molecular information about parent molecules. Previously, ketones formed from the heterogenous oxidation of model organic compounds have been identified and their formation kinetics quantified. However, other possible products, such as alcohols and organic peroxides, have not previously been identified in the VUV-AMS mass spectra or characterized as these are subject to greater fragmentation. Here, we present a method in which the fragmentation pattern is specified for each alcohol isomer formed from the oxidation of two model organic compounds, bis-2-ethylhexl sebacate and squalane. From this we are able to define unique m/z fragments for each isomer from which we derive information about alcohol and abundances. This study demonstrates additional methods for the analysis of mass spectra obtained with the VUV-AMS as well as provides insights into condensed phase oxidation kinetics.

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

    Science.gov (United States)

    Dachipally, Purnachandar; Jonnalagadda, Sreekanth B

    2011-01-01

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

  4. Kinetics and catalysis in co-oxidation of benzaldehyde with alkylaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov, A.M. (Chernovisty State Univ. Ukr. S.S.R.); Chervinskii, K.A.; Mikhailovskaya, T.N.; Pluzhnikov, V.A.; Galabitskii, B.V.; Ivanova, L.A.; Pavlyuk, G.V.

    1978-01-01

    The presence of aldehydes increases the rates of liquid-phase oxidation of alkylaromatic hydrocarbons (AAH), e.g., cumene, ethylbenzene, p-xylene, or toluene, by molecular oxygen at 20/sup 0/-60/sup 0/C to values characteristic for oxidation of AAH alone at 100/sup 0/-120/sup 0/C. Kinetic studies showed that aldehydes cause rapid chain propagation via the formation of R radicals from RH and conversion of relatively unreactive RO/sub 2/ radicals to hydroperoxides. Due to self-inhibition by phenols formed in the chain oxidation of aromatic aldehydes, e.g., benzaldehyde, the process follows steady-state kinetics, which ensures a much larger induction factor for AAH co-oxidation with aromatic than with aliphatic aldehydes, which oxidize in a self-accelerating regime. Although salts of transition metals (mainly cobalt) favor the self-accelerating regime and thus reduce the induction factor, they catalyze oxidation of oxygen compounds present in the system by hydroperoxides (HPO), which, together with the induced HPO decomposition, are the main reactions preventing HPO accumulation.

  5. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst

    Directory of Open Access Journals (Sweden)

    Muhammad Mufti Azis

    2016-03-01

    Full Text Available Exhaust after treatment for lean burn and diesel engine is a complex catalytic system that consists of a number of catalytic units. Pt/Al2O3 is often used as a model Diesel Oxidation Catalyst (DOC that plays an important role to facilitate oxidation of NO to NO2. In the present study, we proposed a detailed kinetic model of NO oxidation as well as low temperature C3H6 inhibition to simulate temperature-programmed reaction (TPR data for NO oxidation over Pt/Al2O3. A steady-state microkinetic model based on Langmuir-Hinshelwood mechanism for NO oxidation was proposed. In addition, low temperature C3H6 inhibition was proposed as a result of site blocking as well as surface nitrite consumption. The model can explain the experimental data well over the studied temperature range. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Azis, M.M., Creaser, D. (2016. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 27-33. (doi:10.9767/bcrec.11.1.403.27-33 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.403.27-33

  6. Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Wang, Zhaohui, E-mail: zhaohuiwang@dhu.edu.cn [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Liu, Jianshe, E-mail: liujianshe@dhu.edu.cn [State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer Sequential photocatalytic reduction-oxidation degradation of TBBPA was firstly examined. Black-Right-Pointing-Pointer Different atmospheres were found to have significant effect on debromination reaction. Black-Right-Pointing-Pointer 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{sub 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{sub 2} system by changing the reaction atmospheres.

  7. Denitrifying kinetics and nitrous oxide emission under different copper concentrations.

    Science.gov (United States)

    Wu, Guangxue; Zhai, Xiaofeng; Jiang, Chengai; Guan, Yuntao

    2014-01-01

    Denitrifying activities and nitrous oxide (N2O) emission during denitrification can be affected by copper concentrations. Different denitrifiers were acclimated in sequencing batch reactors with acetate or methanol as the electron donor and nitrate as the electron acceptor. The effect of copper concentrations on the denitrifying activity and N2O emission for the acclimated denitrifiers was examined in batch experiments. Denitrifying activities of the acclimated denitrifiers declined with increasing copper concentrations, and the copper concentration exhibited a higher effect on denitrifiers acclimated with acetate than those acclimated with methanol. Compared with the control without the addition of copper, at the copper concentration of 1 mg/L, the acetate utilization rate reduced by 89% for acetate-acclimated denitrifiers, while the methanol utilization rate only reduced by 15% for methanol-acclimated denitrifiers. Copper also had different effects on N2O emission during denitrification carried out by various types of denitrifiers. For the acetate-acclimated denitrifiers, N2O emission initially increased and then decreased with increasing copper concentrations, while for the methanol-acclimated denitrifiers, N2O emission decreased with increasing copper concentrations.

  8. Theoretical kinetic study of the low temperature oxidation of ethanol

    CERN Document Server

    Fournet, René; Bounaceur, Roda; Molière, Michel

    2009-01-01

    In order to improve the understanding of the low temperature combustion of ethanol, high-level ab initio calculations were performed for elementary reactions involving hydroxyethylperoxy radicals. These radicals come from the addition of hydroxethyl radicals (?CH3CHOH and ?CH2CH2OH) on oxygen molecule. Unimolecular reactions involving hydroxyethylperoxy radicals and their radical products were studied at the CBS-QB3 level of theory. The results allowed to highlight the principal ways of decomposition of these radicals. Calculations of potential energy surfaces showed that the principal channels lead to the formation of HO2 radicals which can be considered, at low temperature, as slightly reactive. However, in the case of CH3CH(OOH)O? radicals, a route of decomposition yields H atom and formic peracid, which is a branching agent that can strongly enhance the reactivity of ethanol in low temperature oxidation. In addition to these analyses, high-pressure limit rate constants were derived in the temperature rang...

  9. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    Energy Technology Data Exchange (ETDEWEB)

    Chen Wanru [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Huang, Ching-Hua, E-mail: ching-hua.huang@ce.gatech.edu [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States)

    2011-05-15

    Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO{sub 2} at mild conditions (pH 4-9 and 22 {sup o}C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg{sup 2+} or Ca{sup 2+}. Experimental results of TTC indicate that MnO{sub 2} promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO{sub 2} generate little iso-OTC, but occur mainly at the A ring's dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO{sub 2}, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines. - Highlights: > Tetracyclines transform rapidly by MnO{sub 2} to yield complicated products. > Isomerized, (hydr)oxygenated and N-demethylated products are formed. > Transformation product structures may suggest lowered antibacterial activity. - The complex transformation pathways of three popular tetracycline antibiotics (tetracycline, oxytetracycline and chlorotetracycline) with MnO{sub 2} under environmental conditions are systematically evaluated and elucidated.

  10. A kinetic study on the lactoperoxidase catalyzed oxidation of estrogens.

    Science.gov (United States)

    Løvstad, Rolf A

    2006-12-01

    Lactoperoxidase, which is produced in mammary glands, is proposed to be involved in carcinogenesis, because of its ability to react with estrogenic molecules, oxidizing them to free radicals. In the present study the reactivity towards six species (estradiol, ethynylestradiol, estriol, estrone, pregnenolone and mestranol) was investigated by means of a NADH-coupled system. The enzyme activity towards estradiol, ethynylestradiol, estriol and estrone did not vary much, suggesting that the different substituents in the D-ring of the steroid had little effect on the reaction. A somewhat higher K (m)-value was obtained with estriol; possibly because of a more effective splitting of the enzyme-substrate complex into products. Pregnenolone, without resonance in the A-ring, and a methyl group in 19-position, did not react with the enzyme, in spite of having the proposed essential hydroxyl group in 3-position. Mestranol, with a methoxy group in 3-position, did not react with the enzyme either, supporting the suggestion that lactoperoxidase reacts with the 3-hydroxyl group of the estrogens.

  11. Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

    Science.gov (United States)

    Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

    2016-06-02

    The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

  12. Phototrophic sulfide oxidation: environmental insights and a method for kinetic analysis

    Directory of Open Access Journals (Sweden)

    Thomas E Hanson

    2013-12-01

    Full Text Available Previously, we presented data that indicated microbial sulfide oxidation would out-compete strictly chemical, abiotic sulfide oxidation reactions under nearly all conditions relevant to extant ecosystems (Luther et al., 2011. In particular, we showed how anaerobic microbial sulfide oxidation rates were several orders of magnitude higher than even metal catalyzed aerobic sulfide oxidation processes. The fact that biotic anaerobic sulfide oxidation is kinetically superior to abiotic reactions implies that nearly all anaerobic and sulfidic environments should host microbial populations that oxidize sulfide at appreciable rates. This was likely an important biogeochemical process during long stretches of euxinia in the oceans suggested by the geologic record. In particular, phototrophic sulfide oxidation allows the utilization of carbon dioxide as the electron acceptor suggesting that this process should be particularly widespread rather than relying on the presence of other chemical oxidants. Using the Chesapeake Bay as an example, we argue that phototrophic sulfide oxidation may be more important in many environments than is currently appreciated. Finally, we present methodological considerations to assist other groups that wish to study this process.

  13. Observation of temperature-dependent kinetics for catalytic CO oxidation over TiO2-supported Pt catalysts

    Science.gov (United States)

    Yu, Xiaomei; Wang, Yunfei; Kim, Ansoon; Kim, Yu Kwon

    2017-10-01

    TiO2-supported Pt catalysts were prepared for the study of CO oxidation kinetics at reaction conditions of pressures (1-100 Torr) and temperatures (300-500 K). We find two distinct temperature ranges with different reaction kinetics distinguished by an abrupt slope change at around 380 K in the Arrhenius plot only with the excess O2, not with the stoichiometric O2/CO ratio. We propose that Pt oxides are formed during the catalytic reactions with increasing temperatures under the oxidizing condition and the origin of the slope change is due to the changes in the reaction pathways of CO oxidation due to the Pt oxide formation.

  14. Low density lipoprotein for oxidation and metabolic studies. Isolation from small volumes of plasma using a tabletop ultracentrifuge.

    Science.gov (United States)

    Himber, J; Bühler, E; Moll, D; Moser, U K

    1995-01-01

    A rapid method is described for the isolation of small volumes of plasma low density lipoprotein (LDL) free of plasma protein contaminants using the TL-100 Tabletop Ultracentrifuge (Beckman). The isolation of LDL was achieved by a 25 min discontinuous gradient density centrifugation between the density range of 1.006 and 1.21 g/ml, recovery of LDL by tube slicing followed by a 90 min flotation step (d = 1.12 g/ml). The purity of LDL and apolipoprotein B100 (apo B100) were monitored by agarose electrophoresis, sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), radial immunodiffusion and micropreparative fast protein liquid chromatography (FPLC). The ability of LDL oxidation was assessed by following absorbance at 234 nm after addition of copper ions. The functional integrity of the isolated LDL was checked by clearance kinetics after injection of [125I]-labelled LDL in estrogen-treated rats. The additional purification step led to LDL fractions free of protein contamination and left apo B100, alpha-tocopherol and beta-carotene intact. The LDL prepared in this way was free of albumin, as evident from analytic tests and from its enhanced oxidative modification by copper ions. Used for analytical purposes, this method allows LDL preparations from plasma volumes up to 570 microliters. This method is also convenient for metabolic studies in small animals, especially those relating to the determination of kinetic parameters of LDL in which LDL-apo B100 has to be specifically radiolabelled.

  15. Hydrogen production by thermal partial oxidation of ethanol: Thermodynamics and kinetics study

    Energy Technology Data Exchange (ETDEWEB)

    Al-Hamamre, Z. [Chemical Engineering Department, Faculty of Engineering and Technology, University of Jordan, 11942 Amman (Jordan); Hararah, M.A. [Environmental Engineering Department, Faculty of Engineering, Al-Hussein Bin Talal University, Ma' an (Jordan)

    2010-06-15

    In this study thermodynamics and kinetics analysis of the thermal partial oxidation (TPOX) of ethanol for producing hydrogen is performed. Equilibrium and kinetics calculations are performed in order to find the limiting parameters for the thermal partial oxidation. The effects of air ratio {lambda} (the ratio of the oxidizer -to- fuel ratio to the stoichiometric oxidizer -to- fuel ratio) and mixture inlet temperatures (T{sub mix-in}) on the reforming efficiency, the H{sub 2} mole number, the reaction progress, the equilibrium time and the ignition delay time are investigated. Furthermore, the analysis is performed using different kinetics schemes and the results are compared. The optimum practical operating conditions of the partial oxidation process of ethanol are identified. In this way, the results of this work can be useful as a guideline in experimental work. It is found that the reforming efficiency increases with increasing the process temperature for {lambda} < 0.3 and remains nearly constant elsewhere. The efficiency reaches a maximum value of 90% at {lambda} = 0.20 and T{sub mix-in} {>=} 1000 K. The kinetics simulations suggest that three different regions exist during the partial oxidation process of ethanol: the oxidation region, the water gas shift reaction- reforming region and the reforming region. The reforming reactions in the 3rd region are the reaction process limiting step. Additionally, it is found that the equilibrium concentration of a given species is not affected by the pressure when the process temperature lies outside the range of 500 K < T{sub process} < 1700 K. However, the minimum time required for a given species to reach the equilibrium is affected when pressures higher than 1 atm are employed. Pressures higher than 1 atm shift this minimum time towards lower values. Due to preheating limitations (self ignition and reactor material stability) and the kinetics behavior of the TPOX process of ethanol, practical operating conditions

  16. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rau, M.S.; Gennero de Chialvo, M.R. [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina); Chialvo, A.C., E-mail: achialvo@fiq.unl.edu.a [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina)

    2010-07-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H{sub 2}SO{sub 4} solution at different rotation rates ({omega}). 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 {omega}{sup 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.

  17. KINETIC AND MECHANISTIC STUDY OF OXIDATION OF ATENOLOL BY CERIUM (IV IN SULPHURIC ACIDIC MEDIUM

    Directory of Open Access Journals (Sweden)

    Fadnis G Anand

    2012-03-01

    Full Text Available The kinetics of oxidation of antihypertensive drug, atenolol by cerium (IV in sulphuric acidic medium has been studied spectrophotometrically at 360 nm. The reaction between cerium (IV and atenolol in acidic medium has exhibited 2:1 stoichiometry. The order of the reaction with respect to atenolol has been found to be one. The observed pseudo first order rate constants kobs increased with sulphuric acid and hydrogen ion concentrations where as decreased bisulphate ion concentration indicating the formation bisulphato reactive species of cerium (IV in the present reaction. The thermodynamic parameters have been evaluated from the temperature variation kinetic data. A possible mechanism is proposed which has been validated by derived rate law. An attempt has been made to use rate data for kinetic estimation of atenolol.KEYWORDS:

  18. Effect of wall growth on the kinetic modeling of nitrite oxidation in a CSTR.

    Science.gov (United States)

    Dokianakis, Spiros N; Kornaros, Michael; Lyberatos, Gerasimos

    2006-03-05

    A simple kinetic model was developed for describing nitrite oxidation by autotrophic aerobic nitrifiers in a continuous stirred tank reactor (CSTR), in which mixed (suspended and attached) growth conditions prevail. The CSTR system was operated under conditions of constant nitrite feed concentration and varying volumetric flow rates. Experimental data from steady-state conditions in the CSTR system and from batch experiments were used for the determination of the model's kinetic parameters. Model predictions were verified against experimental data obtained under transient operating conditions, when volumetric flow rate and nitrite feed concentration disturbances were imposed on the CSTR. The presented kinetic modeling procedure is quite simple and general and therefore can also be applied to other mixed growth biological systems.

  19. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate

    Indian Academy of Sciences (India)

    G P Panigrahi; Jagannath Panda

    2000-12-01

    Kinetics of oxidation of N-methyl and N-ethyl aniline by peroxomono-phosphoric acid (PMPA) in aqueous and 5% (v/v) acetonitrile medium respectively have been studied in presence of anionic micelles of sodium lauryl sulphate (SLS) at different H. Oxidation rate of both the substrates increases up to a certain [SLS] much below the critical micellar concentration (cmc) after which the rate is retarded. Kinetic data have been used to compute the binding constants of both substrate and oxidant with the micelle. A scheme explaining the kinetic data has been proposed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-21

    Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.

  1. An experimental and kinetic modelling study of the oxidation of the four isomers of butanol

    CERN Document Server

    Moss, J T; Oehlschlaeger, M A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; 10.1021/jp806464p

    2008-01-01

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition delay times. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock tube measurements. Reaction flux and sensitivity analysis indicate that the consumpti...

  2. Kinetics and mechanism of the oxidative bromination of o-xylene in solution

    Energy Technology Data Exchange (ETDEWEB)

    Dorfman, Ya.A.; Emel' yanova, V.S.; Efremenko, I.G.; Doroshkevich, D.M.; Korolev, A.V.

    1988-07-01

    The kinetics of oxidative bromination of aromatic compounds have been studied in HNO/sub 3/-HBr-H/sub 2/SO/sub 4/-H/sub 2/O-O/sub 2/ solution. A kinetic equation which describes the results was derived for P/sub O/sub 2// > 5 /times/ 10/sup 4/ Pa. The equation parameters were determined at a temperature of 323 K. Quantum mechanical CNDO calculations were carried out in order to study the nature of the reactive intermediates involved: NO/sub 2/ NO(OH)/sup +/, N(OH)/sub 2//sup 2 +/, NO(OH)Br, and N(OH)/sub 2/Br/sup +/. A mechanism has been proposed to account for the oxidative bromination of aromatic compounds in HNO/sub 3/-H/sub 2/SO/sub 4/-HBr-O/sub 2/-H/sub 2/ solution.

  3. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  4. Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature

    Institute of Scientific and Technical Information of China (English)

    QIU Ting-sheng; NIE Guang-hua; WANG Jun-feng; CUI Li-feng

    2007-01-01

    Kinetic process of oxidative leaching of chalcopyrite in chloride acid hydroxide medium under oxygen pressure and low temperature was investigated. The effect on leaching rate of chalcopyrite caused by these factors such as ore granularity, vitriol concentration, sodium chloride concentration, oxygen pressure and temperature was discussed. The results show that the leaching rate of chalcopyrite increases with decreasing the ore granularity. At the early stage of oxidative reaction, the copper leaching rate increases with increasing the oxygen pressure and dosage of vitriol concentration, while oxygen pressure affects leaching less at the later stage. At low temperature, the earlier oxidative leaching process of chalcopyrite is controlled by chemical reactions while the later one by diffusion. The chalcopyrite oxidative leaching rate has close relation with ion concentration in the leaching solution. The higher ion concentration is propitious for chalcopyrite leaching.

  5. Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2004-01-01

    Full Text Available The kinetics of oxidation of some amino acids namely, glycine, alanine, aspartic acid, arginine, and histidine, (AA by N-chlorosaccharin (NCSA in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

  6. Adsorption kinetics of organophosphonic acids on plasma-modified oxide-covered aluminum surfaces.

    Science.gov (United States)

    Giza, M; Thissen, P; Grundmeier, G

    2008-08-19

    Tailoring of oxide chemistry on aluminum by means of low-pressure water and argon plasma surface modification was performed to influence the kinetics of the self-assembly process of octadecylphosphonic acid monolayers. The plasma-induced surface chemistry was studied by in situ FTIR reflection-absorption spectroscopy (IRRAS). Ex situ IRRAS and X-ray photoelectron spectroscopy were applied for the analysis of the adsorbed self-assembled monolayers. The plasma-induced variation of the hydroxide to oxide ratio led to different adsorption kinetics of the phosphonic acid from dilute ethanol solutions as measured by means of a quartz crystal microbalance. Water plasma treatment caused a significant increase in the density of surface hydroxyl groups in comparison to that of the argon-plasma-treated surface. The hydroxyl-rich surface led to significantly accelerated adsorption kinetics of the phosphonic acid with a time of monolayer formation of less than 1 min. On the contrary, decreasing the surface hydroxyl density slowed the adsorption kinetics.

  7. A Study of the Kinetics of the Electrochemical Deposition of Ce3+/Ce4+ Oxides

    Science.gov (United States)

    Valov, I.; Guergova, Desislava; Stoychev, D.

    The kinetics of cathodic electrodeposition of Ce3+ and/or Ce4+ oxides from alcoholic electrolytes on gold substrates has been studied. It was found that, depending on the oxygen content in the CeCl3-based electrolyte, Ce2O3 (in oxygen atmosphere) or CeO2 (in an inert atmosphere), respectively, were obtained. XPS studies clearly separated the two valence states of Ce ions in the oxide layers. The microstructure of the coatings was analyzed by atomic force microscopy (AFM).

  8. 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

    ) and total inorganic sulfide, which have all been reported as main constituents of foul sewer gas. Samples of wastewater and biofilm for the experiments were obtained from two locations that differed significantly with respect to occurrence of VSCs. One location represented an odor hot-spot downstream......: total inorganic sulfide > EtSH > MeSH >> DMS. Except for total inorganic sulfide oxidation in wastewater, kinetic parameters for each VSC were of similar magnitude for the two locations. In the wastewater from the odor hot-spot, sulfide oxidation rates were approximately 12 times faster than...

  9. Kinetics and Mechanism of Oxidation of L-Cystine by Hexacyanoferrate(III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Annapurna Nowduri

    2009-01-01

    Full Text Available Kinetics of oxidation of L-cystine by hexacyanoferrate(III was studied in alkaline medium at 30 °C. The reaction was followed spectrophotometrically at λmax = 420 nm. The reaction was found to be first order dependence each on [HCF(III] and [cystine]. It was found that the rate of the reaction increases with increase in [OH-]. The oxidation product of the reaction was found to be cysteic acid. A plausible mechanism has been proposed to account for the experimental results.

  10. Oxidation hardening kinetics of the rheological function G'/('/G') in asphalts

    KAUST Repository

    Juristyarini, Pramitha

    2011-07-29

    The authors used 9 asphalts oxidized at various temperatures and pressures to determine the hardening kinetics for the DSR function, an easily measured and meaningful surrogate for 15C ductility that relates well to age-related binder deterioration. For each asphalt, there is a rapid initial period that slows to a constant rate period. This constant rate period can be represented by carbonyl formation (oxidation) rate times a hardening susceptibility (HS). For the DSR function and viscosity, the HS and initial jump were pressure-but not temperature-dependent. The DSR function initial jump was relatively higher than the viscosity initial jump. © 2011 Taylor & Francis Group, LLC.

  11. 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.

  12. 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.

  13. Wear and isothermal oxidation kinetics of nitrided TiAl based alloys

    Institute of Scientific and Technical Information of China (English)

    赵斌; 吴建生; 孙坚

    2002-01-01

    Gas nitridation of TiAl based alloys in an ammonia atmosphere was c arried out. The evaluation of the surface wear resistance was performed to compare with those of the non-nitrided alloys. It is concluded that high temperature nitridation raised wear resistance of TiAl based alloys markedly. The tribol ogical behaviors of the nitrided alloys were also discussed. The oxidation kinetics of the nitrided TiAl based alloys were investigated at 800~1000 ℃ in hot air. It is concluded that nitridation is detrimental to the oxidation resistance of TiAl based alloys under the present conditions. The nitrided alloys exhibit increased oxidizing rate with the prolongation of nitridation time at 800 ℃. However, alloys nitrided at 940 ℃ for 50 hdisplay a sign of better oxidat ion resistance than the other nitrided alloys at more severe oxidizing conditions. The parabolic rate law is considered as the basis of the data processing and interpretation of the mass gainvs time data. As a comparison with it, attempts were made to fit the data with the power law. The oxidation kinetic parameter kn, kp and n were measured and the trends were discussed.

  14. Kinetic modeling of the oxidative degradation of additive free PE in bleach disinfected water

    Science.gov (United States)

    Mikdam, Aïcha; Colin, Xavier; Billon, Noëlle; Minard, Gaëlle

    2016-05-01

    The chemical interactions between PE and bleach were studied at 60°C in immersion in bleach solutions kept at a free chlorine concentration of 100 ppm and a pH of 5 or 7.2. It was found that the polymer undergoes a severe oxidation from the earliest weeks of exposure, in a superficial layer whose thickness (of about 50-70 µm) is almost independent of the pH value, although the superficial oxidation rate is faster in acidic than in neutral medium. Oxidation leads to the formation and accumulation of a large variety of carbonyl products (mostly ketones and carboxylic acids) and, after a few weeks, to a decrease in the average molar mass due to the large predominance of chain scissions over crosslinking. A scenario was elaborated for explaining such unexpected results. According to this scenario, the non-ionic molecules (Cl2 and ClOH) formed from the disinfectant in the water phase, would migrate deeply into PE and dissociate into highly reactive radicals (Cl• and HO•) in order to initiate a radical chain oxidation. A kinetic model was derived from this scenario for predicting the general trends of the oxidation kinetics and its dependence on environmental factors such as temperature, free chlorine concentration and pH. The validity of this model was successfully checked by comparing the numerical simulations with experimental data.

  15. Use of a palladium(II)-catalyzed oxidative kinetic resolution in synthetic efforts toward bielschowskysin.

    Science.gov (United States)

    Meyer, Michael E; Phillips, John H; Ferreira, Eric M; Stoltz, Brian M

    2013-09-09

    Progress toward the cyclobutane core of bielshowskysin is reported. The core was thought to arise from a cyclopropane intermediate via a furan-mediated cyclopropane fragmentation, followed by a 1,4-Michael addition. The synthesis of the cyclopropane intermediate utilizes a Suzuki coupling reaction, an esterification with 2-diazoacetoacetic acid, and a copper catalyzed cyclopropanation. An alcohol intermediate within the synthetic route was obtained in high enantiopurity via a highly selective palladium(II)-catalyzed oxidative kinetic resolution (OKR).

  16. Estimation of Oxidation Kinetics and Oxide Scale Void Position of Ferritic-Martensitic Steels in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Li Sun

    2017-01-01

    Full Text Available Exfoliation of oxide scales from high-temperature heating surfaces of power boilers threatened the safety of supercritical power generating units. According to available space model, the oxidation kinetics of two ferritic-martensitic steels are developed to predict in supercritical water at 400°C, 500°C, and 600°C. The iron diffusion coefficients in magnetite and Fe-Cr spinel are extrapolated from studies of Backhaus and Töpfer. According to Fe-Cr-O ternary phase diagram, oxygen partial pressure at the steel/Fe-Cr spinel oxide interface is determined. The oxygen partial pressure at the magnetite/supercritical water interface meets the equivalent oxygen partial pressure when system equilibrium has been attained. The relative error between calculated values and experimental values is analyzed and the reasons of error are suggested. The research results show that the results of simulation at 600°C are approximately close to experimental results. The iron diffusion coefficient is discontinuous in the duplex scale of two ferritic-martensitic steels. The simulation results of thicknesses of the oxide scale on tubes (T91 of final superheater of a 600 MW supercritical boiler are compared with field measurement data and calculation results by Adrian’s method. The calculated void positions of oxide scales are in good agreement with a cross-sectional SEM image of the oxide layers.

  17. 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.

  18. Microcalorimetric Investigation on the Kinetics of the Oxidation of Ascorbic Acid with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    MENG,Xiang-Guang(孟祥光); KOU,Xing-Ming(寇兴明); XIE,Jia-Qing(谢家庆); DU,Juan(杜娟); ZENG,Xian-Cheng(曾宪诚)

    2004-01-01

    Based on the thermokinetic theory, a novel thermokinetic research method-self-function regression method,which could be used to determine the kinetic parameters k1, k2 and k 1 of the complex reaction:B+C(k1 k-1)Ik2→ P, was proposed in this paper. The kinetics of the reaction of ascorbic acid (H2A) with hydrogen peroxide was investigated at pH=5-7 and T=298.15 K, and the kinetic parameters k1, k 2 and k-1 were obtained with this method. The kinetics of the reaction was investigated in detail. The kinetic parameters of the oxidation of ascorbic monoanion (HA) and ascorbic dianion (A2-) with hydrogen peroxide were 3.33 × 10-3 s-1 and 25.48 s-1 at 298.15 K, respectively. The molar enthalpy change for the reaction was -554.64 kJ · mol-1 in phosphate buffer solution at pH 7 and at 298.15 K.

  19. The influence of environmental conditions on kinetics of arsenite oxidation by manganese-oxides

    OpenAIRE

    Fischel, Matthew H. H.; Fischel, Jason S.; Lafferty, Brandon J.; Sparks, Donald L.

    2015-01-01

    Background Manganese-oxides are one of the most important minerals in soil due to their widespread distribution and high reactivity. Despite their invaluable role in cycling many redox sensitive elements, numerous unknowns remain about the reactivity of different manganese-oxide minerals under varying conditions in natural systems. By altering temperature, pH, and concentration of arsenite we were able to determine how manganese-oxide reactivity changes with simulated environmental conditions...

  20. Kinetic assay shows that increasing red cell volume could be a treatment for sickle cell disease

    Science.gov (United States)

    Li, Quan; Henry, Eric R.; Hofrichter, James; Smith, Jeffrey F.; Cellmer, Troy; Dunkelberger, Emily B.; Metaferia, Belhu B.; Jones-Straehle, Stacy; Boutom, Sarah; Christoph, Garrott W.; Wakefield, Terri H.; Link, Mary E.; Staton, Dwayne; Vass, Erica R.; Miller, Jeffery L.; Hsieh, Matthew M.; Tisdale, John F.; Eaton, William A.

    2017-01-01

    Although it has been known for more than 60 years that the cause of sickle cell disease is polymerization of a hemoglobin mutant, hydroxyurea is the only drug approved for treatment by the US Food and Drug Administration. This drug, however, is only partially successful, and the discovery of additional drugs that inhibit fiber formation has been hampered by the lack of a sensitive and quantitative cellular assay. Here, we describe such a method in a 96-well plate format that is based on laser-induced polymerization in sickle trait cells and robust, automated image analysis to detect the precise time at which fibers distort (“sickle”) the cells. With this kinetic method, we show that small increases in cell volume to reduce the hemoglobin concentration can result in therapeutic increases in the delay time prior to fiber formation. We also show that, of the two drugs (AES103 and GBT440) in clinical trials that inhibit polymerization by increasing oxygen affinity, one of them (GBT440) also inhibits sickling in the absence of oxygen by two additional mechanisms. PMID:28096387

  1. INFLUENCE OF SAMPLE THICKNESS ON ISOTHERMAL CRYSTALLIZATION KINETICS OF POLYMERS IN A CONFINED VOLUME

    Institute of Scientific and Technical Information of China (English)

    Hui Sun; Zhi-ying Zhang; Shi-zhen Wu; Bin Yu; Chang-fa Xiao

    2005-01-01

    Isothermal crystallization process of polymers in a confined volume was simulated in the case of instantaneous nucleation by use of the Monte Carlo method. The influence of sample thickness on some kinetic parameters of crystallization was quantitatively evaluated. It was found that there was a critical thickness value. Influence of thickness on the crystallization behavior was only found for samples of thickness near and less than the critical value. For thick samples the Avrami plot showed straight lines with a turning point at the late stage of crystallization due to the secondary crystallization. When the thickness was near or less than the critical value a primary turning point appeared in the Avrami plot at the very beginning of the crystallization process. A model was proposed to explain the mechanism of this phenomenon. According to this model the critical thickness value is related to the nucleation density or the average distance between adjacent nuclei, and the primary turning point is an indication of a transformation of crystal growth geometry from a three-dimensional mode to a two-dimensional one. Analysis of experimental results of PEO isothermally crystallized at 53.5℃ was consistent with the proposed model.

  2. 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

  3. Effect of gas composition on the kinetics of iron oxide reduction in a hydrogen production process

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Krzysztof; Lorethova, Hana; Stonawski, Lubor; Wiltowski, Tomasz [Coal Research Center, Southern Illinois University Carbondale, Carbondale, IL (United States); Mondal, Kanchan; Szymanski, Tomasz [Department of Mechanical Engineering and Energy Processes, Carbondale, IL (United States)

    2005-12-01

    Fe{sub 2}O{sub 3} is a suitable oxygen transfer agent for converting CO present in syngas to CO{sub 2} for its eventual separation from H{sub 2}. However, H{sub 2} also reacts with iron oxide to form H{sub 2}O. In order to evaluate the reactions for hydrogen enrichment, investigations into Fe{sub 2}O{sub 3} to FeO reduction kinetics in the presence of syngas constituents were conducted. The reaction kinetic parameters were estimated based on the thermogravimetric data. Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions, based on Johnson-Mehl-Avrami-Erofe'ev equation describing nucleation and growth processes, was applied. The experimental results indicate that the reduction is initially a surface-controlled process, but once a thin layer of lower iron oxides (magnetite, wusite) is formed on the surface, the mechanism shifts to diffusion control. It was concluded that this initial stage of the reaction process could be interpreted as a both phase-boundary-controlled reaction and the two-dimensional nucleation and growth (transformation of the crystallographic lattices of higher oxide to lattices of lower oxide) at the gas/iron oxide interface. Comparison of the reaction courses for both the reducing agents (H{sub 2}, CO) independently and for their mixture was performed. It was found, that the reaction rate increases with, both, temperature and the hydrogen content in inlet gas. The activation energy values were estimated and compared. (author)

  4. Sensitivity analysis in oxidation ditch modelling: the effect of variations in stoichiometric, kinetic and operating parameters on the performance indices

    NARCIS (Netherlands)

    Abusam, A.A.A.; Keesman, K.J.; Straten, van G.; Spanjers, H.; Meinema, K.

    2001-01-01

    This paper demonstrates the application of the factorial sensitivity analysis methodology in studying the influence of variations in stoichiometric, kinetic and operating parameters on the performance indices of an oxidation ditch simulation model (benchmark). Factorial sensitivity analysis investig

  5. Kinetics and Mechanism of Oxidation of t-Butylbenzylamine by Diperiodatoargentate(III in Aqueous Alkali

    Directory of Open Access Journals (Sweden)

    Mahantesh A. Angadi

    2012-01-01

    Full Text Available t-Butylbenzylamine (t-BA is used as a free base in the synthesis of salbutamol drug. Its mechanism of oxidation was proposed from kinetic studies. The kinetics of oxidation of t-butylbenzylamine by diperiodatoargentate(III (DPA was studied spectrophotometrically by monitoring decrease in absorbance of DPA. The reaction was found to be first order each in [DPA] and [t-BA]. The effect of alkali concentration in a wide range on rate of reaction was studied. The rate of reaction was found to be increased with increase in [OH–] in the lower range of [OH–], decreasing effect in the middle range and at higher range again increasing effect on rate of reaction was observed. The added periodate retarded the rate of reaction. The polymerization test revealed that oxidation was occurred with the intervention free radical. A suitable mechanism was proposed for a middle range of [OH–]. The active species of silver(III periodate for all the three different stages of [OH–] are assayed. Rate law was derived and verified. The oxidative product of t-BA was characterized by LC-ESI-MS spectra.

  6. Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: kinetics and intermediates.

    Science.gov (United States)

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

    2012-11-30

    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.

