Science.gov

Sample records for oxidative kinetic resolution

  1. Efficiency in nonenzymatic kinetic resolution.

    PubMed

    Vedejs, Edwin; Jure, Mara

    2005-06-27

    The Walden memorial at the Technical University in Riga is pictured in the frontispiece to mark the recent centennial of the Walden inversion. This is a rare public monument to key events from the first era of exploration in stereocontrolled synthesis, and may be the only such monument to use the language of organic chemistry expressed at the molecular level. The reaction of racemic substrates with chiral nucleophiles is one of many methods currently known to achieve kinetic resolution, a phenomenon that ranks as the oldest and most general approach for the synthesis of highly enantioenriched substances. The first nonenzymatic kinetic resolutions as well as the original forms of the Walden inversion were studied in the 1890s. All of these investigations were conducted within the first generation following the demonstration that carbon is tetrahedral, and provided abundant evidence that the principles and importance of enantiocontrolled syntheses were understood. However, a reliable, rapid technique to quantify results and guide the optimization process was still lacking. Many decades passed before this problem was solved by the advent of HPLC and GLPC assays on chiral supports, which stimulated explosive growth in the synthesis of nonracemic substances by kinetic resolution. The Walden monument is accessible to passers-by for hands-on inspection as well as for contemplation and learning. In a similar way, kinetic resolution is experimentally accessible and can be thought-provoking at several levels. We follow the story of kinetic resolution from the early discoveries through fascinating historical milestones and conceptual developments, and close with a focus on modern techniques that maximize efficiency. PMID:15942973

  2. Oxidation kinetics of aluminum diboride

    NASA Astrophysics Data System (ADS)

    Whittaker, Michael L.; Sohn, H. Y.; Cutler, Raymond A.

    2013-11-01

    The oxidation characteristics of aluminum diboride (AlB2) 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 AlB2 in the onset of oxidation and final conversion fraction, with AlB2 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 AlB2 and Al+2B in both air and oxygen. AlB2 exhibited O2-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O2 than in air. Differences in the composition and morphology between oxidized Al+2B and AlB2 suggested that Al2O3-B2O3 interactions slowed Al+2B oxidation by converting Al2O3 on aluminum particles into a Al4B2O9 shell, while the same Al4B2O9 developed a needle-like morphology in AlB2 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 AlB2, but both appear to be resistant to oxidation in cool, dry environments.

  3. Oxidation kinetics of aluminum diboride

    SciTech Connect

    Whittaker, Michael L.; Sohn, H.Y.; Cutler, Raymond A.

    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. Chemoenzymatic dynamic kinetic resolution of acyloins.

    PubMed

    Odman, Peter; Wessjohann, Ludger A; Bornscheuer, Uwe T

    2005-11-11

    [Reaction: see text]. Acyloins (alpha-hydroxy ketones) are important building blocks in organic synthesis, e.g., for the total synthesis of epothilones. Optically pure acyloins can be obtained by lipase-catalyzed kinetic resolution (KR) of the racemate with, for example, Burkholderia cepacia lipase, but this process suffers from a yield limitation of 50%. To devise a dynamic kinetic resolution (DKR), we studied the racemization of two different acyloins and corresponding esters with various amine bases and ion exchangers. No combination of base and solvent was found that could selectively racemize the acyloin or corresponding ester under the conditions needed for a DKR. In contrast to bases, acidic resins (ARs) were found to racemize the acyloins selectively in n-hexane and in water. Unfortunately, the AR deactivated the lipase, preventing a one-pot DKR. Minor side reactions involving the AR, the substrate acyloin, and the vinyl ester acyl donor were also observed. However, an efficient DKR was made possible by the spatial separation of lipase and ion exchanger, with enzymatic transesterification and AR-catalyzed racemization taking place simultaneously in two compartments connected by a pump loop. The conversion of substrate alcohol was 91%, the selectivity toward the product butyrate ester 90%, and the enantiomeric excess of the (S)-product 93% ee. PMID:16268632

  5. Ultrahigh-performance liquid chromatography-ultraviolet absorbance detection-high-resolution-mass spectrometry combined with automated data processing for studying the kinetics of oxidative thermal degradation of thyroxine in the solid state.

    PubMed

    Neu, Volker; Bielow, Chris; Reinert, Knut; Huber, Christian G

    2014-12-01

    Levothyroxine as active pharmaceutical ingredient of formulations used for the treatment of hypothyroidism is distributed worldwide and taken by millions of people. An important issue in terms of compound stability is its capability to react with ambient oxygen, especially in case of long term compound storage at elevated temperature. In this study we demonstrate that ultrahigh-performance liquid chromatography coupled to UV spectrometry and high-resolution mass spectrometry (UHPLC-UV-HRMS) represent very useful approaches to investigate the influence of ambient oxygen on the degradation kinetics of levothyroxine in the solid state at enhanced degradation conditions. Moreover, the impurity pattern of oxidative degradation of levothyroxine is elucidated and classified with respect to degradation kinetics at different oxygen levels. Kinetic analysis of thyroxine bulk material at 100 °C reveals bi-phasic degradation kinetics with a distinct change in degradation phases dependent on the availability of oxygen. The results clearly show that contact of the bulk material to ambient oxygen is a key factor for fast compound degradation. Furthermore, the combination of time-resolved HRMS data and automated data processing is shown to allow insights into the kinetics and mechanism of impurity formation on individual compound basis. By comparing degradation profiles, four main classes of profiles linked to reaction pathways of thyroxine degradation were identifiable. Finally, we show the capability of automated data processing for the matching of different stressing conditions, in order to extract information about mechanistic similarities. As a result, degradation kinetics is influenced by factors like availability of oxygen, stressing time, or stressing temperature, while the degradation mechanisms appear to be conserved. PMID:25456598

  6. Kinetics of soot oxidation by NO2

    SciTech Connect

    Shrivastava, ManishKumar B.; Nguyen, Anh; Zheng, Zhongqing; Wu, Hao-Wei; Jung, Hee-Jung

    2010-06-15

    Modern technologies use NO2 to promote low temperature soot oxidation for diesel particulate filter regeneration. Most previous methods studied soot oxidation with NO2 using offline methods such as thermo-gravimetric analysis (TGA). In this study, the online aerosol-technique of high-temperature oxidation tandem differential mobility analysis (HTO-TDMA) is used to study kinetics of soot oxidation with NO2 under N2 environment. This method has significant advantages over previous offline methods in reducing heat and mass transfer diffusion limitations to the soot surface. Soot particles are exposed to varying temperature and NO2 concentration inside the furnace resulting from thermal decomposition of NO2 to NO. This causes soot oxidation rates to vary throughout the furnace. In this study, variations in temperatures, NO2 concentrations and particle residence times are thoroughly accounted for the first time, and soot oxidation rates are derived. Soot oxidation rate is calculated as a function of Arrhenius rate constant Asoot, activation energy Esoot, and partial pressure of NO2 PNO2 within the furnace at temperatures ranging 500- 950 C. Results suggest Asoot and Esoot values for soot oxidation with NO2 of 1.68 nm K-0.5 s-1 (Nm-2)-n and 46.5 kJ mol-1 respectively. The activation energy for soot oxidation with NO2 is significantly lower than oxidation with air. However, ppm levels of NO2 cause soot oxidation at low temperatures suggesting NO2 is a stronger oxidant than O2. This study also shows that a semi-empirical approach with just a few kinetic parameters could represent varying soot oxidation rates in a diesel engine cylinder or on a diesel particulate filter. Further studies should be directed towards understanding synergistic effects of other oxidants as O2 and H2O in addition to NO2 using the HTO-TDMA method.

  7. Kinetic Resolution in Asymmetric Epoxidation using Iminium Salt Catalysis

    PubMed Central

    2013-01-01

    The first reported examples of kinetic resolution in epoxidation reactions using iminium salt catalysis are described, providing up to 99% ee in the epoxidation of racemic cis-chromenes. PMID:23862687

  8. Oxidation kinetics and soot formation

    NASA Technical Reports Server (NTRS)

    Glassman, I.; Brezinsky, K.

    1983-01-01

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

  9. Oxidation and hydrolysis kinetic studies on UN

    NASA Astrophysics Data System (ADS)

    Rao, G. A. Rama; Mukerjee, S. K.; Vaidya, V. N.; Venugopal, V.; Sood, D. D.

    1991-11-01

    The reaction of oxygen and water vapour with UN microspheres containing 0.78 and 10.9 mol% UO 2 as impurity was studied under non-isothermal heating conditions in a thermobalance under different partial pressures of oxygen, a fixed pressure of water vapour in argon, and in air. Uranium mononitride was ultimately converted to U 3O 8, with the formation of UO 2 and U 2N 3 as intermediates. The end product of pyrohydrolysis was UO 2. The kinetic parameters were evaluated and the mechanism of the reaction was suggested. Different kinetic models were used to explain the oxidation behaviour of UN.

  10. Chemical kinetic modeling of exhaust hydrocarbon oxidation

    SciTech Connect

    Wu, K.C.; Hochgreb, S.; Norris, M.B. . Dept. of Mechanical Engineering)

    1995-01-01

    Numerical simulations of the oxidation of unburned hydrocarbons from spark ignition engines were made based on full-chemistry, zero-dimensional models and compared with experiments for engine-out hydrocarbons and exhaust port oxidation. Simple correlations can be drawn between calculated results for hydrocarbon oxidation half-lives in plug or stirred reactors and measured hydrocarbon emissions. the extent of reaction through the exhaust port was simulated using calculated temperature histories for each burned gas mass element leaving the cylinder, coupled to detailed chemical kinetic rate equations. The results show that, for the fuels considered, the extent of oxidation of the remaining unburned fuel measured through the exhaust can be bracketed by the calculated results for the well-mixed (average) and core (adiabatically expanded) temperatures in the exhaust. Most of the oxidation is shown to occur at the very early exhaust times. For the paraffins considered, comparisons of simulations and experiments suggest that fuel oxidation is partially controlled by the mixing of cold gases at the initial stages of exhaust, where temperatures are high and the cold unburned mixture emerges from the wall layers into the exhaust jet. These conclusions are supported by the relatively small measured dependence on fuel type of the extent of oxidation in the exhaust, and by the resulting ratio of fuel to nonfuel hydrocarbons in the exhaust port exit.

  11. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Copper-catalyzed divergent kinetic resolution of racemic allylic substrates.

    PubMed

    Pineschi, Mauro; Di Bussolo, Valeria; Crotti, Paolo

    2011-10-01

    When a racemic mixture is fully consumed the products may still be enantiomerically enriched. In particular, the regiodivergent kinetic resolution is a process in which a single chiral catalyst or reagent reacts with a racemic substrate to form regioisomers possessing an opposite configuration on the newly-formed stereogenic centers. This review reports the major advances in the field of the copper-catalyzed regiodivergent and stereodivergent kinetic resolution of allylic substrates with organometallic reagents. The chiral recognition matching phenomena found with particular allylic substrates with the absolute configuration of the chiral catalyst allows in some cases an excellent control of the regio- and stereoselectivity, sheding some light on the so-called "black-box" mechanism of a copper-catalyzed asymmetric allylic alkylation. PMID:21837639

  14. KINETICS AND MECHANISMS FOR TCE OXIDATION BY PERMANGANATE

    EPA Science Inventory

    The oxidation of trichloroethylene (TCE) by permanganate was studied via a series of kinetic experiments. The goal in product identificationa dn parameterization of the oxidation kinetics was to assess the utility of this reaction as the basis for the in-situ remediation of grou...