  7. Kinetics and mechanism of the oxidation of some neutral and acidic -amino acids by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

    The oxidation of eleven amino acids by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid results in the formation of the corresponding carbonyl compounds and ammonia. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with some of the amino acids while others exhibit second-order dependence. It failed to induce polymerization of acrylonitrile. The effect of solvent composition indicate that the rate of reaction increases with increase in the polarity of the medium. Addition of tetrabutylammonium chloride has no effect on the rate of oxidation. Addition of bromide ion causes decrease in the oxidation rate but only to a limiting value. The reaction is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  8. Kinetics of Oxidation of 3-Benzoylpropionic Acid by N-Bromoacetamide in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2011-01-01

    Full Text Available The kinetics of oxidation of 3-benzoylpropionic acid (KA with N-bromoacetamide (NBA have been studied potentiometrically in 50:50 (v/v aqueous acetic acid medium at 298 K The reaction was first order each with respect to [KA], [NBA] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of acetamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. A mechanism consistent with observed results have been proposed and the related rate law was deduced.

  9. Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate

    Indian Academy of Sciences (India)

    Sonu Saraswat; Vinita Sharma; K K Banerji

    2003-02-01

    Oxidation of nine aliphatic primary alcohols by quinolinium bromochromate (QBC) in dimethylsulphoxide leads to the formation of the corresponding aldehydes. The reaction is first order with respect to both QBC and the alcohol. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: obs = + [H+]. The oxidation of [1,1-2H2]ethanol (MeCD2OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analysed using Taft’s and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  10. An experimental and kinetic modeling study of the oxidation of the four isomers of butanol.

    Science.gov (United States)

    Moss, Jeffrey T; Berkowitz, Andrew M; Oehlschlaeger, Matthew A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

    2008-10-30

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock-tube measurements. Reaction flux and sensitivity analysis illustrates the relative importance of the three competing classes of consumption reactions during the oxidation of the four butanol isomers: dehydration, unimolecular decomposition, and H-atom abstraction. Kinetic modeling indicates that the consumption of 1-butanol and iso-butanol, the most reactive isomers, takes place primarily by H-atom abstraction resulting in the formation of radicals, the decomposition of which yields highly reactive branching agents, H atoms and OH radicals. Conversely, the consumption of tert-butanol and 2-butanol, the least reactive isomers, takes place primarily via dehydration, resulting in the formation of alkenes, which lead to resonance stabilized radicals with very low reactivity. To our knowledge, the ignition-delay measurements and oxidation mechanism presented here for 2-butanol, iso-butanol, and tert-butanol are the first of their kind.

  11. Light induced oxidative water splitting in photosynthesis: energetics, kinetics and mechanism.

    Science.gov (United States)

    Renger, Gernot

    2011-01-01

    The essential steps of photosynthetic water splitting take place in Photosystem II (PSII) and comprise three different reaction sequences: (i) light induced formation of the radical pair P680(+)Q(A)(-), (ii) P680(+) driven oxidative water splitting into O(2) and four protons, and (iii) two step plastoquinone reduction to plastoquinol by Q(A)(-). This mini-review briefly summarizes our state of knowledge on energetics, kinetics and mechanism of oxidative water splitting. Essential features of the two types of reactions involved are described: (a) P680(+) reduction by the redox active tyrosine Y(z) and (b) sequence of oxidation steps induced by Y(z)(ox) in the water-oxidizing complex (WOC). The rate of the former reaction is limited by the non-adiabatic electron transfer (NET) step and the multi-phase kinetics shown to originate from a sequence of relaxation processes. In marked contrast, the rate of the stepwise oxidation by Y(z)(ox) of the WOC up to the redox level S(3) is not limited by NET but by trigger reactions which probably comprise proton shifts and/or conformational changes. The overall rate of the final reaction sequence leading to formation and release of O(2) is assumed to be limited by the electron transfer step from the S(3) state of WOC to Y(z)(ox) due to involvement of an endergonic redox equilibrium. Currently discussed controversial ideas on possible pathways are briefly outlined. Several crucial points of the mechanism of oxidative water splitting, like O-O bond formation, role of local proton shift(s), details of hydrogen bonding, are still not clarified and remain a challenging topic of future research.

  12. Implementation of image-guided brachytherapy (IGBT) for patients with uterine cervix cancer: a tumor volume kinetics approach

    Science.gov (United States)

    Mendez, Lucas Castro; Stuart, Silvia Radwanski; Guimarães, Roger Guilherme Rodrigues; Ramos, Clarissa Cerchi Angotti; de Paula, Lucas Assad; de Sales, Camila Pessoa; Chen, André Tsin Chih; Blasbalg, Roberto; Baroni, Ronaldo Hueb

    2016-01-01

    Purpose To evaluate tumor shrinking kinetics in order to implement image-guided brachytherapy (IGBT) for the treatment of patients with cervix cancer. Material and methods This study has prospectively evaluated tumor shrinking kinetics of thirteen patients with uterine cervix cancer treated with combined chemoradiation. Four high dose rate brachytherapy fractions were delivered during the course of pelvic external beam radiation therapy (EBRT). Magnetic resonance imaging (MRI) exams were acquired at diagnosis (D), first (B1), and third (B3) brachytherapy fractions. Target volumes (GTV and HR-CTV) were calculated by both the ellipsoid formula (VE) and MRI contouring (VC), which were defined by a consensus between at least two radiation oncologists and a pelvic expert radiologist. Results Most enrolled patients had squamous cell carcinoma and FIGO stage IIB disease, and initiated brachytherapy after the third week of pelvic external beam radiation. Gross tumor volume volume reduction from diagnostic MRI to B1 represented 61.9% and 75.2% of the initial volume, when measured by VE and VC, respectively. Only a modest volume reduction (15-20%) was observed from B1 to B3. Conclusions The most expressive tumor shrinking occurred in the first three weeks of oncological treatment and was in accordance with gynecological examination. These findings may help in IGBT implementation. PMID:27648083

  13. Nonisothermal denaturation kinetics of human hair and the effects of oxidation.

    Science.gov (United States)

    Wortmann, F-J; Popescu, C; Sendelbach, G

    2006-12-15

    Human hair as alpha-keratin fiber exhibits a complex morphology, which for the context of this investigation is considered as a filament/matrix-composite, comprising the intermediate filaments (IF) and a variety of amorphous protein components as matrix. Differential scanning calorimetry (DSC) under aqueous conditions was used to analyze the denaturation of the alpha-helical material in the IFs and to assess the changes imparted by repeated, oxidative bleaching processes. The DSC curves were submitted to kinetic analysis by applying the Friedman method and assuming first order kinetics. It was found that the course of the denaturation process remains largely unchanged through oxidation, despite the fact that pronounced decreases of denaturation temperature as well as of enthalpy occur. In parallel, the reaction rate constant at the denaturation temperature, k(TD), increases with repeated treatments, that is with cumulative chemical modification. However, this effect is in fact small compared to the overall change of k(T) through the denaturation process. This leads to conclude that once the temperature rise in combination with the chemical change has induced a suitable drop of the viscosity of the matrix around the IFs, denaturation of the remaining helical material occurs along a pathway that is largely independent of temperature and of the pretreatment history. This emphasizes the kinetic control of the matrix over the denaturation process of the helical segments in the filament/matrix composite. Copyright 2006 Wiley Periodicals, Inc.

  14. Kinetic characterization of an oxidative, cooperative HMG-CoA reductase from Burkholderia cenocepacia.

    Science.gov (United States)

    Schwarz, Benjamin H; Driver, Joseph; Peacock, Riley B; Dembinski, Holly E; Corson, Melissa H; Gordon, Samuel S; Watson, Jeffrey M

    2014-02-01

    3-Hydroxy-3-methylglutaryl coenzyme A reductase (HMGR) is a key enzyme in endogenous cholesterol biosynthesis in mammals and isoprenoid biosynthesis via the mevalonate pathway in other eukaryotes, archaea and some eubacteria. In most organisms that express this enzyme, it catalyzes the NAD(P)H-dependent reduction of HMG-CoA to mevalonate. We have cloned and characterized the 6x-His-tagged HMGR from the opportunistic lung pathogen Burkholderia cenocepacia. Kinetic characterization shows that the enzyme prefers NAD(H) over NADP(H) as a cofactor, suggesting an oxidative physiological role for the enzyme. This hypothesis is supported by the fact that the Burkholderia cenocepacia genome lacks the genes for the downstream enzymes of the mevalonate pathway. The enzyme exhibits positive cooperativity toward the substrates of the reductive reaction, but the oxidative reaction exhibits unusual double-saturation kinetics, distinctive among characterized HMG-CoA reductases. The unusual kinetics may arise from the presence of multiple active oligomeric states, each with different Vmax values.

  15. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

    2015-01-01

    Hydrogen oxidation at 50 bar and temperatures of 700–900 K was investigated in a high pressure laminar flow reactor under highly diluted conditions. The experiments provided information about H 2 oxidation at pressures above the third explosion limit. The fuel–air equivalence ratio of the reactants...... was varied from very oxidizing to strongly reducing conditions. The results supplement high-pressure data from RCM (900–1100 K) and shock tubes (900–2200 K). At the reducing conditions ( U = 12), oxidation started at 748–775 K while it was shifted to 798–823 K for stoichiometric and oxidizing conditions ( U...... = 1.03 and 0.05). At very oxidizing conditions (O 2 atmosphere, U = 0.0009), the temperature for onset of reaction was reduced to 775–798 K. The data were interpreted in terms of a detailed chemical kinetic model, drawn mostly from work of Burke and coworkers. In the present study, the rate constants...

  16. Kinetic study of CO oxidation on step decorated Pt(1 1 1) vicinal single crystal electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen Qingsong [Institute of Electrochemistry, University of Alicante, Apartado 99, E-03080 Alicante (Spain); State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Feliu, Juan M., E-mail: juan.feliu@ua.es [Institute of Electrochemistry, University of Alicante, Apartado 99, E-03080 Alicante (Spain); Berna, Antonio; Climent, Victor [Institute of Electrochemistry, University of Alicante, Apartado 99, E-03080 Alicante (Spain); Sun Shigang, E-mail: sgsun@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2011-07-01

    Highlights: > Chronoamperometry has been used to study CO oxidation on Pt stepped surfaces. > Adatoms step decoration allows determination of the role of steps on CO oxidation. > Rate constant decreases after step decoration with adatoms. > Tafel slopes are around 60-90 mV/dec, suggesting a Langmuir-Hinshelwood mechanism. - Abstract: In this work, surface modification at atomic level was applied to study the reactivity of step sites on platinum single crystal surfaces. Stepped platinum single crystal electrodes with (1 1 1) terraces separated by monoatomic step sites with different symmetry were decorated with irreversibly adsorbed adatoms, without blocking the terrace sites, and characterized in 0.1 M HClO{sub 4} solution. The kinetics of CO oxidation on the different platinum single crystal planes as well as on the step decorated surfaces has been studied using chronoamperometry. The apparent rate constants, which were determined by fitting the experimental data to a mean-field model, decrease after the steps of platinum single crystal electrodes have been blocked by the adatoms. This behavior indicates that steps are active sites for CO oxidation. Tafel slopes measured from the potential dependence of the apparent rate constants of CO oxidation were similar in all cases. This result demonstrates that the electrochemical oxidation of the CO adlayer on all the surfaces follows the same Langmuir-Hinshelwood model, irrespectively of step modification.

  17. Corrosion of concrete sewers--the kinetics of hydrogen sulfide oxidation.

    Science.gov (United States)

    Vollertsen, Jes; Nielsen, Asbjørn Haaning; Jensen, Henriette Stokbro; Wium-Andersen, Tove; Hvitved-Jacobsen, Thorkild

    2008-05-01

    Hydrogen sulfide absorption and oxidation by corroding concrete surfaces was quantified in a test rig consisting of 6 concrete pipes operated under sewer conditions. The test rig was placed in an underground sewer monitoring station with access to fresh wastewater. Hydrogen sulfide gas was injected into the pipe every 2nd hour to peak concentrations around 1000 ppm. After some months of operation, the hydrogen sulfide became rapidly oxidized by the corroding concrete surfaces. At hydrogen sulfide concentrations of 1000 ppm, oxidation rates as high as 1 mg S m(-2) s(-1) were observed. The oxidation process followed simple nth order kinetics with a process order of 0.45-0.75. Extrapolating the results to gravity sewer systems showed that hydrogen sulfide oxidation by corroding concrete is a fast process compared to the release of hydrogen sulfide from the bulk water, resulting in low gas concentrations compared with equilibrium. Balancing hydrogen sulfide release with hydrogen sulfide oxidation at steady state conditions demonstrated that significant corrosion rates--several millimeters of concrete per year--can potentially occur at hydrogen sulfide gas phase concentrations well below 5-10 ppm. The results obtained in the study advances the knowledge on prediction of sewer concrete corrosion and the extent of odor problems.

  18. Thermal decomposition of wood in oxidizing atmosphere: A kinetic study from non-isothermal TG experiments

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Rodriguez-Maroto, F.G.; Rodriguez, J.J. (Univ. of Malaga (Spain))

    1991-11-22

    The kinetics of thermal decomposition of four wood species in oxygen-bearing atmospheres of 5, 10 and 20% molar O{sub 2} concentrations have been studied from temperature-programmed experiments carried out at 5, 10 and 20 K min{sup {minus}1} heating rate. Devolatilization as well as combustion of the reamining solid have been considered to analyze the weight loss curves. The homogeneous volume reaction (VR) model has been used to describe devolatilization, whereas for solid combustion the grain model has been also checked. A two-stage approach has been used to fit the conversion-time curves and to derive the corresponding apparent kinetic parameters. The VR/VR (pyrolysis/combustion) combination provided a better description of the experimental {alpha}-t curves than the VR/grain combination. Holm oak and cork oak showed very close reactivities, whereas some differences were observed for aleppo pine and eucalyptus. 6 figs. 8 tabs., 20 refs.

  19. A kinetic study of copper(II) oxide powder reduction with hydrogen, based on thermogravimetry

    Energy Technology Data Exchange (ETDEWEB)

    Jelic, Dijana [Faculty of Medicine, Departmet of Pharmacy - Chair of Physical Chemistry, University of Banja Luka, Banja Luka, Bosnia and Herzegovina (Bosnia and Herzegowina); Tomic-Tucakovic, Biljana [Institute of General and Physical Chemistry, Studentski trg 12, 11158 Belgrade (Serbia); Mentus, Slavko, E-mail: slavko@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12, 11185 Belgrade (Serbia)

    2011-07-10

    Highlights: {yields} The reduction of CuO by hydrogen was studied by thermogravimetry. {yields} The particle size of the samples varied inside the submicron range. {yields} The experimental data were fitted by means of a nucleation-growth model. {yields} The particle size influenced the kinetic parameters but not the reaction model. - Abstract: The reduction of powdery copper(II) oxide was carried out in a stream of gaseous mixture 25% H{sub 2} + Ar, and followed by thermogravimetry. The two samples of different history were studied: the commercial one, and that synthesized by citrate gel combustion method. The characterization of the starting materials, based on X-ray diffractometry and scanning electron microscopy, indicated equal crystal structure, but different particle size and morphology. The particle size and shape of the metallic particles obtained upon the reduction were observed by means of electron microscope. By a nonlinear regression analysis by means of a software Kinetics05, the experimental data were fitted with the nucleation-growth kinetic model, and the corresponding kinetic parameters were determined.

  20. Supercritical water oxidation data acquisition testing. Final report, Volume I

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-11-01

    This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included.

  1. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II ? reactions of organic species

    OpenAIRE

    2005-01-01

    International audience; This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices con...

  2. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Gelß, Patrick, E-mail: p.gelss@fu-berlin.de; Matera, Sebastian, E-mail: matera@math.fu-berlin.de; Schütte, Christof, E-mail: schuette@mi.fu-berlin.de

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO{sub 2}(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  3. Oxidation of glycylglycine by ferricyanide in acid medium: Kinetics and mechanism

    Directory of Open Access Journals (Sweden)

    Krishna K. Yerneni

    2015-12-01

    Full Text Available The oxidative degradation of glycylglycine (GlyGly to formic acid, ammonium ion, and carbon dioxide occurs when it reacts with ferricyanide in acid medium, which has been studied spectrophotometrically at 303 nm at constant temperature. Kinetic runs have been performed under a pseudo-first-order condition of [GlyGly]0 >> [ferricyanide]0. The experimental rate law obtained for the redox reaction is: rate = kı [$ \\text{Fe(CN}^{3 - }_{6} $] [GlyGly]x [H+]y[Pd(II]0, where x and y are fractional orders. Effects of ionic strength and dielectric constant are also investigated. Activation parameters have been evaluated using Arrhenius and Eyring plots. A probable mechanism has been proposed and the derived rate law is consistent with the kinetic data.

  4. Size Resolved High Temperature Oxidation Kinetics of Nano-Sized Titanium and Zirconium Particles.

    Science.gov (United States)

    Zong, Yichen; Jacob, Rohit J; Li, Shuiqing; Zachariah, Michael R

    2015-06-18

    While ultrafine metal particles offer the possibility of very high energy density fuels, there is considerable uncertainty in the mechanism by which metal nanoparticles burn, and few studies that have examined the size dependence to their kinetics at the nanoscale. In this work we quantify the size dependence to the burning rate of titanium and zirconium nanoparticles. Nanoparticles in the range of 20-150 nm were produced via pulsed laser ablation, and then in-flight size-selected using differential electrical mobility. The size-selected oxide free metal particles were directly injected into the post flame region of a laminar flame to create a high temperature (1700-2500 K) oxidizing environment. The reaction was monitored using high-speed videography by tracking the emission from individual nanoparticles. We find that sintering occurs prior to significant reaction, and that once sintering is accounted for, the rate of combustion follows a near nearly (diameter)(1) power-law dependence. Additionally, Arrhenius parameters for the combustion of these nanoparticles were evaluated by measuring the burn times at different ambient temperatures. The optical emission from combustion was also used to model the oxidation process, which we find can be reasonably described with a kinetically controlled shrinking core model.

  5. Adsorption Kinetic Properties of As(III) on Synthetic Nano Fe-Mn Binary Oxides

    Institute of Scientific and Technical Information of China (English)

    Mei Yu; Yanxin Wang; Shuqiong Kong; Evalde Mulindankaka; Yuan Fang; Ya Wu

    2016-01-01

    The adsorptive removal of arsenic by synthetically-prepared nano Fe-Mn binary oxides (FM) was investigated. A novel method using potassium permanganate and ferric chloride as raw materials was used to synthesise FM. The molar ratio of Fe and Mn in the synthetic Fe-Mn binary oxides was 4 : 3. The FM-1 and FM-2 (prepared at different activation temperatures) having high specific surface areas (358.87 and 128.58 m2/g, respectively) were amorphous and of nano particle types. The amount of arsenic adsorbed on FM-1 was higher than that adsorbed on FM-2 particles. After adsorption by FM-1, residual arsenic concentration decreased to less than 10μg/L. The adsorption kinetics data were analyzed using different kinetic models including pseudofirst-order model, pseudo second-order model, Elovich model and in-traparticle diffusion model. Pseudo second-order kinetic model was the most appropriate model to describe the adsorption kinetics. The adsorption percentage of As(III) increased in the pH range of 2–3 while it de-creased with the increase of pH ( 3

  6. Microstructural evolution and growth kinetics of thermally grown oxides in plasma sprayed thermal barrier coatings

    Directory of Open Access Journals (Sweden)

    Xiaoju Liu

    2016-02-01

    Full Text Available The formation of thermally grown oxide (TGO during high temperature is a key factor to the degradation of thermal barrier coatings (TBCs applied on hot section components. In the present study both the CoNiCrAlY bond coat and ZrO2-8 wt.% Y2O3 (8YSZ ceramic coat of TBCs were prepared by air plasma spraying (APS. The composition and microstructure of TGO in TBCs were investigated using scanning electron microscopy (SEM, energy dispersive spectroscopy (EDS and X-ray diffraction (XRD analysis. The growth rate of TGO for TBC and pure BC were gained after isothermal oxidation at 1100 °C for various times. The results showed that as-sprayed bond coat consisted of β and γ/γ′phases, β phase reducesd as the oxidation time increased. The TGO comprised α-Al2O3 formed in the first 2 h. CoO, NiO, Cr2O3 and spinel oxides appeared after 20 h of oxidation. Contents of CoO and NiO reduced while that of Cr2O3 and spinel oxides increased in the later oxidation stage. The TGO eventually consisted of a sub-Al2O3 layer with columnar microstructure and the upper porous CS clusters. The TGO growth kinetics for two kinds of samples followed parabolic laws, with oxidation rate constant of 0.344 μm/h0.5 for TBCs and 0.354 μm/h0.5 for pure BCs.

  7. Microstructural evolution and growth kinetics of thermally grown oxides in plasma sprayed thermal barrier coatings

    Institute of Scientific and Technical Information of China (English)

    Xiaoju Liu; Teng Wang; Caicai Li; Zhenhuan Zheng; Qiang Li

    2016-01-01

    The formation of thermally grown oxide (TGO) during high temperature is a key factor to the degradation of thermal barrier coatings (TBCs) applied on hot section components. In the present study both the CoNiCrAlY bond coat and ZrO2-8 wt.% Y2O3 (8YSZ) ceramic coat of TBCs were prepared by air plasma spraying (APS). The composition and microstructure of TGO in TBCs were investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis. The growth rate of TGO for TBC and pure BC were gained after isothermal oxidation at 1100 °C for various times. The results showed that as-sprayed bond coat consisted of β and γ/γ'phases,β phase reducesd as the oxidation time increased. The TGO comprised α-Al2O3 formed in the first 2 h. CoO, NiO, Cr2O3 and spinel oxides appeared after 20 h of oxidation. Contents of CoO and NiO reduced while that of Cr2O3 and spinel oxides increased in the later oxidation stage. The TGO eventually consisted of a sub-Al2O3 layer with columnar microstructure and the upper porous CS clusters. The TGO growth kinetics for two kinds of samples followed parabolic laws, with oxidation rate constant of 0.344 μm/h0.5 for TBCs and 0.354 μm/h0.5 for pure BCs.

  8. Kinetic and mechanistic evaluation of tetrahydroborate ion electro-oxidation at polycrystalline gold

    Energy Technology Data Exchange (ETDEWEB)

    Iotov, Philip I., E-mail: iotov@uctm.ed [University of Chemical Technology and Metallurgy, Sofia 1756 (Bulgaria); Kalcheva, Sasha V. [University of Chemical Technology and Metallurgy, Sofia 1756 (Bulgaria); Bond, Alan M. [School of Chemistry, Monash University, Clayton, Victoria 3800 (Australia)

    2009-12-01

    The anodic oxidation of tetrahydroborate ion is studied in NaOH at stationary and rotating polycrystalline Au disk electrodes. Linear sweep and cyclic voltammetry are applied varying the scan and rotation rate from 0.005 to 51.200 V s{sup -1} and from 52.3 to 314.1 rad s{sup -1}, correspondingly. The effects of variation of BH{sub 4}{sup -} and NaOH concentrations as well as of the potential limits of the ranges studied have been initially followed. Most of the experiments have been carried out with 10.9 mM NaBH{sub 4} in 1.04 M NaOH at 293 K in the potential range from -1.300 to 0.900 V (vs. Ag/AgCl). It is found that 6 electrons are exchanged in the overall oxidation transformation. The kinetic analysis of the processes determining the two anodic peaks recorded under static conditions at scan rates lower than 0.500 V s{sup -1} shows that 1.4 electrons are exchanged in the potential range of the first one (at ca -0.5 V), while the rate of the second one (at ca +0.3 V) is determined by a quasi-reversible 1-electron transfer reaction. A kinetic evidence for the participation of surface bound intermediates in the electro-oxidation process is provided. Two additional well outlined anodic peaks are recorded in the aforementioned potential range under specific experimental conditions. A quasi-8 electron mechanism involving four oxidation and hydrolysis steps is advanced to explain the experimental results. It accounts for the involvement of borohydride oxidation species and the Au{sup +}/Au{sup 3+} mediator couple.

  9. Monnte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst(Mo-Bi)

    Institute of Scientific and Technical Information of China (English)

    罗正鸿; 詹晓力; 等

    2003-01-01

    Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition over the commercial propylene ammoxidation catalyst(Mo-Bi).The simulation is quite in agreement with experimetal results.Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

  10. 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).

  11. PHOTOCATALYTIC OXIDATION FOR NOx ABATEMENT: DEVELOPMENT OF A KINETIC EXPRESSION AND DESIGN TOOLS

    Energy Technology Data Exchange (ETDEWEB)

    Rajiv Srivastava; M. A. Ebadian

    2000-09-15

    The ''Nitrogen Oxides Emission Reduction Program'' and ''Ozone Non-Attainment Program'' in the 1990 Clean Air Act provide guidelines for controlling NOx (NO and NO{sub 2}) emissions in new and existing stationary sources. NOx emissions have local (air quality), regional (acid rain), and global (ozone production) consequences. This study aids in developing the photocatalyst technology that has potential for use in abatement of NOx. The objective of the proposed project is to apply the principles of chemical engineering fundamentals--reaction kinetics, transport phenomena and thermodynamics--in the process design for a system that will utilize a photocatalytic reactor to oxidize NOx to nitric acid (HNO{sub 3}). HNO{sub 3} can be more easily trapped than NOx on adsorbent surfaces or in water. The project dealt with the engineering aspect of the gas-solid heterogeneous oxidation of NOx. The experiments were conducted in a photocatalyst wash-coated glass flow tube reactor. A mathematical model was developed based on a rigorous description of the physical and chemical processes occurring in the reactor. The mathematical model took into account (1) intrinsic reaction kinetics (i.e., true reaction rates), (2) transport phenomena that deal with the mass transfer effects in the reactor, and (3) the geometry of the reactor. The experimental results were used for validation of the mathematical model that provides the basis for a versatile and reliable method for the purpose of design, scale-up and process control. The NOx abatement was successfully carried out in a flow tube reactor surrounded by black lights under the exploratory grant. Due to lack of funds, a comprehensive kinetic analysis for the photocatalytic reaction scheme could not be carried out. The initial experiments look very promising for use of photocatalysis for NOx abatement.

  12. Study on kinetics of hydrogen dissolution and hydrogen solubility in oxides using imaging plate technique

    Energy Technology Data Exchange (ETDEWEB)

    Hashizume, K., E-mail: hashi@nucl.kyushu-u.ac.jp [Interdisciplinary Graduate School of Engineering Science, Kyushu Univ., Fukuoka (Japan); Ogata, K.; Nishikawa, M.; Tanabe, T. [Interdisciplinary Graduate School of Engineering Science, Kyushu Univ., Fukuoka (Japan); Abe, S.; Akamaru, S.; Hatano, Y. [Hydrogen Isotope Research Center, Univ. of Toyama, Toyama (Japan)

    2013-11-15

    Using a tritium imaging plate technique, kinetics of tritium dissolution and its solubility in several oxides were examined. Mirror-polished single crystals of alumina, spinel and zirconia were used as specimens, which were exposed to 133 Pa of a tritium(T)–deuterium(D) gas mixture (T/(T + D) ∼ 0.17) at temperatures ranging from 673 to 973 K for 1–5 h. The T surface activity on the specimens increased with increasing temperature and exposure time, it almost saturated at 873 K and reached 2 × 10{sup 5} Bq/cm{sup 2} (1 × 10{sup 14} T/cm{sup 2}), and no clear difference appeared among the types of specimens. The T activity in the oxide bulk also increased with temperature, in which there was a trend for the oxides: spinel ≧ zirconia ≧ alumina. In the T dissolution process for all oxides, the concentration gradient due to its diffusion was not observed even for short exposure times: the T density was almost uniform over the specimens in transition states and increased with exposure time up to the saturated value. These experimental results suggested that the rate-controlling process of T dissolution in the temperature region should be not its diffusion in the oxides but dissociation of hydrogen molecules (T–D mixture in this case) into atoms, its adsorption on the surface and/or T penetration from the surface into the bulk.

  13. Kinetic analysis of soil contained pyrene oxidation by a pulsed discharge plasma process

    Science.gov (United States)

    Huijuan, Wang; Guangshun, Zhou; He, Guo; Cong, Geng

    2017-01-01

    A pulsed discharge plasma (PDP) reactor with net anode and net cathode was established for investigating the pyrene degradation in soil under different pulse peak voltage, air flow rate, pyrene content in soil, initial pH value and initial water content of the soil. Pyrene oxidation within the 60 min discharge time was fitting according to the pseudo-first order equation and the corresponding reaction kinetics constants (k values) were calculated. The obtained results show that pyrene oxidation under all the different reaction conditions obeyed the pseudo-first order equation well. Higher pulsed peak voltage and appropriate air flow rate were in favor of the increase of reaction rate of pyrene oxidation. A higher k value could be achieved in the lower initial pyrene content (the value was 100 mg kg-1). The k value of pyrene oxidation in the case of pH = 4 was 11.2 times higher than the value obtained under the condition of pH = 9, while the initial water content of the soil also has a large effect on the oxidation rate of pyrene due to the effect of PDP. Supported by National Natural Science Foundation of China (No. 21207052).

  14. Fenton-Like Oxidation of Malachite Green Solutions: Kinetic and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Saeedeh Hashemian

    2013-01-01

    Full Text Available Oxidation by Fenton-like (Fe3+/H2O2 reactions is proven to be an economically feasible process for destruction of a variety of hazardous pollutants in wastewater. In this study, the degradation and mineralization of malachite green dye are reported using Fenton-like reaction. The effects of different parameters like pH of the solution, the initial concentrations of Fe3+, H2O2, and dye, temperature, and added electrolytes (Cl− and on the oxidation of the dye were investigated. Optimized condition was determined. The efficiency of 95.5% degradation of MAG after 15 minutes of reaction at pH 3 was obtained. TOC removal indicates partial and insignificant mineralization of malachite green dye. The results of experiments showed that degradation of malachite green dye in Fenton-like oxidation process can be described with a pseudo-second-order kinetic model. The thermodynamic constants of the Fenton oxidation process were evaluated. The results implied that the oxidation process was feasible, spontaneous, and endothermic. The results will be useful for designing the treatment systems of various dye-containing wastewaters.

  15. 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

    -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......) and total inorganic sulfide, which have all been reported as the main constituents of foul sewer gas. Samples of wastewater and biofilm for the experiments were obtained from two locations that differed significantly with respect to the occurrence of VSCs. One location represented an odor hot...

  16. [Solution kinetics of magnesium oxide containing granules produced by laboratory scale fluidization].

    Science.gov (United States)

    Rácz, I; Zelkó, R; Bihari, E

    1994-09-01

    In practice of manufacturing industrial pharmaceutical products, the technique of fluidization has been used extensively in the past decades. The authors studied the magnesium oxide-containing granulates made by fluidization granulation in laboratory, to optimize the process, to determine the neutralization kinetic parameters of granulates, to establish the connections between the method of granulation and the release of active substances. According to our findings, the pharmaceutical product's characteristics in the aspects of physics, chemistry, stability and bioavailability may remarkably change without fixing the border conditions of parameters within limits.

  17. Kinetics of Oxidation of Glutathione by Micelle Trapped Tris(benzhydroxamatoiron(III

    Directory of Open Access Journals (Sweden)

    B. L. Hiran

    2007-01-01

    Full Text Available Kinetics of the oxidation of glutathione (GSH by micelle Sodium dodecyl sulphate (SDS trapped tris(benzhydroxamatoiron(III (TBH at pH 3.3 and at 298 K has been described. The reaction is first order in TBS and GSH. Increase in pH decreased the rate. Order in H+ is one The reaction between TBH and GSH on micellar surface (Stern layer differs from that occurring in bulk aqueous phase in absence of micelle (SDS. Reactive FeL3 species on micellar surface is FeL2+.

  18. Kinetics and Mechanism of Oxidation of Some Diols by Dihydroxydiperiodatoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHAN, Jin-Huan; LI, Sheng-Min; HUO, Shu-Ying; SHEN, Shi-Gang; SUN, Han-Wen

    2006-01-01

    The kinetics of oxidation of ethylene glycol and 1,3-butylene glycol by dihydroxydiperiodatoargentate(Ⅲ) in alkaline medium have been studied by spectrophotometry in the range of 298.2-318.2 K. It is shown that the reaction was first order with respect to each reductant and Ag(Ⅲ), and kobs increased with an increase of [OH-]. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between complex and reductants was proposed, which could be applied to explain all experimental phenomena, and the activation parameters of the ratedetermining step have been also calculated.

  19. Kinetics and Mechanism of Oxidation of Glutamic Acid by N-Bromophthalimide in Aqueous Acidic Medium

    OpenAIRE

    2011-01-01

    The kinetics of oxidation of glutamic acid (Glu) with N-bromophthalimide (NBP) was studied in perchloric acid medium at 30 °C by potentiometric method. The reaction is first order each in NBP and glutamic acid and is negative fractional order in [H+]. Addition of KBr or the reaction product, phthalimide had no effect on the rate. Similarly variation of ionic strength of the medium did not affect the rate of the reaction. Also the rate increased with decrease in dielectric constant of the reac...

  20. Phase Stability, Kinetic Diagrams and Diffusion Path in High Temperature Oxidation of Binary Solid-Solution Alloys

    Institute of Scientific and Technical Information of China (English)

    Yan NIU; F. Gesmundo

    2003-01-01

    The phase diagrams of ternary systems involving two metal components and one oxidant are considered first, the limitations to their use is discussed in relation to the high temperature oxidation of binary alloys. Kinetic diagrams,which are useful to predict the conditions for the stability of the two mutually insoluble oxides as the external scale, are then calculated on the basis of thermodynamic and kinetic data concerning both the alloys and the oxides, assuming the validity of the parabolic rate law. A combination of the two types of diagrams provides a more detail information about the oxidation behavior of binary alloys. The calculation of the diffusion paths, which relate the oxidant pressure to the composition of the system in terms of the alloy components both in the alloy and in the scale during an initial stage of the reaction in the presence of the parabolic rate law, is finally developed.

  1. Photodegradation of basic dyes using nanocomposite (Ag-zinc oxide-copper oxide and kinetic studies

    Directory of Open Access Journals (Sweden)

    Nasrin Khorshidi

    2016-05-01

    Full Text Available In this paper, Ag/ZnO/CuO nanocomposite (AZCN synthesized and its dye degradation ability in the presence of UV irradiation from colored wastewater was studied. The characteristics of AZCN were investigated using Fourier transform infrared (FTIR, scanning electron microscope (SEM and X-ray diffraction (XRD. The photocatalytic activity was evaluated by photodegradation of Basic Red 18 (BR18 and Basic Violet 16 (BV16 as a model contaminant. The effects of AZCN dosage, initial dye concentration and salt on dye degradation were investigated. Kinetics analysis indicated that the dye degradation rates could be approximated at pseudo-first order model. The results indicated that AZCN as a photocatalyst could be used to degrade dyes from wastewater.

  2. Kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

    Science.gov (United States)

    Toyoda, Kazuhiro; Tebo, Bradley M.

    2016-09-01

    The kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1 was measured under controlled conditions of the initial Mn(II) concentration, spore concentration, chemical speciation, pH, O2, and temperature. Mn(II) oxidation experiments were performed with spore concentrations ranging from 0.7 to 11 × 109 spores/L, a pH range from 5.8 to 8.1, temperatures between 4 and 58 °C, a range of dissolved oxygen from 2 to 270 μM, and initial Mn(II) concentrations from 1 to 200 μM. The Mn(II) oxidation rates were directly proportional to the spore concentrations over these ranges of concentration. The Mn(II) oxidation rate increased with increasing initial Mn(II) concentration to a critical concentration, as described by the Michaelis-Menten model (Km = ca. 3 μM). Whereas with starting Mn(II) concentrations above the critical concentration, the rate was almost constant in low ionic solution (I = 0.05, 0.08). At high ionic solution (I = 0.53, 0.68), the rate was inversely correlated with Mn(II) concentration. Increase in the Mn(II) oxidation rate with the dissolved oxygen concentration followed the Michaelis-Menten model (Km = 12-19 μM DO) in both a HEPES-buffered commercial drinking (soft) water and in artificial and natural seawater. Overall, our results suggest that the mass transport limitations of Mn(II) ions due to secondary Mn oxide products accumulating on the spores cause a significant decrease of the oxidation rate at higher initial Mn(II) concentration on a spore basis, as well as in more concentrated ionic solutions. The optimum pH for Mn(II) oxidation was approximately 7.0 in low ionic solutions (I = 0.08). The high rates at the alkaline side (pH > 7.5) may suggest a contribution by heterogeneous reactions on manganese bio-oxides. The effect of temperature on the Mn(II) oxidation rate was studied in three solutions (500 mM NaCl, ASW, NSW solutions). Thermal denaturation occurred at 58 °C and spore germination was evident at 40 °C in all three

  3. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    Directory of Open Access Journals (Sweden)

    B. van der Grift

    2014-06-01

    Full Text Available The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II by O2. Seasonal changes in climatic conditions affected the Fe(II oxidation process. Lower pH and lower temperatures in winter (compared to summer resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II oxidation proces which results in P-depleted water before Fe(II is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III-phosphate precipitates. The formation of Fe(III-phosphates at redox gradients

  4. Phenol oxidation by mushroom waste extracts: a kinetic and thermodynamic study.

    Science.gov (United States)

    Pigatto, Gisele; Lodi, Alessandra; Aliakbarian, Bahar; Converti, Attilio; da Silva, Regildo Marcio Gonçalves; Palma, Mauri Sérgio Alves

    2013-09-01

    Tyrosinase activity of mushroom extracts was checked for their ability to degrade phenol. Phenol oxidation kinetics was investigated varying temperature from 10 to 60 °C and the initial values of pH, enzyme activity and phenol concentration in the ranges 4.5-8.5, 1.43-9.54 U/mL and 50-600 mg/L, respectively. Thermodynamic parameters of phenol oxidation and tyrosinase reversible inactivation were estimated. Tyrosinase thermostability was also investigated through residual activity tests after extracts exposition at 20-50 °C, whose results allowed exploring the thermodynamics of enzyme irreversible thermoinactivation. This study is the first attempt to separate the effects of reversible unfolding and irreversible denaturation of tyrosinase on its activity. Extracts were finally tested on a real oil mill wastewater.

  5. Switching Kinetics in Nanoscale Hafnium Oxide Based Ferroelectric Field-Effect Transistors.

    Science.gov (United States)

    Mulaosmanovic, Halid; Ocker, Johannes; Müller, Stefan; Schroeder, Uwe; Müller, Johannes; Polakowski, Patrick; Flachowsky, Stefan; van Bentum, Ralf; Mikolajick, Thomas; Slesazeck, Stefan

    2017-02-01

    The recent discovery of ferroelectricity in thin hafnium oxide films has led to a resurgence of interest in ferroelectric memory devices. Although both experimental and theoretical studies on this new ferroelectric system have been undertaken, much remains to be unveiled regarding its domain landscape and switching kinetics. Here we demonstrate that the switching of single domains can be directly observed in ultrascaled ferroelectric field effect transistors. Using models of ferroelectric domain nucleation we explain the time, field and temperature dependence of polarization reversal. A simple stochastic model is proposed as well, relating nucleation processes to the observed statistical switching behavior. Our results suggest novel opportunities for hafnium oxide based ferroelectrics in nonvolatile memory devices.

  6. Kinetics simulation of luminol chemiluminescence based on quantitative analysis of photons generated in electrochemical oxidation.

    Science.gov (United States)

    Koizumi, Yozo; Nosaka, Yoshio

    2013-08-22

    The kinetics of electrogenerated chemiluminescence (ECL) of luminol at a gold electrode in alkaline solution was investigated by measuring the absolute number of photons emitted in an integrating sphere. The ECL efficiency as the ratio of photon to electric charge was 0.0004 in cyclic voltammography and 0.0005 in chronoamperometry. By numerically solving the rate equations based on a diffusion layer model, the observed time profile of the luminescence intensity could be successfully simulated from the oxidation current of luminol in the chronoamperometry. In the simulation, the rate constant for the oxidation of luminol by superoxide radicals in alkaline solution was determined to be 6 × 10(5) M(-1) s(-1). The present methodology and the achievement could be widely applicable to various analytical techniques using chemiluminescence.

  7. 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...... and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the CH 3 OH + HO 2⇌ CH 2 OH +H2O2reaction....

  8. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Oxidation of sulfite is an important process in wet flue gas desulfurization.Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus,the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions.The reaction order of the reagents and the activation energy were obtained.The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy,but have an influence on the reaction rate constant.The mechanism of the intrinsic reaction is proposed.The results derived with this mechanism are in good agreement with the experimental re-sults.

  9. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions

    Institute of Scientific and Technical Information of China (English)

    WANG LiDong; ZHAO Yi; LI QiangWei; CHEN ZhouYan; LIU SongTao; MA YongLiang; HAO JiMing

    2009-01-01

    Oxidation of sulfite is an important process in wet flue gas desulfurization. Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus, the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions. The reaction order of the reagents and the activation energy were obtained. The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy, but have an influence on the reaction rate constant. The mechanism of the intrinsic reaction is proposed. The results derived with this mechanism are in good agreement with the experimental re-sults.

  10. Kinetic and thermodynamic properties of the aerial oxidation of hydroquinone in developer solutions

    Institute of Scientific and Technical Information of China (English)

    NASEHZADEH, Asadollah; RESA, Sayyed Hossain; KHOSRAVAN, Azita

    2000-01-01

    The aerial oxidation kinetics of hydroquinone in a freshly prepared developer solution at different temperatures and pHs has been studied. The activation parameters, Ea, △G#,△S# , △H# and enthalpy of formation of activated complex,△Hof(X# ), are determined. The large negative value of free energy of activation △G# proves that hydroquinone extremely tends to be oxidized by air at optimum temperature (20℃)and optimum pH (10.5) and converts to the activated complex semiquinone. It was also found that if the pH of the developer solution is increased from 9.3 to 10.5 the reaction rate will increase by a factor of 2.

  11. Extracting copper from copper oxide ore by a zwitterionic reagent and dissolution kinetics

    Institute of Scientific and Technical Information of China (English)

    Jiu-shuai Deng; Shu-ming Wen; Jian-ying Deng; Dan-dan Wu

    2015-01-01

    Sulfamic acid (SA), which possesses a zwitterionic structure, was applied as a leaching reagent for the first time for extracting copper from copper oxide ore. The effects of reaction time, temperature, particle size, reagent concentration, and stirring speed on this leach-ing were studied. The dissolution kinetics of malachite was illustrated with a three-dimensional diffusion model. A novel leaching effect of SA on malachite was eventually demonstrated. The leaching rate increased with decreasing particle size and increasing concentration, reac-tion temperature and stirring speed. The activation energy for SA leaching malachite was 33.23 kJ/mol. Furthermore, the effectiveness of SA as a new reagent for extracting copper from copper oxide ore was confirmed by experiment. This approach may provide a solution suitable for subsequent electrowinning. In addition, results reported herein may provide basic data that enable the leaching of other carbonate miner-als of copper, zinc, cobalt and so on in an SA system.

  12. Kinetics of the Oxidative Dehydrogenation of Propane over a VMgO Catalyst

    Institute of Scientific and Technical Information of China (English)

    L. L(a)te; E.A. Blekkan

    2002-01-01

    The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts forthe dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, theonly by-products were CO and CO2. The reaction rate of propane was found to be first order in propaneand close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with theactivation of the hydrocarbon as the rate determining step. The activation energy of the conversion ofpropane was found to be 122±6 kJ/mol.

  13. Kinetics of Oxidative Dehydrogenation of Propance over a VMgO Catalyst

    Institute of Scientific and Technical Information of China (English)

    L.Late; E.A.Blekkan

    2002-01-01

    The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃ over a VMgO catalyst,Vanadium-magnesium-oxides are among the moste selective and active catalysts for the dehydrogenation of propance to propylene Selectivity to propylene up to about 60% was obtained at 10% conversion ,but the selectivity decreased with increasing conversion.No oxygenates were detected,the only by-products were CO and CO2 ,The reaction rate of propane was found to be first order in propane and close to zero order in oxygen ,which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate detemining step.The activation energy,of the conversion of propane was found to be 122±6 kJ/mol.

  14. Kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium

    Institute of Scientific and Technical Information of China (English)

    WANG Yun-shan; LI Zuo-hu; LI Hao-ran

    2005-01-01

    The kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium was investigated in terms of the gas-flow rate, stirring rate, reaction time, reaction temperature and partial pressure of oxygen on the ratio of manganese conversion in ocean polymetallic nodules. The category of the rate controlling step was determined. The process of the liquid-phase oxidation reaction can be described by surface chemical reaction-controlled non-reaction shrinking core model(SCM), the apparent activation energy was achieved and the rate equation was put forward. From the equation, it can be concluded that the reaction rate mainly depends on the reaction temperature and the partial pressure of oxygen.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bartling, Stephan, E-mail: stephan.bartling@uni-rostock.de; Meiwes-Broer, Karl-Heinz; Barke, Ingo [Department of Physics, University of Rostock, Universitätsplatz 3, D-18051 Rostock (Germany); Pohl, Marga-Martina [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), Albert-Einstein-Str. 29a, D-18059 Rostock (Germany)

    2015-09-21

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

  16. Growth Kinetics of Anodic Oxide Films Formed on Zircaloy-2 in Various Electrolytes

    Directory of Open Access Journals (Sweden)

    V. Jeevana Jyothi

    2009-01-01

    Full Text Available The Kinetics of anodic oxidation of zircaloy-2 have been studied at current densities ranging from 4 to 12 mA cm-2 at room temperature in order to investigate the dependence of ionic current density on the field across the oxide film. Thickness of the anodic films was estimated from capacitance data. The formation rate, current efficiency and differential field were found to increase with increase in the ionic current density for zircaloy-2. Plots of logarithm of formation rate vs. logarithm of current density is fairly linear. From linear plots of logarithm of ionic current density vs. differential field and applying the Cabrera - Mott theory, the half - jump distance (a and height of energy barrier (W were deduced.

  17. Oxidation kinetics of the combustible fraction of construction and demolition wastes.

    Science.gov (United States)

    Chang, N B; Lin, K S; Sun, Y P; Wang, H P

    2001-01-01

    Proper disposal of construction and demolition wastes (CDW) has received wide attention recently due to significantly large quantities of waste streams collected from razed or retrofitted buildings in many metropolitan regions. Burning the combustible fractions of CDW (CCDW) and possibly recovering part of the heat content for economic uses could be valuable for energy conservation. This paper explores the oxidation kinetics of CCDW associated with its ash characterization. Kinetic parameters for the oxidation of CCDW were numerically calculated using thermal gravimetric analysis (TGA) and the resultant rate equations were therefore developed for illustrating the oxidation processes of CCDW simultaneously. Based on three designated heating rates, each of the oxidation processes can be featured distinctively with five different stages according to the rate of weight change at the temperature between 300 K and 923 K. In addition, Fourier transform infrared (FTIR) spectroscopy was employed, associated with a lab-scale fixed-bed incinerator for monitoring the composition of flue gas. Carbon dioxide (CO2) was found as a major component in the flue gas. The fuel analysis also included an ash composition analysis via the use of X-ray powder diffraction (XRD), atomic absorption (AA) spectroscopy, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDX). The ash streams were identified as nonhazardous materials based on the toxicity characteristic leaching procedure (TCLP). Overall, the scientific findings gained in this study will be helpful for supporting a sound engineering design of real-world CCDW incineration systems.

  18. Kinetics of oxidation of dimethyl trisulfide by potassium permanganate in drinking water

    Institute of Scientific and Technical Information of China (English)

    XiaoyanMA; Shifei HU; Hongyu WANG; Jun LI; Jing HUANG; Yun ZHANG; Weigang LU; Qingsong LI

    2012-01-01

    Metabolites of algae such as geosmin, 2- methylisoborneol etc. are reported to induce pungent odors into drinking water and attract additional scientifc attention. Recently, in China, taste and odor outbreaks in drinking water supply have become increasingly common. In source water affected by eutrophication, dimethyl trisulfide, speculated to be produced by decayed algae, was found to be the source of taste and odor issues and can be removed effectively by usual oxidation agents. In this experimental study, batch scale tests were carried out focusing on the removal of dimethyl trisulfide. Reaction kinetics of dimethyl trisulfide oxidized by potassium permanganate in water had been studied; influence factors such as pH, organic substrate, other existed taste, and odor contaminant in equivalent concentration were also dis- cussed. Results showed that dimethyl trisulfide can be removed by potassium permanganate efficiently; the ratio can reach more than 70% with oxidant dosage of 4 mg. L~ and contact time prolonged to 120 min. The dimethyl trisulfide decomposition followed a second-order kinetics pattern with a rate constant k -- 0.00213 L.(min.mg)-1. Typically, the degradation rate of dimethyl trisulfide was increased with the increasing KMnO4 dosage, but dramatically dropped with the increasing levels of humic acid (1.8-4.5 mg. L-1) and other odor-causing compounds (e.g. fl-cyclocitral, 0-1886.0 pg.L-1). Solution pH (5.2- 9.0) and initial dimethyl trisulfide concentration did not significantly affected the degradation. This study demon- strates that KMnO4 oxidation is an effective option to remove dimethyl trisulfide from water.

  19. Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics.

    Science.gov (United States)

    Ashraf, Chowdhury; van Duin, Adri C T

    2017-02-09

    A detailed insight of key reactive events related to oxidation and pyrolysis of hydrocarbon fuels further enhances our understanding of combustion chemistry. Though comprehensive kinetic models are available for smaller hydrocarbons (typically C3 or lower), developing and validating reaction mechanisms for larger hydrocarbons is a daunting task, due to the complexity of their reaction networks. The ReaxFF method provides an attractive computational method to obtain reaction kinetics for complex fuel and fuel mixtures, providing an accuracy approaching ab-initio-based methods but with a significantly lower computational expense. The development of the first ReaxFF combustion force field by Chenoweth et al. (CHO-2008 parameter set) in 2008 has opened new avenues for researchers to investigate combustion chemistry from the atomistic level. In this article, we seek to address two issues with the CHO-2008 ReaxFF description. While the CHO-2008 description has achieved significant popularity for studying large hydrocarbon combustion, it fails to accurately describe the chemistry of small hydrocarbon oxidation, especially conversion of CO2 from CO, which is highly relevant to syngas combustion. Additionally, the CHO-2008 description was obtained faster than expected H abstraction by O2 from hydrocarbons, thus underestimating the oxidation initiation temperature. In this study, we seek to systemically improve the CHO-2008 description and validate it for these cases. Additionally, our aim was to retain the accuracy of the 2008 description for larger hydrocarbons and provide similar quality results. Thus, we expanded the ReaxFF CHO-2008 DFT-based training set by including reactions and transition state structures relevant to the syngas and oxidation initiation pathways and retrained the parameters. To validate the quality of our force field, we performed high-temperature NVT-MD simulations to study oxidation and pyrolysis of four different hydrocarbon fuels, namely, syngas

  20. Effect of graphene oxide sheet size on the curing kinetics and thermal stability of epoxy resins

    Science.gov (United States)

    Wang, Xiao; Jin, Jie; Song, Mo; Lin, Yue

    2016-10-01

    This work revealed the influences of graphene oxide (GO) sheet size on the curing kinetics and thermal stability of epoxy resins. A series of GO/epoxy nanocomposites were prepared by the incorporation of three different sized GO sheets, namely GO-1, GO-2 and GO-3, the average size of which was 10.79 μm, 1.72 μm and 0.70 μm, respectively. The morphologies of the nanocomposites were observed by field emission gun scanning electron microscope. The dispersion quality of each sized GO was comparable in the epoxy matrix. The curing kinetics was investigated by means of differential scanning calorimetry and analyzed based on kinetics model. Addition of a small amount of GO (0.1 wt%) exhibited strong catalytic effect on the curing reaction of epoxy resin. The activation energy was reduced by 18.9%, 28.8% and 14.6% with addition of GO-1, GO-2 and GO-3, respectively. GO-2 with medium size (1.72 μm) showed the most effective catalysis on the cure. The thermal stability of the cured resins was evaluated based on thermogravimetric analysis. GO/epoxy nanocomposites showed improved thermal stability in the range of 420 °C-500 °C, compared with the pure resin. A ˜ 4% more residue was obtained in each of the incorporated system. The variations of GO sheet size did not influence the enhancement effect on the thermal stability.

  1. Chemical kinetic study of the oxidation of toluene and related cyclic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mehl, M; Frassoldati, A; Fietzek, R; Faravelli, T; Pitz, W; Ranzi, E

    2009-10-01

    Chemical kinetic models of hydrocarbons found in transportation fuels are needed to simulate combustion in engines and to improve engine performance. The study of the combustion of practical fuels, however, has to deal with their complex compositions, which generally involve hundreds of compounds. To provide a simplified approach for practical fuels, surrogate fuels including few relevant components are used instead of including all components. Among those components, toluene, the simplest of the alkyl benzenes, is one of the most prevalent aromatic compounds in gasoline in the U.S. (up to 30%) and is a promising candidate for formulating gasoline surrogates. Unfortunately, even though the combustion of aromatics been studied for a long time, the oxidation processes relevant to this class of compounds are still matter of discussion. In this work, the combustion of toluene is systematically approached through the analysis of the kinetics of some important intermediates contained in its kinetic submechanism. After discussing the combustion chemistry of cyclopentadiene, benzene, phenol and, finally, of toluene, the model is validated against literature experimental data over a wide range of operating conditions.

  2. Stoichiometry and kinetics of the anaerobic ammonium oxidation (Anammox) with trace hydrazine addition.

    Science.gov (United States)

    Yao, Zongbao; Lu, Peili; Zhang, Daijun; Wan, Xinyu; Li, Yulian; Peng, Shuchan

    2015-12-01

    Purpose of this study is to investigate the stoichiometry and kinetics of anaerobic ammonium oxidation (Anammox) with trace hydrazine addition. The stoichiometry was established based on the electron balance of Anammox process with trace N2H4 addition. The stoichiometric coefficients were determined by the proton consumption and the changes in substrates and products. It was found that trace N2H4 addition can increase the yield of Anammox bacteria (AnAOB) and reduce NO3(-) yield, which enhances the Anammox. Subsequently, kinetic model of Anammox with trace N2H4 addition was developed, and the parameters of the anaerobic degradation model of N2H4 were obtained for the first time. The maximum specific substrate utilization rate, half-saturation constant and inhibition constant of N2H4 were 25.09mgN/g VSS/d, 10.42mgN/L and 1393.88mgN/L, respectively. These kinetic parameters might provide important information for the engineering applications of Anammox with trace N2H4 addition.

  3. Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

    Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

  4. Kinetics and mechanism of arsenate removal by nanosized iron oxide-coated perlite.

    Science.gov (United States)

    Mostafa, M G; Chen, Yen-Hua; Jean, Jiin-Shuh; Liu, Chia-Chuan; Lee, Yao-Chang

    2011-03-15

    This study discussed the adsorption kinetics of As(V) onto nanosized iron oxide-coated perlite. The effects of pH, initial concentration of As(V) and common anions on the adsorption efficiency were also investigated. It was observed that a 100% As(V) adsorption was achieved at pH value of 4-8 from the initial concentration containing 1.0 mg-As(V)L(-1) and the adsorption percentage depended on the initial concentration; the phosphate and silicate ions would not interfere with the adsorption efficiency. Furthermore, nanosized iron oxide-coated perlite (IOCP) has been shown to be an effective adsorbent for the removal of arsenate from water. The adsorption kinetics were studied using pseudo-first- and pseudo-second-order models, and the experimental data fitted well with the pseudo-second-order model. Moreover, it suggests that the Langmuir isotherm is more adequate than the Freundlich isotherm in simulating the adsorption isotherm of As(V). The adsorption rate constant is 44.84 L mg(-1) and the maximum adsorption capacity is 0.39 mg g(-1). These findings indicate that the adsorption property of IOCP gives the compound a great potential for applications in environmental remediation.

  5. Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

    Science.gov (United States)

    Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

    2017-06-01

    Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

  6. Enhanced charge separation and oxidation kinetics of BiVO4 photoanode by double layer structure

    Science.gov (United States)

    Yang, Lin; Xiong, Yuli; Dong, Hongmei; Peng, Huarong; Zhang, Yunhuai; Xiao, Peng

    2017-03-01

    Monoclinic bismuth vanadate (BiVO4) is a promising semiconductor for photoelectrochemical water splitting. Here, we developed a facile fabrication of BiVO4 double layer photoanode on the fluorine-doped tin oxide substrate by electrodeposition. The BiVO4 double layer photoanode is composed by a dense BiVO4 film as the inner layer and a nanoporous BiVO4 film as the outer layer. Compared to the BiVO4 single layer photoanode, the optimized BiVO4 double layer photoanode produced a much higher photocurrent of 1.15 mA/cm2 at 0.6 V vs. Ag/AgCl under AM 1.5G (100 mW/cm2) illumination. The results of the photoelectric conversion kinetics for different samples revealed that the charge separation and oxidation kinetics efficiencies for the BiVO4 double layer are 47.2% and 51.6% at 0.6 V vs. Ag/AgCl, while the values for BiVO4 single layer are 32.3% and 35.8%, respectively. The improved photoelectrochemical performance for BiVO4 double layer is mainly ascribed to the decrease of defect state at the interface after inserting a dense BiVO4 as an inner layer to prevent the recombination of photogenerated electron-hole pairs.

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

    Science.gov (United States)

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

    2013-02-21

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

  8. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

  9. 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] 

  10. 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

    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...... 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...... the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C2H4 are more complex than those prevailing...

  11. Methane oxidation in a landfill cover soil reactor: Changing of kinetic parameters and microorganism community structure.

    Science.gov (United States)

    Xing, Zhi L; Zhao, Tian T; Gao, Yan H; Yang, Xu; Liu, Shuai; Peng, Xu Y

    2017-02-23

    Changing of CH4 oxidation potential and biological characteristics with CH4 concentration was studied in a landfill cover soil reactor (LCSR). The maximum rate of CH4 oxidation reached 32.40 mol d(-1) m(-2) by providing sufficient O2 in the LCSR. The kinetic parameters of methane oxidation in landfill cover soil were obtained by fitting substrate diffusion and consumption model based on the concentration profile of CH4 and O2. The values of [Formula: see text] (0.93-2.29%) and [Formula: see text] (140-524 nmol kgsoil-DW(-1)·s(-1)) increased with CH4 concentration (9.25-20.30%), while the values of [Formula: see text] (312.9-2.6%) and [Formula: see text] (1.3 × 10(-5) to 9.0 × 10(-3) nmol mL(-1) h(-1)) were just the opposite. MiSeq pyrosequencing data revealed that Methylobacter (the relative abundance was decreased with height of LCSR) and Methylococcales_unclassified (the relative abundance was increased expect in H 80) became the key players after incubation with increasing CH4 concentration. These findings provide information for assessing CH4 oxidation potential and changing of biological characteristics in landfill cover soil.

  12. Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

    Institute of Scientific and Technical Information of China (English)

    Bambang VERIANSYAH; Jae-Duck KIM; Youn-Woo LEE

    2006-01-01

    Supercritical water oxidation (SCWO) has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate(DMMP), which is similar to the nerve agent VX and GB(Sarin) in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633 ℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon (TOC) on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

  13. Kinetics of oxidation of bilirubin and its protein complex by hydrogen peroxide in aqueous solutions

    Science.gov (United States)

    Solomonov, A. V.; Rumyantsev, E. V.; Antina, E. V.

    2010-12-01

    A comparative study of oxidation reactions of bilirubin and its complex with albumin was carried out in aqueous solutions under the action of hydrogen peroxide and molecular oxygen at different pH values. Free radical oxidation of the pigment in both free and bound forms at pH 7.4 was shown not to lead to the formation of biliverdin, but to be associated with the decomposition of the tetrapyrrole chromophore into monopyrrolic products. The effective and true rate constants of the reactions under study were determined. It was assumed that one possible mechanism of the oxidation reaction is associated with the interaction of peroxyl radicals and protons of the NH groups of bilirubin molecules at the limiting stage with the formation of a highly reactive radical intermediate. The binding of bilirubin with albumin was found to result in a considerable reduction in the rate of the oxidation reaction associated with the kinetic manifestation of the protein protection effect. It was found that the autoxidation of bilirubin by molecular oxygen with the formation of biliverdin at the intermediate stage can be observed with an increase in the pH of solutions.

  14. Destruction of OPA from munitions demilitarization in supercritical water oxidation: kinetics of total organic carbon disappearance.

    Science.gov (United States)

    Veriansyah, Bambang; Kim, Jae-Duck; Lee, Jong-Chol; Hong, Deasik

    2006-01-01

    The destruction of OPA from munitions demilitarization has been accomplished in supercritical water oxidation (SCWO) with oxygen as oxidant in an isothermal continuous-flow reactor. The experiments were conducted at a temperature of 689-887 K and a fixed pressure of 25 MPa, with a residence time that ranged from 7 s to 14 s. The destruction efficiency was measured by total organic carbon (TOC) conversion. At the reaction condition, the initial TOC concentrations of OPA were varied from 1.41 mmol/L to 19.57 mmol/L and the oxygen concentrations were varied from 15.03 mmol/L to 81.85 mmol/L. Experimental data showed that all the TOC conversions were >80% under the above experimental conditions. The kinetics of TOC disappearance, which is essential for the design, optimization, and control of reliable commercial SCWO reactor was developed by taking into account the dependence of the oxidant and TOC concentration on the reaction rate. A global TOC disappearance rates expression was regressed from the data of 38 experiments, to a 95% confidence level. The resulting activation energy was determined to be 44.01 +/- 1.52 kJ/mol, and the pre-exponential factor was (1.67 +/- 0.45) x 10(2) L(1.14) mmol(-0.14) s(-1). The reaction orders for the TOC and the oxidant were 0.98 +/- 0.01 and 0.16 +/- 0.02, respectively.

  15. Oxidation kinetics of hydrogenated amorphous carbon (a-CH(x)) overcoats for magnetic data storage media.

    Science.gov (United States)

    Yun, Yang; Ma, Xiaoding; Gui, Jing; Broitman, Esteban; Gellman, Andrew J

    2007-05-08

    The oxidation kinetics of a-CHx overcoats during exposure to oxygen and water vapor have been measured using X-ray photoemission spectroscopy (XPS) in an apparatus that allows oxidation and analysis of freshly deposited a-CHx overcoats without prior exposure of the overcoats to air. The uptake of oxygen on the surfaces of the a-CHx overcoats has been measured at O2 and H2O pressures in the range 10(-7)-10(-3) Torr at room temperature. The uptake of oxygen during O2 exposures on the order of 10(7) Langmuirs leads to saturation of the a-CHx overcoat surfaces at oxidation levels on the order of 20%. This indicates that the surfaces of a-CHx overcoats are relatively inert to oxidation in the sense that the dissociative sticking coefficient of O2 is approximately 10(-6). Oxygen uptake during exposure to H2O vapor is similar to the uptake during exposure to O2 gas. Although the surfaces of the a-CHx overcoats are quite inhomogeneous, it has been possible to model the uptake of oxygen on their surfaces using a fairly simple Langmuir-Hinshelwood mechanism. Interestingly, the saturation coverage of oxygen during exposure to air at atmospheric pressure is approximately 6%, significantly lower than that obtained during low-pressure exposure to O2 gas or H2O vapor.

  16. Kinetic studies on the oxidation of semiquinone and hydroquinone forms of Arabidopsis cryptochrome by molecular oxygen.

    Science.gov (United States)

    van Wilderen, Luuk J G W; Silkstone, Gary; Mason, Maria; van Thor, Jasper J; Wilson, Michael T

    2015-01-01

    Cryptochromes (crys) are flavoprotein photoreceptors present throughout the biological kingdom that play important roles in plant development and entrainment of the circadian clock in several organisms. Crys non-covalently bind flavin adenine dinucleotide (FAD) which undergoes photoreduction from the oxidised state to a radical form suggested to be active in signalling in vivo. Although the photoreduction reactions have been well characterised by a number of approaches, little is known of the oxidation reactions of crys and their mechanisms. In this work, a stopped-flow kinetics approach is used to investigate the mechanism of cry oxidation in the presence and absence of an external electron donor. This in vitro study extends earlier investigations of the oxidation of Arabidopsis cryptochrome1 by molecular oxygen and demonstrates that, under some conditions, a more complex model for oxidation of the flavin than was previously proposed is required to accommodate the spectral evidence (see P. Müller and M. Ahmad (2011) J. Biol. Chem. 286, 21033-21040 [1]). In the absence of an electron donor, photoreduction leads predominantly to the formation of the radical FADH(•). Dark recovery most likely forms flavin hydroperoxide (FADHOOH) requiring superoxide. In the presence of reductant (DTT), illumination yields the fully reduced flavin species (FADH(-)). Reaction of this with dioxygen leads to transient radical (FADH(•)) and simultaneous accumulation of oxidised species (FAD), possibly governed by interplay between different cryptochrome molecules or cooperativity effects within the cry homodimer.

  17. 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

  18. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III ? gas phase reactions of inorganic halogens

    OpenAIRE

    Atkinson, R.; Baulch, D. L.; Cox, R A; J. N. Crowley; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; M. J. Rossi; Troe, J.

    2007-01-01

    International audience; This article, the third in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of inorganic halogen species, which were last published in J. Phys. Chem. Ref. Data, in 2000 (Atkinson et al., 2000), were updated on the IUPAC website in 2003 and are updated again in the present evaluation. The article consists of a summary sheet...

  19. Methane and methanol oxidation in supercritical water: Chemical kinetics and hydrothermal flame studies

    Energy Technology Data Exchange (ETDEWEB)

    Steeper, R.R.

    1996-01-01

    Supercritical water oxidation (SCWO) is an emerging technology for the treatment of wastes in the presence of a large concentration of water at conditions above water`s thermodynamic critical point. A high-pressure, optically accessible reaction cell was constructed to investigate the oxidation of methane and methanol in this environment. Experiments were conducted to examine both flame and non-flame oxidation regimes. Optical access enabled the use of normal and shadowgraphy video systems for visualization, and Raman spectroscopy for in situ measurement of species concentrations. Flame experiments were performed by steadily injecting pure oxygen into supercritical mixtures of water and methane or methanol at 270 bar and at temperatures from 390 to 510{degrees}C. The experiments mapped conditions leading to the spontaneous ignition of diffusion flames in supercritical water. Above 470{degrees}C, flames spontaneously ignite in mixtures containing only 6 mole% methane or methanol. This data is relevant to the design and operation of commercial SCWO processes that may be susceptible to inadvertent flame formation. Non-flame oxidation kinetics experiments measured rates of methane oxidation in supercritical water at 270 bar and at temperatures from 390 to 442{degrees}C. The initial methane concentration was nominally 0.15 gmol/L, a level representative of commercial SCWO processes. The observed methane concentration histories were fit to a one-step reaction rate expression indicating a reaction order close to two for methane and zero for oxygen. Experiments were also conducted with varying water concentrations (0 to 8 gmol/L) while temperature and initial reactant concentrations were held constant. The rate of methane oxidation rises steadily with water concentration up to about 5 gmol/L and then abruptly falls off at higher concentrations.

  20. Destruction kinetic of PCDDs/Fs in MSWI fly ash using microwave peroxide oxidation.

    Science.gov (United States)

    Chang, Yu-Min; Fang, Wen-Bin; Tsai, Kuo-Sheng; Kao, Jimmy C M; Lin, Kae-Long; Chen, Ching-Ho

    2015-01-01

    Microwave peroxide oxidation is a less greenhouse gas emission and energy-efficient technology to destroy toxic organic compounds in hazardous waste. The research novelty is to adopt the innovative microwave peroxide oxidation in H2SO4/HNO3 solution to efficiently destroy the polychlorinated dibenzo-p-dioxins (PCDDs)/Fs in municipal solid waste incineration fly ash. The major objective of this paper is to study dynamic destruction of PCDDs/Fs using the microwave peroxide oxidation. Almost all PCDDs/Fs in the raw fly ash can be destructed in 120 min at a temperature of 423 K using the microwave peroxide oxidation treatment. It was found that the microwave peroxide oxidation provides the potential to destruct the PCDDs/Fs content in municipal solid waste incinerator (MSWI) fly ash to a low level as a function of treatment time. A useful kinetic correlation between destruction efficiency and treatment conditions is proposed on the basis of the experimental data obtained in this study. The significance of this work in terms of practical engineering applications is that the necessary minimum treatment time can be solved using a proposed graphic illustration method, by which the minimum treatment time is obtained if the desired destruction efficiency and treatment temperature are known. Because of inorganic salt dissolution, the temperature would be a critical factor facilitating the parts of fly ash dissolution. Material loss problem caused by the microwave peroxide oxidation and the effects of treatment time and temperature are also discussed in this paper.

  1. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    Science.gov (United States)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  2. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots.

    Science.gov (United States)

    Powell, C L; Goltz, M N; Agrawal, A

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  3. In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.; Olszta, Matthew J.; Baer, Donald R.; Bruemmer, Stephen M.; Zhou, Guangwen; Wang, Chong M.

    2016-01-20

    We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the change of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.

  4. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2002-02-01

    Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced Vision 21 plants that employ coal and natural gas and produce electric power and clean transportation fuels. These Vision 21 plants will require highly clean coal gas with H{sub 2}S below 1 ppm and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation Vision 21 plants. To this end, a novel process is now under development at Research Triangle Institute (RTI) in which the H{sub 2}S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The objective of this research is to support the near- and long-term DOE efforts to commercialize this direct oxidation technology. Specifically, we aim to: Measure the kinetics of direct oxidation of H{sub 2}S to elemental sulfur over selective catalysts in the

  5. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2004-01-01

    The direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and the hot-gas desulfurization using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process. The objective of this research is to support the near- and long-term process development efforts to commercialize this direct oxidation technology. The objectives of this research are to measure kinetics of direct oxidation of H{sub 2}S to elemental sulfur in the presence of a simulated coal gas mixture containing SO{sub 2}, H{sub 2}, and moisture, using 160-{micro}m C-500-04 alumina catalyst particles and a micro bubble reactor, and to develop kinetic rate equations and model the direct oxidation process to assist in the design of large-scale plants. This heterogeneous catalytic reaction has gaseous reactants such as H{sub 2}S and SO{sub 2}. However, this heterogeneous catalytic reaction has heterogeneous products such as liquid elemental sulfur and steam. To achieve the above-mentioned objectives, experiments on conversion of hydrogen sulfide into liquid elemental sulfur were carried out for the space time range of 1-6 milliseconds at 125-155 C to evaluate effects of reaction temperature, moisture concentration, reaction pressure on conversion of hydrogen sulfide into liquid elemental sulfur. Simulated coal gas mixtures consist of 70 v% hydrogen, 2,500-7,500-ppmv hydrogen sulfide, 1,250-3,750 ppmv sulfur dioxide, and 0-15 vol% moisture, and nitrogen as remainder. Volumetric feed rates of a simulated coal gas mixture to a micro bubble reactor are 100 cm{sup 3}/min at room temperature and atmospheric pressure. The temperature of the reactor is controlled in an oven at 125-155 C. The

  6. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2005-01-01

    The direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and the hot-gas desulfurization using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process. The objective of this research is to support the near- and long-term process development efforts to commercialize this direct oxidation technology. The objectives of this research are to measure kinetics of direct oxidation of H{sub 2}S to elemental sulfur in the presence of a simulated coal gas mixture containing SO{sub 2}, H{sub 2}, and moisture, using 160-{micro}m C-500-04 alumina catalyst particles and a micro bubble reactor, and to develop kinetic rate equations and model the direct oxidation process to assist in the design of large-scale plants. This heterogeneous catalytic reaction has gaseous reactants such as H{sub 2}S and SO{sub 2}. However, this heterogeneous catalytic reaction has heterogeneous products such as liquid elemental sulfur and steam. To achieve the above-mentioned objectives, experiments on conversion of hydrogen sulfide into liquid elemental sulfur were carried out for the space time range of 0.059-0.87 seconds at 125-155 C to evaluate effects of reaction temperature, H{sub 2}S concentration, reaction pressure, and catalyst loading on conversion of hydrogen sulfide into liquid elemental sulfur. Simulated coal gas mixtures consist of 62-78 v% hydrogen, 3,000-7,000-ppmv hydrogen sulfide, 1,500-3,500 ppmv sulfur dioxide, and 10 vol % moisture, and nitrogen as remainder. Volumetric feed rates of a simulated coal gas mixture to a micro bubble reactor are 50 cm{sup 3}/min at room temperature and atmospheric pressure. The temperature of the reactor is controlled in an

  7. A comparison of the kinetics of low-density lipoprotein oxidation initiated by copper or by azobis (2-amidinopropane).