  15. Charting oxidized methylcytosines at base resolution

    PubMed Central

    Wu, Hao; Zhang, Yi

    2015-01-01

    DNA cytosine methylation (5-methylcytosines) represents a key epigenetic mark and is required for normal development. Iterative oxidation of 5mC by TET family of DNA dioxygenases generates three oxidized nucleotides, 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC), and 5-carboxycytosine (5caC), in the mammalian genome. Recent advances in genomic mapping techniques for these oxidized bases suggest that 5hmC/5fC/5caC are not only functionally relevant to the process of active reversal of 5mC, but may also possess unique regulatory functions. This perspective highlights the potential gene regulatory functions of these oxidized cytosine bases in the mammalian genome, and discusses the principles and limitations of recently developed base-resolution mapping technologies. PMID:26333715

  16. Enzymatic kinetic resolution of racemic ibuprofen: past, present and future.

    PubMed

    José, Carla; Toledo, María Victoria; Briand, Laura E

    2016-10-01

    This review is a journey concerning the investigations of the kinetic resolution of racemic ibuprofen for the last 20 years. The relevancy of the pharmacological uses of the S( + ) enantiomer along with its higher cost compared with racemic profen are the driving forces of a variety of scientific research studies addressing the enzymatic resolution of ibuprofen through enantiomeric esterification using lipases as biocatalysts. Lipases of fungal sources such as Candida rugosa, Rhizomucor miehei and the lipase B of Candida antarctica have been extensively studied both in homogeneous and heterogeneous (immobilized on solid supports) processes. In this context, the various alcohols and organic co-solvents frequently used in the esterification of racemic ibuprofen are summarized and discussed in this review. Moreover, recent investigations using membranes as reactors coupled with the separation of the desired product and microfluidic devices are presented. Finally, some guidelines about future perspectives regarding the technology of the kinetic resolution of profens and research niches are given. PMID:26121932

  17. Exploiting Enzymatic Dynamic Reductive Kinetic Resolution (DYRKR) in Stereocontrolled Synthesis

    PubMed Central

    Applegate, Gregory A.; Berkowitz, David B.

    2015-01-01

    Over the past two decades, the domains of both frontline synthetic organic chemistry and process chemistry and have seen an increase in crosstalk between asymmetric organic/organometallic approaches and enzymatic approaches to stereocontrolled synthesis. This review highlights the particularly auspicious role for dehydrogenase enzymes in this endeavor, with a focus on dynamic reductive kinetic resolutions (DYRKR) to “deracemize” building blocks, often setting two stereocenters in so doing. The scope and limitations of such dehydrogenase-mediated processes are overviewed, as are future possibilities for the evolution of enzymatic DYRKR. PMID:26622223

  18. Asymmetric synthesis of QUINAP via dynamic kinetic resolution.

    PubMed

    Bhat, Vikram; Wang, Su; Stoltz, Brian M; Virgil, Scott C

    2013-11-13

    A palladium-catalyzed, atroposelective C-P coupling process has been developed for the asymmetric synthesis of QUINAP and its derivatives in high enantiomeric excess. Bromide, triflate (OTf) and 4-methanesulfonylbenzenesulfonate (OSs) precursors were studied, leading in the case of the triflate to a novel dynamic kinetic resolution involving isomerization of an arylpalladium intermediate. The operationally simple methods described in this communication afford these important ligands in good to high yields and selectivity using low catalyst loading (≤3 mol % Pd). PMID:24152221

  19. IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

    EPA Science Inventory

    The presence of molecular oxygen in the test environment promotes oxidative coupling (polymer formation) of phenolic compounds on the surface of granular activated carbon (GAC). Both adsorption equilibria and adsorption kinetics are affected by these chemical reactions. Lack of...

  20. Recent Results in Quantum Chemical Kinetics from High Resolution Spectroscopy

    SciTech Connect

    Quack, Martin

    2007-12-26

    We outline the approach of our group to derive intramolecular kinetic primary processes from high resolution spectroscopy. We then review recent results on intramolecular vibrational redistribution (IVR) and on tunneling processes. Examples are the quantum dynamics of the C-H-chromophore in organic molecules, hydrogen bond dynamics in (HF){sub 2} and stereomutation dynamics in H{sub 2}O{sub 2} and related chiral molecules. We finally discuss the time scales for these and further processes which range from 10 fs to more than seconds in terms of successive symmetry breakings, leading to the question of nuclear spin symmetry and parity violation as well as the question of CPT symmetry.

  1. The kinetics of sulfation of calcium oxide

    SciTech Connect

    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.

  2. First principles Tafel kinetics of methanol oxidation on Pt(111)

    NASA Astrophysics Data System (ADS)

    Fang, Ya-Hui; Liu, Zhi-Pan

    2015-01-01

    Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) → CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.

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

    NASA Astrophysics Data System (ADS)

    Sabourin, Justin L.

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

  4. Dissolution kinetics of high-resolution novolac resists

    NASA Astrophysics Data System (ADS)

    Itoh, Katsuyuki; Yamanaka, Koji; Nozue, Hiroshi; Kasama, Kunihiko

    1991-06-01

    Dissolution kinetics, as well as the formation mechanism of a surface insoluble layer produced by dipping into TMAH (tetramethylammonium hydroxide) developer, have been investigated. In the previous paper, we mentioned that dissolution rate characteristics of high resolution novolac resist are clearly divided into three regions. To investigate this dissolution mechanism, we evaluated the temperature dependence of R (Dissolution rate) by changing the exposure dose, PAC (photoactive compound equals dissolution inhibitor) and the TMAH concentration. From Arrhenius Plots of these resist systems, it is considered that R is determined by two competitive reactions in the presence of TMAH; i.e., (a) the complex formation between PAC and novolac resin which produces dissolution inhibition effect, (b) TMAH induced deprotonation of phenolic hydroxy groups in novolac resin which accelerates the dissolution of the resist. Furthermore, we also describe the formation mechanism of a surface insoluble layer produced by dipping into a TMAH developer followed by water rinse, on the basis of the dissolution time of this layer (ts). The resist surface was also analyzed by using FT-IR (Fourier transform infrared spectroscopic measurement) and XPS (X-ray photoelectron spectroscopy). As a result, it was found that (a) water rinse is essential for the surface insoluble layer formation, (b) the ts value is not directly correlated with PAC accumulation in the resist surface and (c) the ts value becomes longer when the amount of penetrated TMAH into the resist increases. These results suggest that the surface insoluble layer is produced via water rinse of PAC-novolac complex described above.

  5. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  6. EFFECTS OF PHOTOCHEMICAL KINETIC MECHANISMS ON OXIDANT MODEL PREDICTIONS

    EPA Science Inventory

    The comparative effects of kinetic mechanisms on oxidant model predictions have been tested using two different mechanisms (the Carbon-Bond Mechanism II (CBM-II) and the Demerjian Photochemical Box Model (DPBM) mechanism) in three air quality models (the OZIPM/EKMA, the Urban Air...

  7. Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

    SciTech Connect

    Coloma Ribera, R. Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.

    2015-08-07

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

  8. Chemical kinetics of homogeneous atmospheric oxidation of sulfur dioxide

    NASA Technical Reports Server (NTRS)

    Sander, S. P.; Seinfeld, J. H.

    1976-01-01

    A systematic evaluation of known homogeneous SO2 reactions which might be important in air pollution chemistry is carried out. A mechanism is developed to represent the chemistry of NOx/hydrocarbon/SO2 systems, and the mechanism is used to analyze available experimental data appropriate for quantitative analysis of SO2 oxidation kinetics. Detailed comparisons of observed and predicted concentration behavior are presented. In all cases, observed SO2 oxidation rates cannot be explained solely on the basis of those SO2 reactions for which rate constants have been measured. The role of ozone-olefin reactions in SO2 oxidation is elucidated.

  9. Enzymatic kinetic resolution and chemoenzymatic dynamic kinetic resolution of delta-hydroxy esters. An efficient route to chiral delta-lactones.

    PubMed

    Pàmies, Oscar; Bäckvall, Jan-E

    2002-02-22

    A successful kinetic resolution of a racemic mixture of delta-hydroxy esters 1 was obtained via lipase-catalyzed transesterification (E value up to 360). The combination of the enzymatic kinetic resolution with a ruthenium-catalyzed alcohol racemization led to an efficient dynamic kinetic resolution (ee up to 99% and conversion up to 92%). The synthetic utility of this procedure was illustrated by the practical syntheses of delta-lactones (R)-6-methyl- and (R)-6-ethyl-tetrahydropyran-2-one and (S)-5-(tert-butyldimethylsiloxy)heptanal. The former are important building blocks in the synthesis of natural products and biologically active compounds, and the latter is a key intermediate in the synthesis of widely used commercial insecticide Spinosyn A. PMID:11846671

  10. Kinetics of methane oxidation in selected mineral soils

    NASA Astrophysics Data System (ADS)

    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.

  11. Oxidation kinetics of pentachlorophenol by manganese dioxide.

    PubMed

    Zhao, Ling; Yu, Zhiqiang; Peng, Pingán; Huang, Weilin; Feng, Shunqing; Zhou, Haiyan

    2006-11-01

    This study examined the abiotic transformation kinetics of pentachlorophenol (PCP) by manganese dioxide (MnO2) at different solution chemistry and initial concentrations of PCP and MnO2. The measured PCP transformation rates were found to be on the order of 1.07 with respect to [PCP] and 0.91 and 0.87 with respect to [MnO2] and [H+], respectively. Dissolved Mn2+ and Ca2+ as background electrolytes considerably decreased the reaction rate because of their adsorption and hence blocking of active sites on MnO2 surfaces. The dechlorination number, 0.59 chloride ions per transformed PCP after a 1-h reaction, suggests that a fraction of the transformed PCP was not dechlorinated and may be coupled directly to dimeric products. Gas chromatography/ mass spectrometry and liquid chromatography/mass spectrometry/mass spectrometry techniques were used to identify two isomeric nonachlorohydroxybiphenylethers as major products and 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol as minor products. Product identification suggested that the reaction may include two parallel reactions to form either dimers or 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol via simultaneous dehydrochlorination and hydroxylation. PMID:17089714

  12. Neptunium_Oxide_Precipitation_Kinetics_AJohnsen

    SciTech Connect

    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.

  13. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect

    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.

  14. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect

    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.

  15. Kinetics of ethylene oxide desorption from sterilized materials.

    PubMed

    Mendes, Gisela C; Brandão, Teresa R S; Silva, Cristina L M

    2013-01-01

    Ethylene oxide gas is commonly used to sterilize medical devices, and concerns about using this agent on biological systems are well-established. Medical devices sterilized by ethylene oxide must be properly aerated to remove residual gas and by-products. In this work, kinetics of ethylene oxide desorption from different sterilized materials were studied in a range of aeration temperatures. The experimental data were well-described by a Fickian diffusion mass transfer behavior, and diffusivities were estimated for two textile and two polymeric materials within the temperature range of 1.5 to 59.0 degrees C. The results will allow predictions of ethylene oxide desorption, which is a key step for the design of sterilization/aeration processes, contributing to an efficient removal of residual ethylene oxide content. PMID:23513954

  16. Oxidation Kinetics of K Basin Fuel (OCRWM)

    SciTech Connect

    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. Catalytic Kinetic Resolution of Disubstituted Piperidines by Enantioselective Acylation: Synthetic Utility and Mechanistic Insights.