    Science.gov (United States)

    Thomas, M J; Chen, Q; Franklin, C; Rudel, L L

    1997-01-01

    This article describes the kinetics of low density lipoprotein (LDL) oxidation catalyzed by azobis (2-amidinopropane) dihydrochloride, ABAP, or by copper. The LDLs were isolated from nonhuman primates fed diets enriched in one of three types of fatty acids: saturated fatty acids, monounsaturated fatty acids, predominantly, oleic acid, or polyunsaturated fatty acids, predominantly linoleic acid. Oxidation was followed by monitoring the formation of conjugated diene hydroperoxides from polyunsaturated fatty acids (PUFA). For both copper and ABAP-initiated oxidation, the rate of LDL oxidation depended on the concentrations of initiator, PUFA, and LDL. Except for the dependence on PUFA concentration the rate of LDL oxidation was not directly influenced by the fatty acid composition of the LDL particle. The two initiators had very different dependence on initiator concentration. Because LDL particles are essentially small, lipid-rich droplets, the kinetic descriptions of LDL oxidation assumed: (1), that there was only one chain per particle, and (2) that the radical chain was terminated when a second radical either entered or was formed in the particle. When two LDL samples having very different lag times were mixed, the oxidation profile was bimodal. This finding demonstrated that the oxidation of native LDL particles was independent of the oxidation state of the other native LDL particles in solution, i.e., LDL particles do not rapidly exchange radicals, for example, hydroperoxyl radicals. Oxidation initiated by ABAP was proportional to [ABAP]0.5, suggesting that hydroperoxyl radical recombination between the lipid hydroperoxyl radical and the ABAP-hydroperoxyl radical was the chain-terminating step. The reciprocal of the rate of copper oxidation was linearly related to the reciprocal copper concentration, demonstrating that the binding of copper to LDL was necessary to initiate oxidation. This binding constant showed considerable variability among LDL samples. The

  8. Mechanistic chemistry of oxidation of balsalazide with acidic chloramine-T and bromamine-T: A comparative spectrophotometric kinetic study

    Indian Academy of Sciences (India)

    Puttaswamy; S Dakshayani

    2014-11-01

    Balsalazide (BSZ) belongs to a class of non-steroidal anti-inflammatory drugs. Kinetics and mechanism of oxidation of BSZ with sodium N-halo-p-toluenesulfonamides viz., chloramine-T(CAT) and bromamine-T(BAT) in HClO4 medium have been spectrophotometrically investigated (max =357nm) at 303 K. Under comparable experimental conditions, reactions with both the oxidants follow a first-order dependence of rate on [BSZ] and fractional-order dependence on each [oxidant] and [HClO4]. Activation parameters and reaction constants have been computed. 2-hydroxy-5-nitroso-benzoic acid and 3-(4-nitroso-benzoylamino)-propionic acid are identified as the oxidation products of BSZ with both CAT and BAT. The rate of oxidation of BSZ is about five-fold faster with BAT than with CAT. Plausible mechanism and related rate law have been deduced for the observed kinetics.

  9. 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-Fe2O3) and alumina (α-Al2O3) 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 O2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2014-10-01

    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.

  11. Kinetics and mechanism of the oxidation of pentathionate ion by chlorine dioxide in a slightly acidic medium.

    Science.gov (United States)

    Xu, Li; Csekő, György; Petz, Andrea; Horváth, Attila K

    2014-02-27

    The chlorine dioxide-pentathionate reaction has been studied at a slightly acidic medium by conventional UV-vis spectroscopy monitoring the absorbance at 430 nm. We have shown that pentathionate was oxidized to sulfate, but chlorate is also a marginal product of the reaction besides the chloride ion. The stoichiometry of the reaction can be established as a linear combination of two limiting stoichiometries under our experimental conditions. Kinetics of the reaction was found to be also complex because initial rate studies revealed that formal kinetic orders of both the hydrogen ion and chlorine dioxide is far from unity. Moreover, log-log plot of the initial rate against pentathionate concentration indicated a nonconstant formal kinetic order. We also observed a significant catalytic effect of chloride ion. Based on our observations and simultaneous evaluation of the kinetic curves, an 11-step kinetic model is obtained with 6 fitted rate coefficients. A relatively simple rate equation has also been derived and discussed.

  12. Chemical kinetic study of the oxidation of a biodiesel-bioethanol surrogate fuel: methyl octanoate-ethanol mixtures.

    Science.gov (United States)

    Togbé, C; May-Carle, J-B; Dayma, G; Dagaut, P

    2010-03-25

    There is a growing interest for using bioethanol-biodiesel fuel blends in diesel engines but no kinetic data and model for their combustion were available. Therefore, the kinetics of oxidation of a biodiesel-bioethanol surrogate fuel (methyl octanoate-ethanol) was studied experimentally in a jet-stirred reactor at 10 atm and constant residence time, over the temperature range 560-1160 K, and for several equivalence ratios (0.5-2). Concentration profiles of reactants, stable intermediates, and final products were obtained by probe sampling followed by online FTIR, and off-line gas chromatography analyses. The oxidation of this fuel in these conditions was modeled using a detailed chemical kinetic reaction mechanism consisting of 4592 reversible reactions and 1087 species. The proposed kinetic reaction mechanism yielded a good representation of the kinetics of oxidation of this biodiesel-bioethanol surrogate under the JSR conditions. The modeling was used to delineate the reactions triggering the low-temperature oxidation of ethanol important for diesel engine applications.

  13. Oxidation of triclosan by ferrate: Reaction kinetics, products identification and toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Yang Bin [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Ying Guangguo, E-mail: guang-guo.ying@csiro.au [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhao Jianliang; Zhang Lijuan; Fang Yixiang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Nghiem, Long Duc [School of Civil Mining and Environmental Engineering, University of Wollongong, Wollongong, NSW 2522 (Australia)

    2011-02-15

    Research highlights: {yields} Triclosan reacted rapidly with ferrate. {yields} Oxidation resulted in a decrease in algal toxicity. {yields} No inhibition of algae growth from ferrate. - Abstract: The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k{sub app}, being 754.7 M{sup -1} s{sup -1} at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7({+-}1.9) x 10{sup 2} M{sup -1} s{sup -1}, while that measured for anionic triclosan was 7.6({+-}0.6) x 10{sup 3} M{sup -1} s{sup -1}. The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth.

  14. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  15. Effect of Y Distribution on the Oxidation Kinetics of NiCoCrAlY Bond Coat Alloys

    OpenAIRE

    Nijdam, T.J.; Sloof, W.G.

    2007-01-01

    The relation between the Y distribution in the alloy and the growth kinetics of the developing oxide scale was studied for the thermal oxidation of two Ni–20Co–19Cr–24Al–0.2Y (at.%) alloys at 1,373 K: (i) a coarse-grain cast alloy with large Ni5Y intermetallic precipitates, and (ii) a fine-grain freestanding coating with small Ni5Y precipitates. Using a combination of experiments and model calculations, it is shown that the average growth kinetics of a NiCoCrAlY alloy are dependent on the siz...

  16. New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms.

    Science.gov (United States)

    Ji, Yuefei; Dong, Changxun; Kong, Deyang; Lu, Junhe

    2015-03-21

    The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides.

  17. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides.

    Science.gov (United States)

    Björkbacka, Åsa; Yang, Miao; Gasparrini, Claudia; Leygraf, Christofer; Jonsson, Mats

    2015-09-28

    One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO˙). Both H2O2 and HO˙ are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO˙ are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

  18. Oxidation of Tetracaine Hydrochloride by Chloramine-B in Acid Medium: Kinetic Modeling

    Directory of Open Access Journals (Sweden)

    Jayachamarajapura Pranesh Shubha

    2014-01-01

    Full Text Available Tetracaine hydrochloride (TCH is one of the potent local anaesthetics. A kinetic study of oxidation of tetracaine hydrochloride by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB has been carried in HClO4 medium at 303 K. The rate shows first-order dependence on [CAB]o, shows fractional–order dependence on [substrate]o, and is self-governing on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increased the rate. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction was found to be 1 : 5 and the oxidation products were identified by spectral analysis. The conjugate free acid C6H5SO2NHCl of CAB is postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

  19. Catalytic oxidation ofS(IV) on activated carbon in aqueous suspension: kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brodzinsky, R.

    1981-02-01

    Activated carbon and combustion produced soot particles have been studied for their catalytic effect on the oxidation of aqueous sulfur(IV) species. Detailed kinetic studies of the reaction were performed on three different activated carbons and on a soot collected in a highway tunnel. Combustion produced soots were tested for their catalytic behavior and found to be similar to the activated carbons. The reaction rate was found to be linearly dependent on the concentration of carbon particles in the solution. The rate was found to follow a Langmuir adsorption isotherm for its dependence on oxygen and the product of two adsorption isotherms for S(IV). The reaction is independent of the pH of the solution when the pH is below 7.6. The reaction does not occur when the pH is above 7.6. The three aqueous S(IV) species are catalyzed in their oxidation by the carbon particles in a similar manner. Activation energies for the reactions on the different carbons are all about 8.5 kcal/mole. A possible four-step reaction mechanism is proposed. It consists of the adsorption of a dissolved oxygen molecule onto the carbon surface, followed by the adsorption of two S(IV) molecules or ions. These are oxidized on the surface to sulfate, which desorbs from the surface, regenerating the catalytically active site.

  20. Kinetics of nonisothermal heterogeneous oxidation of fossil coals and their spontaneous heating

    Energy Technology Data Exchange (ETDEWEB)

    Grekov, S.P.; Koshovsky, B.I.; Cygankiewicz, J. [RESPIRATOR, Donetsk (Ukraine). Research-and-Manufacturing Association on Mine Rescue Work

    2001-07-01

    Influence of breakage of coals on change of their reaction surface is studied. The dependence of the reaction surface on fraction of combustibles, diameter of particles, temperature in pre- and postcritical ranges of spontaneous heating, humidity is obtained. The compensation effect in the interrelationship of the activation energy with the preexponential factor in the Arrhenius reaction of coal oxidation is studied. The dependence of increase in the reaction surface of coals on reaching their critical temperature is determined. The dependences of change in moisture fraction in coal by its spontaneous heating and that ones of change of the specific surface of coals in the process of their heating and moisture vaporization are established. A mathematical model of kinetics of nonisothermal heterogeneous oxidation of coal is formulated, and its analytical solution is obtained. The initial-and-boundary problem of description of the self-heating process of the coal particle in the form of a micropore grain is formulated. The approximate analytical solution of the problem and the exact one according to assumption that carbon content in coal is constant are obtained. Satisfactory coincidence of measured and calculated dependences of coal temperatures is shown on the examples of the experimental investigations of heterogeneous oxidation of coals. 18 refs., 1 fig.

  1. Kinetics and Product Yields of the OH Driven Oxidation of Hydroxymethyl Hydroperoxide

    Science.gov (United States)

    Allen, H.; Teng, A.; Bates, K. H.; Crounse, J.; Thayer, M. P.; Rivera, J. C.; Keutsch, F. N.; St Clair, J. M.; Wennberg, P. O.

    2016-12-01

    Hydroperoxides play a significant role in altering the atmosphere's oxidative potential by acting as a sink and mobile reservoir of OH and odd oxygen species. Hydroxymethyl hydroperoxide (HMHP), formed primarily via the reaction of the C1 criegee with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important removal processes for HMHP, to date, no experimental study of HMHP and OH has been reported. Here, we present a laboratory study of the kinetics and product distributions formed in the reaction of HMHP with OH. Synthesized HMHP was oxidized by OH in an environmental chamber, and the decay of the hydroperoxide was monitored over time via CF3O- chemical ionization mass spectrometry (CIMS). Product yields, primarily formic acid and formaldehyde, were characterized by CIMS and by laser induced fluorescence (LIF). We use these measurements to interpret HMHP measurements obtained during SOAS and SEAC4RS. We further use global simulations with GEOS-Chem to evaluate the global importance of different HMHP sinks and the impact of HMHP oxidation on global formaldehyde and formic acid concentrations.

  2. A kinetic assessment of substantial oxidation by sulfolobus acidocaldarius in pyrite dissolution

    Energy Technology Data Exchange (ETDEWEB)

    Vitaya, V.B.; Koizumi, J.; Toda, K. (King Mongkuts Institute of Technology, Bangkok (Thailand). Dept. of Chemical Engineering)

    1994-01-01

    The relative contributions of biological and chemical reactions to the total rate of pyrite oxidation in the presence of Sulfolobus acidocaldarius were studied on the basis of experimental work coupled with mathematical modeling. Kinetic constants for the individual reactions were determined in independent experiments. The specific growth rate of cells on the pyrite surface, which is the only unknown parameter, was assumed to be [mu](s) 0.1 h[sup -1] and justified by the agreement of the simulated results of a proposed model and the experimental results. The model includes: reversible adsorption, biological dissolution of pyrite by the adsorbed cells, chemical dissolution of pyrite accompanied by the reduction of ferric ions to ferrous ions, biochemical oxidation of ferrous ions to ferric ions by free cells, and change of the surface area of pyrite particles. It is suggested that the contributions of direct (biological) and indirect (chemical) reaction to the total rate of pyrite oxidation were in a ratio of 2:1.

  3. Oxidation Kinetics of a NiPtTi High Temperature Shape Memory Alloy

    Science.gov (United States)

    Smialek, James L.; Humphrey, Donald L.; Noebe, Ronald D.

    2007-01-01

    A high temperature shape memory alloy (HTSMA), Ni30Pt50Ti, with an M(sub s) near 600 C, was isothermally oxidized in air for 100 hr over the temperature range of 500 to 900 C. Parabolic kinetics were confirmed by log-log and parabolic plots and showed no indication of fast transient oxidation. The overall behavior could be best described by the Arrhenius relationship: k(sub p) = 1.64 x 10(exp 12)[(-250 kJ/mole)/RT] mg(sup 2)/cm(sup 4)hr. This is about a factor of 4 reduction compared to values measured here for a binary Ni47Ti commercial SMA. The activation energy agreed with most literature values for TiO2 scale growth measured for elemental Ti and other NiTi alloys. Assuming uniform alloy depletion of a 20 mil (0.5 mm) dia. HTSMA wire, approx. 1 percent Ti reduction is predicted after 20,000 hr oxidation at 500 C, but becomes much more serious at higher temperatures.

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

    Institute of Scientific and Technical Information of China (English)

    Xiaofang Xie; Yongqing Zhang; Weilin Huang; Shaobing Huang

    2012-01-01

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

  5. Kinetic model of the inhibition of respiration by endogenous nitric oxide in intact cells.

    Science.gov (United States)

    Aguirre, Enara; Rodríguez-Juárez, Félix; Bellelli, Andrea; Gnaiger, Erich; Cadenas, Susana

    2010-05-01

    Nitric oxide (NO) inhibits mitochondrial respiration by decreasing the apparent affinity of cytochrome c oxidase (CcO) for oxygen. Using iNOS-transfected HEK 293 cells to achieve regulated intracellular NO production, we determined NO and O(2) concentrations and mitochondrial O(2) consumption by high-resolution respirometry over a range of O(2) concentrations down to nanomolar. Inhibition of respiration by NO was reversible, and complete NO removal recovered cell respiration above its routine reference values. Respiration was observed even at high NO concentrations, and the dependence of IC(50) on [O(2)] exhibits a characteristic but puzzling parabolic shape; both these features imply that CcO is protected from complete inactivation by NO and are likely to be physiologically relevant. We present a kinetic model of CcO inhibition by NO that efficiently predicts experimentally determined respiration at physiological O(2) and NO concentrations and under hypoxia, and accurately predicts the respiratory responses under hyperoxia. The model invokes competitive and uncompetitive inhibition by binding of NO to the reduced and oxidized forms of CcO, respectively, and suggests that dissociation of NO from reduced CcO may involve its O(2)-dependent oxidation. It also explains the non-linear dependence of IC(50) on O(2) concentration, and the hyperbolic increase of c(50) as a function of NO concentration.

  6. Light intensity dependence of the kinetics of the photocatalytic oxidation of nitrogen(II) oxide at the surface of TiO2.

    Science.gov (United States)

    Dillert, Ralf; Engel, Astrid; Große, Julia; Lindner, Patrick; Bahnemann, Detlef W

    2013-12-28

    Air pollution by nitrogen oxides represents a serious environmental problem in urban areas where numerous sources of these pollutants are concentrated. One approach to reduce the concentration of these air pollutants is their light-induced oxidation in the presence of molecular oxygen and a photocatalytically active building material which uses titanium dioxide as the photocatalyst. Herein, results of an investigation concerning the influence of the photon flux and the pollutant concentration on the rate of the photocatalytic oxidation of nitrogen(ii) oxide in the presence of molecular oxygen and UV(A) irradiated titanium dioxide powder are presented. A Langmuir-Hinshelwood-type rate law for the photocatalytic NO oxidation inside the photoreactor comprising four kinetic parameters is derived being suitable to describe the influence of the pollutant concentration and the photon flux on the rate of the photocatalytic oxidation of nitrogen(ii) oxide.

  7. Effects of 2 different prior endurance exercises on whole-body fat oxidation kinetics: light vs. heavy exercise.

    Science.gov (United States)

    Chenevière, Xavier; Borrani, Fabio; Droz, David; Gojanovic, Boris; Malatesta, Davide

    2012-10-01

    This study aimed to compare the effects of 2 different prior endurance exercises on subsequent whole-body fat oxidation kinetics. Fifteen men performed 2 identical submaximal incremental tests (Incr2) on a cycle ergometer after (i) a ∼40-min submaximal incremental test (Incr1) followed by a 90-min continuous exercise performed at 50% of maximal aerobic power-output and a 1-h rest period (Heavy); and (ii) Incr1 followed by a 2.5-h rest period (Light). Fat oxidation was measured using indirect calorimetry and plotted as a function of exercise intensity during Incr1 and Incr2. A sinusoidal equation, including 3 independent variables (dilatation, symmetry and translation), was used to characterize the fat oxidation kinetics and to determine the intensity (Fat(max)) that elicited the maximal fat oxidation (MFO) during Incr. After the Heavy and Light trials, Fat(max), MFO, and fat oxidation rates were significantly greater during Incr2 than Incr1 (p < 0.001). However, Δ (i.e., Incr2-Incr1) Fat(max), MFO, and fat oxidation rates were greater in the Heavy compared with the Light trial (p < 0.05). The fat oxidation kinetics during Incr2(Heavy) showed a greater dilatation and rightward asymmetry than Incr1(Heavy), whereas only a greater dilatation was observed in Incr2(Light) (p < 0.05). This study showed that although to a lesser extent in the Light trial, both prior exercise sessions led to an increase in Fat(max), MFO, and absolute fat oxidation rates during Incr2, inducing significant changes in the shape of the fat oxidation kinetics.

  8. Kinetics and mechanisms of oxidation of 2D woven C/SiC composites; 1: Experimental approach

    Energy Technology Data Exchange (ETDEWEB)

    Lamouroux, F.; Camus, G. (UMR 47, Pessac (France). Lab. des Composites Thermostructuraux); Thebault, J. (Societe Europeenne de Propulsion, Saint Medard-en-Jalles (France))

    1994-08-01

    The oxidation behavior of a 2D woven C/SiC composite partly protected with a SiC seal coating and heat-treated (stabilized) at 1,600 C in inert gas has been investigated through an experimental approach based on thermogravimetric analyses and optical/electron microscopy. Results of the tests, performed under flowing oxygen, have shown that the oxidation behavior of the composite material in terms of oxidation kinetics and morphological evolutions is related to the presence of thermal microcracks in the seal coating as well as in the matrix. Three different temperature domains exist. At low temperatures (< 800 C), the mechanisms of reaction between carbon and oxygen control the oxidation kinetics and are associated with a uniform degradation of the carbon reinforcement. At intermediate temperatures, (between 800 and 1,100 C), the oxidation kinetics are controlled by the gas-phase diffusion through a network of microcracks in the SiC coatings, resulting in a nonuniform degradation of the carbon phases. At high temperatures (> 1,100 C), such diffusion mechanisms are limited by sealing of the microcracks by silica; therefore, the degradation of the composite remains superficial. The study of the oxidation behavior of (i) the heat-treated composite in a lower oxygen content environment (dry air) and (ii) the as-processed (unstabilized) composite in dry oxygen confirms the different mechanisms proposed to explain the oxidation behavior of the composite material.

  9. OXIDATION OF SALBUTAMOL BY CHLORAMINE-B IN HClO4 MEDIUM: A KINETIC AND MECHANISTIC APPROACH

    Directory of Open Access Journals (Sweden)

    Diwya

    2012-06-01

    Full Text Available Oxidation of Salbutamol (SBL by sodium – N- chloro benzenesulphonamide(Chloramine-B or CAB in HClO4 medium has been studied at 303K by kinetic method. Oxidation reaction follows first order kinetics with [CAB], positive fractional order dependence on [SBL] and negative fractional order dependence on [HClO4]. Effect of halide ions, added benzenesulphonamide had no effect on the rate of reaction. Variation in ionic strength had no effect on the rate of the reaction indicating that non-ionic species are involved in the rate limiting step. Dielectric effect of the medium showed negative effect. Kinetic parameters were evaluated by studying the reaction at different temperatures. Addition of reaction mixture to aqueous acrylamide did not initiate polymerization showing the absence of free radical species. Oxidation products were identified. TsNHCl of CAB, the reactive oxidant combines with the substrate to give the product. Based on kinetic results, reaction stoichiometry and oxidation products, a suitable mechanism have been proposed.

  10. Low-volume aluminum and aluminum / titanium nitride bilayer lumped-element kinetic inductance detectors for far-infrared astronomy

    Science.gov (United States)

    Glenn, Jason; Fyhrie, Adalyn; Wheeler, Jordan; Day, Peter K.; Eom, Byeong H.; Leduc, Henry G.

    2016-07-01

    We present the design and characterization of low-volume, lumped-element aluminum kinetic inductance de- tectors for sensitive far-infrared astronomy observations. The lumped-element kinetic inductance detectors are comprised of meandered inductors that serve as radiation absorbers in parallel with interdigitated capacitors, forming high quality factor resonators. Low inductor volumes lead to low noise equivalent powers by raising quasiparticles densities, and hence responsivities, with respect to larger volumes. Low volumes are achieved with thin (20 nm), narrow (150 nm) inductors. The interdigitated capacitor architecture is designed to mitigate two-level system noise by lowering electric fields in the silicon substrate. Resonance frequencies are in the range of 190 to 500 MHz, with measured internal quality factors in excess of 1 x 105. In a prior incarnation, a titanium nitride layer on top of the aluminum served as a protective layer, but complicated the superconducting proper- ties. These results were reported previously. In the current incarnation, the aluminum layer is left bare with no titanium nitride over-layer. The results for these bare aluminum devices include a yield of 88%, frequency responsivity of 109 W-1, and noise equivalent power of 1 x 10-17 W Hz-1/2 for a 350μm array. There is no evidence for 1=f noise down to at least 200 mHz. The sensitivity is currently limited by white noise, very likely from stray light in the testbed; for this detector design, sensitivities limited by generation-recombination noise in a lower-background environment should be several orders of magnitude lower.

  11. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal

    Science.gov (United States)

    Kispersky, Vincent Frederick

    adsorbed CO2 proved less competitive for NOx sorption sites, explaining the weak reduction of NSC by CO2 on low Ba loadings. Contrary to CO2, H2O exhibited both beneficial and inhibitory effects on the NSC. Over long periods of time, and at high Ba loadings, the addition of H2O in the feed increased the NSC, attributed to enhanced O2 spillover on the hydroxylated Ba surface allowing greater access to available NOx storage sites. When the Ba loading was reduced, the interaction sphere of Pt particles with the Ba storage component required for O2 to spillover to assist in NOx storage was reduced. Thus, despite the enhanced spillover capacity of oxygen on the hydroxylated storage component other NSC decreasing effects of H2O addition, such as Ba agglomeration, became more dominant and reduced the NSC. Recent developments in selective catalytic reduction have shown Cu and Fe/chabazite (CHA) based zeolites to be particularly well suited to sustaining high catalytic rates without degradation in the harsh environment of diesel engine exhaust. Little has been published about these catalysts as the academic community has just recently learned about the materials and their commercial implementation. Using operando X-ray absorption spectroscopy, combined with first-principles thermodynamics simulations and kinetic analysis, we have studied the nature of the Cu active site on Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-5. Examining the catalysts under operando standard SCR conditions (300 ppm NO, 300 ppm NH3, 5% O2, 5% H2O and 5% CO2) showed the catalyst to be in a mixed Cu(I)-Cu(II) oxidation state. Neither the amount of Cu(I) nor Cu(II) individually correlated with the different rates measured on the various zeolite catalysts, and so we proposed that the SCR reaction progresses via a redox mechanism requiring both Cu(I) and Cu(II). First principles thermodynamic calculations found that the redox couple of Cu(I)H2O and Cu(II)(OH)2 were the most thermodynamically stable species of any of the Ox

  12. The effect of substrate orientation on the kinetics and thermodynamics of initial oxide-film growth on metals

    Energy Technology Data Exchange (ETDEWEB)

    Reichel, Friederike

    2007-11-19

    This thesis addresses the effect of the parent metal-substrate orientation on the thermodynamics and kinetics of ultra-thin oxide-film growth on bare metals upon their exposure to oxygen gas at low temperatures (up to 650 K). A model description has been developed to predict the thermodynamically stable microstructure of a thin oxide film grown on its bare metal substrate as function of the oxidation conditions and the substrate orientation. For Mg and Ni, the critical oxide-film thickness is less than 1 oxide monolayer and therefore the initial development of an amorphous oxide phase on these metal substrates is unlikely. Finally, for Cu and densely packed Cr and Fe metal surfaces, oxide overgrowth is predicted to proceed by the direct formation and growth of a crystalline oxide phase. Further, polished Al single-crystals with {l_brace}111{r_brace}, {l_brace}100{r_brace} and {l_brace}110{r_brace} surface orientations were introduced in an ultra-high vacuum system for specimen processing and analysis. After surface cleaning and annealing, the bare Al substrates have been oxidized by exposure to pure oxygen gas. During the oxidation, the oxide-film growth kinetics has been established by real-time in-situ spectroscopic ellipsometry. After the oxidation, the oxide-film microstructures were investigated by angle-resolved X-ray photoelectron spectroscopy and low energy electron diffraction. Finally, high-resolution transmission electron microscopic analysis was applied to study the microstructure and morphology of the grown oxide films on an atomic scale. (orig.)

  13. Determination of the column hold-up volume in supercritical fluid chromatography using nitrous-oxide.

    Science.gov (United States)

    Vajda, Péter; Guiochon, Georges

    2013-09-27

    This study introduces a new tracer that is useful for the determination of the hold-up time or volume of packed columns, particularly of those used in supercritical fluid chromatography. The thermodynamic void volume of three columns packed with different adsorbents were determined using the weight difference method. These void volumes were used as the reference point in the further discussion. The hold-up volumes of these columns were determined under dynamic conditions, using nitrous oxide dissolved in methanol as the hold-up time marker. Changes in the hold-up volumes of these columns were monitored during changes of the volumetric flow rate of pure supercritical carbon dioxide and of dilute mixtures of organic modifier and supercritical carbon dioxide. The results suggest significant methanol enrichment on the adsorbent surface.

  14. Validation and updating of detailed kinetic mechanisms: The case of ethane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Bonini, F.; Servida, A.; Morbidelli, M.; Carra, S. (Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata)

    1994-11-01

    The authors have investigated experimentally the oxidation of ethane in a perfectly stirred reactor in the temperature range 870--1,080 K and for fuel-air stoichiometric ratio ranging from 0.25 to 1.27. The concentrations of the main molecular species have been measured by probe sampling and GC analysis. These experimental results have been compared with predictions of three popular detailed kinetic mechanisms previously presented in the literature. A reasonable agreement between the experimental results and the model predictions has been found for almost all the species and the mechanisms. The only relevant exception is acetylene, which is greatly overpredicted by one of the mechanisms for all the investigated conditions. Parametric sensitivity analysis has been used for updating such a mechanism in order to improve the agreement with the experimental observations.

  15. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)] anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25—40 ℃. The order of the redox reaction of lactic acid and DDA was found to be first-order. The rates increased with the increase in [OH-] and decreased with the increase in [tellurate]. No free radical was detected. In the view of this the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed, and the rate equation derived from the mechanism can be used to explain all the experimental results. The activation parameters(25 ℃) and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  16. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ)in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHANJin-huan; WANGLi; LIUBao-sheng; SHENShi-gang

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ)species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃)and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  17. Zinc Oxide Hydrogen Sulfide Removal Catalyst/ Preparation, Activity Test and Kinetic Study

    Directory of Open Access Journals (Sweden)

    Ameel. M. Rahman

    2008-01-01

    Full Text Available Hydrogen sulfide removal catalyst was prepared chemically by precipitation of zinc bicarbonate at a controlled pH. The physical and chemical catalyst characterization properties were investigated. The catalyst was tested for its activity in adsorption of H2S using a plant that generates the H2S from naphtha hydrodesulphurization and a unit for the adsorption of H2S. The results comparison between the prepared and commercial catalysts revealed that the chemical method can be used to prepare the catalyst with a very good activity.It has observed that the hydrogen sulfide removal over zinc oxide catalyst follows first order reaction kinetics with activation energy of 19.26 kJ/mole and enthalpy and entropy of activation of 14.49 kJ/mole and -220.41 J/mole respectively.

  18. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    Science.gov (United States)

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.

  19. UNMIXING KINETICS AND ITS MORPHOLOGY OF POLY (ETHYLENE OXIDE) WITH POLYETHERSULPHONES BLENDS

    Institute of Scientific and Technical Information of China (English)

    SONG MO

    1993-01-01

    Unmixing kinetics in a binary polymer mixture of polyethersulphones with poly (ethylene oxide) by spinodal decomposition has been investigated with time-resolved light scattering and microscope methods. The results showed that time evolution of scattered light intensity is of an exponential growth The maximum growth rate R(qm) of phase separation has been obtained. The experimental data did not satisfy the condition that the plot of R(q)/q2 vs q2 should be linear For unmixing system annealing at 30 ℃ for three hours, its morphology manifested dish structure The experimental data of the Bragg spacing, Dm can be correlated with a straight line which expresses the power-law relation, Dm=btα.

  20. Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-01

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

  2. 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.

  3. Dissolution kinetics of macronutrient fertilizers coated with manufactured zinc oxide nanoparticles.

    Science.gov (United States)

    Milani, Narges; McLaughlin, Mike J; Stacey, Samuel P; Kirby, Jason K; Hettiarachchi, Ganga M; Beak, Douglas G; Cornelis, Geert

    2012-04-25

    The solubility of Zn in Zn fertilizers plays an important role in the agronomic effectiveness of the fertilizer. On the basis of thermodynamics, zinc oxide (ZnO) nanoparticles (NPs) should dissolve faster and to a greater extent than bulk ZnO particles (equivalent spherical diameter >100 nm). These novel solubility features of ZnO NPs might be exploited to improve the efficiency of Zn fertilizers. In this study, we compared the Zn solubility and dissolution kinetics of ZnO nanoparticles and bulk ZnO particles coated onto two selected granular macronutrient fertilizers, urea and monoammonium phosphate (MAP). The main Zn species on coated MAP and urea granules were zinc ammonium phosphate and ZnO, respectively. Coated MAP granules showed greater Zn solubility and faster dissolution rates in sand columns compared to coated urea granules, which may be related to pH differences in the solution surrounding the fertilizer granules. The kinetics of Zn dissolution was not affected by the size of the ZnO particles applied for coating of either fertilizer type, possibly because solubility was controlled by formation of the same compounds irrespective of the size of the original ZnO particles used for coating.

  4. Efficient removal of cobalt from aqueous solution by zinc oxide nanoparticles. Kinetic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Khezami, L.; Modwi, A. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Taha, Kamal K. [Al Imam Mohammad Ibn Saud Islamic Univ. (IMSIU), Riyadh (Saudi Arabia). Dept. of Chemistry; Univ. of Bahri, Khartoum (Sudan). College of Applied and Industrial Sciences

    2017-08-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg.g{sup -1} of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  5. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Science.gov (United States)

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

  6. Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

    Directory of Open Access Journals (Sweden)

    J. E. N. Brainer

    2014-12-01

    Full Text Available The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar, in a mechanically agitated slurry reactor (MASR. The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10-4 dm³/mol.

  7. The kinetic studies of direct methane oxidation to methanol in the plasma process

    Institute of Scientific and Technical Information of China (English)

    INDARTO Antonius; CHOI Jae-Wook; LEE Hwaung; SONG Hyung Keun

    2008-01-01

    The research outlined here includes a study of methanol production from direct methane conversion by means of thermal and plasma method. The kinetic study, derived from thermal-based approach, was carried out to investigate thoroughly the possible intermediate species likely to be presented in the process. A set of plasma experiments was undertaken by using dielectric barrier discharge (DBD), classified as non-thermal plasma, done at atmospheric pressure and room temperature. Plasma proc-ess yields more methanol than thermal process at the same methane conversion rates and methane to oxygen feed ratios. Oxidation reaction of thermal process resulted CO and CO2 as the most dominant products and the selectivity reached 19% and 68%, respectively. Moreover, more CO and less CO2 were produced in plasma process than in thermal process. The selectivity of CO and CO2 by plasma was 47% and 20%, respectively. Ethane (C2H6) was detected as the only higher hydrocarbon with a signifi-cant concentration. The concentration of ethane reached 9% of the total products in plasma process and 17% in thermal process. The maximum selectivity of methanol, the target material of this research, was 12% obtained by plasma method and less than 5% by thermal process. In some certain points, the kinetic model closely matched with the experimental results.

  8. Crystalline Grain Interior Configuration Affects Lithium Migration Kinetics in Li-Rich Layered Oxide.

    Science.gov (United States)

    Yu, Haijun; So, Yeong-Gi; Kuwabara, Akihide; Tochigi, Eita; Shibata, Naoya; Kudo, Tetsuichi; Zhou, Haoshen; Ikuhara, Yuichi

    2016-05-11

    The electrode kinetics of Li-ion batteries, which are important for battery utilization in electric vehicles, are affected by the grain size, crystal orientation, and surface structure of electrode materials. However, the kinetic influences of the grain interior structure and element segregation are poorly understood, especially for Li-rich layered oxides with complex crystalline structures and unclear electrochemical phenomena. In this work, cross-sectional thin transmission electron microscopy specimens are "anatomized" from pristine Li1.2Mn0.567Ni0.167Co0.067O2 powders using a new argon ion slicer technique. Utilizing advanced microscopy techniques, the interior configuration of a single grain, multiple monocrystal-like domains, and nickel-segregated domain boundaries are clearly revealed; furthermore, a randomly distributed atomic-resolution Li2MnO3-like with an intergrown LiTMO2 (TM = transitional metals) "twin domain" is demonstrated to exist in each domain. Further theoretical calculations based on the Li2MnO3-like crystal domain boundary model reveal that Li(+) migration in the Li2MnO3-like structure with domain boundaries is sluggish, especially when the nickel is segregated in domain boundaries. Our work uncovers the complex configuration of the crystalline grain interior and provides a conceptual advance in our understanding of the electrochemical performance of several compounds for Li-ion batteries.

  9. Efficient Removal of Cobalt from Aqueous Solution by Zinc Oxide Nanoparticles: Kinetic and Thermodynamic Studies

    Science.gov (United States)

    Khezami, L.; Taha, Kamal K.; Modwi, A.

    2017-05-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg·g-1 of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  10. Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling.

    Science.gov (United States)

    Wu, Lei; Liu, Lin; Gao, Bin; Muñoz-Carpena, Rafael; Zhang, Ming; Chen, Hao; Zhou, Zuhao; Wang, Hao

    2013-12-10

    Although graphene oxide (GO) has been used in many applications to improve human life quality, its environmental fate and behavior are still largely unknown. In this work, a novel approach that combines experimental measurements and theoretical calculations was used to determine the aggregation kinetics of GO sheets in aqueous solutions under different chemistry conditions (e.g., cation valence and pH). Experimental data showed that both cation valence and pH showed significant effect on the aggregation of GO sheets. The measured critical coagulation concentrations were in good agreement with the predictions of the extended Schulze-Hardy rule. Ca(2+) and Mg(2+) were more effective than Na(+) in aggregating the GO sheets, which could be attributed to the cross-linking between GO sheets by the divalent cations through "bridging" the functional groups at the edges of the GO sheets. When solution pH increases, deprotonation of carboxylic groups was found to play a key role in increasing GO sheet stability and surface charge development. These results suggested that edge-to-edge and face-to-face interactions were the dominant modes of GO aggregation in the presence of divalent metal ions and H(+), respectively. A modified attachment efficiency (α) model was developed on the basis of the Maxwell approach with considerations of both primary and secondary minima. The model predictions matched the experimental measurements of the aggregation kinetics of GO sheets in aqueous solutions under all of the tested experimental conditions well.

  11. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

    KAUST Repository

    Zhang, Tao

    2016-05-04

    Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

  12. Modeling Degradation in Solid Oxide Electrolysis Cells - Volume II

    Energy Technology Data Exchange (ETDEWEB)

    Manohar Motwani

    2011-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential,, within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, non-equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  13. KINETICS OF OXIDATION OF SALBUTAMOL BY CHLORAMINE-B IN NaOH MEDIUM: A MECHANISTIC APPROACH

    Directory of Open Access Journals (Sweden)

    Iyengar Pushpa

    2012-04-01

    Full Text Available The kinetics of oxidation of salbutamol (SBL by N-chlorobenzenesulphonamide (CAB in NaOH medium has been investigated at 303K. The reaction rate shows a first order dependence on [CAB]0 , fractional order with respect to [SBL]0 and a negative fractional order with respect to [OH-] . The addition of the reduction product, benzenesulphonamide , retards the reaction rate. The effect of dielectric constant of the medium by varying [MeOH] shows an inverse effect. The addition of chloride ions and variation of ionic strength of the medium have no significant effect on the rate of the reaction. The reaction fails to initiate polymerization of acrylamide. The oxidation products were identified. The Michaelis – Menten type of kinetics has been proposed. The reaction was studied at different temperatures and the values of thermodynamic parameters were computed. A mechanism consistent with the observed kinetics is proposed.

  14. Kinetics and selectivity of the copper-catalysed oxidative coupling of 4-(2 ',6 '-dimethylphenoxyl-2,6-dimethylphenol

    NARCIS (Netherlands)

    Baesjou, PJ; Driessen, WL; Challa, G; Reedijk, J

    1999-01-01

    The kinetics of the copper/N-methylimidazole catalysed oxidative coupling reaction with the C-O coupled dimer of 2,6-dimethylphenol (DMP or monomer), viz. 4-(2',6'-dimethylphenoxy)-2,6-dimethylphenol (dimer), as the substrate have been studied. The reaction was found to obey Michaelis-Menten

  15. 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

  16. The kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane over Li/Na/MgO catalysts

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Toebes, A.; Toebes, A.; van Ommen, J.G.; Seshan, Kulathuiyer; Ross, J.R.H.; Ross, J.R.H.

    1992-01-01

    Kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane catalysed by Li/MgO and Li/Na/MgO have been investigated. Initial rate measurements at 600°C; revealed that the Li/MgO catalyst produced C2H4, CO2, CO and H2 by parallel reactions whereas the sodium-promoted catalyst produced

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

    Science.gov (United States)

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

    2016-11-01

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

  18. Intrinsic kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts

    Institute of Scientific and Technical Information of China (English)

    Benzhen Yao; Jin Chen; Dianhua Liu; Dingye Fang

    2008-01-01

    The intrinsic reaction kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts was studied in the quartz pipe-reactor under ordinary pressure with the temperature ranging from 913.15 to 973.15 K and the space velocity from 700 to 2100 ml/(g-h). The Langmuir-Hinshelwood model was chosen to describe the intrinsic kinetics while Levenberg-Marquardt method was selected to determine the parameters in the kinetic model. Statistical test and residual error distribution diagrams showed that experimental data were in good agreement with calculated data, and Langmuir-Hinshelwood model was suitable for the description of the intrinsic kinetics of methane aromatization under the reaction conditions discussed in this article.

  19. Thermodynamics and kinetics of cadmium adsorption onto oxidized granular activated carbon

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Cadmium sorption behavior of granular activated carbon oxidized with nitric acid was systematically studied by sets of the equilibrium and time-based experiments under various conditions. The cadmium adsorption capacity of oxidized granular activated carbon enlarged with an increase in pH, and reduced with an increase in ionic strength. Experimental data were evaluated to find out kinetic characteristics. Adsorption processes were found to follow pseudo-second order rate equation. Adsorption isotherms correlate well with the Langmuir isotherm model and the maximum sorption capacity of cadmium evaluated is 51.02 μmol/g. Thermodynamic parameters were calculated based on Van't Hoff equation. Equilibrium constant Kd was evaluated from Freundlich isotherm model constants, Langmuir isotherm model constants and isotherms, respectively. The average change of standard adsorption heat ΔHo is -25.29 kJ/mol. Negative ΔHo and ΔGo values indicate the adsorption process for cadmium onto the studied activated carbon is exothermic and spontaneous. The standard entropy ΔSo is also negative, which suggests a decrease in the freedom of the system.

  20. Oxidative degradation of N-Nitrosopyrrolidine by the ozone/UV process: Kinetics and pathways.

    Science.gov (United States)

    Chen, Zhi; Fang, Jingyun; Fan, Chihhao; Shang, Chii

    2016-05-01

    N-Nitrosopyrrolidine (NPYR) is an emerging contaminant in drinking water and wastewater. The degradation kinetics and mechanisms of NPYR degradation by the O3/UV process were investigated and compared with those of UV direct photolysis and ozonation. A synergistic effect of ozone and UV was observed in the degradation of NPYR due to the accelerated production of OH• by ozone photolysis. This effect was more pronounced at higher ozone dosages. The second-order rate constants of NPYR reacting with OH• and ozone was determined to be 1.38 (± 0.05) × 10(9) M(-1) s(-1) and 0.31 (± 0.02) M(-1) s(-1), respectively. The quantum yield by direct UV photolysis was 0.3 (± 0.01). An empirical model using Rct (the ratio of the exposure of OH• to that of ozone) was established for NPYR degradation in treated drinking water and showed that the contributions of direct UV photolysis and OH• oxidation on NPYR degradation were both significant. As the reaction proceeded, the contribution by OH• became less important due to the exhausting of ozone. Nitrate was the major product in the O3/UV process by two possible pathways. One is through the cleavage of nitroso group to form NO• followed by hydrolysis, and the other is the oxidation of the intermediates of amines by ozonation.

  1. Degradation kinetics of peptide-coupled alginates prepared via the periodate oxidation reductive amination route.

    Science.gov (United States)

    Dalheim, Marianne Ø; Ulset, Ann-Sissel T; Jenssen, Ina Beate; Christensen, Bjørn E

    2017-02-10

    Biomaterials based on peptide-coupled alginates must provide both optimal biological environments and tuneable stability/degradation profiles. The present work investigates the degradation pattern and kinetics of peptide-coupled alginates prepared via the periodate oxidation reductive amination route. Alginates degrade slowly (non-enzymatically) under physiological conditions by acid-catalysed hydrolysis and alkali-catalysed β-elimination, both operating simultaneously but dominated by the latter. While periodate oxidation alone largely increases the rate of β-elimination, substitution restores the susceptibility towards β-elimination to that of the parent alginate. For acid hydrolysis the rate of depolymerization is proportional to the degree of substitution, being approximately one order of magnitude larger than the parent alginate, but still lower than for the corresponding materials with fully reduced dialdehydes. Results also suggest a composition-dependent preference for substitution at C2 or C3. These results demonstrate how the various chemistries introduced by the coupling provide useful means to tune the biodegradability profiles.

  2. Kinetics of Wet Air Oxidation of Wastewater from Natural Fiber Web Desizing

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    This work described the application of wet air oxidation (WAO) to the treatment of desizing wastewater from natural fiber processing. A two-liter autoclave batch reactor was used for the experiments. The range of operating temperature examined was between 150 and 290℃, and partial pressure of oxygen ranged from 0.375 to 2.25 MPa standardized at 25℃. Variations in Chemical Oxygen Demand(COD) and Total Organic Carbon(TOC) were monitored during each experiment and used to assess the performance of the process. Experimental results showed that WAO can be an efficient method for the treatment of desizing wnstewater. Furthermore, Catalytic Wet Air Oxidation (CWAO) was applied to reduce the reaction temperature and pressure in WAO process. A higher COD removal ratio was achieved under more mild reaction condition with the aid of CWAO. A mathematical model was also proposed to simulate the WAO process of desizing wastewater, in which three distinct kinetics steps were considered to describe the degradation of starch. The model simulations were in well agreement with the experimental data.

  3. Large pore volume mesoporous aluminum oxide synthesized via nano-assembly

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A new nano-assembly approach has been proposed for the preparation of macropore volume mesoporous aluminum oxide supports. Secondary nano-assembly and a frame structure mechanism for large pore volume mesoporous supports have been proposed. In a primary nano-assembly supersoluble micelle,aluminum hydroxide nanoparticles were precipitated in situ in surfactants with a volume balance (VB) less than 1,followed by secondary nano-assembly in linear and cylindrical shapes. The secondary nano-assembly of cylindrical aluminum hydroxides was calcined to form nano cylindrical aluminum oxides. For the formation of macropore volume mesoporous supports,we utilized a frame structure mechanism of mesoporous support,in which the exterior surface of the carrier may not be continuous. This macropore volume support has been used for the hydrotreatment of a residual oil catalyst,which possesses the following physical characteristics:pore volume 1.8―2.7 mL·g-1,specific surface area 180―429 m2·g-1,average pore diameter 17―57 nm,average pore diameter more than 10 nm (81%―94%),porosity 87%―93%,and crush strength 7.7―25 N·mm-1.

  4. Kinetic parameter determination of roasted and unroasted argan oil oxidation under Rancimat test conditions

    Directory of Open Access Journals (Sweden)

    Zaanoun, I.

    2014-09-01

    Full Text Available The present study investigated the Kinetic parameter determination of edible argan oil (coldpressed from roasted argan kernels and cosmetic argan oil (cold-pressed from unroasted argan kernels under the Rancimat test conditions. The physicochemical parameters of edible and cosmetic argan oil immediately after preparation and after accelerated oxidation test Rancimat at different temperatures 90 °C, 100 °C, 110 °C, 120 °C, 130 °C and 140 °C were determined and compared. The natural logarithms of the kinetic rate constant (kvalue varied linearly with respect to temperature. An increasing rate of oxidation could be observed as temperature increased. On the basis of the Arrhenius equation and the activated complex theory, frequency factors A, activation energies Ea, Q10 numbers, activation enthalpies ΔH, and activation entropies ΔS for oxidative stability of the vegetable oils were calculated. The accelerated oxidation and Kinetic parameters have shown that edible argan oil can be stored much better than cosmetic oil.En presente estudio se determinaron los parámetros cinéticosde aceites de argán comestible (prensado en frío a partir de granos tostados de argán y cosmético (prensado en frío a partir de granos de argán sin tostar bajo las condiciones del método Rancimat. Se determinó y comparó los parámetros físico-químicos de aceites de argán comestible y cosmético inmediatamente después de la preparación y después de la oxidación acelerada mediante Rancimat a temperaturas de 90 °C, 100 °C, 110 °C, 120 °C, 130 °C y 140 °C Los logaritmos naturales de la constante de velocidad cinética (valor k variaron linealmente con respecto a la temperatura. Se pudo observar un valor creciente de la oxidación conel aumento de la temperatura. Se calculó para la estabilidad oxidativa de los aceites vegetalesy sobre la base de la ecuación de Arrhenius y la teoría del complejo activado, la frecuencia de los factores A, energ

  5. Kinetics of Direct Oxidation of H2S in Coal Gas to Elemental Sulfur

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2005-11-01

    kinetics of direct oxidation of H{sub 2}S to elemental sulfur in the presence of a simulated coal gas mixture containing SO{sub 2}, H{sub 2}, and moisture, using 160-{micro}m C-500-04 alumina catalyst particles and 400 square cells/inch{sup 2}, {gamma}-Al{sub 2}O{sub 3}-wash-coated monolithic catalyst, and various reactors such as a micro packed-bed reactor, a micro bubble reactor, and a monolithic catalyst reactor, and to develop kinetic rate equations and model the direct oxidation process to assist in the design of large-scale plants. This heterogeneous catalytic reaction has gaseous reactants such as H{sub 2}S and SO{sub 2}. However, this heterogeneous catalytic reaction has heterogeneous products such as liquid elemental sulfur and steam.

  6. 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.

  7. Application of normal pulse voltammetry to the kinetic study of formic acid oxidation on a carbon supported Pd electrocatalyst

    Science.gov (United States)

    Wang, Yujiao; Wu, Xiaochen; Wu, Bing; Gao, Ying

    The kinetic parameters of formic acid oxidation on a carbon supported Pd electrode, such as the charge transfer coefficient (α) and apparent diffusion coefficient (D) are obtained by applying the technique of normal pulse voltammetry. The standard rate constant (k 0) of formic acid oxidation on a Pd/C electrode is estimated. The results show that formic acid oxidation is more sensitive to temperature at relatively high potential because the activation energy is significantly increased as the potential rose above 0.6 V.

  8. Kinetic analysis of the role of histidine chloramines in hypochlorous acid mediated protein oxidation.

    Science.gov (United States)

    Pattison, David I; Davies, Michael J

    2005-05-17

    Hypochlorous acid (HOCl) is a powerful oxidant generated from H(2)O(2) and chloride ions by the heme enzyme myeloperoxidase (MPO) released from activated leukocytes. In addition to its potent antibacterial effects, excessive HOCl production can lead to host tissue damage, with this implicated in human diseases such as atherosclerosis, cystic fibrosis, and arthritis. HOCl reacts rapidly with biological materials, with proteins being major targets. Chlorinated amines (chloramines) formed from Lys and His side chains and alpha-amino groups on proteins are major products of these reactions; these materials are however also oxidants and can undergo further reactions. In this study, the kinetics of reaction of His side-chain chloramines with other protein components have been investigated by UV/visible spectroscopy and stopped flow methods at pH 7.4 and 22 degrees C, using the chloramines of the model compound 4-imidazoleacetic acid and N-alpha-acetyl-histidine. The second-order rate constants decrease in a similar order (Cys > Met > disulfide bonds > Trp approximately alpha-amino > Lys > Tyr > backbone amides > Arg) to the corresponding reactions of HOCl, but are typically 5-25 times slower. These rate constants are consistent with His side-chain chloramines being important secondary oxidants in HOCl-mediated damage. These studies suggest that formation and subsequent reactions of His side-chain chloramines may be responsible for the targeted secondary modification of selected protein residues by HOCl that has previously been observed experimentally and highlight the importance of chloramine structure on their subsequent reactivity.

  9. Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway.

    Science.gov (United States)

    Yang, Xiaoling; Huang, Jun; Zhang, Kunlun; Yu, Gang; Deng, Shubo; Wang, Bin

    2014-03-01

    Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H2O2), alkaline ozonation (O3, pH = 11), peroxone (O3/H2O2), and Fenton reagent oxidation (Fe(2+)/H2O2). UV/H2O2 was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C7 to C2), while sulfate (SO4 (2-)) and fluoride (F(-)) were found to be the final products. The high yields of SO4 (2-) and F(-) indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H2O2 condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential "flake off" of CF2 unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.

  10. Sulfate radical-based oxidation of fluoroquinolone antibiotics: Kinetics, mechanisms and effects of natural water matrices.

    Science.gov (United States)

    Jiang, Canlan; Ji, Yuefei; Shi, Yuanyuan; Chen, Jifei; Cai, Tianming

    2016-12-01

    Widespread occurrence of fluoroquinolone antibiotics (FQs) in surface water, groundwater, soil and sediment has been reported and their remediation is essentially needed. Sulfate radical (SO4(-)) based advanced oxidation processes (SR-AOPs) are promising technologies for soil and groundwater remediation. In this study, the degradation kinetics, mechanisms, and effects of natural water matrices on heat-activated persulfate (PS) oxidation of FQs were systematically investigated. Experimental results clearly demonstrated that 92% of CIP was removed within 180 min (pH = 7, 60 °C). Higher temperature and lower pH facilitated the degradation of ciprofloxacin (CIP). The piperazine moiety of CIP was identified as the reactive site for SO4(-) attack by comparison with substructural analogs, flumequine (FLU) and 1-(2-fluorophenyl) piperazine (FPP). A comparison of the degradation of CIP, norfloxacin (NOR), enrofloxacin (ENR) and ofloxacin (OFL) confirmed that the presence of cyclopropane ring also influence the degradation of FQs. Water matrix significantly influenced the degradation of CIP and ENR, and the degradation rate followed the order of Milli-Q water (pH = 7) > groundwater > artificial seawater > artificial surface water > lake water. Degradation products of CIP in different water matrix were enriched by solid phase extraction (SPE) and then analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). Detailed transformation pathways of CIP were proposed and were compared with respect to different water matrices. Four transformation pathways including stepwise piperazine ring oxidation, OH/F substitution, hydroxylation, and cyclopropane ring cleavage were proposed for CIP degradation. Results clearly show that the water matrix influenced the degradation of FQs appreciably, a phenomenon that should be taken into consideration when applying SR-AOPs for remediation of soil and groundwater contaminated by

  11. Kinetics and mechanism of the oxidation of some vicinal and non-vicinal diols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Jaya Gosain; Pradeep K Sharma

    2003-04-01

    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 respect to TBATB. Michaelis-Menten type kinetics is observed with respect to diols. The reaction fails to induce the polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The oxidation of [1,1,2,2-2H4] ethanediol shows the absence of any primary kinetic isotope effect. Values of solvent isotope effect, (H2O)/(D2O), at 288 K for the oxidation of ethanediol, propane-1,3-diol and 3-methoxybutan-1-ol are 3.41, 0.98 and 1.02 respectively. A mechanism involving a glycol-bond fission has been proposed for the oxidation of vicinal diols. Non-vicinal diols are oxidised by a hydride-transfer mechanism, as they are monohydric alcohols.

  12. Oxidation of aliphatic alcohols by triethylammonium chlorochromate in non-aqueous medium – A kinetic and mechanistic study

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2014-07-01

    Full Text Available The oxidation of some aliphatic alcohols by triethylammonium chlorochromate (TriEACC in dimethyl sulfoxide leads to the formation of the corresponding carbonyl compounds. The reaction is first order with respect to TriEACC. The reaction exhibited Michaelis–Menten type kinetics with respect to alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a + b[H+]. The oxidation of [1,1-2H2] ethanol (MeCD2OH exhibits a substantial primary kinetic isotope effect. Oxidation of aliphatic alcohol was studied in 19 different organic solvents. The solvent effect has been analysed using Kamlet’s and Swain’s multi-parametric equation. A suitable mechanism has been proposed.

  13. Kinetics and Mechanism of Oxidation of Phenyl Acetic Acid and Dl-Mandelic Acid by Permanganate in Acid Medium

    Directory of Open Access Journals (Sweden)

    B.Syama Sundar

    2014-06-01

    Full Text Available Kinetics of oxidation of phenyl acetic acid and DL- Mandelic acid by potassium permanganate in aqueous acetic acid and perchloric acid mixture reveals that the kinetic orders are first order in oxidant, first order in H+ and zero order in substrate for phenyl acetic acid. DL-Mandelic acid exhibits first order in oxidant and zero order in substrate. The results are rationalised by a mechanism involving intermediate formation of mandelic acid in case of Phenyl acetic acid and ester formation with Mn (VII in case of DL-Mandelic acid. The following order of reactivity is observed: DL-Mandelic acid > Phenyl acetic acid. The high reactivity of DL-Mandelic acid over phenyl acetic acid may be due to different mechanisms operating with the two substrates and benzaldehyde is the final product in both the cases.

  14. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    K.C. Kwon

    2003-01-01

    The direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The objective of this research is to support the near- and long-term DOE efforts to commercialize this direct oxidation technology. The objectives of this research are to measure kinetics of direct oxidation of H{sub 2}S to elemental sulfur in the presence of a simulated coal gas mixture containing SO{sub 2}, H{sub 2}, and moisture, using 60-{micro}m C-500-04 alumina catalyst particles and a PFA differential fixed-bed micro reactor, and to develop kinetic rate equations and model the direct oxidation process to assist in the design of large-scale plants. To achieve the above-mentioned objectives, experiments on conversion of hydrogen sulfide into elemental sulfur were carried out for the space time range of 0.01-0.047 seconds at 125-155 C to evaluate effects of reaction temperatures, moisture concentrations, reaction pressures on conversion of hydrogen sulfide into elemental sulfur. Simulated coal gas mixtures consist of 61-89 v% hydrogen, 2,300-9,200-ppmv hydrogen sulfide, 1,600-4,900 ppmv sulfur dioxide, and 2.6-13.7 vol % moisture, and nitrogen as remainder. Volumetric feed rates of a simulated coal gas mixture to the reactor are 100-110 cm{sup 3}/min at room temperature and atmospheric pressure (SCCM). The temperature of the reactor is controlled in an oven at 125-155 C. The pressure of the reactor is maintained at 28-127 psia. The following results were obtained based on experimental data generated from the differential reactor system, and their interpretations, (1) Concentration of moisture and concentrations of both H{sub 2}S and SO{sub 2} appear to affect slightly reaction

  15. Photoelectrocatalytic/photoelectro-Fenton coupling system using a nanostructured photoanode for the oxidation of a textile dye: Kinetics study and oxidation pathway.

    Science.gov (United States)

    Almeida, Lucio C; Silva, Bianca F; Zanoni, Maria V B

    2015-10-01

    In this study, a coupled photoelectrocatalytic/photoelectro-Fenton reactor was designed to enhance the degradation efficiency of organic pollutants and tested using the azo dye Orange G as a model compound. Pt-decorated TiO2 nanotubes were used as a photoanode with an air-diffusion polytetrafluoroethylene cathode for H2O2 generation. The sum of individual effects of coupling the photoelectrocatalytic and photoelectro-Fenton processes was evaluated as a function of the decolorization and mineralization of Orange G solutions. The dye solutions were only completely decolorized in more acidic conditions (pH 3.0). The mineralization of the Orange G solutions increased in the sequence photoelectrocatalyticproduction of OH radicals. Total organic carbon reductions of 80% for photoelectrocatalysis, 87% for electro-Fenton and 97% for the coupled processes were obtained when using an applied electric charge per unit volume of electrolyzed solution of 200 mA h L(-1). The Orange G decays for all treatments followed pseudo-first-order kinetics, suggesting the attack of a constant concentration of OH radicals. Aromatics such as naphthalenic and benzenic compounds were formed as by-products and were identified using LC-MS/MS analysis. In addition, the generated aliphatic acids were identified using ion-exclusion high-performance liquid chromatography. The final by-products of oxalic and formic acid were identified as ultimate by-products and formed Fe(III) complexes that were rapidly mineralized to CO2 by UV-Vis irradiation. Then, according to the identified oxidation by-products, a plausible pathway was proposed for the degradation of Orange G dye by the coupled process.

  16. Comparison and Parametric Study of Flameless Oxidation in a Gas Turbine Using Two Kinetics Mechanisms

    Directory of Open Access Journals (Sweden)

    Mohamed Hamdi

    2008-01-01

    Full Text Available The so-called “Flameless Oxidation” is a novel combustion mode, in which combustion products are re-circulated and mixed into the fresh incoming fuel and air streams. This reduces the concentration of the reactants and thereby reducing the reaction rate through avoiding the formation of sharp high temperature zones in the combustion chamber. Flameless combustion has been acknowledged as one of the most interesting combustion technologies to meet both the targets of high energy efficiency and low pollutant emissions. This technology has already been successfully applied and exploited in industrial burners. The present investigation is concerned with the application of the flameless combustion mode to an adiabatic combustor, typically used in gas turbine engines. Detailed chemical kinetics calculations, by means of a specific zero-dimensional loop reactor model, have been performed to analyze its chemical aspects. The model simulates the combustor by a number of reactors that represent different zones in the combustion chamber. The main objective of this study is to increase the understanding of NOx formation from flameless mode, where currently very few experimental data are available. The investigation is focused on a comparison of the influence of pressure, residence time and temperature on the NOx and CO emissions, using two reaction mechanisms of the C/H/O/N system: the Miller-Bowman mechanism and the GRI_MECH3.0 mechanism. Simulation results clearly illustrate that even at high operating temperatures and pressures, NOx emissions could be reduced by flameless combustion to very low levels. A comparison between the predictions obtained by using the two chemical kinetics mechanisms is presented and discussed. It is shown that the predictions of the Miller-Bowman mechanism deviate from the predictions of the GRI3.0 mechanism in many aspects, especially as related to NOx emission results.

  17. Chlorine dioxide oxidation of Escherichia coli in water - A study of the disinfection kinetics and mechanism.

    Science.gov (United States)

    Ofori, Isaac; Maddila, Suresh; Lin, Johnson; Jonnalagadda, Sreekantha B

    2017-06-07

    This study investigated the kinetics and mechanism of chlorine dioxide (ClO2) inactivation of a Gram-negative bacteria Escherichia coli (ATCC 35218) in oxidant demand free (ODF) water in detail as a function of disinfectant concentration (0.5-5.0 mg/L), water pH (6.5-8.5), temperature variations (4-37°C) and bacterial density (10(5)-10(7) cfu/mL). The effects of ClO2 on bacterial cell morphology, outer membrane permeability, cytoplasmic membrane disruption and intracellular enzymatic activity were also studied to elucidate the mechanism of action on the cells. Increasing temperature and disinfectant concentration were proportional to the rate of cell killing, but efficacy was found to be significantly subdued at 0.5 mg/L and less dependent on the bacterial density. The bactericidal efficiency was higher at alkaline pH of 8 or above as compared to neutral and slightly acidic pH of 7 and 6.5 respectively. The disinfection kinetic curves followed a biphasic pattern of rapid inactivation within the initial 2 min which were followed by a tailing even in the presence of residual biocide. The curves were adequately described by the Cavg Hom model. Transmission Electron Microscopy images of the bacteria cells exposed to lethal concentrations of ClO2 indicated very little observable morphological damage to the outer membranes of the cells. ClO2 however was found to increase the permeability of the outer and cytoplasmic membranes leading to the leakage of membrane components such as 260 nm absorbing materials and inhibiting the activity of the intracellular enzyme β-D-galactosidase. It is suggested that the disruption of the cytoplasmic membrane and subsequent efflux of intracellular components result in the inactivation of the Gram-negative bacteria.

  18. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    Science.gov (United States)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  19. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    Energy Technology Data Exchange (ETDEWEB)

    O' Day, Peggy A. [Univ. of California, Merced, CA (United States); Asta, Maria P. [Univ. of California, Merced, CA (United States); Kanematsu, Masakazu [Univ. of California, Merced, CA (United States); Beller, Harry [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhou, Peng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Steefel, Carl [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  20. Kinetics of carbon dioxide formation during catalytic oxidation of p-Xylene and of the products of its conversion

    Energy Technology Data Exchange (ETDEWEB)

    Ariko, N.G.; Mitskevich, M.I.; Samtsevich, V.S.

    1985-10-01

    In order to establish the routes of CO/sub 2/ formation, the authors studied the kinetics of decarboxylation in the course of oxidation of p-xylene, p-tolualdehyde, p-methylbenzyl alcohol, and p-toluic acid at various catalyst and substrate concentration. When p-xylene was oxidized in solutions of labeled acetic acid, most (greater than 80%) of the carbon dioxide evolved during oxidation of p-xylene is formed from the solvent. Some results are presented from experiments on oxidation of p-methylbenzyl alcohol and p-toluic acid. The decarboxylation rates in these reactions are comparable with the values of /SUP W/ CO/sub 2/ during oxidation of p-xylene. The week dependence of the induction factor on the substrate concentration indicates that in these systems, as in the case of p-xylene, acetic acid is the main source of CO/sub 2/.

  1. Kinetics of Oxidation of L-Leucine by Mono-and Bimetallic Gold and Silver Nanoparticles in Hydrogen Peroxide Solution

    Institute of Scientific and Technical Information of China (English)

    P.VENKATESAN; J.SANTHANALAKSHMI

    2012-01-01

    The catalytic activity of surfactant stabilized mono- and bimetallic Au and Ag nanoparticles for the oxidation of an amino acid,L-leucine,was studied using hydrogen peroxide as the oxidant.The Au and Ag nanoparticle catalysts exhibited very good catalytic activity and the kinetics of the reaction were found to be pseudo-first order with respect to the amino acid.The effects of several factors,such as oxidant concentration,ionic strength,pH,and catalyst concentration on the reaction,were also investigated.In particular,optimal oxidant and catalyst concentrations were determined.Very high concentrations of the metal nano-catalysts or the oxidant led to a dramatic increase in reaction rate.Moreover,bimetallic Au-Ag catalysts provided higher selectivity than pure Au or Ag.

  2. Mechanistic and kinetic analysis of the oxidative dehydrogenation of ethane via novel supported alkali chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Universitaet Muenchen (Germany). Catalysis Research Center

    2013-11-01

    The oxidative dehydrogenation of ethane over advanced catalysts is promising to selectively produce ethylene, an essential building block for the chemical industry. In this way, ethane from shale gas can be efficiently valorized. Supported alkali chloride catalysts are investigated in this work. Essential feature of those materials is the presence of a solid core (magnesium oxide in part doped with Dy{sub 2}O{sub 3}) covered under reaction conditions with a molten alkali chloride shell. It is shown that especially the lowered melting point of eutectic mixtures of LiCl with other alkali/alkaline earth metals is the key to taylor highly efficient materials. Elucidating the ODH reaction mechanism is essential to understand the reactivity of this novel catalyst class and provides the basis for improving performances. Information about elementary steps and the rate determining step were extracted from kinetic measurements, both in steady state and in transient configuration. Furthermore, isotopic labelling studies were performed, i.e. SSITKA studies and temperature programmed isotopic exchange experiments. Step experiments showed a significant oxygen uptake by the catalysts. Retained oxygen reacted quantitatively with ethane at nearly 100% selectivity to ethylene and conversion rates were comparable with rates observed during steady state operation. Thus, chemically bound oxygen in the melt is the active and selective intermediate in the ODH. Therefore, it is required to consider an intermediate and the activation is concluded to relate to the oxygen dissociation. The total concentration of stored oxygen can be correlated to the steady-state activity, while the viscosity of the melts mainly influences the selectivity towards ethene. Properties of the solid core impact on the catalyst efficiency suggesting that the oxygen species forms at the interface between support and overlayer. The quantity of retained oxygen additionally depends on the properties of the chloride

  3. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms.

    Directory of Open Access Journals (Sweden)

    Desirée Villahermosa

    Full Text Available Nitrate decreases sulfide release in wastewater treatment plants (WWTP, but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm showed low sulfide production (0.31 μmol cm-3 h-1 and oxygen consumption rates (0.01 μmol cm-3 h-1. The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1. Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB. This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1 an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2 a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR

  4. Comparative dissolution kinetics of biogenic and chemogenic uraninite under oxidizing conditions in the presence of carbonate

    Science.gov (United States)

    Ulrich, Kai-Uwe; Ilton, Eugene S.; Veeramani, Harish; Sharp, Jonathan O.; Bernier-Latmani, Rizlan; Schofield, Eleanor J.; Bargar, John R.; Giammar, Daniel E.

    2009-10-01

    The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO 2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ˜10 -8 M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO 2.0 to UO 2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO 2.25 (U 4O 9) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested

  5. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

    Science.gov (United States)

    Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

    2016-01-01

    Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

  6. Difference in kinematics and kinetics between high- and low-velocity resistance loading equated by volume: implications for hypertrophy training.

    Science.gov (United States)

    Mohamad, Nur Ikhwan; Cronin, John B; Nosaka, Ken K

    2012-01-01

    Although it is generally accepted that a high load is necessary for muscle hypertrophy, it is possible that a low load with a high velocity results in greater kinematics and kinetics than does a high load with a slow velocity. The purpose of this study was to determine if 2 training loads (35 and 70% 1 repetition maximum [1RM]) equated by volume, differed in terms of their session kinematic and kinetic characteristics. Twelve subjects were recruited in this acute randomized within-subject crossover design study. Two bouts of a half-squat exercise were performed 1 week apart, one with high load-low velocity (HLLV = 3 sets of 12 reps at 70% 1RM) and the other with low-load high-velocity (LLHV = 6 sets of 12 reps at 35% 1RM). Time under tension (TUT), average force, peak force (PF), average power (AP), peak power (PP), work (TW), and total impulse (TI) were calculated and compared between loads for the eccentric and concentric phases. For average eccentric and concentric single repetition values, significantly (p eccentric and concentric TUT, PF, AP, PP, and TW. The only variable that was significantly greater for the HLLV protocol than for the LLHV protocol was TI (∼20-24%). From these results, it seems that the LLHV protocol may offer an equal if not better training stimulus for muscular adaptation than the HLLV protocol, because of the greater time under tension, power, force, and work output when the total volume of the exercise is equated.