    PubMed

    Wanner, Benedikt; Kreituss, Imants; Gutierrez, Osvaldo; Kozlowski, Marisa C; Bode, Jeffrey W

    2015-09-01

    The catalytic kinetic resolution of cyclic amines with achiral N-heterocyclic carbenes and chiral hydroxamic acids has emerged as a promising method to obtain enantio-enriched amines with high selectivity factors. In this report, we describe the catalytic kinetic resolution of disubstituted piperdines with practical selectivity factors (s, up to 52) in which we uncovered an unexpected and pronounced conformational effect resulting in disparate reactivity and selectivity between the cis- and trans-substituted piperidine isomers. Detailed experimental and computational studies of the kinetic resolution of various disubstituted piperidines revealed a strong preference for the acylation of conformers in which the α-substituent occupies the axial position. This work provides further experimental and computational support for the concerted 7-member transition state model for acyl transfer reagents and expands the scope and functional group tolerance of the secondary amine kinetic resolution. PMID:26308097

  18. Kinetics and spectroscopic observations of atrazine dealkylation on manganese oxides

    SciTech Connect

    Malengreau, N.; Sposito, G.; Cheney, M.A.; Crowley, D.E.

    1997-12-31

    Abiotic transformations of organic pollutants are often neglected in remediation scenarios but nonetheless can contribute significantly to detoxification. Mn oxide minerals are capable of degrading organic pollutants adsorbed to their surfaces by both redox and proton-promoted mechanisms. Concurrently with calorimetric, gas-pressure, chromatographic, and ESR methods, we used ICP, DRS, DRIFT, and FTIR spectroscopies to investigate atrazine degradation on three Mn oxides. We found that N-dealkylation can occur abiotically, leading to the formation of deethylatrazine and deisopropylatrazine. The Mn extractability after degradation of atrazine was highly dependent on the Mn oxide. Extractable Mn increased with time for cryptomelane, was constant for pyrolusite, and remained very low for birnessite. The extractable Mn is Mn(II). UV signatures of atrazine by-products were different from one another and were used to trace degradation products at the Mn oxide surface. Mechanistic interpretation of the in situ reaction kinetics and thermodynamics will be discussed.

  19. Reduction Kinetics of Graphene Oxide Determined by Temperature Programmed Desorption

    NASA Astrophysics Data System (ADS)

    Ventrice, Carl; Clark, Nicholas; Field, Daniel; Geisler, Heike; Jung, Inhwa; Yang, Dongxing; Piner, Richard; Ruoff, Rodney

    2009-10-01

    Graphene oxide, which is an electrical insulator, shows promise for use in several technological applications such as dielectric layers in nanoscale electronic devices or as the active region of chemical sensors. In principle, graphene oxide films could also be used as a precursor for the formation of large-scale graphene films by either thermal or chemical reduction of the graphene oxide. In order to determine the thermal stability and reduction kinetics of graphene oxide, temperature program desorption (TPD) measurements have been performed on multilayer films of graphene oxide deposited on SiO2/Si(100) substrates. The graphene oxide was exfoliated from the graphite oxide source material by slow-stirring in aqueous solution, which produces single-layer platelets with an average lateral size of ˜10 μm. From the TPD measurements, it was determined that the decomposition process begins at ˜80 ^oC. The primary desorption products of the graphene oxide films for temperatures up to 300 ^oC are H2O, CO2, and CO, with only trace amounts of O2 being detected. An activation energy of 1.4 eV/molecule was determined by assuming an Arrhenius dependence for the decomposition process.

  20. Expanded substrate scope and catalyst optimization for the catalytic kinetic resolution of N-heterocycles.

    PubMed

    Hsieh, Sheng-Ying; Binanzer, Michael; Kreituss, Imants; Bode, Jeffrey W

    2012-09-14

    The scope, reactivity, and selectivity of the chiral hydroxamic acid-catalyzed kinetic resolution of chiral amines are improved by a new catalyst structure and a more environmentally friendly reaction protocol. In addition to increasing selectivity across all substrates, these conditions make possible the resolution of N-heterocycles containing lactams or other basic functional groups that can inhibit the catalyst. PMID:22842709

  1. The kinetic of photoreactions in zinc oxide microrods

    NASA Astrophysics Data System (ADS)

    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.

  2. Oxidation kinetics of antibiotics during water treatment with potassium permanganate.

    PubMed

    Hu, Lanhua; Martin, Heather M; Strathmann, Timothy J

    2010-08-15

    The ubiquitous occurrence of antibiotics in aquatic environments raises concerns about potential adverse effects on aquatic ecology and human health, including the promotion of increased antibiotic resistance. This study examined the oxidation of three widely detected antibiotics (ciprofloxacin, lincomycin, and trimethoprim) by potassium permanganate [KMnO(4); Mn(VII)]. Reaction kinetics were described by second-order rate laws, with apparent second-order rate constants (k(2)) at pH 7 and 25 degrees C in the order of 0.61 +/- 0.02 M(-1) s(-1) (ciprofloxacin) < 1.6 +/- 0.1 M(-1) s(-1) (trimethoprim) < 3.6 +/- 0.1 M(-1) s(-1) (lincomycin). Arrhenius temperature dependence was observed with apparent activation energies (E(a)) ranging from 49 kJ mol(-1) (trimethoprim) to 68 kJ mol(-1) (lincomycin). Rates of lincomycin and trimethoprim oxidation exhibited marked pH dependences, whereas pH had only a small effect on rates of ciprofloxacin oxidation. The effects of pH were quantitatively described by considering parallel reactions between KMnO(4) and individual acid-base species of the target antibiotics. Predictions from a kinetic model that included temperature, KMnO(4) dosage, pH, and source water oxidant demand as input parameters agreed reasonably well with measurements of trimethoprim and lincomycin oxidation in six drinking water utility sources. Although Mn(VII) reactivity with the antibiotics was lower than that reported for ozone and free chlorine, its high selectivity and stability suggests a promising oxidant for treating sensitive micropollutants in organic-rich matrices (e.g., wastewater). PMID:20704243

  3. Kinetic Modeling of Oxidative Coagulation for Arsenic Removal

    SciTech Connect

    Kim, Jin-Wook; Kramer, Timothy A.

    2004-03-31

    A model of oxidative coagulation consisting of Fenton's reagent (Fe(II)/H2O2 at pH 7.0) was established. The optimum condition was found when the mole ratio of As(III):H2O2:Fe(II)=1:15:20. In this optimum condition, all of Fe(II) was converted to HFO (am-Fe(OH)3) and precipitated to be used as the oxidized arsenic(V) adsorbent and particle coagulant. Two sorption models consisting of a surface complexation model and a kinetic model were developed and coupled. Using the coupled sorption model, the kinetics of HFO surface charge/potential during As(V) sorption was calculated. Further, during arsenic sorption, the colloid stability kinetics resulting from the perikinetic coagulation mechanism was calculated by considering interparticle forces. Colloid surface potential was decreased from 60 mv to 12 mv in proportion to the amount of arsenic adsorbed onto HFO and this surface potential directly affected the colloid stability (collision efficiency).

  4. On the kinetics of phenol oxidation in supercritical water

    SciTech Connect

    Krajnc, M.; Levec, J.

    1996-07-01

    Phenol oxidation in supercritical water was carried out in a tubular laboratory-scale reactor operated at a temperature range of 380 C to 450 C and pressures between 230 and 265 bar. The phenol feed concentrations were between 500 and 1,000 mg/L, while oxygen was fed into the reactor at 50 to 1,000% of the stoichiometric amount needed to oxidize phenol completely to carbon dioxide. Phenol conversions from 16 to 96% were attained as the reactor residence times varied from 15 to 203 s. The oxidation obeys a parallel-consecutive reaction scheme that involves multi-ring, intermediate products such as phenoxyl-phenol, biphenol, dibenzo-dioxin, maleic acid, and succinic acid. Experimental results showed that the phenol disappearance rate is represented well by a power-law kinetic model in which the rate is proportional to the 0.4 power of the oxygen mole fraction and roughly linearly proportional to the phenol mole fraction. The pressure effect on the disappearance rate was appropriately accounted for by introducing the molar volume of the reaction mixture, which was readily calculated by an equation of state. Total organic carbon reduction can be estimated by a lumped kinetic equation. In the P-T region the activation energy of the phenol disappearance was 124.7 kJ/mol.

  5. Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Couet, Adrien; Motta, Arthur T.; Comstock, Robert J.

    2014-08-01

    The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport.

  6. Kinetics of phyllosemiquinone oxidation in the Photosystem I reaction centre of Acaryochloris marina.

    PubMed

    Santabarbara, Stefano; Bailleul, Benjamin; Redding, Kevin; Barber, James; Rappaport, Fabrice; Telfer, Alison

    2012-02-01

    Light-induced electron transfer reactions in the chlorophyll a/d-binding Photosystem I reaction centre of Acaryochloris marina were investigated in whole cells by pump-probe optical spectroscopy with a temporal resolution of ~5ns at room temperature. It is shown that phyllosemiquinone, the secondary electron transfer acceptor anion, is oxidised with bi-phasic kinetics characterised by lifetimes of 88±6ns and 345±10ns. These lifetimes, particularly the former, are significantly slower than those reported for chlorophyll a-binding Photosystem I, which typically range in the 5-30ns and 200-300ns intervals. The possible mechanism of electron transfer reactions in the chlorophyll a/d-binding Photosystem I and the slower oxidation kinetics of the secondary acceptors are discussed. PMID:22037394

  7. Differential scanning calorimetry in determining kinetics parameter of Si oxidation

    NASA Astrophysics Data System (ADS)

    Faruque, Sk. Abdul Kader Md.; Chakraborty, Supratic

    2016-05-01

    Differential scanning calorimetry (DSC) technique is employed here to study the oxidation of silicon by solid-gas reaction at a constant heating rate. The diffusion coefficient of oxygen into silicon at 900 °C is estimated from the kinetic equation of 1-dimensional diffusion controlled growth. The diffusion coefficient, D estimated as 4.5 × 10-5 exp (1.01ev/κBT) m2/s, as is in well agreement with the standard value available in literature.

  8. Kinetic Parameters of Binary Iron/Oxidant Pyrolants

    NASA Astrophysics Data System (ADS)

    Shamsipur, Mojtaba; Mahdi Pourmortazavi, Seied; Fathollahi, Manochehr

    2012-04-01

    The thermal properties of pyrotechnic mixtures containing iron powder as fuel and KNO3, KClO3, and KClO4 as oxidants are reported. The thermogravimetry-differential thermal analysis results for pure components and corresponding pyrotechnic mixtures revealed that the melting point, decomposition temperature, and rate of oxygen releasing of the oxidants have dominant effects on ignition reaction of the pyrotechnic mixtures. The apparent activation energy and activation parameters for the combustion processes were evaluated from the differential scanning calorimetry experiments. Based on the ignition temperatures obtained and the resulting kinetic data, the thermal reactivity of the pyrotechnic mixtures was found to decrease as in the order Fe + KClO3 > Fe + KNO3 > Fe + KClO4.