  7. A Kinetically Mechanistic Investigation of Oxidation of 1,4-Butanediamine by Ag(Ⅲ)Complex in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SONG,Changying; SHAN,Jinhuan; Shen,Shigang; Sun,Hanwen

    2009-01-01

    Kinetics and mechanism of oxidation of 1,4-butanediamine by a Ag (Ⅲ)complex were studied spectropho-tometrically in alkaline medium at constant ion strength. The reaction shows first order with respect to the Ag(Ⅲ)complex and 1,4.butanediamine respectively. The second order rate constant,k`:increased with the increasing in[OH-],and decreased with the increasing in[IO4-4].A plausible mechanism was proposed from the kinetics study.The rate equations derived from the mechanism Can explain all experimental phenomena. The activation parameters were calculated.

  8. Kinetics and Mechanism of Oxidation of Leucine and Alanine by Ag(III Complex in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Changying Song

    2008-01-01

    Full Text Available Kinetics and mechanism of oxidation of leucine and alanine by Ag(III complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III complex and amino acids (leucine, alanine. The second-order rate constant, k−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.

  9. Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II

    Directory of Open Access Journals (Sweden)

    Basim H. Asghar

    2016-09-01

    Full Text Available The kinetics of permanganate oxidation of two substituted azinylformamidines (Azn-Fs, namely N,N-dimethyl-N′-(pyridin-2-ylformamidine (Py and N,N-dimethyl-N′-(pyrimidin-2-ylformamidine (Pym, in sulfuric acid were investigated using conventional spectrophotometry. Kinetic evidence for the formation of 1:1 intermediate complexes between the oxidant and substrates was obtained. The reactions of both substrates with permanganate showed similar kinetics, i.e. first order in [MnO4−]0 and fractional-first-order with respect to both [Azn-F]0 and [H+]. The initial product, Mn2+, was found to autocatalyze the oxidation process. Changes in the ionic strength and dielectric constant of the medium had no significant effect on the rate. The final oxidation products of Py and Pym were identified as 2-aminopyridine and 2-aminopyrimidine, respectively, in addition to dimethylamine and carbon dioxide. A plausible reaction mechanism is suggested and the reaction constants involved in the mechanism were evaluated.

  10. Optical and kinetics studies of titanium-zinc-niobium-tellurim oxides glass

    Science.gov (United States)

    Yousef, E.; Al-Salami, A. E.; Salem, A.; Shaaban, E. R.

    2011-01-01

    Glass of composition 75TeO2/15ZnO2/5Nb2O5/5TiO2 (mol.%) was made by the conventional melting and quenching process. The different physical properties, namely optical and thermal properties such as the density, molar volume, refractive index, third-order nonlinear susceptibility, polarizability, molar refraction, energy gap, metallization, glass transition temperature, activation energy of glass transition and activation energy of crystallization, of this glass were carefully investigated. The values of experimental nonlinear refractive index were determined by using degenerate four-wave mixing. In addition, the kinetics of crystallization of the prepared glass was studied under nonisothermal conditions by applying differential thermal analysis measurements carried out at different heating rates. Finally, the phases at which the glassy alloy crystallizes after the thermal process were identified by x-ray diffraction. The diffractogram of the transformed material indicates the presence of microcrystallites of TiTe3O8 and Zn3TeO6 in tempered glass at different annealing temperatures.

  11. Influence of Yttrium Ion-implantation on Oxidation Kinetics of Co-40Cr Alloy and Property of Oxide/Substrate Interface

    Institute of Scientific and Technical Information of China (English)

    JIN Huiming; WU Dan; FELIX Congrado; AROYAVE Hayara

    2007-01-01

    The isothermal and cyclic oxidizing kinetics of Co-40Cr alloy and its yttrium ion-implanted samples were studied at 1000℃ in air by thermal-gravity analysis (TGA). Scanning electronic microscopy (SEM) was used to examine the Cr2O3 oxide film's morphology after oxidation. Secondary ion mass spectroscopy (SIMS) method was used to examine the binding energy change of chromium caused by yttrium doping. Acoustic emission (AE) method was used in situ to monitor the cracking and spalling of oxide films formed on both samples during oxidizing and subsequent air-cooling stages. It is found that yttrium implantation remarkably reduces the isothermal oxidizing rate of Co-40Cr and improves the anti-cracking and anti-spalling properties of Cr2O3 oxide film. The reasons for the improvements are mainly that implanted yttrium reduces the grain size of Cr2O3 oxide, increases the high temperature plasticity of oxide film, and remarkably reduces the number and size of Cr2O3/Co-40Cr interfacial defects.

  12. 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.)

  13. Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

    Science.gov (United States)

    Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

    2015-01-21

    The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

  14. 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

    2015-11-01

    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

  15. Modeling aerosol surface chemistry and gas-particle interaction kinetics with K2-SURF: PAH oxidation

    Science.gov (United States)

    Shiraiwa, M.; Garland, R.; Pöschl, U.

    2009-04-01

    Atmospheric aerosols are ubiquitous in the atmosphere. They have the ability to impact cloud properties, radiative balance and provide surfaces for heterogeneous reactions. The uptake of gaseous species on aerosol surfaces impacts both the aerosol particles and the atmospheric budget of trace gases. These subsequent changes to the aerosol can in turn impact the aerosol chemical and physical properties. However, this uptake, as well as the impact on the aerosol, is not fully understood. This uncertainty is due not only to limited measurement data, but also a dearth of comprehensive and applicable modeling formalizations used for the analysis, interpretation and description of these heterogeneous processes. Without a common model framework, comparing and extrapolating experimental data is difficult. In this study, a novel kinetic surface model (K2-SURF) [Ammann & Pöschl, 2007; Pöschl et al., 2007] was used to describe the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs). Integrated into this consistent and universally applicable kinetic and thermodynamic process model are the concepts, terminologies and mathematical formalizations essential to the description of atmospherically relevant physicochemical processes involving organic and mixed organic-inorganic aerosols. Within this process model framework, a detailed master mechanism, simplified mechanism and parameterizations of atmospheric aerosol chemistry are being developed and integrated in analogy to existing mechanisms and parameterizations of atmospheric gas-phase chemistry. One of the key aspects to this model is the defining of a clear distinction between various layers of the particle and surrounding gas phase. The processes occurring at each layer can be fully described using known fluxes and kinetic parameters. Using this system there is a clear separation of gas phase, gas-surface and surface bulk transport and reactions. The partitioning of compounds can be calculated using the flux

  16. UV spectra and OH-oxidation kinetics of gaseous phase morpholinic compounds

    KAUST Repository

    Rachidi, Mariam El

    2014-05-01

    This paper presents an experimental study of the UV spectra as well as the kinetics of gaseous phase OH-oxidation of morpholine, N-formylmorpholine (NFM) and N-acetlymorpholine (NAM). The spectra recorded using a UV spectrometer in the spectral range 200-280nm show that the analytes mainly absorb at wavelengths less than 280nm. This indicates that their photolysis potential in the troposphere is insignificant. Meanwhile, the OH-reactivity of these analytes was studied using a triple-jacket 2m long reactor equipped with a multi-reflection system and coupled to an FTIR spectrometer. The experiments were carried out at 295 and 313K for the amine and amides, respectively. The study was conducted in the relative mode using isoprene and benzaldehyde as reference compounds. The rate constants obtained are 14.0±1.9, 4.0±1.1 and 3.8±1.0 (in units of 10-11cm3molecule-1s-1) for morpholine, NFM and NAM respectively. These results are discussed in terms of reactivity and compared to those obtained for other oxy-nitrogenated species. In addition, the determined rate constants are used to estimate effective atmospheric lifetimes of the investigated morpholinic compounds with respect to reaction with OH radicals. © 2014 Elsevier Ltd.

  17. Removal of microcystin-LR and microcystin-RR by graphene oxide: adsorption and kinetic experiments.

    Science.gov (United States)

    Pavagadhi, Shruti; Tang, Ai Ling Lena; Sathishkumar, Muthuswamy; Loh, Kian Ping; Balasubramanian, Rajasekhar

    2013-09-01

    Graphene oxide (GO) was employed in the present study for removal of two commonly occurring algal toxins, microcystin-LR (MC-LR) and microcystin-RR (MC-RR), from water. The adsorption performance of GO was compared to that of commercially available activated carbon. Further, adsorption experiments were conducted in the presence of other environmental pollutants to understand the matrix effects of contaminated water on the selective adsorption of MC-LR and MC-RR onto GO. The environmental pollutants addressed in this study included different anions (nitrate NO3-, nitrite NO2-, sulphate SO4(2-), chloride (Cl(-)), phosphate PO4(3-) and fluoride (F(-))) and cations (sodium (Na(+)), potassium (K(+)), magnesium (Mg(2+)) and calcium (Ca(2+))). GO showed very a high adsorption capacity of 1700 μg/g for removal of MC-LR and 1878 μg/g for MC-RR while the maximum adsorption capacity obtained with the commercial activated carbon was 1481.7 μg/g and 1034.1 μg/g for MC-LR and MC-RR, respectively. The sorption kinetic experiments revealed that more than 90% removal of both MC-LR/RR was achieved within 5 min for all the doses studied (500, 700 and 900 μg/L). GO could be reused as an adsorbent following ten cycles of adsorption/desorption with no significant loss in its adsorption capacity.

  18. The influence of particle size on the kinetics of UO 2 oxidation in aqueous powder suspensions

    Science.gov (United States)

    Roth, Olivia; Bönnemark, Tobias; Jonsson, Mats

    2006-07-01

    Previous studies have indicated that the rate of a heterogeneous liquid-solid reaction depends on the size of the solid particles. It has been suggested that both the pre-exponential factor and the activation energy depend on the particle size. The processes involved in dissolution of UO 2 have been extensively studied because of their importance for the safety analysis of a future deep repository for spent nuclear fuel and in many of these studies powder suspensions of UO 2 are used as a model system. Therefore, it is of importance to investigate and quantify the particle size effect on the kinetics of UO 2 oxidation in order to enable comparison of data from studies on different solid substrates. In this work the influence of particle size on the second order rate constant and on the activation energy of the reaction between MnO4- and UO 2 was studied using aqueous UO 2-particle suspensions of four different size distributions. A comparative study of the activation energy for the reaction using a UO 2 pellet was also performed.

  19. Curing kinetics and morphology of a nanovesicular epoxy/stearyl-block-poly(ethylene oxide) surfactant system.

    Science.gov (United States)

    Bogaerts, K; Lavrenova, A; Spoelstra, A B; Boyard, N; Goderis, B

    2015-08-21

    Brittle epoxy based thermosets can be made tougher by introducing structural inhomogeneities at the micro- or nanoscale. In that respect, nano vesicles and worm-like micelles from self-assembling blockcopolymers have been shown to be very effective. This paper describes the curing kinetics and morphology of an epoxy composed of diglycidyl ether of bisphenol A (DGEBA) and 4,4'-methylenedianiline (MDA), modified by 20% of the surfactant stearyl-block-poly(ethylene oxide). Time resolved, synchrotron small-angle X-ray scattering demonstrates that at any time during the epoxy curing process, the surfactant predominantly adopts a bilayer vesicular nano-morphology. Transmission electron microscopy on fully cured systems reveals the coexistence of spherical and worm-like micelles. Differential scanning calorimetry experiments prove that the presence of surfactant reduces the epoxy curing rate but that ultimately full curing is accomplished. The material glass transition temperature falls below that of the pure resin due to plasticization. It is suggested that favorable secondary interactions between the PEO segments and the epoxy resin are responsible for the observed phenomena.

  20. Effects of natural organic matter properties on the dissolution kinetics of zinc oxide nanoparticles

    Science.gov (United States)

    Jiang, Chuanjia; Aiken, George R.; Hsu-Kim, Heileen

    2015-01-01

    The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L–1) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

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

    Science.gov (United States)

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

    2010-09-02

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

  2. Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

    Science.gov (United States)

    Bansal, Narottam P.; Gamble, Eleanor A.

    2005-01-01

    Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

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

    Science.gov (United States)

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

    2017-03-01

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

  4. Advanced oxidation processes applied to tannery wastewater containing Direct Black 38-Elimination and degradation kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Sauer, Ticiane Pokrywiecki [Department of Chemical and Food Engineering, Federal University of Santa Catarina, Campus Universitario-Trindade, P.O. Box 476, 88040-900 Florianopolis, Santa Catarina (Brazil)]. E-mail: sauer@enq.ufsc.br; Casaril, Leonardo [Department of Chemical and Food Engineering, Federal University of Santa Catarina, Campus Universitario-Trindade, P.O. Box 476, 88040-900 Florianopolis, Santa Catarina (Brazil)]. E-mail: leonardocasaril@ufsc.grad.br; Oberziner, Andre Luiz Bertoldi [Department of Chemical and Food Engineering, Federal University of Santa Catarina, Campus Universitario-Trindade, P.O. Box 476, 88040-900 Florianopolis, Santa Catarina (Brazil)]. E-mail: andreoberzine@hotmail.com; Jose, Humberto Jorge [Department of Chemical and Food Engineering, Federal University of Santa Catarina, Campus Universitario-Trindade, P.O. Box 476, 88040-900 Florianopolis, Santa Catarina (Brazil)]. E-mail: humberto@enq.ufsc.br; Moreira, Regina de Fatima Peralta Muniz [Department of Chemical and Food Engineering, Federal University of Santa Catarina, Campus Universitario-Trindade, P.O. Box 476, 88040-900 Florianopolis, Santa Catarina (Brazil)]. E-mail: regina@enq.ufsc.br

    2006-07-31

    The application of advanced oxidation processes (H{sub 2}O{sub 2}/UV, TiO{sub 2}/H{sub 2}O{sub 2}/UV and TiO{sub 2}/UV) to treat tannery wastewater was investigated. The experiments were performed in batch and continuous UV reactors, using TiO{sub 2} as a catalyst. The effect of the hydrogen peroxide concentration on the degradation kinetics was evaluated in the concentration range 0-1800 mg L{sup -1}. We observed that the degradation rate increased as the hydrogen peroxide increased, but excessive H{sub 2}O{sub 2} concentration was detrimental because it acted as a hydroxyl radical scavenger since it can compete for the active sites of the TiO{sub 2}. In the H{sub 2}O{sub 2}/UV treatment, the COD removal reached around 60% in 4 h of reaction, indicating that the principal pollutants were chemically degraded as demonstrated by the results for BOD, COD, nitrate, ammonium and analysis of the absorbance at 254 nm. Artemia salina toxicity testing performed in parallel showed an increase in toxicity after AOP treatment of the tannery wastewater.

  5. Electro-oxidation of diclofenac at boron doped diamond: Kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Xu; Hou Yining; Liu Huijuan; Qiang Zhimin [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China); Qu Jiuhui [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China)], E-Mail: jhqu@mail.rcees.ac.cn

    2009-07-01

    Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at boron doped diamond electrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

  6. Adsorption Properties of Doxorubicin Hydrochloride onto Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies

    Directory of Open Access Journals (Sweden)

    Zonghua Wang

    2013-05-01

    Full Text Available Doxorubicin hydrochloride (DOX is an effective anticancer agent for leukemia chemotherapy, although its clinical use has been limited because of its side effects such as cardiotoxicity, alopecia, vomiting, and leucopenia. Attention has been focussed on developing new drug carriers with high adsorption capacity and rapid adsorption rate in order to minimize the side effects of DOX. Graphene oxide (GO, a new type of nanomaterial in the carbon family, was prepared by Hummers method and used as adsorbent for DOX from aqueous solution. The physico-chemical properties of GO were characterized by transmission electron microscope (TEM, Fourier transform infrared spectroscopy (FTIR, zeta potential, and element analysis. The adsorption properties of DOX on GO were studied as a function of contact time, adsorbent dosage, temperature and pH value. The results showed that GO had a maximum adsorption capacity of 1428.57 mg/g and the adsorption isotherm data fitted the Langmuir model. The kinetics of adsorption fits a pseudo-second-order model. The thermodynamic studies indicate that the adsorption of DOX on GO is spontaneous and endothermic in nature.

  7. Stabilization and oxidation kinetics of iron in hydrothermal plumes above the East Scotia Ridge

    Science.gov (United States)

    Hawkes, J.; Connelly, D.; Achterberg, E. P.

    2011-12-01

    Two hydrothermal vent fields were recently discovered along the East Scotia Ridge (a back arc basin spreading centre) in the Southern Ocean. These are the most southerly high-temperature vents discovered to date. End-member fluids and the associated hydrothermal plumes were sampled for total, dissolved and 'soluble' (cathodic stripping voltammetry (CLE-CSV) experiments. In doing so, we present a first evaluation of the relationship between ligand and colloid stabilization mechanisms in hydrothermal plume settings. Plume samples are discussed in relation to the end-member fluid chemistry of the vent fields, which have relatively low dissolved metal concentrations (~1 mM Fe) and very high H2S:Fe ratios (~8) compared with typical mid-ocean ridge settings. The bottom water oxygen concentration is 175 μM (c.f. North Atlantic: 250 μM, North Pacific: 104 μM), and background dissolved organic carbon (DOC) concentrations are ~43 μM. Ambient seawater temperature at plume depth (~2200m) is close to 0°C. All of these features may play a part in the observed Fe(II) oxidation kinetics and Fe(III) stabilization and therefore the impact of hydrothermal Fe input on Southern Ocean biogeochemistry. The likelihood of long range transport of dissolved iron from this type of high-temperature hydrothermal system will be discussed.

  8. UV spectra and OH-oxidation kinetics of gaseous phase morpholinic compounds

    Science.gov (United States)

    Al Rashidi, M.; El Masri, A.; Roth, E.; Chakir, A.

    2014-05-01

    This paper presents an experimental study of the UV spectra as well as the kinetics of gaseous phase OH-oxidation of morpholine, N-formylmorpholine (NFM) and N-acetlymorpholine (NAM). The spectra recorded using a UV spectrometer in the spectral range 200-280 nm show that the analytes mainly absorb at wavelengths less than 280 nm. This indicates that their photolysis potential in the troposphere is insignificant. Meanwhile, the OH-reactivity of these analytes was studied using a triple-jacket 2 m long reactor equipped with a multi-reflection system and coupled to an FTIR spectrometer. The experiments were carried out at 295 and 313 K for the amine and amides, respectively. The study was conducted in the relative mode using isoprene and benzaldehyde as reference compounds. The rate constants obtained are 14.0 ± 1.9, 4.0 ± 1.1 and 3.8 ± 1.0 (in units of 10-11 cm3 molecule-1 s-1) for morpholine, NFM and NAM respectively. These results are discussed in terms of reactivity and compared to those obtained for other oxy-nitrogenated species. In addition, the determined rate constants are used to estimate effective atmospheric lifetimes of the investigated morpholinic compounds with respect to reaction with OH radicals.

  9. Reductive reactivity of iron(III oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

    Directory of Open Access Journals (Sweden)

    Liang-Jin Chen

    Full Text Available Reactive Fe(III oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite. Also the reactivity of Fe(III oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III oxides, k' (rate constant and γ (heterogeneity of reactivity, enable a quantitative characterization of Fe(III oxide reactivity in a standardized way. Amorphous Fe(III oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III suggests that the m 0 may represent Fe(III oxide assemblages spanning amorphous and crystalline Fe(III oxides. Maximum microbially available Fe(III predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III phases.

  10. 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 (p<0.01). Fat oxidation kinetics were characterized by similar translation, significantly lower dilatation and left-shift symmetry in O compared with L (p<0.05). During whole exercise, a blunted lipolysis was found in O [lower glycerol/fat mass (FM) in O than in L (p ≤ 0.001)], likely associated with higher insulin concentrations in O than in L (p<0.01). Non-esterified fatty acids (NEFA) were significantly higher in O compared with L (p<0.05). Despite the blunted lipolysis, O presented higher NEFA availability, likely due to larger amounts of FM. Therefore, a lower Fat(max), a left-shifted and less dilated curve and a lower reliance on fat oxidation 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.

  11. Atmospheric reactivity of vinyl acetate: kinetic and mechanistic study of its gas-phase oxidation by OH, O3, and NO3.

    Science.gov (United States)

    Picquet-Varrault, B; Scarfogliero, M; Doussin, J-F

    2010-06-15

    Vinyl acetate is widely used in industry. It has been classified as a high-production volume (HPV) chemical in the United States. To evaluate its impact on the environment and air quality, its atmospheric reactivity toward the three main tropospheric oxidants (OH, NO(3), and O(3)) has been investigated. Kinetic and mechanistic experiments have been conducted at room temperature and atmospheric pressure using an indoor Pyrex simulation chamber coupled to Fourier transform infrared (FTIR) and UV-visible spectrometers. Rate constants for the reactions of vinyl acetate with OH, NO(3), and O(3) were equal to (2.3 +/- 0.3) x 10(-11), (7.3 +/- 1.8) x 10(-15), and (3.0 +/- 0.4) x 10(-18) cm(3) molecule(-1) s(-1), respectively. From these data, tropospheric lifetimes of vinyl acetate have been estimated as follows: tau(OH) = 6 h, tau(NO(3)) = 6 days, and tau(O(3)) = 5 days. This demonstrates that reaction with OH radicals is the main tropospheric loss process of this compound. From the mechanistic experiments, main oxidation products have been identified and quantified and oxidation schemes have been proposed for each studied reaction.

  12. Thermal aging stability of infiltrated solid oxide fuel cell electrode microstructures: A three-dimensional kinetic Monte Carlo simulation

    Science.gov (United States)

    Zhang, Yanxiang; Ni, Meng; Yan, Mufu; Chen, Fanglin

    2015-12-01

    Nanostructured electrodes are widely used for low temperature solid oxide fuel cells, due to their remarkably high activity. However, the industrial applications of the infiltrated electrodes are hindered by the durability issues, such as the microstructure stability against thermal aging. Few strategies are available to overcome this challenge due to the limited knowledge about the coarsening kinetics of the infiltrated electrodes and how the potentially important factors affect the stability. In this work, the generic thermal aging kinetics of the three-dimensional microstructures of the infiltrate electrodes is investigated by a kinetic Monte Carlo simulation model considering surface diffusion mechanism. Effects of temperature, infiltration loading, wettability, and electrode configuration are studied and the key geometric parameters are calculated such as the infiltrate particle size, the total and percolated quantities of three-phase boundary length and infiltrate surface area, and the tortuosity factor of infiltrate network. Through parametric study, several strategies to improve the thermal aging stability are proposed.

  13. Mechanistic Investigations of Oxidation of Some Dipeptides by Sodium N-chloro-p-toluenesulfonamide in Alkaline Medium: A Kinetic Study

    Institute of Scientific and Technical Information of China (English)

    PUTTASWAMY; VAZ Nirmala; RAJENAHALLY VGOWDA Jagadeesh

    2008-01-01

    The kinetics of oxidation of five dipeptides (DPP) viz., glycylglycine (Gly-Gly), L-alanyl-L-alanine (Ala-Ala),L-valyl-L-valine (Val-Val), L-leucyl-L-leucine (Leu-Leu) and phenylglycyl-phenylglycine (Phg-Phg) by sodium N-chloro-p-toluenesuifonamide or chloramine-T (CAT) in NaOH medium was studied at 308 K. The reactions follow identical kinetics for all the dipeptides, being first-order dependence each on [CAT]o, [DPP]o and fractional-order on [OH-]. Addition of p-toluenesulfonamide or halide ions (CI- or Br-) has no significant effect on the rate of reaction. The reaction rate was found to increase with increase in ionic strength of the medium. The solvent isotope effect was studied using D2O. The activation parameters for the reaction were computed from Arrhenius plots. Equilibrium and decomposition constants were evaluated. The oxidation products of the dipeptides were identiffed as their corresponding aldehydes. An isokinetic relationship was observed with β=352 K, indicating that enthalpy factors control the reaction rate. CH3C6H4SO2NCl- of the oxidant has been postulated as the reactive oxidizing species. Under comparable experimental conditions, the rate of oxidation of the dipeptides increases in the order: Phg-Phg>Ala-Ala>Val-Val>Leu-Leu>Gly-Gly. The kinetics of oxidation of the dipeptides have also been compared with those of their corresponding monomer amino acids. The observed results have been explained by a plausible mechanism and the related rate law has been deduced.

  14. Kinetic Monte Carlo Simulation of the oscillatory catalytic CO oxidation using a modified Ziff-Gulari-Barshad model

    Science.gov (United States)

    Sinha, Indrajit; Mukherjee, Ashim K.

    2014-03-01

    The oxidation of CO on Pt-group metal surfaces has attracted widespread attention since a long time due to its interesting oscillatory kinetics and spatiotemporal behavior. The use of STM in conjunction with other experimental data has confirmed the validity of the surface reconstruction (SR) model under low pressure and the more recent surface oxide (SO) model which is possible under sub-atmospheric pressure conditions [1]. In the SR model the surface is periodically reconstructed below a certain low critical CO-coverage and this reconstruction is lifted above a second, higher critical CO-coverage. Alternatively the SO model proposes periodic switching between a low-reactivity metallic surface and a high-reactivity oxide surface. Here we present an overview of our recent kinetic Monte Carlo (KMC) simulation studies on the oscillatory kinetics of surface catalyzed CO oxidation. Different modifications of the lattice gas Ziff-Gulari-Barshad (ZGB) model have been utilized or proposed for this purpose. First we present the effect of desorption on the ZGB reactive to poisoned irreversible phase transition in the SR model. Next we discuss our recent research on KMC simulation of the SO model. The ZGB framework is utilized to propose a new model incorporating not only the standard Langmuir-Hinshelwood (LH) mechanism, but also introducing the Mars-van Krevelen (MvK) mechanism for the surface oxide phase [5]. Phase diagrams, which are plots between long time averages of various oscillating quantities against the normalized CO pressure, show two or three transitions depending on the CO coverage critical threshold (CT) value beyond which all adsorbed oxygen atoms are converted to surface oxide.

  15. Kinetics and Mechanism of the Oxidation of Naphthol Green B by Peroxydisulphate Ion in Aqueous Acidic Medium

    Directory of Open Access Journals (Sweden)

    B. Myek

    2014-01-01

    Full Text Available The kinetics of the oxidation of naphthol green B (NGB3− by peroxydisulphate ion has been carried out in aqueous acidic medium at λmax of 700 nm, T=23±1°C, and I=0.50 mol dm−3 (NaCl. The reaction shows a first-order dependence on oxidant and reductant concentration, respectively. The stoichiometry of the NGB—S2O82- reaction is 1 : 2. Change in hydrogen ions concentration of the reaction medium has no effect on the rate of the reaction. Added cations and anions decreased the rate of the reaction. The results of spectroscopic and kinetic investigation indicate that no intermediate complex is probably formed in the course of this reaction.

  16. Kinetics of the oxidative hydroxylation of tetraphosphorus in the presence of copper(II chloride modified by humic (fulvo- acid

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available It was established that in mild conditions (50-70 oC, РО2= 1 atm white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II chloride modified by humic (fulvo- acid to give mainly phosphoric acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final products, optimum conditions of new catalytic reaction of P4 oxidation by oxygen in water medium were defined by kinetics, volumometry, redox-potentiometry, 31Р{1Н} NMR spectroscopy and  titration. 

  17. Kinetics of the oxidative hydroxylation of sodium hypophosphite in the presence of copper (II chloride modified by humic (fulvo- acid

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available It was established that in soft conditions (50-70oC, PO2 = 1 atm sodium hypophosphite effectively is oxidized by oxygen in water solutions of copper(II chloride  to give mainly a phosphorous acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, the intermediate and final products, optimal conditions of new catalytic reaction of NaH2PO2 oxidation by oxygen in water solution were defined by kinetics, volumometry, redox-potentiometry and a titration.

  18. Kinetic Studies on State of the Art Solid Oxide Cells – A Comparison between Hydrogen/Steam and Reformate Fuels

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg

    2015-01-01

    Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen/steam and refor......Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen....../steam fuel split into two processes with opposing temperature behavior in the reformate fuels. An 87.5% reduction in active electrode area diminishes the gas conversion impedance in the hydrogen/steam fuel at high fuel flow rates. In both reformates, the second and third lowest frequency processes merged...

  19. Oxidation rate of nuclear-grade graphite IG-110 in the kinetic regime for VHTR air ingress accident scenarios

    Science.gov (United States)

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

    2014-03-01

    The oxidation rates of nuclear-grade graphite IG-110 in the kinetically-controlled temperature regime of graphite oxidation were predicted and compared in Very High Temperature Reactor air ingress accident scenarios. The oxidative mass loss of graphite was measured thermogravimetrically from 873 to 1873 K in 100% air (21 mol%). The activation energy was found to be 222.07 kJ/mol, and the order of reaction with respect to oxygen concentration is 0.76. The surfaces of the samples were characterized by Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy before and after oxidation. These results are compared with those available in the literature, and our recently reported results for NBG-18 nuclear-grade graphite using the same technique.

  20. Kinetic Study of the Electro-Catalytic Oxidation of Hydrazine on Cobalt Hydroxide Modified Glassy Carbon Electrode

    Institute of Scientific and Technical Information of China (English)

    HASANZADEH,Mohammad; KARIM-NEZHAD,Ghasem; SHADJOU,Nasrin; KHALILZADEH,Balal; SAGHATFOROUSH,Lotali; ERSHAD,Sohrab; KAZEMAN,Isa

    2009-01-01

    Electrocatalytic oxidation of hydrazine was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution.The process of oxidation involved and its kinetics were established by using cyclic voltammetry,chronoamperometry techniques as well as steady state polarization measurements.In cyclic voltammetry (CV) studies,in the presence of hydrazine the peak current increase of the oxidation of cobalt hydroxide is followed by a decrease in the corresponding cathodic current.This indicates that hydrazine is oxidized on the redox mediator that is immobilized on the electrode surface via an electrocatalytic mechanism.A mechanism based on the electrochemical generation of Co(IV) active sites and their subsequent consumption by the hydrazine in question was also investigated.

  1. The kinetics of sulfides oxidation in the coal mine spoils of the Upper Silesian coal basin. Pilot scale test

    Energy Technology Data Exchange (ETDEWEB)

    Witczak, S.; Postawa, A. (University of Mining and Metallurgy, Cracow (Poland). Department of Hydrogeology, Engineering and Mining Geology)

    1993-01-01

    Presents results of six years of pilot-scale geochemical tests into sulfide oxidation. Environmental impacts of oxidized sulfides contained in coal mine waste are investigated. Materials and methods used for investigations are described. Kinetics of sulfides oxidation and the effect of ambient temperature and precipitation are studied. High sulfate contents were found in the leachate of a 1.5 m high column of coal mine waste. Values of pH changed during the test from 2.64 to 4.4 in the end without any visible changes in sulfide oxidation rate. Total amount of reactive sulfides at the beginning of tests was estimated at 0.192 wt % of sulfide sulfur. Half-decomposition time was found to be 2,735 days. It is concluded that the detrimental effect of the mine waste tested can have an environmental impact for about 33 years. 6 refs.

  2. Effect of Humic Acid on As Redox Transformation and Kinetic Adsorption onto Iron Oxide Based Adsorbent (IBA

    Directory of Open Access Journals (Sweden)

    Hoda Fakour

    2014-10-01

    Full Text Available Due to the importance of adsorption kinetics and redox transformation of arsenic (As during the adsorption process, the present study elucidated natural organic matter (NOM effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA, as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions.

  3. Leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system

    Institute of Scientific and Technical Information of China (English)

    WANG Rui-xiang; TANG Mo-tang; YANG Sheng-hai; ZHAGN Wen-hai; TANG Chao-bo; HE Jing; YANG Jian-guang

    2008-01-01

    The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size,reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined.The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69μm, holding at 80℃ for 60min, sum ammonia concentration of 7.5mol/L, the molar ratio of ammonium to ammonia being 2:1, and the ratio (g/mL) of solid to liquid being 1:10.

  4. High production volume chemical Amine Oxide [C8-C20] category environmental risk assessment

    DEFF Research Database (Denmark)

    Sanderson, Hans; Tibazarwa, Caritas; Greggs, William

    2009-01-01

    An environmental assessment of amine oxides has been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Amine Oxides Consortium. Amine oxides are primarily used in conjunction with surfactants in cleaning...... and personal care products. Given the lack of persistence or bioaccumulation, and the low likelihood of these chemicals partitioning to soil, the focus of the environmental assessment is on the aquatic environment. In the United States, the E-FAST model is used to estimate effluent concentrations in the United...... States from manufacturing facilities and from municipal facilities resulting from consumer product uses. Reasonable worst-case ratios of predicted environmental concentration (PEC) to predicted no effect concentration (PNEC) range from 0.04 to 0.003, demonstrating that these chemicals are a low risk...

  5. Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex in perchloric acid medium

    Indian Academy of Sciences (India)

    T V N Partha Sarathi; A Kalyan Kumar; K Krishna Kishore; P Vani

    2005-07-01

    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 reactive species of the substrate is the zwitterionic form and that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law as elucidated.

  6. The effect of solvent on the kinetics of the oxidation of benzaldehydes by quinolinium chlorochromate in aqueous organic solvent media

    Directory of Open Access Journals (Sweden)

    G. FATIMA JEYANTHI

    2002-12-01

    Full Text Available The kinetics of the oxidation of benzaldehyde and para-substituted benzaldehydes by quinolinium chlorochromate in water-dimethylformamide mixtures has been studied under pseudo-first-order conditions at 25±0.2°C. The operation of non-specific and specific solvent-solute interactions was explored by correlating the rate data with solvent parameters through a correlation analysis technique. Both electron-releasing and electron-withdrawing substitutents enhance the rate of oxidation and the Hammett plot shows a break in the reactivity order indicating the applicability of a dual mechanism.

  7. Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

    Science.gov (United States)

    Chen, Yiling; Zhang, Huichun

    2013-10-01

    Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

  8. Oxidation of tricyclic antidepressant drugs with chloramine-T in acidic solutions: kinetic, mechanistic and thermodynamic studies.

    Science.gov (United States)

    Sukhdev, Anu; Puttaswamy, Puttaswamy

    2013-12-01

    The kinetics of the oxidation of two tricyclic antidepressants (TCA) namely, imipramine (IMP) and clomipramine (CLM) with sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in HClO4 medium was studied at 300 K. The two reactions followed identical kinetics with a first-order dependence of rate on [CAT]o and fractional order dependence on [TCA]o. The reaction is catalyzed by H(+) ions with a fractional order dependence. The reaction was studied at different temperatures and activation parameters were evaluated. The reaction constants involved in the mechanism were computed. The solvent isotope effect was studied using D2O. Addition of p-toluenesulfonamide retards the reaction rate. The rate increased with decreasing dielectric constant of the medium. Variation of ionic strength of the medium and addition of halide ions (Cl(-) or Br(-)) showed no effect on the rate. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as imipramine-5-N-oxide and clomipramine-5-N-oxide. The rate of oxidation of IMP is faster than CLM. The observed results have been explained in terms of a mechanism and a relevant rate law has been deduced.

  9. Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

    OpenAIRE

    Karla Herrera Delgado; Lubow Maier; Steffen Tischer; Alexander Zellner; Henning Stotz; Olaf Deutschmann

    2015-01-01

    An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented i...

  10. Homogeneous kinetics and equilibrium predictions of coking propensity in the anode channels of direct oxidation solid-oxide fuel cells using dry natural gas

    Science.gov (United States)

    Walters, Kevin M.; Dean, Anthony M.; Zhu, Huayang; Kee, Robert J.