  9. Interaction of Nitric Oxide with Catalase: Structural and Kinetic Analysis

    PubMed Central

    2011-01-01

    We present the structures of bovine catalase in its native form and complexed with ammonia and nitric oxide, obtained by X-ray crystallography. Using the NO generator 1-(N,N-diethylamino)diazen-1-ium-1,2-diolate, we were able to generate sufficiently high NO concentrations within the catalase crystals that substantial occupation was observed despite a high dissociation rate. Nitric oxide seems to be slightly bent from the heme normal that may indicate some iron(II) character in the formally ferric catalase. Microspectrophotometric investigations inline with the synchrotron X-ray beam reveal photoreduction of the central heme iron. In the cases of the native and ammonia-complexed catalase, reduction is accompanied by a relaxation phase. This is likely not the case for the catalase NO complex. The kinetics of binding of NO to catalase were investigated using NO photolyzed from N,N′-bis(carboxymethyl)-N,N′-dinitroso-p-phenylenediamine using an assay that combines catalase with myoglobin binding kinetics. The off rate is 1.5 s–1. Implications for catalase function are discussed. PMID:21524057

  10. Phenol oxidation kinetics in water solution using iron(3)-oxide-based nano-catalysts.

    PubMed

    Zelmanov, Grigory; Semiat, Raphael

    2008-08-01

    The influence of inorganic ions (HCO(3), PO(4)/HPO(4)/H(2)PO(4), Cl, SO(4), Ca, Na and Mg) on the advanced chemical oxidation process of organic compounds dissolved in water is reported here. The catalytic behavior of iron(3)-oxide-based nano-particles was investigated together with inorganic ions and hydrogen peroxide concentrations, and pH level. Phenol was chosen as a typical organic contaminant for this study as a simulating pollutant. The limiting concentrations of radical scavengers making the oxidation process inefficient were identified. The strong effect of concentration of radical scavengers HCO(3), PO(4)/HPO(4)/H(2)PO(4), the nano-catalyst and hydrogen peroxide concentrations, and pH on the phenol oxidation rate and lag time period before reaction starts was determined. It was shown that Cl, SO(4), Ca, Na and Mg ions had no significant effect on the kinetics of phenol oxidation. PMID:18657285

  11. Stereochemically Rich Polycyclic Amines from the Kinetic Resolution of Indolines through Intramolecular Povarov Reactions.

    PubMed

    Min, Chang; Seidel, Daniel

    2016-07-25

    Under control of a chiral Brønsted acid catalyst, racemic indolines undergo intramolecular Povarov reactions with achiral aromatic aldehydes bearing a pendent dienophile. One enantiomer of the indoline reacts preferentially, resulting in the highly enantio- and diastereoselective formation of polycyclic heterocycles with four stereogenic centers. This kinetic resolution approach exploits the differential formation/reactivity of diastereomeric ion pairs. PMID:27346876

  12. Enantioselective Selenocyclization via Dynamic Kinetic Resolution of Seleniranium Ions by Hydrogen-Bond Donor Catalysts

    PubMed Central

    2015-01-01

    Highly enantioselective selenocyclization reactions are promoted by the combination of a new chiral squaramide catalyst, a mineral acid, and an achiral Lewis base. Mechanistic studies reveal that the enantioselectivity originates from the dynamic kinetic resolution of seleniranium ions through anion-binding catalysis. PMID:25380129

  13. Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies

    SciTech Connect

    White, M.G.; Hightower, J.W.

    1983-07-01

    Classical kinetic experiments together with pulse microreactor studies involving deuterium and carbon-13-labeled isotopic tracers were used to investigate the oxidative dehydrogenation dimerization (OXDD) of propylene to 1,5-hexadiene and benzene over bismuth oxide between 748 and 898/sup 0/K. The kinetic data, which indicated that the OXDD reaction is of variable order with respect to oxygen and propylene concentrations, could be fit to rate equations based on either the Langmuir-Hinshelwood model or the Mars-van Krevelen model, although the former gave more linear Arrhenius plots. A significant kinetic isotope effect (k/sub H//k/sub D/ = 1.7 at 873/sup 0/K) shows that the rate-limiting step for the OXDD reaction involves C-H cleavage, and there is only a small amount of H/D scrambling among reactant and product molecules. Analysis of liquid products by infrared spectroscopy indicated that both 1,5-hexadiene and 1,3-cyclohexadiene are stable reaction intermediates; microreactor results involving unlabeled propylene, 1,5-hexadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene as reactants confirmed the infrared findings. Pulse microreactor experiments with /sup 13/C-labeled propylene clearly showed that deep oxidation (complete combustion) occurs via a consecutive-parallel network involving the partially oxidized intermediates as well as the starting propylene. Changes in the particle size do not alter the overall activity, although larger particles have lower selectivities for C/sub 6/ products than do smaller particles.

  14. Kinetically driven instabilities and selectivities in methane oxidation

    SciTech Connect

    Park, Y.K.; Vlachos, D.G.

    1997-08-01

    Ignitions, extinctions, and Hopf bifurcations in methane oxidation were studied as a function of pressure and inlet fuel composition. A continuous stirred-tank reactor was modeled with numerical bifurcation techniques, using the 177 reaction/31 species mechanism. Sensitivity and reaction pathway analyses were performed at turning points to identify the most important reactions and reactive species. Then, simulations were compared with experimental data. Multiple ignitions and extinctions as well as oscillations that are purely kinetically driven were found. Ignition to a partially ignited state with considerable reactivity of methane indicates possible narrow operation windows with high selectivities to partial oxidation products. At 0.1 atm, the authors found a selectivity of up to 80% to CO at 70% CH{sub 4} conversion. The ignition to a fully ignited branch is associated with high selectivity to CO{sub 2} and H{sub 2}O. The C2 chemistry inhibits the ignition of methane to the partially ignited branch. The methane ignition temperature exhibits two branches with respect to pressure, with only the low-pressure branch being dominant. Reaction path analysis at ignition conditions shows that the preferred pathway of CH{sub 4} oxidation is to form CO and CO{sub 2} though CH{sub 2}O and CH{sub 2}(s) intermediates. However, at intermediate to high pressures, the recombination of CH{sub 3} to C{sub 2}H{sub 6} also becomes quite significant.

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

    PubMed

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-01

    Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. PMID:27214003

  16. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1974-01-01

    Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

  17. The role of layer structure in tin oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Duhalde, S.; Arcondo, B.; Sirkin, H.

    1991-11-01

    Tin exhibits different oxidation kinetics which are composition dependent, when it forms intermetallic compounds with the chalcogenides S and Se. This phenomenon is related to the layer compounds SnS2 and SnSe2 crystalline structure. These minerals have anisotropic bonding characteristics, due to Van der Waals bonds presence between chalcogenides adjoining planes. The mentioned weak bonds allow the oxygen diffusion to the bulk, favouring the reaction with the inner tin atoms. In this work we study samples of Sn-S alloy with different thermal treatment by XRD and Mössbauer spectroscopy. Results are discussed and compared with those obtained for Sn-Se alloy in an early work [1].

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

    NASA Astrophysics Data System (ADS)

    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. Kinetics of Uranium Extraction from Uranium Tailings by Oxidative Leaching

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  20. Kinetic spectrophotometric determination of certain cephalosporins using oxidized quercetin reagent

    NASA Astrophysics Data System (ADS)

    Saleh, Gamal A.; El-Shaboury, Salwa R.; Mohamed, Fardous A.; Rageh, Azza H.

    2009-09-01

    A simple, precise and accurate kinetic spectrophotometric method for determination of cefoperazone sodium, cefazolin sodium and ceftriaxone sodium in bulk and in pharmaceutical formulations has been developed. The method is based upon a kinetic investigation of the reaction of the drug with oxidized quercetin reagent at room temperature for a fixed time of 30 min. The decrease in absorbance after the addition of the drug was measured at 510 nm. The absorbance concentration plot was rectilinear over the range 80-400 μg mL -1 for all studied drugs. The concentration of the studied drugs was calculated using the corresponding calibration equation for the fixed time method. The determination of the studied drugs by initial rate, variable time and rate-constant methods was feasible with the calibration equations obtained but the fixed time method has been found to be more applicable. The analytical performance of the method, in terms of accuracy and precision, was statistically validated; the results were satisfactory. The method has been successfully applied to the determination of the studied drugs in commercial pharmaceutical formulations. Statistical comparison of the results with a well established reported method showed excellent agreement and proved that there is no significant difference in the accuracy and precision.

  1. Kinetic-dependent Killing of Oral Pathogens with Nitric Oxide

    PubMed Central

    Backlund, C.J.; Worley, B.V.; Sergesketter, A.R.

    2015-01-01

    Nitric oxide (NO)–releasing silica nanoparticles were synthesized via the co-condensation of tetramethyl orthosilicate with aminosilanes and subsequent conversion of secondary amines to N-diazeniumdiolate NO donors. A series of ~150 nm NO-releasing particles with different NO totals and release kinetics (i.e., half-lives) were achieved by altering both the identity and mol% composition of the aminosilane precursors. Independent of identical 2 h NO-release totals, enhanced antibacterial action was observed against the periodontopathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis with extended NO-release kinetics at pH 7.4. Negligible bactericidal effect was observed against cariogenic Streptococcus mutans at pH 7.4, even when using NO-releasing silica particles with greater NO-release totals. However, antibacterial activity was observed against S. mutans at lower pH (6.4). This result was attributed to more rapid proton-initiated decomposition of the N-diazeniumdiolate NO donors and greater NO-release payloads. The data suggest a differential sensitivity to NO between cariogenic and periodontopathogenic bacteria with implications for the future development of NO-releasing oral care therapeutics. PMID:26078424

  2. Kinetics of the catalytic oxidation of phenol over manganese oxide in supercritical water

    SciTech Connect

    Oshima, Yoshito; Tomita, Kengo; Koda, Seiichiro

    1999-11-01

    A kinetic analysis was made for the phenol disappearance rate in catalytic oxidation of phenol over MnO{sub 2} in supercritical water at a fixed temperature of 425 C and pressures between 22.7 and 27.2 MPa. The nonsupported MnO{sub 2} catalyst possessed a strong activity for promoting phenol oxidation, though the overall reaction rate was appreciably influenced by internal mass-transfer resistance. From the kinetic analysis on the reaction rate of the phenol disappearance, the global rate expression of the surface reaction was obtained, where the reaction orders with respect to phenol, oxygen, and water were almost unity, 0.7, and {minus}2.0, respectively. A Langmuir-type mechanism, in which phenol and oxygen adsorbed on the catalytic sites and water adsorbed on the same site to inhibit the phenol and oxygen adsorption, was proposed to explain the reaction orders for phenol, oxygen, and water.

  3. High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Redmond, M. C.; Shiller, A. M.; Arrington, E. C.; Valentine, D. L.; Colombo, F.

    2015-12-01

    Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

  4. Oxidation kinetics and chemostat growth kinetics of Thiobacillus ferrooxidans on tetrathionate and thiosulfate.

    PubMed

    Eccleston, M; Kelly, D P

    1978-06-01

    Growth of Thiobacillus ferrooxidans in batch culture on 10 mM potassium tetrathionate was optimal at pH 2.5 (specific growth rate, 0.092 h-1). Oxygen electrode studies on resting cell suspensions showed that the apparent Km for tetrathionate oxidation (0.13 to 8.33 mM) was pH dependent, suggesting higher substrate affinity at higher pH. Conversely, oxidation rates were greatest at low pH. High substrate concentrations (7.7 to 77 mM) did not affect maximum oxidation rates at pH 3.0, but produced substrate inhibition at other pH values. Tetrathionate-grown cell suspensions also oxidized thiosulfate at pH 2.0 to 4.0. Apparent Km values (1.2 to 25 mM) were of the same order as for tetrathionate, but kinetics were complex. Continuous culture on growth-limiting tetrathionate at pH 2.5, followed by continuous culture on growth-limiting thiosulfate at pH 2.5, indicated true growth yield values (grams [dry weight] per gram-molecule of substrate) of 12.2 and 7.5, and maintenance coefficient values (millimoles of substrate per gram [dry weight) of organisms per hour) of 1.01 and 0.97 for tetrathionate and thiosulfate, respectively. Yield was increased on both media at low dilution rates by increase in CO2 supply. The apparent maintenance coefficient was lowered without affecting YG, suggesting better energy coupling in CO2-rich environments. Prolonged continuous cultivation on tetrathionate or thiosulfate did not affect the ability of the organism to grow subsequently in ferrous iron medium. PMID:26665

  5. Kinetic Modeling of Toluene Oxidation for Surrogate Fuel Applications

    SciTech Connect

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

    2009-04-21

    New environmental issues, like the effect of combustion-generated greenhouse gases, provide motivation to better characterize oxidation of hydrocarbons. Transportation, in particular, significantly contributes to energy consumption and CO{sub 2} emissions. Kinetic studies about the combustion of fuels under conditions typical of internal combustion engines provides important support to improve mechanism formulation and to eventually provide better computational tools that can be used to increase the engine performance. It is foreseeable that at least in the next 30 years the main transportation fuels will be either gasoline or diesel. Unfortunately, these fuels are very complex mixtures of many components. Moreover, their specifications and performance requirements significantly change the composition of these fuels: gasoline and diesel mixtures are different if coming from different refineries or they are different from winter to summer. At the same time a fuel with a well defined and reproducible composition is needed for both experimental and modeling work. In response to these issues, surrogate fuels are proposed. Surrogate fuels are defined as mixtures of a small number of hydrocarbons whose relative concentrations is adjusted in order to approximate the chemical and physical properties of a real fuel. Surrogate fuels are then very useful both for the design of reproducible experimental tests and also for the development of reliable kinetic models. The primary reference fuels (PRF) are a typical and old example of surrogate fuel: n-heptane and iso-octane mixtures are used to reproduce antiknock propensity of complex mixtures contained in a gasoline. PRFs are not able to surrogate gasoline in operating conditions different from standard ones and new surrogates have been recently proposed. Toluene is included in all of them as a species able to represent the behavior of aromatic compounds. On the other side, the toluene oxidation chemistry is not so well

  6. Kinetics and fixed-bed reactor modeling of butane oxidation to maleic anhydride

    SciTech Connect

    Sharma, R.K.; Cresswell, D.L. ); Newson, E.J. )

    1991-01-01

    This paper reports on selective oxidation kinetics of n-butane to maleic anhydride in air studied over a commercial, fixed-bed vanadium-phosphor oxide catalyst. The temperature range was 573-653 K with butane concentrations up to 3 mol % in the feed, which is within flammability limits but below ignition temperatures. The rate data were modeled using power law kinetics with product inhibition and included total oxidation and decomposition reactions. Kinetic parameters were estimated using a multiresponse, nonlinear regression algorithm showing intercorrelation effects. The kinetics were combined with independent measurements of catalyst diffusivity and reactor heat transfer using a one- dimensional heterogeneous reactor model.

  7. Effect of temperature on Candida antartica lipase B activity in the kinetic resolution of acebutolol

    NASA Astrophysics Data System (ADS)

    Rajin, Mariani; Kamaruddin, A. H.

    2016-06-01

    Thermodynamic studies of free Candida antartica lipase B in kinetic resolution of acebutolol have been carried out to characterize the temperature effects towards enzyme stability and activity. A decreased in reaction rate was observed in temperature above 40oC. Thermodynamic studies on lipase deactivation exhibited a first-order kinetic pattern. The activation and deactivation energies were 39.63 kJ/mol and 54.90 kJ/mol, respectively. The enthalpy and entropy of the lipase deactivation were found to be 52.12 kJ/mol and -0.18 kJ/mol, respectively.

  8. Fenton Oxidation Kinetics and Intermediates of Nonylphenol Ethoxylates

    PubMed Central

    Cui, Kai; Yi, Hao; Zhou, Zi-jian; Zhuo, Qiong-fang; Bing, Yong-xin; Guo, Qing-wei; Xu, Zhen-cheng

    2014-01-01

    Abstract Removal of nonylphenol ethoxylates (NPEOs) in aqueous solution by Fenton oxidation process was studied in a laboratory-scale batch reactor. Operating parameters, including initial pH temperature, hydrogen peroxide, and ferrous ion dosage, were thoroughly investigated. Maximum NPEOs reduction of 84% was achieved within 6 min, under an initial pH of 3.0, 25°C, an H2O2 dosage of 9.74×10−3 M, and a molar ratio of [H2O2]/[Fe2+] of 3. A modified pseudo-first-order kinetic model was found to well represent experimental results. Correlations of reaction rate constants and operational parameters were established based on experimental data. Results indicated that the Fenton oxidation rate and removal efficiency were more dependent on the dosage of H2O2 than Fe2+, and the apparent activation energy (ΔE) was 17.5 kJ/mol. High-performance liquid chromatography and gas chromatograph mass spectrometer analytical results indicated degradation of NPEOs obtained within the first 2 min stepwise occurred by ethoxyl (EO) unit shortening. Long-chain NPEOs mixture demonstrated a higher degradation rate than shorter-chain ones. Nonylphenol (NP), short-chain NPEOs, and NP carboxyethoxylates were identified as the primary intermediates, which were mostly further degraded. PMID:24868141

  9. High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Morris, R. V.; Ming, D. W.; Lauer, H. V., Jr.

    1994-01-01

    Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).

  10. Kinetics of pyrite oxidation in sodium carbonate solutions

    SciTech Connect

    Ciminelli, V.S.T.; Osseo-Asare, K.

    1995-04-01

    The kinetics of pyrite oxidation in sodium carbonate solutions were investigated in a stirred vessel, under temperatures ranging from 50 C to 85 C, oxygen partial pressures from 0 to 1 atm, particle size fractions from {minus}150 + 106 to {minus}38 + 10 {mu}m ({minus}100 + 150 Mesh to {minus}400 Mesh + 10 {mu}m) and pH values of up to 12.5. The rate of the oxidation reaction is described by the following expression: {minus}dN/dt = SbkpO{sup 0.5}{sub 2} [OH{sup {minus}}]{sup 0.1} where N represents moles of pyrite, S is the surface area of the solid particles, b is a stoichiometric factor, k is an apparent rate constant, pO{sub 2} is the oxygen partial pressure, and [OH{sup {minus}}] is the hydroxyl ion concentration. The experimental data were fitted by a stochastic model for chemically controlled reactions, represented by the following fractional conversion (X) vs time (t) equation: (1 {minus} X){sup {minus}2/3} {minus} 1 = k{sub ST}t. The assumption behind this model, i.e., surface heterogeneity leading to preferential dissolution, is supported by the micrographs of reacted pyrite particles, showing pits created by localized dissolution beneath an oxide layer. In addition to the surface texture, the magnitude of the activation energy (60.0 kJ/mol or 14.6 {+-} 2.7 kcal/mol), the independence of rate on the stirring speed, the inverse relationship between the rate constant and the initial particle diameter, and the fractional reaction orders are also in agreement with a mechanism controlled by chemical reaction.

  11. Kinetics of pyrite oxidation in sodium hydroxide solutions

    NASA Astrophysics Data System (ADS)

    Ciminelli, V. S. T.; Osseo-Asare, K.

    1995-08-01

    The kinetics of pyrite oxidation in sodium hydroxide solution were investigated in a stirred reactor, under temperatures ranging from 50 °C to 85 °C, oxygen partial pressures of up to 1 atm, particle size fractions from -150 + 106 to -38 + 10µm (-100 + 150 mesh to -400 mesh + 10 µ), and pH values of up to 12.5. The surface reaction is represented by the rate equation:- dN/dt = Sbk″pO0.5 2[oH- 0.25/(1 + k‴ pO2 0.5) where N represents moles of pyrite, S is the surface area of the solid particles, k″ and k″ are constants, b is a stoichiometric factor, pO2 is the oxygen partial pressure, and [OH-] is the hydroxyl ion concentration. The corresponding fractional conversion ( X) vs time behavior follows the shrinking particle model for chemical reaction control: 1 - (1 - X)1/3 = k ct The rate increases with the reciprocal of particle size and has an activation energy of 55.6 kJ/mol (13.6 kcal/mol). The relationship between reaction rate and oxygen partial pressure resembles a Langmuir-type equation and thus suggests that the reaction involves adsorption or desorption of oxygen at the interface. The square-root rate law may be due to the adsorption of a dissociated oxygen molecule. The observed apparent reaction order with respect to the hydroxyl ion concentration is a result of a complex combination of processes involving the oxidation and nydrolysis of iron, oxidation and hydrolysis of sulfur, and the oxygen reduction.

  12. Kinetics of pyrite oxidation in sodium carbonate solutions

    NASA Astrophysics Data System (ADS)

    Ciminelli, V. S. T.; Osseo-Asare, K.

    1995-04-01

    The kinetics of pyrite oxidation in sodium carbonate solutions were investigated in a stirred vessel, under temperatures ranging from 50 °C to 85 °C, oxygen partial pressures from 0 to 1 atm, particle size fractions from -150 + 106 to -38 + 10 µm (-100 + 150 Mesh to -400 Mesh + 10 µm) and pH values of up to 12.5. The rate of the oxidation reaction is described by the following expression: -dN/dt = SbkpO{2/0.5} [OH-]0.1 where N represents moles of pyrite, S is the surface area of the solid particles, b is a stoichiometric factor, k is an apparent rate constant, pO```2`` is the oxygen partial pressure, and [OH-] is the hydroxyl ion concentration. The experimental data were fitted by a stochastic model for chemically controlled reactions, represented by the following fractional conversion (X) vs time ( t) equation: (1-X)-2/3-1 = k STt The assumption behind this model, i.e., surface heterogeneity leading to preferential dissolution, is supported by the micrographs of reacted pyrite particles, showing pits created by localized dissolution beneath an oxide layer. In addition to the surface texture, the magnitude of the activation energy (60.9 kJ/mol or 14.6 ± 2.7 kcal/mol), the independence of rate on the stirring speed, the inverse relationship between the rate constant and the initial particle diameter, and the fractional reaction orders are also in agreement with a mechanism controlled by chemical reaction.

  13. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    PubMed

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained. PMID:19552446

  14. Origin of enantioselectivity in benzotetramisole-catalyzed dynamic kinetic resolution of azlactones.

    PubMed

    Liu, Peng; Yang, Xing; Birman, Vladimir B; Houk, K N

    2012-07-01

    Density functional theory (DFT) calculations were performed to investigate the origins of enantioselectivity in benzotetramisole (BTM)-catalyzed dynamic kinetic resolution of azlactones. The transition states of the fast-reacting enantiomer are stabilized by electrostatic interactions between the amide carbonyl group and the acetate anion bound to the nucleophile. The chiral BTM catalyst confines the conformation of the α-carbon and the facial selectivity of the nucleophilic attack to promote such electrostatic attractions. PMID:22686505

  15. Synergistic Kinetic Resolution and Asymmetric Propargyl Claisen Rearrangement for the Synthesis of Chiral Allenes.

    PubMed

    Liu, Yangbin; Liu, Xiaohua; Hu, Haipeng; Guo, Jing; Xia, Yong; Lin, Lili; Feng, Xiaoming

    2016-03-14

    The asymmetric propargyl Claisen rearrangement provides a convenient entry to chiral allene motifs. Herein, we describe the development of a kinetic resolution and asymmetric rearrangement of racemic propargyl vinyl ethers. This transformation afforded chiral allene products along with the enantiomerically enriched substrate in good yields with excellent diastereo- and enantioselectivity. The complete chirality transfer and facially selective rearrangement enabled the simultaneous construction of an axially chiral allenic unit and a quaternary carbon stereocenter. PMID:26889758

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

    PubMed Central

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

    2014-01-01

    The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k2′), their final oxidation step (k1′), and the direct conversion to endproducts step (k3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

  17. Kinetics and dynamics of oxidation reactions involving an adsorbed CO species on bulk and supported platinum and copper-oxide

    SciTech Connect

    Harold, M.P.