    Direct electrochemical oxidation (DECO) solid-oxide fuel cells (SOFCs) offer the potential to generate electrical power from hydrocarbon fuels without the need for upstream fuel processing, such as reforming. However, with pure hydrocarbon fuel entering the flow channels at temperatures typically above 700 °C, fuel pyrolysis can cause molecular-weight growth and the formation of deleterious carbonaceous deposits. This paper, which develops a plug-flow model for fuel (natural gas surrogate) within the anode channels, considers the elementary gas-phase chemical kinetics of fuel pyrolysis and oxidation. It also considers the limiting case of local chemical equilibrium. Formation of cyclic hydrocarbon species is used to indicate deposit propensity. Results show that the likelihood of deposit formation depends strongly on cell temperature, current density, and residence time. Generally speaking, equilibrium favors deposit formation early in the channel whereas, owing to limited residence time, the homogeneous finite-rate kinetics predicts relatively low levels of deposit precursors. In the downstream portions, because of electrochemical oxygen flux though the electrode-electrolyte membrane, chemical equilibrium shifts strongly away from deposit formation to volatile carbon-oxygen species. However, the homogeneous finite-rate kinetics predictions show a continuing increase in coking propensity.

  11. Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process.

    Science.gov (United States)

    Xiang, Yingying; Fang, Jingyun; Shang, Chii

    2016-03-01

    The UV/chlorine advanced oxidation process (AOP), which forms reactive species such as hydroxyl radicals (HO) and reactive chlorine species (RCS) such as chlorine atoms (Cl) and Cl2(-), is being considered as an alternative to the UV/H2O2 AOP for the degradation of emerging contaminants. This study investigated the kinetics and pathways of the degradation of a recalcitrant pharmaceutical and personal care product (PPCP)-ibuprofen (IBP)-by the UV/chlorine AOP. The degradation of IBP followed the pseudo first-order kinetics. The first-order rate constant was 3.3 times higher in the UV/chlorine AOP than in the UV/H2O2 AOP for a given chemical molar dosage at pH 6. The first-order rate constant decreased from 3.1 × 10(-3) s(-1) to 5.5 × 10(-4) s(-1) with increasing pH from 6 to 9. Both HO and RCS contributed to the degradation, and the contribution of RCS increased from 22% to 30% with increasing pH from 6 to 9. The degradation was initiated by HO-induced hydroxylation and Cl-induced chlorine substitution, and sustained through decarboxylation, demethylation, chlorination and ring cleavage to form more stable products. Significant amounts of chlorinated intermediates/byproducts were formed from the UV/chlorine AOP, and four chlorinated products were newly identified. The yield of total organic chlorine (TOCl) was 31.6 μM after 90% degradation of 50 μM IBP under the experimental conditions. The known disinfection by-products (DBPs) comprised 17.4% of the TOCl. The effects of water matrix in filtered drinking water on the degradation were not significant, demonstrating the practicality of the UV/chlorine AOP for the control of some refractory PPCPs. However, the toxicity of the chlorinated products should be further assessed.

  12. Micellar effect on the kinetics of oxidation of methyl blue by Ce(IV in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    Mohammed Hassan

    2015-01-01

    Full Text Available The kinetics of oxidation of methyl blue (MB by Ce(IV in aqueous and surfactant media has been carried out to explore the micellar effect on the rate and kinetic parameters of the reaction. The reaction was found to be first order with respect to both oxidant and substrate and fractional order with respect to H+. The active kinetic species of the oxidant was found to be Ce(SO4+2 based on the effect of ionic strength and sulfate ion on the rate of the reaction. The presence of micelles was found to inhibit the reaction and this effect has been explained by the association of one of the reactants with the micelles leaving the other reactant in the bulk solution. The binding constant and first order rate constant in micellar medium has been obtained by the application of pseudo-phase model to the experimental data. Interestingly, the temperature dependence of the reaction reveals that the reaction has negative activation energy in the absence of micelles, which turns to a positive value in the presence of micelles.

  13. Kinetics and Mechanism for Oxidation of L-Proline by Bis(hydrogen periodato) argentate (Ⅲ) Complex Anion

    Institute of Scientific and Technical Information of China (English)

    SUN Han-Wen; SHI Hong-Mei; SHEN Shi-Gang; FANG Wei-Jun; GUO Zhi-Feng

    2008-01-01

    Oxidation of L-proline by bis(hydrogen periodato)argentate(Ⅲ) complex anion, [Ag(HIO6)2]5-, has been studied in aqueous alkaline medium in the temperature range of 25-40 ℃ by use of conventional spectrophotometry.Under the conditions for kinetic measurements, the oxidation results in decarboxylation of proline, giving rise to γ-aminobutyrate as identified by mass spectrometry. The oxidation kinetics is first order with respect to the silver(Ⅲ)and proline concentrations; the second-order rate constants, decreasing with increasing [periodate], are essentially independent of [OH-]. The kinetic results were interpreted in terms of a reaction mechanism which involves a pre-equilibrium between [Ag(HIO6)2]5- and [Ag(HIO6)(H2O)(OH)]2-, a mono-periodate coordinated silver(Ⅲ)complex. Both Ag(Ⅲ) complexes are reduced parallelly by the fully deprotonated form of proline in reductant and shows a lower reactivity than [Ag(HIO6)(OH)(H2O)]2-.

  14. Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles

    Directory of Open Access Journals (Sweden)

    R. C. Sullivan

    2004-01-01

    Full Text Available The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels.

  15. A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Z; Pitz, W J; Fournet, R; Glaude, P; Battin-Leclerc, F

    2009-12-18

    An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene, decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C{sub 4} + C{sub 2} species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C{sub 6}H{sub 4}CH{sub 3} radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C{sub 6}H{sub 4}CH{sub 3} radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

  16. Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Yuan; Zhang, Chenxi; Yang, Wenbo; Hu, Jingtian [Environment Research Institute, Shandong University, Jinan 250100 (China); Sun, Xiaomin, E-mail: sxmwch@sdu.edu.cn [Environment Research Institute, Shandong University, Jinan 250100 (China); State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy Of Science, Lanzhou 730000 (China)

    2012-03-01

    Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311 + G(3df,2p)//MPWB1K/6-31 + G(d,p) level. The study shows that H abstraction reaction from the CH{sub 3} group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH{sub 3}O){sub 2}POOH (P1), CCl{sub 3}CHOHPOOH(OCH{sub 3}) (P2), CH{sub 3}OPO{sub 2} (P3), CCl{sub 3}COPO(OCH{sub 3}){sub 2} (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800 K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study. - Highlights: Black-Right-Pointing-Pointer The H-abstracted reaction and OH addition reaction are favorable channels. Black-Right-Pointing-Pointer The Arrhenius formulas of rate constants with the temperature are fitted. Black-Right-Pointing-Pointer The rate constants of TCF relative to OH radical is 4.95 Multiplication-Sign 10{sup -15} cm{sup 3} molecule{sup -1} s{sup -1}.

  17. Adsorption properties of tetracycline onto graphene oxide: equilibrium, kinetic and thermodynamic studies.

    Directory of Open Access Journals (Sweden)

    Ehsan Ezzatpour Ghadim

    Full Text Available Graphene oxide (GO nanoparticle is a high potential effective absorbent. Tetracycline (TC is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π-π interaction and cation-π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742-0.5362 g/mg min (at different temperatures. The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K. The mean energy of adsorption was determined 1.83 kJ/mol (298 K based on the Dubinin-Radushkevich (D-R adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet.

  18. OXIDATION OF PROPRANOLOL USING CHLORAMINE – T IN HClO4 MEDIUM: A KINETIC AND MECHANISTIC STUDY

    Directory of Open Access Journals (Sweden)

    Range Gowda Ramachandrappa

    2012-06-01

    Full Text Available Kinetics and oxidation of Propranolol (PPL ((RS-1-(1-methylethylamino-3-(1-naphthyloxypropan-2-ol by sodium – N- chloro – p- toluenesulphonamide (Chloramine – T or CAT in HClO4 medium at 298K have been studied. The rate was first order in [CAT]o, fractional order in [PPL] and zero order in [H+]. Addition of p-toluenesulphonamide, NaCl and NaBr did not affect the rate of the reaction. Variation in ionic strength did not affect the rate of the reaction indicating that non – ionic species are involved in the rate limiting step. The dielectric effect of the medium was positive. Rate increased with increase in temperature from 288K to 318K. From the linear Arrhenius plot, activation parameters were computed. Addition of reaction mixture to aqueous acrylonitrile solution did not initiate polymerization, showing the absence of free radicals species. Oxidation products were identified. TsNClNa, the reactive species, oxidizes the substrate. Based on kinetic results, reaction stoichiometry and oxidation products, a suitable mechanism have been proposed.

  19. Transient kinetic modeling of the ethylene and carbon monoxide oxidation over a commercial automotive exhaust gas catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Harmsen, J.M.A.; Hoebink, J.H.B.J.; Schouten, J.C.

    2000-03-01

    The transient kinetics of ethylene oxidation by oxygen over a commercial Pt/Rh/CeO{sub 2}/{gamma}-Al{sub 2}O{sub 3} three-way catalyst were modeled. Experiments were carried out in a fixed-bed microreactor with two separate inlets, enabling alternate feeding of ethylene and oxygen with frequencies up to {1/4} Hz. The experimental conditions resemble the cold-start period of an Otto engine in a car. Two types of adsorbed ethylene species seem to exist. A selective catalyst deactivation for oxygen adsorption, due to deposition of carbonaceous species, was found. A kinetic model was developed, based on elementary reaction steps, that allows one to describe the experiments quantitatively. Furthermore, this model was combined with the published model for transient carbon monoxide oxidation over the same catalyst, which enables one to predict the results of simultaneous ethylene and carbon monoxide oxidation. Both components react in rather distinct zones, with ethylene being converted only when carbon monoxide oxidation is almost complete.

  20. Methane steam reforming kinetics over Ni-YSZ anode materials for Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Mogensen, David

    intrinsic kinetics, and in a stack configuration to determine the rate observed under realistic SOFC conditions. The kinetic expressions obtained from respectively the packed bed measurements and the stack measurements are shown in Equations 3 and 4. Furthermore, a simple model was derived, which can...... with SEM, TEM, XRD and EXAFS....

  1. Kinetics of thermal oxidation of 6H silicon carbide in oxygen plus trichloroethylene

    OpenAIRE

    Yang, BL; Lin, LM; Lo, HB; Lai, PT; Chan, CL

    2005-01-01

    In this work, the behaviors of the trichloroethylene (TCE) thermal oxidation of 6H silicon carbide (SiC) are investigated. The oxide growth of 6H SiC under different TCE concentrations (ratios of TCE to O2) follows the linear-parabolic oxidation law derived for silicon oxidation by Deal and Grove, J. Appl. Phys., 36 (1965). The oxidation rate with TCE is much higher than that without TCE and strongly depends on the TCE ratio in addition to oxidation temperature and oxidation time. The increas...

  2. KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

    Directory of Open Access Journals (Sweden)

    Mohammad Sadiq

    2015-08-01

    Full Text Available Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68% and selectivity (100% for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

  3. INHIBITION KINETICS DURING THE OXIDATION OF BINARY MIXTURES OF PHENOL WITH CATECHOL, RESORCINOL AND HYDROQUINONE BY PHENOL ACCLIMATED ACTIVATED SLUDGE

    Directory of Open Access Journals (Sweden)

    C. C. Lobo

    Full Text Available Abstract In this work the aerobic degradation of phenol (PH, catechol (CA, resorcinol (RE, hydroquinone (HY and of the binary mixtures PH+CA, PH+RE, PH+HY by phenol-acclimated activated sludge was studied. Single substrate experiments show a Haldane-type dependence of the respiration rate on PH, RE and HY, while CA corresponded to the Monod model. Binary substrate experiments demonstrated that the presence of a second substrate only affected the kinetics, but not the stoichiometry of the oxidation of the compounds tested. While CA inhibited the oxidation of PH, PH inhibited the oxidation of RE and HY. A mathematical model was developed to represent the aerobic biodegradation of the phenolic compounds tested. The agreement between the proposed model and the experimental data indicates that the proposed model can be useful for predicting substrate and dissolved oxygen concentrations in bioreactors treating phenolic wastewaters.

  4. Adsorptive kinetic mechanism of heavy metal cations on the surface of graphite oxide and its SiO2 composite

    Science.gov (United States)

    Sheet, Imtithal; Kabbani, Ahmad; Holail, Hanafy

    2017-02-01

    Nanomaterials have gained great attention because of their novel size- and shape-dependent properties, large specific surface area and high reaction activity. Moreover, nanomaterials have a wide range of applications, as in the technological and environmental challenges in the areas of solar energy conversion, catalysis, medicine, and water treatments. In the present study, nanostructured graphite oxide, silica/graphite oxide composites and silica nanoparticles were used for the removal of the heavy metal ions from aqueous solutions by a batch adsorption method and the adsorptive kinetic mechanism of heavy metal cations on the surface of graphite oxide and its SiO2 composite was evaluated. The experimental results revealed a strong adsorption of the metal cations on the surface of graphite oxide, this is reflected in the shifts in wave numbers after adsorption with nanostructured graphite oxide and the big shift in wave numbers (Δv¯) for nickel ions reflects chemosorption type of adsorption. This is confirmed by the coherence between Δv¯, removal percentage and crystal field stabilization energy (CFSE). Silica/ GO (2:3) composite showed the greatest removal percentage at different concentrations compared to pure graphite oxide and silica nanoparticles. The higher removal percentage of nickel ions by silica /GO composite (2:3) was observed at 180 min contact time and basic pH. The kinetic studies showed that silica/ GO (2:3) composite had rapid adsorption rate and efficiency and it was found to follow first order rate expression or an exponential decay of the metal cations from water study.

  5. Moringa Oleifera Lam Mitigates Oxidative Damage and Brain Infarct Volume in Focal Cerebral Ischemia

    Directory of Open Access Journals (Sweden)

    Woranan Kirisattayakul

    2012-01-01

    Full Text Available Problem statement: At present, the therapeutic outcome of cerebral ischemia is still not in the satisfaction level. Therefore, the preventive strategy is considered. Based on the protective effect against oxidative damage of Moringa oleifera Lam. Leaves extract, we hypothesized that this plant extract might protect against cerebral ischemia, one of the challenge problems nowadays. In order to test this hypothesis, we aimed to determine the protective effect of M.oleifera leaves extract in animal model of focal cerebral ischemia induced by permanent occlusion of right middle cerebral artery. Approach: Male Wistar rats, weighing 300-350 g, were orally given the extract once daily at doses of 100, 200 and 400 mg kg-1 BW at a period of 2 weeks, then, they were permanently occluded the right Middle Cerebral Artery (MCAO. The animals were assessed the cerebral infarction volume and oxidative damage markers including MDA level and the activities of SOD, CAT and GSHPx enzymes at 24 h after occlusion. Results: Rats subjected to M.oleifera extract at all doses used in this study significantly decreased brain infarct volume both at cortical and subcortical structures in accompany with the elevation of SOD activity in both hippocampus and striatum while only the rats exposed to the extract at doses of 100 and 400 mg kg-1 BW showed the increased GSHPx activity in hippocampus. No the changes were observed. Therefore, our results demonstrates the potential benefit of M.oleifera leaves to decrease oxidative stress damage and brain infarct volume. Conclusion: This study is the first study to demonstrate the neuroprotective effect against focal cerebral ischemia of M.oleifera leaves. It suggests that M.oleifera may be served as natural resource for developing neuroprotectant against focal cerebral ischemia. However, the precise underlying mechanism and possible active ingredient are still required further study.

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

    Directory of Open Access Journals (Sweden)

    Karina Gomes Angilelli

    2017-05-01

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

  7. Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric optimization and mineralization pathway

    Directory of Open Access Journals (Sweden)

    Hicham Zazou

    2017-01-01

    Full Text Available Oxidative degradation of herbicide 2,4,5-T was studied by electrochemical advanced oxidation processes anodic oxidation and electro-Fenton (EF using Pt/carbon felt and BDD/carbon felt cells. The effect of main operating parameters on oxidation of 2,4,5-T and mineralization of its aqueous solution were investigated. The rate constant for oxidation of 2,4,5-T by ·≡OH was determined as (3.7 ± 0.2 × 109 M−1 s−1 using competition kinetics method. The EF process with BDD anode was shown to be very efficient reaching 94% mineralization in 3 h treatment. Based on identified aromatic intermediates, short-chain carboxylic acids, released inorganic ions and total organic carbon removal measurements, a plausible oxidation pathway for mineralization of 2,4,5-T by hydroxyl radical was proposed. In addition, the evolution of solution toxicity during treatment was monitored by Microtox method showing the formation of toxic aromatic/cyclic intermediates. The results showed also that EF process was able to remove efficiently toxic intermediates and consequently solution toxicity.

  8. A study of kinetic modelling and reaction pathway of 2,4-dichlorophenol transformation by photo-fenton-like oxidation.

    Science.gov (United States)

    Chu, W; Kwan, C Y; Chan, K H; Kam, S K

    2005-05-20

    The degradation of 2,4-dichlorophenol (2,4-DCP) by the photo-Fenton-like (Fe3+/H2O2/UVC) process under various reaction conditions was investigated. It was interesting to find that the reaction kinetics of 2,4-DCP in Fe3+/H2O2/UVC systems varied depending on the initial [Fe3+] concentration. A pseudo first-order kinetic and a non-conventional kinetic were discovered at low and higher [Fe3+] concentrations, respectively. A model was used to simulate the non-conventional kinetic process, where two character parameters (the initial decay rate and the final decay fraction) were found to be critical in determining the process. The two parameters successfully quantify the photo-Fenton-like oxidation under different concentrations of [Fe3+] and [H2O2] and the corresponding ratios of Fe(III)/H2O2. The reaction intermediates were identified by an LC/MS analysis and a reaction mechanism was proposed.

  9. Kinetic Study of Methyl Acetate Oxidation in a Pt/Al2O3 Fixed-Bed Reactor

    Science.gov (United States)

    Hoy, Michael; Li, K. Y.; Li, Jeffrey S.; Chen, S. M.; Yaws, C. L.; Chu, H. W.; Simon, W. E.

    1994-01-01

    To support technology development for future long-term missions, a metabolic simulator will be used in a closed chamber to test the functions of a Controlled Ecological Life Support System (CELSS). Methyl acetate (MA) was selected as the fuel because its metabolic respiratory quotient is near that of humans. A kinetic study of the catalytic oxidation of MA over Pt/Al203 was then conducted to support the design and operation of the simulator. Kinetic data were obtained as a conversion percentage of MA versus retention time. The reaction was studied at one atmosphere and temperatures from 220 to 340 deg. C. The inlet MA concentration was varied from 100 to 2000 ppm with retention times from 0.01 to 10 sec. A first-order rate law and a Langmuir-Hinshelwood rate equation were tested by nonlinear regression of the kinetic data to estimate rate constants in the rate law. Regression results of the L-H equation explain the kinetic data better than the results of the first-order rate law. A Taguchi experimental design was used to study the effects of temperature, retention time, and concentrations of MA, CO2, and O2 on the conversion of MA. Results indicate that temperature has greatest effect, followed by retention time, and finally MA concentration. It was further determined that the effects of CO2 and O2 concentrations, and the cross effects, are negligible.

  10. Adsorption kinetics, isotherms and thermodynamics of atrazine on surface oxidized multiwalled carbon nanotubes.

    Science.gov (United States)

    Chen, Guang-Cai; Shan, Xiao-Quan; Zhou, Yi-Quan; Shen, Xiu-e; Huang, Hong-Lin; Khan, Shahamat U

    2009-09-30

    The adsorption kinetics, isotherms and thermodynamic of atrazine on multiwalled carbon nanotubes (MWCNTs) containing 0.85%, 2.16%, and 7.07% oxygen was studied. Kinetic analyses were performed using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. The regression results showed that the pseudo-second-order law fit the adsorption kinetics. The calculated thermodynamic parameters indicated that adsorption of atrazine on MWCNTs was spontaneous and exothermic. Standard free energy (DeltaG(0)) became less negative when the oxygen content of MWCNTs increased from 0.85% to 7.07% which is consistent with the low adsorption affinity of MWCNTs for atrazine.

  11. The kinetics of oxidation of bilirubin and ascorbic acid in solution

    Science.gov (United States)

    Solomonov, A. V.; Rumyantsev, E. V.; Kochergin, B. A.; Antina, E. V.

    2012-07-01

    The results of a comparative study of the oxidation of bilirubin, ascorbic acid, and their mixture in aqueous solutions under the action of air oxygen and hydrogen peroxide are presented. The observed and true rate constants for the oxidation reactions were determined. It was shown that the oxidation of tetrapyrrole pigment occurred under these conditions bypassing the stage of biliverdin formation to monopyrrole products. Simultaneous oxidation of bilirubin and ascorbic acid was shown to be accompanied by the inhibition of ascorbic acid oxidation by bilirubin, whereas ascorbic acid itself activated the oxidation of bilirubin.

  12. Free-radical-induced oxidative and reductive degradation of fluoroquinolone pharmaceuticals: kinetic studies and degradation mechanism.

    Science.gov (United States)

    Santoke, Hanoz; Song, Weihua; Cooper, William J; Greaves, John; Miller, George E

    2009-07-09

    Fluoroquinolones, as a class of broad-spectrum antibiotics, have been detected in both surface and ground waters, and advanced oxidation/reduction processes (AO/RPs) are currently in development to remove these and other pharmaceuticals from wastewater because currently utilized treatment methods have proven to be ineffective. This article reports the reaction kinetics of six common fluoroquinolones with hydroxyl radicals and hydrated electrons, which are the major reactive species involved in AO/RPs. The bimolecular reaction rate constants (M(-1) s(-1)) for orbifloxacin, flumequine, marbofloxacin, danofloxacin, enrofloxacin, and the model compound, 6-fluoro-4-oxo-1,4-dihydro-3-quinoline carboxylic acid, with *OH are (6.94 +/- 0.08) x 10(9), (8.26 +/- 0.28) x 10(9), (9.03 +/- 0.39) x 10(9), (6.15 +/- 0.11) x 10(9), (7.95 +/- 0.23) x 10(9), (7.65 +/- 0.20) x 10(9), and with e(aq)(-), (2.25 +/- 0.02) x 10(10), (1.83 +/- 0.01) x 10(10), (2.41 +/- 0.02) x 10(10), (1.68 +/- 0.02) x 10(10), (1.89 +/- 0.02) x 10(10), and (1.49 +/- 0.01) x 10(10). These rate constants are related to the functional groups attached to the quinolone core, particularly the steric hindrance of the piperazine ring, making it possible to obtain a preliminary estimate of the *OH rate constant of an arbitrary fluoroquinolone by observing the ring constituents. In addition, the products of gamma-irradiation degradation of fluoroquinolones were analyzed by LC-MS to elucidate the probable pathways of AO/RPs degradation. Results indicate that preliminary degradation pathways include hydroxyl radical attack on the aromatic ring with subsequent hydroxylation, the substitution of a fluorine atom with a hydroxyl group, and the removal of the piperazine-derived side chain.

  13. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  14. The investigation of the kinetics of hydrochemical oxidation of metal sulphides with the aim of determination of the optimal conditions for the selective extraction of molybdenum from ores

    Directory of Open Access Journals (Sweden)

    Lutsik V.

    2005-01-01

    Full Text Available The kinetics of the oxidation of molybdenyte, pyrite and sphalerite in solutions of nitric acid, hydrogen peroxide, and sodium hypochlorite was studied by the rotating disk method. The influence of the molar concentration of reagent, pH of solution, temperature, disk rotation frequency, and duration of measurements on the specific rate of hydrochemical oxidation of sulpfides was determined. The kinetic models allowing to calculate the dissolution rate of sulphides when these parameters change simultaneously were obtained. The conditions of kinetically and diffusion-controlled processes were detected. The details of mechanism of the studied processes were revealed. The nature of intermediate solid products, the reasons and the conditions of their formation as well as the character of their influence on the kinetics of dissolution processes were determined. The probable schemes of interactions corresponding to the observable kinetic dependences were offered. The conditions of the effective and selective molybdenum leaching directly from ore without its concentration were found.

  15. Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

    Science.gov (United States)

    Chang, Shenteng; Lu, Chungsying; Lin, Kun-Yi Andrew

    2015-01-01

    Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

  16. Oxidative coupling of methane in a fixed bed reactor over perovskite catalyst: A simulation study using experimental kinetic model

    Institute of Scientific and Technical Information of China (English)

    Nakisa Yaghobi; Mir Hamid Reza Ghoreishy

    2008-01-01

    The oxidative coupling of methane (OCM) to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx (CO2, CO), and C2 (C2H4 and C2H6) was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity (GHSV) and the methane conversion also decreases by increasing the methane to oxygen ratio.

  17. Kinetics of Zr-alloy cladding oxidation in the mixture of air and steam at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyung Tae; Park, Kwang Heon; Park, Joo Young [Kyunghee University, Yongin (Korea, Republic of)

    2012-05-15

    In Fukushima Daiichi Nuclear Power Plant accident, No.4 plant was exploded by hydrogen explosion. There was a strong speculation about the possibility of the reaction between the overheated fuels and the steam-air mixture in the storage pool. Later, it turned out to be due to the hydrogen leaked from No.3 plant. However, the reaction of the hot fuels with the steam-air mixture became an important issue. There have been a lot of data accumulated about Zr-alloy interaction with steam. However, Zr-alloy interactions with air and steam-air mixtures have not been studied relatively much. In this study, we measured the oxidation kinetics of Zry-4 and Zirlo claddings in air, and steam-air mixtures, and analyzed the kinetics

  18. Reduced kinetic mechanism of n-heptane oxidation in modeling polycyclic aromatic hydrocarbon formation in opposed-flow diffusion flames

    Institute of Scientific and Technical Information of China (English)

    Beijing ZHONG; Jun XI

    2008-01-01

    A reduced mechanism, which could couple with the multidimensional computational fluid dynamics code for quantitative description of a reacting flow, was developed for chemical kinetic modeling of polycyclic aro-matic hydrocarbon formation in an opposed-flow dif-fusion flame. The complete kinetic mechanism, which comprises 572 reactions and 108 species, was reduced to a simplified mechanism that includes only 83 reactions and 56 species through sensitivity analysis. The results computed via this reduced mechanism are nearly indistin-guishable from those via the detailed mechanism, which demonstrate that the model based on this reduced mech-anism can properly describe n-heptane oxidation chem-istry and quantitatively predict polycyclic aromatic hydrocarbon (such as benzene, naphthalene, phenan-threne and pyrene) formation in opposed-flow diffusion flames.

  19. Effects, Uptake, and Depuration Kinetics of Silver Oxide and Copper Oxide Nanoparticles in a Marine Deposit Feeder, Macoma balthica

    DEFF Research Database (Denmark)

    Dai, Lina; Syberg, Kristian; Banta, Gary Thomas

    2013-01-01

    Ag and CuO engineered nanoparticles (ENPs) have wide applications in industry and commercial products and may be released from wastewater into the aquatic environment. Limited information is currently available on metal ENP effects, uptake, and depuration kinetics in aquatic organisms. In the pre...

  20. Elementary kinetic modelling applied to solid oxide fuel cell pattern anodes and a direct flame fuel cell system

    Energy Technology Data Exchange (ETDEWEB)

    Vogler, Marcel

    2009-05-27

    In the course of this thesis a model for the prediction of polarisation characteristics of solid oxide fuel cells (SOFC) was developed. The model is based on an elementary kinetic description of electrochemical reactions and the fundamental conservation principles of mass and energy. The model allows to predict the current-voltage relation of an SOFC and offers ideal possibilities for model validation. The aim of this thesis is the identification of rate-limiting processes and the determination of the elementary pathway during charge transfer. The numerical simulation of experiments with model anodes allowed to identify a hydrogen transfer to be the most probable charge-transfer reaction and revealed the influence of diffusive transport. Applying the hydrogen oxidation kinetics to the direct flame fuel cell system (DFFC) showed that electrochemical oxidation of CO is possible based on the same mechanism. Based on the quantification of loss processes in the DFFC system, improvements on cell design, predicting 80% increase of efficiency, were proposed. (orig.)

  1. Kinetic and stoichiometric characterization of anoxic sulfide oxidation by SO-NR mixed cultures from anoxic biotrickling filters.

    Science.gov (United States)

    Mora, Mabel; Fernández, Maikel; Gómez, José Manuel; Cantero, Domingo; Lafuente, Javier; Gamisans, Xavier; Gabriel, David

    2015-01-01

    Monitoring the biological activity in biotrickling filters is difficult since it implies estimating biomass concentration and its growth yield, which can hardly be measured in immobilized biomass systems. In this study, the characterization of a sulfide-oxidizing nitrate-reducing biomass obtained from an anoxic biotrickling filter was performed through the application of respirometric and titrimetric techniques. Previously, the biomass was maintained in a continuous stirred tank reactor under steady-state conditions resulting in a growth yield of 0.328 ± 0.045 g VSS/g S. To properly assess biological activity in respirometric tests, abiotic assays were conducted to characterize the stripping of CO2 and sulfide. The global mass transfer coefficient for both processes was estimated. Subsequently, different respirometric tests were performed: (1) to solve the stoichiometry related to the autotrophic denitrification of sulfide using either nitrate or nitrite as electron acceptors, (2) to evaluate the inhibition caused by nitrite and sulfide on sulfide oxidation, and (3) to propose, calibrate, and validate a kinetic model considering both electron acceptors in the overall anoxic biodesulfurization process. The kinetic model considered a Haldane-type equation to describe sulfide and nitrite inhibitions, a non-competitive inhibition to reflect the effect of sulfide on the elemental sulfur oxidation besides single-step denitrification since no nitrite was produced during the biological assays.

  2. Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate: methyl propanoate radicals with oxygen molecule.

    Science.gov (United States)

    Le, Xuan T; Mai, Tam V T; Ratkiewicz, Artur; Huynh, Lam K

    2015-04-23

    This paper presents a computational study on the low-temperature mechanism and kinetics of the reaction between molecular oxygen and alkyl radicals of methyl propanoate (MP), which plays an important role in low-temperature oxidation and/or autoignition processes of the title fuel. Their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The potential energy surfaces of the reactions between three primary MP radicals and molecular oxygen, namely, C(•)H2CH2COOCH3 + O2, CH3C(•)HCOOCH3 + O2, and CH3CH2COOC(•)H2 + O2, were constructed using the accurate composite CBS-QB3 method. Thermodynamic properties of all species as well as high-pressure rate constants of all reaction channels were derived with explicit corrections for tunneling and hindered internal rotations. Our calculation results are in good agreement with a limited number of scattered data in the literature. Furthermore, pressure- and temperature-dependent rate constants for all reaction channels on the multiwell-multichannel potential energy surfaces were computed with the quantum Rice-Ramsperger-Kassel (QRRK) and the modified strong collision (MSC) theories. This procedure resulted in a thermodynamically consistent detailed kinetic submechanism for low-temperature oxidation governed by the title process. A simplified mechanism, which consists of important reactions, is also suggested for low-temperature combustion at engine-like conditions.

  3. Study of Degradation Kinetics of Parathion Methyl On Mixed Nanocrystalline Titania-Zirconium and Titania-Cerium Oxides

    Science.gov (United States)

    Kuráň, Pavel; Pšenička, Martin; Šťastný, Martin; Benkocká, Monika; Janoš, Pavel

    2016-10-01

    The unique surface properties of some nanocrystalline metal oxides and their application for removal of various toxic compounds were reported in early 1990s. Recently, a reliable method for the preparation of reactive cerium dioxide sorbent and its application for degradation of the organophosphate pesticides, such as parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) was published. This paper reports on the kinetics study of degradation of parathion methyl as a representative organophosphate on nanocrystalline metal oxides TiO2, ZrO2, CeO2 and their mixtures in different molar ratios of particular elements. The tested sorbents except of CeO2 were prepared by different methods (e.g. sol-gel, precipitation) in cooperation with Institute of Inorganic Chemistry (Rez, Czech Republic). The degradation kinetics of parathion methyl on tested sorbents was followed by HPLC equipped with diode array detector. The basic kinetics parameters (half-lives of parathion methyl degradation, rate constants of degradation product formation) were calculated for each sorbent from Weber-Morris equation of 1st order diffusion kinetic model. The results proved the ability of prepared sorbents to degrade parathion methyl under formation of 4-nitrophenol as the main degradation product. The most efficient sorbents were TiCe (2:8), TiCe (1:1), TiCe (0:1) (50-70 %) followed by TiZr (1:1), TiCe (8:2), TiZr (8:2), TiZr (2:8) (20-30%) and TiO2, ZrO2 (less than 5 %).

  4. Dissolution kinetics and thermodynamic analysis of vanadium trioxide during pressure oxidation

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The dissolution kinetics of vanadium trioxide in sulphuric acid-oxygen medium was examined. It was determined that the concentration of sulphuric acid and stirring speed above 800 r min 1 did not significantly affect vanadium extraction. The dissolution rate increased with increasing temperature and oxygen partial pressure, but decreased with increasing particle size. The dissolution kinetics was controlled by the chemical reaction at the surface with the estimated activation energy of 43.46 kJ·mol-1. The l...

  5. Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers

    NARCIS (Netherlands)

    Jensen, H.S.; Lens, P.N.L.; Nielsen, J.L.; Bester, K.; Nielsen, A.H.; Hvitved-Jacobsen, Th.; Vollertsen, J.

    2011-01-01

    Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria,

  6. Adsorption of cadmium and lead onto oxidized nitrogen-doped multiwall carbon nanotubes in aqueous solution: equilibrium and kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Aguilar, Nancy Veronica [Environmental Sciences Department, Institute for Scientific and Technological Research of San Luis Potosi (Mexico); Munoz-Sandoval, Emilio [Advanced Materials Department, Institute for Scientific and Technological Research of San Luis Potosi (Mexico); Diaz-Flores, Paola Elizabeth; Rangel-Mendez, Jose Rene, E-mail: rene@ipicyt.edu.m [Environmental Sciences Department, Institute for Scientific and Technological Research of San Luis Potosi (Mexico)

    2010-02-15

    Nitrogen-doped multiwall carbon nanotubes (CNx) were chemically oxidized and tested to adsorb cadmium and lead from aqueous solution. Physicochemical characterization of carbon nanotubes included morphological analysis, textural properties, and chemical composition. In addition, the cadmium adsorption capacity of oxidized-CNx was compared with commercially available activated carbon and single wall carbon nanotubes. Carboxylic and nitro groups on the surface of oxidized CNx shifted the point of zero charge from 6.6 to 3.1, enhancing their adsorption capacity for cadmium and lead to 0.083 and 0.139 mmol/g, respectively, at pH 5 and 25 {sup o}C. Moreover, oxidized-CNx had higher selectivity for lead when both metal ions were in solution. Kinetic experiments for adsorption of cadmium showed that the equilibrium was reached at about 4 min. Finally, the small size, geometry, and surface chemical composition of oxidized-CNx are the key factors for their higher adsorption capacity than activated carbon.

  7. Kinetics of the electrolytic Fe+2/Fe+3 oxidation on various anode materials

    Directory of Open Access Journals (Sweden)

    Cifuentes, L.

    2003-08-01

    Full Text Available The kinetics of the electrolytic Fe+2/Fe+3 oxidation, relevant to hydro-electrometallurgical processing, have been studied on lead, platinum, ruthenium oxide, iridium oxide and graphite anodes in ferrous sulfate-sulfuric acid solutions. The oxidation rate depends on ferrous sulfate concentration, solution temperature and degree of agitation. Potentiodynamic studies show that: a the highest oxidation rate is obtained on platinum; b lead is unsuitable as anodic material for the said reaction; c the remaining anode materials show a similar and satisfactory performance.