    1991-07-01

    The proposed research is an integrated experimental and modeling study of oxidation reactions involving CO as a key player -- be it a reactant, adsorbed intermediate, and/or partial oxidation product -- in the catalytic sequence and chemistry. The reaction systems of interest in the project include CO, formaldehyde, and methanol oxidation by O{sub 2} and CO oxidation by NO, on both Pt and copper oxide catalysts. These reactions are of importance in automobile exhaust catalysis. There is a paucity of rate data in the literature for these important environmental control reactions. The goal of this research is to better understand the catalytic chemistry and kinetics of oxidations reactions involving CO as an adsorbed intermediate. Successfully meeting this goal requires an integration of basic kinetic measurements, in situ catalyst surface monitoring, kinetic modeling, and nonlinear mathematical tools.

  18. Oxidative degradation and kinetics of chlorinated ethylenes by potassium permanganate

    NASA Astrophysics Data System (ADS)

    Yan, Y. Eugene; Schwartz, Frank W.

    1999-04-01

    The oxidative treatment of chlorinated ethylenes in ground water using permanganate was investigated in a series of batch kinetic tests. Five chlorinated ethylenes including tetrachloroethylene (PCE), trichloroethylene (TCE), and three isomers of dichloroethylenes (DCEs) were examined. The degradation process was rapid with pseudo-first-order rate constants ranging from 4.5×10 -5 to 0.03 s -1 at MnO 4-=1 mM. The rate increased with a decreasing number of chlorine substituents on the ethylene. The higher reactivity of trans-DCE ( kobs=30×10 -3 s -1 at MnO 4-=1 mM) as compared to cis-DCE ( kobs=0.9×10 -3 s -1 at MnO 4-=1 mM) is thought to be caused by a significant steric effect due to the formation of a large cyclic activated complex. TCE oxidation as a second-order reaction was confirmed and the rate constant, k=0.67±0.03 M -1 s -1, is independent of pH over the range of 4-8. The activity of both Cl - and hydrogen ions was monitored over time and suggests essentially complete dechlorination, making the degradation products less harmful than the parent compounds. Competition for MnO 4- from other organic compounds in ground water or highly contaminated ground water was also evaluated in experiments. A simple and quick approach was demonstrated to estimate permanganate consumption by other organic compounds for field applications and to predict the TCE degradation rate in a system involving multiple contaminants. The modeling results suggest that the effect of autocatalysis by MnO 2 on TCE degradation is significant when the system contains high concentration levels of MnO 4- and TOC.

  19. Kinetics of photocatalytic oxidation of organic solutes over titanium dioxide

    SciTech Connect

    Matthews, R.W.

    1988-06-01

    The kinetics of photooxidation to CO/sub 2/ of 22 organic solutes over a UV illuminated film of Degussa P25 titanium dioxide have been studied over a 100-fold concentration range for each solute, generally from about 1 to 100 mg/liter. The dependence of the photooxidation rate on concentration obeyed a simple two-coefficient Langmuir expression for each solute. The coefficients reflecting the degree of adsorption on the TiO/sub 2/ and the limiting rate at high concentrations enable the prediction of photocatalytic rates in any TiO/sub 2/-based photoreactor of a similar type once a reference rate has been determined for one of the solutes. A reaction mechanism is proposed for the oxidation of aromatic compounds involving peroxyhydroxycyclohexadienyl- and mucondialdehyde-type compounds as important intermediates. The solutes studied were benzoic acid, salicylic acid, phenol, biphthalate, 2-chlorophenol, 4-chlorophenol, monochlorobenzene, nitrobenzene, methanol, ethanol, n-propanol, 2-propanol, acetone, ethyl acetate, acetic acid, formic acid, sucrose, 2-naphthol, umbelliferone, chloroform, trichloroethylene, and dichloroethane.

  20. The kinetics of iodide oxidation by the manganese oxide mineral birnessite

    USGS Publications Warehouse

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

    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.

  1. Lipase-catalyzed kinetic resolution of (±)-1-(2-furyl) ethanol in nonaqueous media.

    PubMed

    Devendran, Saravanan; Yadav, Ganapati D

    2014-06-01

    S-1-(2-Furyl) ethanol serves as an important chiral building block for the preparation of various natural products, fine chemicals, and is widely used in the chemical and pharmaceutical industries. In this work, lipase-catalyzed kinetic resolution of (R/S)-1-(2-furyl) ethanol using different acyl donors was investigated. Vinyl esters are good acyl donors vis-à-vis alkyl esters for kinetic resolution. Among them, vinyl acetate was found to be the best acyl donor. Different immobilized lipases such as Rhizomucor miehei lipase, Thermomyces lanuginosus lipase, and Candida antarctica lipase B were evaluated for this reaction, among which C. antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-heptane as solvent. The effect of various parameters was studied in a systematic manner. Maximum conversion of 47% and enantiomeric excess of the substrate (ees ) of 89% were obtained in 2 h using 5 mg of enzyme loading with an equimolar ratio of alcohol to vinyl acetate at 60 °C at a speed of 300 rpm in a batch reactor. From the analysis of progress curve and initial rate data, it was concluded that the reaction followed the ordered bi-bi mechanism with dead-end ester inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is more economical, green, and easily scalable than the chemical processes. PMID:24733779

  2. Microwave assisted enzymatic kinetic resolution of (±)-1-phenyl-2-propyn-1-ol in nonaqueous media.

    PubMed

    Devendran, Saravanan; Yadav, Ganapati D

    2014-01-01

    Kinetic resolution of 1-phenyl-2-propyn-1-ol, an important chiral synthon, was studied through trans-esterification with acyl acetate to investigate synergism between microwave irradiation and enzyme catalysis. Lipases from different microbial origins were employed for the kinetic resolution of (R/S)-1-phenyl-2-propyn-1-ol, among which Candida antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-hexane as solvent. Vinyl acetate was the most effective among different acyl esters studied. The effect of various parameters was studied in a systematic manner. Definite synergism between microwave and enzyme was observed. The initial rate was improved around 1.28 times under microwave irradiation than conventional heating. Under optimum conditions, maximum conversion (48.78%) and high enantiomeric excess (93.25%) were obtained in 2 h. From modeling studies, it is concluded that the reaction follows the Ping-Pong bi-bi mechanism with dead end alcohol inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is green, clean, and easily scalable as compared to the chemical process. PMID:24707487

  3. Microwave Assisted Enzymatic Kinetic Resolution of (±)-1-Phenyl-2-propyn-1-ol in Nonaqueous Media

    PubMed Central

    Devendran, Saravanan; Yadav, Ganapati D.

    2014-01-01

    Kinetic resolution of 1-phenyl-2-propyn-1-ol, an important chiral synthon, was studied through trans-esterification with acyl acetate to investigate synergism between microwave irradiation and enzyme catalysis. Lipases from different microbial origins were employed for the kinetic resolution of (R/S)-1-phenyl-2-propyn-1-ol, among which Candida antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-hexane as solvent. Vinyl acetate was the most effective among different acyl esters studied. The effect of various parameters was studied in a systematic manner. Definite synergism between microwave and enzyme was observed. The initial rate was improved around 1.28 times under microwave irradiation than conventional heating. Under optimum conditions, maximum conversion (48.78%) and high enantiomeric excess (93.25%) were obtained in 2 h. From modeling studies, it is concluded that the reaction follows the Ping-Pong bi-bi mechanism with dead end alcohol inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is green, clean, and easily scalable as compared to the chemical process. PMID:24707487

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

    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. PMID:27088669

  6. Carotenoid Excited State Kinetics in Bacterial RCs with the Primary Electron Donor Oxidized

    NASA Astrophysics Data System (ADS)

    Lin, Su; Katilius, Evaldas; Woodbury, Neal W.

    Carotenoid singlet excited state kinetics in wild type reaction centers from Rhodobacter sphaeroides was investigated using ultrafast laser spectroscopy under conditions where the primary electron donor is either neutral or oxidized.

  7. Composition effects on the early-stage oxidation kinetics of (001) Cu-Au alloys

    NASA Astrophysics Data System (ADS)

    Zhou, G.-W.; Eastman, J. A.; Birtcher, R. C.; Baldo, P. M.; Pearson, J. E.; Thompson, L. J.; Wang, L.; Yang, J. C.

    2007-02-01

    An in situ environmental transmission electron microscopy study of the nucleation and growth of oxide islands during the early-stage oxidation of (001) Cu1-xAux alloys (x⩽38at.%) was undertaken in order to investigate the effects of alloying on oxide island nucleation behavior and growth kinetics. The kinetic data reveal that Au enhances the nucleation density of oxide islands and suppresses their growth rate. Our results provide insight into reasons for the decreased passivation properties of Cu when alloyed with Au.

  8. Kinetic isotopic effects in oxidative dehydrogenation of propane on vanadium oxide catalysts

    SciTech Connect

    Chen, K.; Iglesia, E.; Bell, A.T.

    2000-05-15

    Kinetic isotopic effects (KIEs) for oxidative dehydrogenation of propane were measured on 10 wt% V{sub 2}O{sub 5}/ZrO{sub 2}. Normal KIEs were obtained using CH{sub 3}CH{sub 2}CH{sub 3} and CD{sub 3}CD{sub 2}CD{sub 3} as reactants for primary dehydrogenation (2.8) and combustion (1.9) of propane and for secondary combustion of propene (2.6), suggesting that in all cases C-H bond dissociation is a kinetically relevant step. CH{sub 3}CH{sub 2}CH{sub 3} and CH{sub 3}CD{sub 2}CH{sub 3} reactants led to normal KIEs for dehydrogenation (2.7) and combustion (1.8) of propane, but to a very small KIE (1.1) for propene combustion. These results show that the methylene C-H bond is activated in the rate-determining steps for propane dehydrogenation and combustion reactions. The rate-determining step in secondary propene combustion involves the allylic C-H bond. In each reaction, the weakest C-H bond in the reactant is cleaved in the initial C-H bond activation step. The measured propane oxidative dehydrogenation KIEs are in agreement with theoretical estimates using a sequence of elementary steps, reaction rate expression, and transition state theory. The much smaller KIE for propane oxidative dehydrogenation (2.8) than the maximum KIE (6) expected for propane thermal dehydrogenation indicates the participation of lattice oxygen. The different KIE values for propane primary dehydrogenation and combustion suggest that these two reactions involve different lattice oxygen sites.

  9. Rhodium-Catalyzed Asymmetric Cycloisomerization and Parallel Kinetic Resolution of Racemic Oxabicycles.

    PubMed

    Loh, Charles C J; Schmid, Matthias; Webster, Robert; Yen, Andy; Yazdi, Shabnam K; Franke, Patrick T; Lautens, Mark

    2016-08-16

    While desymmetrizations by intermolecular asymmetric ring-opening reactions of oxabicyclic alkenes with various nucleophiles have been reported over the past two decades, the demonstration of an intramolecular variant is unknown. Reported herein is the first rhodium-catalyzed asymmetric cycloisomerization of meso-oxabicyclic alkenes tethered to bridgehead nucleophiles, thus providing access to tricyclic scaffolds through a myriad of enantioselective C-O, C-N, and C-C bond formations. Moreover, we also demonstrate a unique parallel kinetic resolution, whereby racemic oxabicycles bearing two different bridgehead nucleophiles can be resolved enantioselectively. PMID:27416818

  10. Asymmetric Synthesis of Diverse Glycolic Acid Scaffolds via Dynamic Kinetic Resolution of α-Keto Esters

    PubMed Central

    Steward, Kimberly M.; Corbett, Michael T.; Goodman, C. Guy; Johnson, Jeffrey S.

    2012-01-01

    The dynamic kinetic resolution of α-keto esters via asymmetric transfer hydrogenation has been developed as a technique for the highly stereoselective construction of structurally diverse β-substituted-α-hydroxy carboxylic acid derivatives. Through the development of a privileged m-terphenylsulfonamide for (arene)RuCl(monosulfonamide) complexes with a high affinity for selective α-keto ester reduction, excellent levels of chemo-, diastereo-, and enantiocontrol can be realized in the reduction of β-aryl- and β-chloro-α-keto esters. PMID:23186551

  11. Regio- and Enantioselective Synthesis of Azole Hemiaminal Esters by Lewis Base Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Piotrowski, David W; Kamlet, Adam S; Dechert-Schmitt, Anne-Marie R; Yan, Jiangli; Brandt, Thomas A; Xiao, Jun; Wei, Liuqing; Barrila, Mark T

    2016-04-13

    We report a modular three-component dynamic kinetic resolution (DKR) that affords enantiomerically enriched hemiaminal esters derived from azoles and aldehydes. The novel and scalable reaction can be used to synthesize valuable substituted azoles in a regioselective manner by capping (e.g., acylation) of the equilibrating azole-aldehyde adduct. With the use of a prolinol-derived DMAP catalyst as the chiral Lewis base, the products can be obtained in high chemical yield and with high enantiomeric excess. The DKR was performed on a multikilogram scale to produce a tetrazole prodrug fragment for a leading clinical candidate that posed formidable synthesis challenges. PMID:27003237

  12. Recyclable Ligands for the Non-Enzymatic Dynamic Kinetic Resolution of Challenging α-Amino Acids.

    PubMed

    Nian, Yong; Wang, Jiang; Zhou, Shengbin; Wang, Shuni; Moriwaki, Hiroki; Kawashima, Aki; Soloshonok, Vadim A; Liu, Hong

    2015-10-26

    Structurally simple and inexpensive chiral tridentate ligands were employed for substantially advancing the purely chemical dynamic kinetic resolution (DKR) of unprotected racemic tailor-made α-amino acids (TM-α-AAs), enabling the first DKR of TM-α-AAs bearing tertiary alkyl chains as well as multiple unprotected functional groups. Owing to the operationally convenient conditions, virtually complete stereoselectivity, and full recyclability of the source of chirality, this method should find wide applications for the preparation of TM-α-AAs, especially on large scale. PMID:26367134

  13. Kinetic Resolution of 2H-Azirines by Asymmetric Imine Amidation.

    PubMed

    Hu, Haipeng; Liu, Yangbin; Lin, Lili; Zhang, Yuheng; Liu, Xiaohua; Feng, Xiaoming

    2016-08-16

    Highly efficient kinetic resolution of 2H-azirines by an asymmetric imine amidation was achieved in the presence of a chiral N,N'-dioxide/Sc(III) complex, thus providing a promising method to obtain the enantioenriched 2H-azirine derivatives and protecting-group free aziridines at the same time. It is rare to find an example of N1 of an oxindole participating in a reaction over C3. Moreover, chiral 2H-azirines were stereospecifically transformed into an unprotected aziridine and α-amino ketone. PMID:27384910

  14. Origin of Kinetic Resolution of Hydroxy Esters through Catalytic Enantioselective Lactonization by Chiral Phosphoric Acids.

    PubMed

    Changotra, Avtar; Sunoj, Raghavan B

    2016-08-01

    Kinetic resolution is a widely used strategy for separation and enrichment of enantiomers. Using density functional theory computations, the origin of how a chiral BINOL-phosphoric acid catalyzes the selective lactonization of one of the enantiomers of α-methyl γ-hydroxy ester is identified. In a stepwise mechanism, the stereocontrolling transition state for the addition of the hydroxyl group to the si face of the ester carbonyl in the case of the S isomer exhibits a network of more effective noncovalent interactions between the substrate and the chiral catalyst. PMID:27463593

  15. Chiral Phosphoric Acid Catalyzed Asymmetric Ugi Reaction by Dynamic Kinetic Resolution of the Primary Multicomponent Adduct.

    PubMed

    Zhang, Yun; Ao, Yu-Fei; Huang, Zhi-Tang; Wang, De-Xian; Wang, Mei-Xiang; Zhu, Jieping

    2016-04-18

    Reaction of isonitriles with 3-(arylamino)isobenzofuran-1(3H)-ones in the presence of a catalytic amount of an octahydro (R)-binol-derived chiral phosphoric acid afforded 3-oxo-2-arylisoindoline-1-carboxamides in high yields with good to high enantioselectivities. An enantioselective Ugi four-center three-component reaction of 2-formylbenzoic acids, anilines, and isonitriles was subsequently developed for the synthesis of the same heterocycle. Mechanistic studies indicate that the enantioselectivity results from the dynamic kinetic resolution of the primary Ugi adduct, rather than from the C-C bond-forming process. The resulting heterocycle products are of significant medicinal importance. PMID:26997306

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

    PubMed

    Zhang, Tao; Chen, Yin; Leiknes, TorOve

    2016-06-01

    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) for this process is a constant that is related to the reaction condition and can be easily determined. The reaction rate constants of these benzothiazoles toward sulfate radical are (3.3 ± 0.3) × 10(9), (1.4 ± 0.3) × 10(9), (1.5 ± 0.1) × 10(9), and (4.7 ± 0.5) × 10(9) M(-1) s(-1), respectively (pH 7 and 20 °C). On the basis of 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 that are reactive toward common oxidants. For OHBT oxidation, the thiazole ring is preferentially broken down. 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 dissolved organic carbon waters like urban runoff or polluted groundwater. PMID:27144396

  17. Energy resolution and efficiency of phonon-mediated kinetic inductance detectors for light detection

    NASA Astrophysics Data System (ADS)

    Cardani, L.; Colantoni, I.; Cruciani, A.; Di Domizio, S.; Vignati, M.; Bellini, F.; Casali, N.; Castellano, M. G.; Coppolecchia, A.; Cosmelli, C.; Tomei, C.

    2015-08-01

    The development of sensitive cryogenic light detectors is of primary interest for bolometric experiments searching for rare events like dark matter interactions or neutrino-less double beta decay. Thanks to their good energy resolution and the natural multiplexed read-out, Kinetic Inductance Detectors (KIDs) are particularly suitable for this purpose. To efficiently couple KIDs-based light detectors to the large crystals used by the most advanced bolometric detectors, active surfaces of several cm2 are needed. For this reason, we are developing phonon-mediated detectors. In this paper, we present the results obtained with a prototype consisting of four 40 nm thick aluminum resonators patterned on a 2 × 2 cm2 silicon chip, and calibrated with optical pulses and X-rays. The detector features a noise resolution σE = 154 ± 7 eV and an (18 ± 2)% efficiency.

  18. Size control, quantum confinement, and oxidation kinetics of silicon nanocrystals synthesized at a high rate by expanding thermal plasma

    SciTech Connect

    Han, Lihao E-mail: A.H.M.Smets@tudelft.nl; Zeman, Miro; Smets, Arno H. M. E-mail: A.H.M.Smets@tudelft.nl

    2015-05-25

    The growth mechanism of silicon nanocrystals (Si NCs) synthesized at a high rate by means of expanding thermal plasma chemical vapor deposition technique are studied in this letter. A bimodal Gaussian size distribution is revealed from the high-resolution transmission electron microscopy images, and routes to reduce the unwanted large Si NCs are discussed. Photoluminescence and Raman spectroscopies are employed to study the size-dependent quantum confinement effect, from which the average diameters of the small Si NCs are determined. The surface oxidation kinetics of Si NCs are studied using Fourier transform infrared spectroscopy and the importance of post-deposition passivation treatments of hydrogenated crystalline silicon surfaces are demonstrated.

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

    PubMed

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

    2014-08-19

    Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems. PMID:25072394

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

    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. PMID:27192837

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Chemical kinetic modeling of propane oxidation behind shock waves

    NASA Technical Reports Server (NTRS)

    Mclain, A. G.; Jachimowski, C. J.

    1977-01-01

    The stoichiometric combustion of propane behind incident shock waves was studied experimentally and analytically over a temperature range from 1700 K to 2600 K and a pressure range from 1.2 to 1.9 atm. Measurements of the concentrations of carbon monoxide (CO) and carbon dioxide (CO2) and the product of the oxygen atom and carbon dioxide concentrations (O)(CO) were made after passage of the incident shock wave. A kinetic mechanism was developed which, when used in a computer program for a flowing, reacting gas behind an incident shock wave predicted experimentally measured results quite well. Ignition delay times from the literature were also predicted quite well. The kinetic mechanism consisted of 59 individual kinetic steps.

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

    PubMed

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

    2013-12-01

    CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model. PMID:24640915

  5. Origin of the chemical and kinetic stability of graphene oxide.

    PubMed

    Zhou, Si; Bongiorno, Angelo

    2013-01-01

    At moderate temperatures (≤ 70°C), thermal reduction of graphene oxide is inefficient and after its synthesis the material enters in a metastable state. Here, first-principles and statistical calculations are used to investigate both the low-temperature processes leading to decomposition of graphene oxide and the role of ageing on the structure and stability of this material. Our study shows that the key factor underlying the stability of graphene oxide is the tendency of the oxygen functionalities to agglomerate and form highly oxidized domains surrounded by areas of pristine graphene. Within the agglomerates of functional groups, the primary decomposition reactions are hindered by both geometrical and energetic factors. The number of reacting sites is reduced by the occurrence of local order in the oxidized domains, and due to the close packing of the oxygen functionalities, the decomposition reactions become - on average - endothermic by more than 0.6 eV. PMID:23963517

  6. Evaluation of a new protocol for enzymatic dynamic kinetic resolution of 3-hydroxy-3-(aryl)propanoic acids.

    PubMed

    Koszelewski, Dominik; Zysk, Małgorzata; Brodzka, Anna; Żądło, Anna; Paprocki, Daniel; Ostaszewski, Ryszard

    2015-12-01

    The application of tandem metal-enzyme dynamic kinetic resolution (DKR) is a powerful tool for the manufacture of high-value chemical commodities. A new protocol of kinetic resolution based on irreversible enzymatic esterification of carboxylic acids with orthoesters was introduced to obtain optically active β-hydroxy esters. This procedure was combined with metal catalyzed racemization of the target substrate providing both (R) and (S) enantiomers of ethyl 3-hydroxy-3-(4-nitrophenyl)propanoate with a high yield of 89% at 40 °C. A substantial influence of the enzyme type, organic co-solvent, and metal catalyst on the conversion and enantioselectivity of the enzymatic dynamic kinetic resolution was noted. PMID:26383530

  7. On the oxidation of (U, Pu)C fuel: Experimental and kinetic aspects, practical issues

    NASA Astrophysics Data System (ADS)

    Mazaudier, F.; Tamani, C.; Galerie, A.; Marc, Y.

    2010-11-01

    The oxidation of mixed (U, Pu) carbide fuel was studied to meet some of the general requirements applicable to the back- and front-end of the nuclear fuel cycle. Data are unfortunately scarce in this field. Based on an experimental study and a kinetic treatment, it was proved that the oxidation of solid or powdered mixed carbide fuel does not involve any unwanted kinetic transition and does not have the intrinsic ability to self-sustain. We never observed the formation of a protective oxide layer on the samples. The oxidation products were always low-density, finely-divided oxide powder expanding and tending to slow down the process. The low thermal activation observed demonstrates the key role of gas transport when using powders. Practical solutions have been derived from this work.