    Se ha estudiado la cinética de la oxidación electrolítica Fe+2/Fe+3 -relevante para el procesamiento hidroelectrometalúrgico- sobre plomo, platino, óxido de rutenio, óxido de iridio y grafito en soluciones de sulfato ferroso en ácido sulfúrico. La velocidad de oxidación depende de la concentración de sulfato ferroso, la temperatura de la solución y el grado de agitación. Estudios potenciodinámicos demuestran que: a las mayores velocidades de oxidación se obtienen sobre platino; b el plomo es inadecuado como material anódico para la reacción mencionada; c los materiales anódicos restantes exhiben un desempeño similar y satisfactorio.

  8. Oxygen concentrators performance with nitrous oxide at 50:50 volume

    Directory of Open Access Journals (Sweden)

    Jorge Ronaldo Moll

    2014-06-01

    Full Text Available Background and objectives: Few investigations have addressed the safety of oxygen from concentrators for use in anesthesia in association with nitrous oxide. This study evaluated the percent of oxygen from a concentrator in association with nitrous oxide in a semi-closed rebreathing circuit. Methods: Adult patients undergoing low risk surgery were randomly allocated into two groups, receiving a fresh gas flow of oxygen from concentrators (O293 or of oxygen from concentrators and nitrous oxide (O293N2O. The fraction of inspired oxygen and the percentage of oxygen from fresh gas flow were measured every 10 min. The ratio of FiO2/oxygen concentration delivered was compared at various time intervals and between the groups. Results: Thirty patients were studied in each group. There was no difference in oxygen from concentrators over time for both groups, but there was a significant improvement in the FiO2 (p < 0.001 for O293 group while a significant decline (p < 0.001 for O293N2O. The FiO2/oxygen ratio varied in both groups, reaching a plateau in the O293 group. Pulse oximetry did not fall below 98.5% in either group. Conclusion: The FiO2 in the mixture of O293 and nitrous oxide fell during the observation period although oxygen saturation was higher than 98.5% throughout the study. Concentrators can be considered a stable source of oxygen for use during short anesthetic procedures, either pure or in association with nitrous oxide at 50:50 volume.

  9. Kinetic spectrophotometric determination of rutin by its inhibitory effect on the oxidation of amaranth by potassium periodate.

    Science.gov (United States)

    Wang, Shuhao; Du, Lingyun; Yao, Xingjun; Niu, Xueli; Zhuang, Huisheng

    2005-01-01

    A novel kinetic spectrophotometric method is described for the determination of rutin. The method is based on the inhibitory effect of rutin on the oxidation reaction of amaranth by potassium periodate in acidic media at 100 degrees C. The linear range for the determination of rutin is 0.02 - 0.50 microg/ml, and the detection limit is 0.014 microg/ml. The method has been successfully applied to the determination of rutin in medicine of rutin tablet and traditional Chinese medicine.

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

    OpenAIRE

    2007-01-01

    International audience; This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appen...

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

    OpenAIRE

    2004-01-01

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

  12. Kinetics of Passive Oxidation of Hi-Nicalon-S SiC Fibers in Wet Air: Relationships between Si02 Scale Thickness, Crystallization, and Fiber Strength (Preprint)

    Science.gov (United States)

    2012-07-01

    crystallize to cristobalite and tridymite in 100 hours at 1000°C or in one hour at 1300°C. Crystallization kinetics for oxidation in wet air were...measured by TEM. Oxidation initially produces an amorphous scale that starts to crystallize to cristobalite and tridymite in 100 hours at 1000°C or in...using reflected light interference fringes observed by optical microscopy. Cross-sectional TEM specimens were prepared from oxidized fibers by

  13. REDUCTION OF NITRIC OXIDE BY CARBON MONOXIDE OVER A SILICA SUPPORTED PLATINUM CATALYST: INFRARED AND KINETIC STUDIES

    Energy Technology Data Exchange (ETDEWEB)

    Lorimer, D.H.

    1978-08-01

    The reduction of nitric oxide by carbon monoxide over a 4.5 weight precent platinum catalyst supported on silica was studied at 300 C. Reaction rate data was obtained together with in situ infrared spectra of species on the catalyst surface. The kinetics of the system were found to exhibit two distinct trends, depending on the molar ratio of CO/NO in the reactor. For net reducing conditions (CO/NO> 1) the catalyst underwent a transient deactivation, the extent of which was dependent on the specific CO/NO ratio during reaction. Reactivation of the catalyst was obtained with both oxidizing and reducing pretreatments. For molar feed ratios of CO/NO less than one, carbon monoxide conversion was typically 95 to 100%, resulting in strongly oxidizing conditions over the catalyst. Under these conditions no deactivation was apparent. Infrared spectra recorded under reaction conditions revealed intense bands at 2075 and 2300 cm{sup -1} , which were identified as carbon monoxide adsorbed on Pt and Si-NCO, respectively. Isocyanate bands formed under reducing conditions were more intense and exhibited greater stability than those formed under oxidizing conditions. A reaction mechanism based on the dissociation of nitric oxide as the rate-limiting step was used to correlate nitric oxide reaction rates and nitrous oxide selectivities observed under reducing conditions. As part of this mechanism it is assumed that nitrous bxide is formed via a Langmuir-Hinshelwood process in which an adsorbed nitrogen atom reacts with an adsorbed nitric oxide molecule. The nitric oxide reaction rate was found to be first order in nitric oxide partial pressure, and inverse second order in carbon monoxide partial pressure. A mechanism is proposed to qualitatively explain the deactivation process observed under reducing conditions. The essential part of this mechanism is the formation of an isocyanate species on the Pt crystallites of the catalyst and the subsequent transient diffusion of these

  14. Analysis of Absorption and Reaction Kinetics in the Oxidation of Organics in Effluents Using a Porous Electrode Ozonator

    Institute of Scientific and Technical Information of China (English)

    Alexander P. Mathews; ishora K. Panda

    2012-01-01

    A novel electrode design for the in situ generation of ozone in the reaction zone of a tubular reactor is described in this work. The ozone generator uses a porous inner electrode tube in the corona discharge assembly, and the ozone generated around the outer periphery of the porous tube diffuses into the tubular reactor and reacts with the contaminants in the fluid that is being treated. A mathematical model that includes absorption and second order reaction in the film is developed to describe ozonation kinetics of a contaminant dye in the tubular reactor. The model describes the experimental data for dye decolorization, oxidation byproducts, dissolved ozone, and ozone gas concentrations well. Model analysis indicates that the fast dye decolorization reaction occurs partly in the liquid film and partly in the bulk fluid. The model can be used in the selection of appropriate gas-liquid contactors for efficient oxidation of contaminants in effluents.

  15. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才

    2004-01-01

    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  16. Mechanism of oxidation of L-methionine by iron(III)-1,10-phenanthroline complex - A kinetic study

    Indian Academy of Sciences (India)

    P Vani; K Krishna Kishore; R Rambabu; L S A Dikshitulu

    2001-08-01

    Kinetics and mechanism of oxidation of L-methionine by iron(III)-1, 10-phenanthroline complex have been studied in perchloric acid medium. The reaction is first order each in iron(III) and methionine. Increase in [phenanthroline] increases the rate while increase in [HClO4] decreases it. While the reactive species of the substrate is the zwitterionic form, that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law $$\\dfrac{d[Fe(phen)^{2+}_3]}{dt} = \\dfrac{k_2 K_4 K_3 K^2_2 [Fe^{III}] [\\text{phen}^2] [\\text{Met}]}{(1+K_1 [H^+]) ([H^+]^2 + K_4 K_3 K^2_2[\\text{phen}]^2)}.$$

  17. Kinetics and Photodegradation Study of Aqueous Methyl tert-Butyl Ether Using Zinc Oxide: The Effect of Particle Size

    Directory of Open Access Journals (Sweden)

    Zaki S. Seddigi

    2013-01-01

    Full Text Available Zinc oxide of different average particle sizes 25 nm, 59 nm, and 421 nm as applied in the photodegradation of MTBE. This study was carried out in a batch photoreactor having a high pressure mercury lamp. Zinc oxide of particle size of 421 nm was found to be the most effective in degrading MTBE in an aqueous solution. On using this type of ZnO in a solution of 100 ppm MTBE, the concentration of MTBE has decreased to 5.1 ppm after a period of five hours. The kinetics of the photocatalytic degradation of MTBE was found to be a first order reaction.

  18. Absorption of calcium ions on oxidized graphene sheets and study its dynamic behavior by kinetic and isothermal models

    Directory of Open Access Journals (Sweden)

    Mahmoud Fathy

    2016-07-01

    Full Text Available Abstract Sorption of calcium ion from the hard underground water using novel oxidized graphene (GO sheets was studied in this paper. Physicochemical properties and microstructure of graphene sheets were investigated using Raman spectrometer, thermogravimetry analyzer, transmission electron microscope, scanning electron microscope. The kinetics adsorption of calcium on graphene oxide sheets was examined using Lagergren first and second orders. The results show that the Lagergren second-order was the best-fit model that suggests the conception process of calcium ion adsorption on the Go sheets. For isothermal studies, the Langmuir and Freundlich isotherm models were used at temperatures ranging between 283 and 313 K. Thermodynamic parameters resolved at 283, 298 and 313 K indicating that the GO adsorption was exothermic spontaneous process. Finally, the graphene sheets show high partiality toward calcium particles and it will be useful in softening and treatment of hard water.

  19. Kinetics of Heterogeneous Solvent-free Liquid Phase Oxidation of Alcohol Using ZrO2 Catalyst with Molecular Oxygen

    Institute of Scientific and Technical Information of China (English)

    ILYAS Mohammad; SADIQ Mohammad

    2008-01-01

    Clean liquid phase solvent-free oxidation of alcohol to aldehyde/ketone using ZrO2 catalyst with molecular oxygen has been studied.Monoclinic phase ZrO2 has been synthesized and characterized by XRD,SEM,EDX and surface and pore size analyses.Oxidation of alcohol was carded out in a typical batch reactor at different sDeed of agitation(150-1200 r/min),temperature(373-413 K),catalyst loading(50-300 mg)and partial pressure of oxygen(12-101 kPa).These parameters influence alcohol conversion as well as selectivity.A handy touch of kinetics was given to the experimental data and apparent activation energy was calculated.

  20. OH- Initiated Heterogeneous Oxidation of Saturated Organic Aerosols in the Presence of SO2: Uptake Kinetics and Product Identification.

    Science.gov (United States)

    Richards-Henderson, N. K.; Ward, M.; Goldstein, A. H.; Wilson, K. R.

    2014-12-01

    Gas-phase oxidation mechanisms for organic gases are often used as a starting point to understand heterogeneous oxidation. The reaction of a simple alkane hydrocarbon by OH proceeds through hydrogen abstraction and under ambient conditions leads to peroxy radical (RO2) formation. RO2 can further react to form: (1) smaller molecular weight products (i.e. fragmentation) via alkoxy radical formation and dissociation and/or (2) higher molecular weight products with oxygenated functional groups (i.e. functionalization). The ability to perturb these two pathways (functionalization vs. fragmentation) is critical for understanding the detailed reaction mechanism that control atmospheric aging chemistry of particles. At high temperatures the presence of sulfur dioxide (SO2) during organic-OH gas-phase oxidation enhances the fragmentation pathway leading to increased alkoxy formation. It is unknown if a comparative affect occurs at room temperature during a heterogeneous reaction. We used the heterogeneous reaction of OH radicals with sub-micron squalane particles in the presence and absence of SO2 as a model system to explore changes in individual mechanistic pathways. Detailed kinetic measurements were made in a flow tube reactor using a vacuum ultraviolet (VUV) photoionization aerosol mass spectrometer and oxidation products are identified from samples collected on quartz filters using thermal desorption two-dimensional chromatographic separation and ionization by either VUV (10.5 eV) or electron impact (70 eV), with detection by high resolution time of flight mass spectrometry (GCxGC-VUV/EI-HRTOFMS). In the presence of SO2 the yields of alcohols were enhanced compared to without SO2, suggesting that the alkoxy formation pathway was dominant. The results from this work will provide an experimentally-confirmed kinetic framework that could be used to model atmospheric aging mechanisms.

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

    Science.gov (United States)

    2010-12-28

    Fuel Cells " Ann. Rev. Anal. Chem., 3 151-174 (2010). 2. B. C. Eigenbrodt1, M. B. Pomfret, D. A. Steinhurst, J. C. Owrutsky and R. A. Walker "Direct...in situ optical studies of solid oxide fuel cells operating with methanol and methane" J. Phys. Chem. C available online at ASAP. (Content from...Mapping of Surface Electrolyte Oxide Concentration in Solid Oxide Fuel Cells " submitted to Analytical Methods, accepted pending revisions. 4. J. D

  2. Experimental study and kinetic analysis of the oxidation of light hydrocarbons mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Bonini, F.; Morbidelli, M.; Carra, S. [Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata

    1996-07-01

    The combustion of various C{sup 1}-C{sub 2} hydrocarbon mixtures has been experimentally investigated in a continuous perfectly stirred reactor, in a temperature range from 1,000 to 1,300 K, and at stoichiometric ratio values between 0.5 and 1.5. The concentration values of several molecular species have been measured by GC analysis. The data obtained have been compared with the predictions of two different detailed kinetic models; both fail to predict the experimental trends in various situations. This leads to the conclusion that experimental data based on mixtures of hydrocarbons must be obtained to validate detailed kinetic mechanisms.

  3. Adsorption characteristics of graphene oxide as a solid adsorbent for aniline removal from aqueous solutions: Kinetics, thermodynamics and mechanism studies

    Directory of Open Access Journals (Sweden)

    Ali Fakhri

    2017-01-01

    Full Text Available The aim of this study is to investigate the possibility of graphene oxide (GO as an alternative adsorbent for aniline removal from aqueous solution. Adsorption properties of GO for aniline removal were regularly investigated, including pH effect, adsorbent dose, temperature, contact time and initial concentration. The adsorption amount of aniline decreased with increasing pH. The experimental data were evaluated by Langmuir, Freundlich, Temkin and Harkins–Jura models in order to describe the equilibrium isotherms. Equilibrium data fitted well to the Langmuir model. The kinetic parameters achieved at different concentrations were analyzed using a pseudo first-order, pseudo second-order kinetic equation and intra-particle diffusion model. The experimental data fitted very well the pseudo second-order kinetic model. Thermodynamic parameters (free energy change, enthalpy change, and entropy change announced that the removal of aniline from GO was endothermic and spontaneous. The study showed that GO could be used as an efficient adsorbent material for the adsorption of aniline from aqueous solution.

  4. Kinetics of Carbon Monoxide Electro-Oxidation in Solid-Oxide Fuel Cells from Ni-YSZ Patterned-Anode Measurements

    KAUST Repository

    Hanna, J.

    2013-04-17

    A mathematical model is developed around the framework of a reduced mechanism describing electrochemical oxidation of carbon monoxide on Ni-YSZ patterned anodes. The electro-oxidation mechanism involves three reactions, one describing adsorption/ desorption of COonNi, and two single-electron charge-transfer steps inwhich the surface adsorbate CO(Ni) participates directly. These steps are coupled with surface transport in a reaction-diffusion model for which analytic equilibrium and steady-state solutions are derived. As much as possible, we make use of existing, independent, published information about heterogeneous chemistry, surface transport, and other model parameters. The only unknowns in our model are taken to be the kinetic rate constants of the electrochemical reactions, which we evaluate by fitting the model predictions to previously published patterned-anode experiments [B. Habibzadeh, Ph.D. Thesis, University of Maryland, College Park, MD, USA (2007)]. The results show that diffusion of CO on the Ni surface to the three-phase boundary is the rate-controlling process for CO electro-oxidation. Moreover, from a reaction standpoint, the charge-transfer process is dominated by a slow step involving CO(Ni). These findings collectively demonstrate the critical dependence of the electro-oxidation process to the direct participation of CO. © 2013 The Electrochemical Society. All rights reserved.

  5. Effect of oxidizing environment on the strength and oxidation kinetics of HTGR graphites. Part I. Reactivity and strength loss of H451, PGX and IG-11 graphites

    Energy Technology Data Exchange (ETDEWEB)

    Eto, M.; Growcock, F.B.

    1981-09-01

    The effects of oxidizing atmosphere and temperature on the reactivities and strengths of PGX, H451, and IG-11 were examined. Preliminary measurements of the oxidation kinetics of these graphites in H/sub 2/O-, CO/sub 2/- and O/sub 2/-containing atmospheres indicated that the reactivities of H451 graphite toward O/sub 2/ and H/sub 2/O are quite similar to those of IG-11 graphite. The apparent activation energy for oxidation of these in O/sub 2/ were estimated to be approx. 175 kJ/mol while that in H/sub 2/O is probably approx. 200 kJ/mol. The apparent activation energy of IG-11 graphite oxidized in CO/sub 2/ is 255 +- 18 kJ/mol. PGX graphite was found to be quite variable in its reactivity toward H/sub 2/O. A linear dependence with (Fe) was determined, but other intrinsic properties were found to affect its absolute reactivity by as much as a factor of X50.

  6. Low-volume interval training improves muscle oxidative capacity in sedentary adults.

    Science.gov (United States)

    Hood, Melanie S; Little, Jonathan P; Tarnopolsky, Mark A; Myslik, Frank; Gibala, Martin J

    2011-10-01

    High-intensity interval training (HIT) increases skeletal muscle oxidative capacity similar to traditional endurance training, despite a low total exercise volume. Much of this work has focused on young active individuals, and it is unclear whether the results are applicable to older less active populations. In addition, many studies have used "all-out" variable-load exercise interventions (e.g., repeated Wingate tests) that may not be practical for all individuals. We therefore examined the effect of a more practical low-volume submaximal constant-load HIT protocol on skeletal muscle oxidative capacity and insulin sensitivity in middle-aged adults, who may be at a higher risk for inactivity-related disorders. Seven sedentary but otherwise healthy individuals (three women) with a mean ± SD age, body mass index, and peak oxygen uptake (VO(2peak)) of 45 ± 5 yr, 27 ± 5 kg·m(-2), and 30 ± 3 mL·kg(-1)·min(-1) performed six training sessions during 2 wk. Each session involved 10 × 1-min cycling at ∼60% of peak power achieved during a ramp VO(2peak) test (eliciting ∼80%-95% of HR reserve) with 1 min of recovery between intervals. Needle biopsy samples (vastus lateralis) were obtained before training and ∼72 h after the final training session. Muscle oxidative capacity, as reflected by the protein content of citrate synthase and cytochrome c oxidase subunit IV, increased by ∼35% after training. The transcriptional coactivator peroxisome proliferator-activated receptor γ coactivator 1α was increased by ∼56% after training, but the transcriptional corepressor receptor-interacting protein 140 remained unchanged. Glucose transporter protein content increased ∼260%, and insulin sensitivity, on the basis of the insulin sensitivity index homeostasis model assessment, improved by ∼35% after training. Constant-load low-volume HIT may be a practical time-efficient strategy to induce metabolic adaptations that reduce the risk for inactivity-related disorders

  7. Induction of Inducible Nitric Oxide Synthase by Lipopolysaccharide and the Influences of Cell Volume Changes, Stress Hormones and Oxidative Stress on Nitric Oxide Efflux from the Perfused Liver of Air-Breathing Catfish, Heteropneustes fossilis: e0150469

    National Research Council Canada - National Science Library

    Mahua G Choudhury; Nirmalendu Saha

    2016-01-01

    ...) (a bacterial endotoxin), and (b) to determine the effects of hepatic cell volume changes due to anisotonicity or by infusion of certain metabolites, stress hormones and by induction of oxidative stress on production of NO from...

  8. Kinetic behavior of anti-inflammatory drug ibuprofen in aqueous medium during its degradation by electrochemical advanced oxidation.

    Science.gov (United States)

    Ambuludi, Silvia Loaiza; Panizza, Marco; Oturan, Nihal; Özcan, Ali; Oturan, Mehmet A

    2013-04-01

    The electrochemical abatement of the drug ibuprofen (2-(4-isobutylphenyl)propionic acid) from aqueous solution has been carried out by anodic oxidation. The electrolyses have been performed at constant current using a small, undivided cell equipped with a Pt or thin-film boron-doped diamond (BDD) anode and a carbon-felt cathode. The results have shown that ibuprofen has been destroyed under all the conditions tested, following pseudo-first-order kinetics; however, BDD enables higher removal rates than Pt, because the former produces greater quantity of (•)OH. Using BDD anode, the pseudo-first-order rate constant increased with applied current and when NaCl replaced Na2SO4 as supporting electrolyte, while it is almost unaffected by ibuprofen concentration. Mineralization of ibuprofen aqueous solutions was followed by total organic carbon (TOC) measurements. After 8 h of electrolysis, TOC removal varied from 91% to 96% applying a current in the range of 50-500 mA. The reaction by-products were quantified by chromatographic techniques, and in particular, aliphatic acids (oxalic, glyoxylic, formic, acetic, and pyruvic) have been the main intermediates formed during the electrolyses. The absolute rate constant for the oxidative degradation of ibuprofen have also been determined, by competition kinetic method, as 6.41 × 10(9) M(-1) s(-1).

  9. Kinetics and Mechanistic Studies on Oxidation of Levocarnitine by Bromamine-T in HCl Medium Catalyzed by Ru(III

    Directory of Open Access Journals (Sweden)

    R. Ramachandrappa

    2013-01-01

    Full Text Available A kinetic study on RuCl3-catalysed oxidation of levocarnitine (LC by sodium N-bromo-p-toluenesulphonamide or bromamine-T (BAT has been carried out in HCl medium at 303 K. The reaction rate shows a first order dependence on [BAT]0 and fractional order with respect to both [LC]0 and [H+]. Addition of the reaction product, p-toluenesulphonamide, retards the rate. The addition of RuCl3 and chloride ions to the reaction mixture shows an increase in the rate of the reaction. The dielectric effect is positive. The variation of ionic strength of the medium has no significant effect on the rate of the reaction. The reaction fails to initiate polymerization of acrylamide. Michaelis-Menten type of kinetics has been proposed. Thermodynamic parameters have been computed from Arrhenius plot by studying the reaction at different temperatures. The reaction stoichiometry and oxidation products were identified. Based on the experimental observations a suitable mechanism was proposed and rate law deduced.

  10. Thermodynamic, kinetic and mechanistic investigations of Piperazine oxidation by Diperiodatocuprate(III) complex in aqueous alkaline medium

    Indian Academy of Sciences (India)

    Vijay P Pattar; Prashant A Magdum; Deepa G Patil; Sharanappa T Nandibewoor

    2016-03-01

    The kinetics of oxidation of piperazine by the copper complex, diperiodatocuprate(III) in alkaline medium was studied at 298 K, at an ionic strength of 2.0*10-2 mol dm-3. The reaction between piperazine and diperiodatocuprate(III) in aqueous alkaline medium exhibited 1:2 stoichiometry. The oxidation products were identified by UV-Visible, GC-MS and IR spectral studies. In the present study we have obtained different kinetic observations. The reaction exhibited unit order in case of diperiodatocuprate(III), while less than unit order with respect to piperazine. The addition of alkali and periodate retarded the rate of reaction. The effects of added products, ionic strength and dielectric constant on the rate of the reaction were also studied. The active species of diperiodatocuprate(III) in alkaline media is [Cu(OH)2(H3IO6)]-. The activation parameters with respect to the rate determining step and the thermodynamic quantities with respect to the equilibrium steps were evaluated and discussed. The plausible mechanism consistent with the experimental results was proposed and discussed in detail.

  11. Oxidation pathways for ozonation of azo dyes in a semi-batch reactor: a kinetic parameters approach.

    Science.gov (United States)

    Lopez, A; Benbelkacem, H; Pic, J S; Debellefontaine, H

    2004-03-01

    In this study ozone and the H2O2/O3 oxidation system are used to decolorize aqueous solutions of Orange II (Or-II) and Acid Red 27 (AR-27). Investigations are carried out in a semi-batch bubble column reactor. A system of series-parallel reactions is proposed to describe the mechanism of dye oxidation. The stoichiometric ratio for the first reaction is found to be 1 mol dye per mol O3, while the overall ozone demand for both reactions one and two is found to be 5 and 6 moles for Or-II and AR-27 respectively. Molecular and radical kinetics are compared: a radical scavenger, t-butanol, can be added to ensure only the molecular reaction of ozone, or hydrogen peroxide can be supplied through a peristaltic pump, to initiate radical reactivity. Results reveal that colour removal is ensured by direct ozone attack. For both dyes, TOC removal efficiencies of 50 - 60 % are obtained by the action of the hydroxyl free radical. However, this is not improved by addition of H2O2, thus demonstrating that organic species alone ensure HO degrees radical production during ozonation. Both the mass transfer and the ozone reactivity with the dyes are considered to evaluate the kinetic parameters for the molecular pathway.

  12. Extraction/oxidation kinetics of low molecular weight compounds in wine brandy resulting from different ageing technologies.

    Science.gov (United States)

    Canas, Sara; Caldeira, Ilda; Belchior, A Pedro

    2013-06-15

    This study provides innovative information on the influence of new technologies of ageing (stainless steel tanks with wood staves or wood tablets of chestnut or Limousin oak), in comparison with traditional technology (oak wooden barrels), on the extraction/oxidation kinetics of low molecular weight compounds of wine brandy. The brandy was sampled and analysed by HPLC during the first year of ageing. The results show that most of the compounds tend to increase over the time, but their extraction/oxidation kinetics depend on the ageing technology. The wooden barrels promote greater enrichment in the majority of the compounds. However, gallic acid, ellagic acid and syringaldehyde, and vanillin and 5-methylfurfural, which are strong antioxidants and key-odourant compounds, respectively, present higher contents in the brandy aged with the alternative technologies. Chestnut proves to be a suitable alternative to Limousin oak for the ageing of brandy in all the studied technologies, inducing faster evolution and high quality. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Dissolution Kinetics of Oxidative Etching of Cubic and Icosahedral Platinum Nanoparticles Revealed by in Situ Liquid Transmission Electron Microscopy.

    Science.gov (United States)

    Wu, Jianbo; Gao, Wenpei; Yang, Hong; Zuo, Jian-Min

    2017-02-28

    Dissolution due to atom-level etching is a major factor for the degradation of Pt-based electrocatalysts used in low-temperature polymer electrolyte membrane fuel cells. Selective surface etching is also used to precisely control shapes of nanoparticles. Dissolution kinetics of faceted metal nanoparticles in solution however is poorly understood despite considerable progress in understanding etching of two-dimensional surfaces. We report here the application of in situ liquid transmission electron microscopy for quantitative analysis of oxidative etching of cubic and icosahedral Pt nanoparticles. The experiment was carried out using a liquid flow cell containing aqueous HAuCl4 solution. The data show that oxidative etching of these faceted nanocrystals depends on the location of atoms on the surface, which evolves with time. A quantitative kinetic model was developed to account for the mass lost in electrolyte solutions over time, showing the dissolutions followed the power law relationship for Pt nanocrystals of different shapes. Dissolution coefficients of different surface sites were obtained based on the models developed in this study.

  14. Assessing the kinetics of high temperature oxidation of Inconel 617 in a dedicated HTR impure helium facility coupling thermogravimetry and gas phase chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Chapovaloff, J., E-mail: chpvlff@aol.com [AREVA NP, Centre Technique, Département Corrosion-Chimie, 30 Bd de l’industrie, 71200 Le Creusot (France); Ecole Nationale Supérieure des Mines, SMS-EMSE, CNRS: UMR5146, LCG, 158 Cours Fauriel, 42023 Saint Etienne (France); Rouillard, F., E-mail: fabien.rouillard@cea.fr [CEA, DEN, DPC, SCCME, Laboratoire d’Etude de la Corrosion Non Aqueuse, 91191 Gif sur Yvette (France); Combrade, P., E-mail: pierre.combrade@orange.fr [AREVA NP, Centre Technique, Département Corrosion-Chimie, 30 Bd de l’industrie, 71200 Le Creusot (France); ACXCOR, 63, chemin de l’Arnica, 42660 Le Bessat (France); Pijolat, M., E-mail: mpijolat@emse.fr [Ecole Nationale Supérieure des Mines, SPIN-EMSE, CNRS: UMR5148, LCG, 158 Cours Fauriel, 42023 Saint Etienne (France); Wolski, K., E-mail: wolski@emse.fr [Ecole Nationale Supérieure des Mines, SMS-EMSE, CNRS: UMR5146, LCG, 158 Cours Fauriel, 42023 Saint Etienne (France)

    2013-10-15

    Graphical abstract: Display Omitted -- Highlights: •New facility coupling thermogravimetry (TGA) with gas phase chromatography (GPC). •Dedicated for HT oxidation study in VHTR impure helium containing CO, H{sub 2}O and H{sub 2}. •The oxidation kinetics obeys a complete parabolic law due to a mixed kinetic regime. •CO contributes during initial stage of oxidation only for very low H{sub 2}O partial pressure. •Long-term oxidation of Inconel 617 by H{sub 2}O is diffusion controlled with constant kp. -- Abstract: A new facility coupling thermogravimetric analysis (TGA) with gas phase chromatography (GPC) has been developed. This facility is dedicated for studying high temperature oxidation of Inconel 617 in impure helium environment containing H{sub 2}O, H{sub 2} and CO at very low partial pressures (in the Pa range), which is representative of the high temperature reactor (HTR) concept developed within the Generation IV Forum. Simultaneous acquisition of mass gain and gas composition has allowed the influence of carbon monoxide and water vapour on the kinetics of oxidation to be studied. GPC measurements of gas consumption have allowed the plotting of individual mass gain curves for oxidation by H{sub 2}O and CO. During isothermal exposure at 1123 K for 20 h, the oxidation was mainly due to water vapour with a minor contribution of carbon monoxide during the first hours. The contribution of water vapour to the oxidation kinetics was extracted. It was shown to obey a complete parabolic law and to be limited by an interfacial reaction during the first few hours of oxidation and to be controlled by a mixed interfacial and diffusion process, diffusion becoming the rate-determining step for long term oxidation. There was very good agreement between GPC measurements and the experimental TGA results.

  15. Anodically generated manganese(III) sulphate for the oxidation of dipeptides in aqueous sulphuric acid medium: A kinetic study

    Indian Academy of Sciences (India)

    M N Kumara; D Channe Gowda; A Thimme Gowda; K S Rangappa

    2004-01-01

    The kinetic of oxidation of dipeptides (DP) namely valyl-glycine (Val-Gly), alanyl-glycine (Ala-Gly) and glycyl-glycine (Gly-Gly), by Mn(III) have been studied in the presence of sulphate ions in acid medium at 26°C. The reaction was followed spectrophotometrically at max = 500 nm. A firstorder dependence of the rate on both [Mn(III)]$_o$ and [DP]o was observed. The rate is independent of the concentration of reduction product, Mn(II) and hydrogen ions. The effects of varying the dielectric constant of the medium and addition of anions such as sulphate, chloride and perchlorate were studied. The activation parameters have been evaluated using Arrhenius and Eyring plots. The oxidation products were isolated and characterized. A mechanism involving the reaction of DP with Mn(III) in the ratelimiting step is suggested. An apparent correlation was noted between the rate of oxidation and the hydrophobicity of these dimers, where increased hyphobicity results in increased rate of oxidation.

  16. Kinetics of Air Oxidation and Oxygen Oxidation of Paraffin%石蜡氧气氧化和空气氧化动力学

    Institute of Scientific and Technical Information of China (English)

    方静; 杨基和; 刘英杰

    2011-01-01

    The esterification wax was synthesized by one-step oxygen oxidation and esterification process from mixed paraffin and microcrystalline with the mass ratio of 6:4. The results were compared with traditional air oxidation process. The kinetic models of the oxygen and air oxidation were established, respectively. The model parameters were obtained by linear regression of saponification values under different reaction temperatures The activation energy is 6.49 kJ/mol for oxygen oxidation and 11.56 KJ/mol for air oxidaomtion, while pre-exponent factor is 3.09 h-1 and 11.33 h-1, respectively. Compared with air oxidation, the product of oxygen oxidation possesses higher esterification number, less off-gas discharge and quicker reaction rate.%石蜡与微晶蜡质量比6∶4的混合原料,经纯氧氧化、酯化一步法合成高酯值蜡.与传统的空气氧化法进行了对比研究,并以皂化值为参数建立了两种氧化法的动力学模型.由不同反应温度下的实验数据回归得到氧气氧化反应的活化能为6.49 kJ/mol,指前因子为3.09h-1;空气氧化反应的活化能为11.56 kJ/mol,指前因子为11.33 h-1.研究表明,相对于空气氧化法,氧气氧化法具有产品酯化值高、尾气排放量少以及反应速率快的优点

  17. Dissociation against oxidation kinetics for the conversion of VOCs in non-thermal plasmas of atmospheric gases

    Science.gov (United States)

    Pasquiers, Stéphane; Blin-Simiand, Nicole; Magne, Lionel

    2016-08-01

    The kinetics of four volatile organic compounds (VOCs) (propene, propane, acetaldehyde, acetone) were studied in plasmas of atmospheric gases using a photo-triggered discharge (homogeneous plasma) or a dielectric barrier discharge (filamentary plasma). It was shown for the homogeneous plasma that quenchings of nitrogen metastable states, A3Ʃ+u and the group of singlets a' 1Ʃ-u, a 1Πg and w 1∆u, are important processes for the decomposition of such molecules. Recent measurements of the H2 concentration produced in the N2/C3H6 mixture emphasize that the hydrogen molecule can be an exit route for propene dissociation. It is also found that H2 and CO molecules are efficiently produced following the dissociation of CH3COCH3 and the subsequent chemical reactivity induced by radicals coming from acetone. Addition of oxygen to a N2/VOC mixture can change drastically the kinetics. However, the quenching processes of N2 metastables by the VOC are always present and compete with oxidation reactions for the conversion of the pollutant. At low temperature, oxidations by O or by OH are not always sufficiently effective to induce an increase of the molecule decomposition when oxygen is added to the mixture. In particular, the presence of O2 has a detrimental effect on the acetone removal. Also, as evidenced for acetaldehyde and propane, some kinetic analogies appear between filamentary and homogeneous plasmas. Contribution to the topical issue "6th Central European Symposium on Plasma Chemistry (CESPC-6)", edited by Nicolas Gherardi, Ester Marotta and Cristina Paradisi

  18. Kinetics of Alcohol Dehydrogenase-Catalyzed Oxidation of Ethanol Followed by Visible Spectroscopy

    Science.gov (United States)

    Bendinskas, Kestutis; DiJiacomo, Christopher; Krill, Allison; Vitz, Ed

    2005-01-01

    The effect of substrate concentration on the rate of enzymatic reaction was investigated and typical Michaelis-Mentin kinetics was observed during the first week. The first order reaction at relatively low concentrations of ethanol and the pseudo zero-order reaction at high concentrations of ethanol were emphasized.

  19. Solid oxide electrode kinetics in light of in situ surface studies

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    2014-01-01

    The combination of in situ and in particular in operando characterization methods such as electrochemical impedance spectroscopy (EIS) on both technical and model electrode are well known ways to gain some practical insight in electrode reaction kinetics. Yet, is has become clear that in spite...

  20. KINETICS OF THE OXIDATION OF FERROUS CHELATES OF EDTA AND HEDTA IN AQUEOUS-SOLUTION

    NARCIS (Netherlands)

    WUBS, HJ; BEENACKERS, AACM

    1993-01-01

    The kinetics of the reaction of oxygen with ferrous chelates of EDTA and HEDTA was studied in a stirred cell reactor under industrial conditions. The temperature was varied from 20 to 60-degrees-C and the concentration of the ferrous chelate ranged from 0 to 100 mol/m3. The initial pH was 7.5. Under