  8. Chemoenzymatic dynamic kinetic resolution of primary amines using a recyclable palladium nanoparticle catalyst together with lipases.

    PubMed

    Gustafson, Karl P J; Lihammar, Richard; Verho, Oscar; Engström, Karin; Bäckvall, Jan-E

    2014-05-01

    A catalyst consisting of palladium nanoparticles supported on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was used in chemoenzymatic dynamic kinetic resolution (DKR) to convert primary amines to amides in high yields and excellent ee's. The efficiency of the nanocatalyst at temperatures below 70 °C enables reaction conditions that are more suitable for enzymes. In the present study, this is exemplified by subjecting 1-phenylethylamine (1a) and analogous benzylic amines to DKR reactions using two commercially available lipases, Novozyme-435 (Candida antartica Lipase B) and Amano Lipase PS-C1 (lipase from Burkholderia cepacia) as biocatalysts. The latter enzyme has not previously been used in the DKR of amines because of its low stability at temperatures over 60 °C. The viability of the heterogeneous Pd-AmP-MCF was further demonstrated in a recycling study, which shows that the catalyst can be reused up to five times. PMID:24724828

  9. Development of dynamic kinetic resolution on large scale for (±)-1-phenylethylamine.

    PubMed

    Thalén, Lisa K; Bäckvall, Jan-E

    2010-01-01

    Candida antarctica lipase B (CALB) and racemization catalyst 4 were combined in the dynamic kinetic resolution (DKR) of (±)-1-phenylethylamine (1). Several reaction parameters have been investigated to modify the method for application on multigram scale. A comparison of isopropyl acetate and alkyl methoxyacetates as acyl donors was carried out. It was found that lower catalyst loadings could be used to obtain (R)-2-methoxy-N-(1-phenylethyl)acetamide (3) in good yield and high ee when alkyl methoxyacetates were used as acyl donors compared to when isopropyl acetate was used as the acyl donor. The catalyst loading could be decreased to 1.25 mol % Ru-catalyst 4 and 10 mg CALB per mmol 1 when alkyl methoxyacetates were used as the acyl donor. PMID:20978623

  10. Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives.

    PubMed

    Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria

    2016-04-01

    A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100). PMID:26922853

  11. Kinetic resolution of 2-hydroxybutanoate racemic mixtures by NAD-independent L-lactate dehydrogenase.

    PubMed

    Gao, Chao; Zhang, Wen; Ma, Cuiqing; Liu, Peng; Xu, Ping

    2011-04-01

    Optically active D-2-hydroxybutanoate is an important building block intermediate for medicines and biodegradable poly(2-hydroxybutanoate). Kinetic resolution of racemic 2-hydroxybutanoate may be a green and desirable alternative for D-2-hydroxybutanoate production. In this work, D-2-hydroxybutanoate at a high concentration (0.197 M) and a high enantiomeric excess (99.1%) was produced by an NAD-independent L-lactate dehydrogenase (L-iLDH) containing biocatalyst. 2-Oxobutanoate, another important intermediate, was co-produced at a high concentration (0.193 M). Using a simple ion exchange process with the macroporous anion exchange resin D301, D-2-hydroxybutanoate was separated from the biotransformation system with a high recovery of 84.7%. PMID:21295977

  12. Development of a Diastereoselective Phosphorylation of a Complex Nucleoside via Dynamic Kinetic Resolution.

    PubMed

    Tran, Kristy; Beutner, Gregory L; Schmidt, Michael; Janey, Jacob; Chen, Ke; Rosso, Victor; Eastgate, Martin D

    2015-05-15

    The development of a diastereoselective nucleoside phosphorylation is described, which produces a single isomer of a complex nucleoside monophosphate pro-drug. A stable phosphoramidic acid derivative is coupled to the nucleoside, in a process mediated by HATU and quinine, to deliver the coupled product in high chemical yield and good diastereoselectivity. This unusual process was shown to proceed through a dynamic kinetic resolution of a 1:1 mixture of activated phosphonate ester diastereoisomers. The optimized conditions afforded the product with a combined [S,S(P)] and [S,R(P)] in-process yield of 89% and a ∼7:1 [S,S(P):S,R(P)] diastereomeric ratio. Isolation of the major isomer was facilitated by single crystallization from anisole, where the product was obtained in 57% isolated yield, excellent purity (>95%), and a high diastereomeric ratio (>50:1). PMID:25840459

  13. In situ investigation of mesoporous silicon oxidation kinetics using infrared emittance spectroscopy.

    PubMed

    Bardet, Benjamin; De Sousa Meneses, Domingos; Defforge, Thomas; Billoué, Jérôme; Gautier, Gaël

    2016-07-21

    In this paper, we study the thermal oxidation kinetics of mesoporous silicon layers, synthesized by electrochemical anodization, from 260 °C up to 1100 °C. A specific apparatus is employed to heat the mesoporous samples in air and to record at the same time their infrared emittance. Based on Bruggeman effective medium approximation, an optical model is set up to realistically approximate the dielectric function of the porous material with an emphasis on the surface chemistry and oxide content. A transition temperature of 600 °C is evidenced from data processing which gives evidence of two oxidation mechanisms with distinct kinetics. Between 260-600 °C, the oxidation is surface-limited with kinetics dependent on the hydrogen desorption rate. However, above 600 °C, the oxide growth is limited by oxygen diffusion through the existing oxide layer. A parabolic law is employed to fit the oxidation rate and to extract the high-temperature activation energy (EA = 1.5 eV). A precise control of the oxide growth can thus be achieved. PMID:27333267

  14. Natural realgar and amorphous AsS oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Lengke, Maggy F.; Tempel, Regina N.

    2003-03-01

    The oxidation rates of natural realgar and amorphous synthetic AsS by dissolved oxygen were evaluated using mixed flow reactors at pH 7.2 to 8.8 and dissolved oxygen contents of 5.9 to 16.5 ppm over a temperature range of 25 to 40°C. The ratios of As/S are stoichiometric for all amorphous AsS oxidation experiments except for two experiments conducted at pH ˜8.8. In these experiments, stoichiometric ratios of As/S were only observed in the early stages of AsS (am) oxidation whereas lower As/S ratios were observed during steady state. For realgar oxidation experiments, the As/S ratio is less than the stoichiometric ratio of realgar, ranging between 0.61 and 0.71. This nonstoichiometric release of As and S to solution indicates that realgar oxidation is more selective for S after the rates of oxidation become constant. All measured oxidation rates at 25°C can be described within experimental uncertainties as follows: Table 1

  15. Synthesis of a Racemic Ester and Its Lipase Catalyzed Kinetic Resolution

    NASA Astrophysics Data System (ADS)

    Stetca, Delia; Arends, Isabel W. C. E.; Hanefeld, Ulf

    2002-11-01

    A first-year organic chemistry laboratory experiment is described in which an enzyme is utilized for the kinetic resolution of a racemic ester. In the first step, the racemic ester is synthesized from racemic 1-phenylethanol and acetic anhydride in the presence of pyridine. In the second step, only one of the two enantiomers of the racemic ester is selectively hydrolyzed. This reaction is enzyme-catalyzed and it clearly demonstrates the great ease with which enzymes can be used for the synthesis of enantiomerically-enriched compounds. The two enantiomerically-enriched compounds formed are isolated and analyzed for their optical purity. In these experiments the students are exposed to enzyme chemistry in combination with standard organic methods. Indeed, all the products are purified by techniques that are applied in the research laboratory (column chromatography and distillation), ensuring that these experiments come as close to the research environment as possible. By means of these experiments, topics such as enantioselective synthesis, enzymes in synthesis, enzyme kinetics, and analytical techniques such as IR, TLC, and optical rotation can be introduced to the students.

  16. High-resolution Hybrid Simulations of Kinetic Plasma Turbulence at Proton Scales

    NASA Astrophysics Data System (ADS)

    Franci, Luca; Landi, Simone; Matteini, Lorenzo; Verdini, Andrea; Hellinger, Petr

    2015-10-01

    We investigate properties of plasma turbulence from magnetohydrodynamic (MHD) to sub-ion scales by means of two-dimensional, high-resolution hybrid particle-in-cell simulations. We impose an initial ambient magnetic field perpendicular to the simulation box, and we add a spectrum of large-scale magnetic and kinetic fluctuations with energy equipartition and vanishing correlation. Once the turbulence is fully developed, we observe an MHD inertial range, where the spectra of the perpendicular magnetic field and the perpendicular proton bulk velocity fluctuations exhibit power-law scaling with spectral indices of -5/3 and -3/2, respectively. This behavior is extended over a full decade in wavevectors and is very stable in time. A transition is observed around proton scales. At sub-ion scales, both spectra steepen, with the former still following a power law with a spectral index of ∼ -3. A -2.8 slope is observed in the density and parallel magnetic fluctuations, highlighting the presence of compressive effects at kinetic scales. The spectrum of the perpendicular electric fluctuations follows that of the proton bulk velocity at MHD scales, and flattens at small scales. All these features, which we carefully tested against variations of many parameters, are in good agreement with solar wind observations. The turbulent cascade leads to on overall proton energization with similar heating rates in the parallel and perpendicular directions. While the parallel proton heating is found to be independent on the resistivity, the number of particles per cell, and the resolution employed, the perpendicular proton temperature strongly depends on these parameters.

  17. Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines.

    PubMed

    Yan, Liang; Xu, Jing-Kun; Huang, Chao-Fan; He, Zeng-Yang; Xu, Ya-Nan; Tian, Shi-Kai

    2016-09-01

    A new strategy has been established for the kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl-hydrazide-catalyzed asymmetric OH-substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]2 , 4 mol % (S)-SegPhos, and 10 mol % 2,5-dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcohols were smoothly resolved with selectivity factors of more than 400 through an asymmetric allylic alkylation of monosubstituted hydrazines under air at room temperature. Importantly, this kinetic resolution process provided various allylic alcohols and allylic hydrazine derivatives with high enantiopurity. PMID:27339655

  18. Biomimetic Kinetic Resolution: Highly Enantio- and Diastereoselective Transfer Hydrogenation of Aglain Ketones To Access Flavagline Natural Products

    PubMed Central

    2015-01-01

    We have previously reported asymmetric syntheses and absolute configuration assignments of the aglains (+)-ponapensin and (+)-elliptifoline and proposed a biosynthetic kinetic resolution process to produce enantiomeric rocaglamides and aglains. Herein, we report a biomimetic approach for the synthesis of enantiomerically enriched aglains and rocaglamides via kinetic resolution of a bridged ketone utilizing enantioselective transfer hydrogenation. The methodology has been employed to synthesize and confirm the absolute stereochemistries of the pyrimidone rocaglamides (+)-aglaiastatin and (−)-aglaroxin C. Additionally, the enantiomers and racemate of each metabolite were assayed for inhibition of the heat-shock response, cytotoxicity, and translation inhibition. PMID:25514979

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

    PubMed

    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. PMID:20097402

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

    NASA Technical Reports Server (NTRS)

    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.

  1. Oxidation kinetics of a continuous carbon phase in a nonreactive matrix

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  2. Probing Protein Folding Kinetics with High-resolution, Stabilized Optical Tweezers

    NASA Astrophysics Data System (ADS)

    Wong, Wesley; Halvorsen, Ken

    2009-03-01

    Single-molecule techniques provide a powerful means of exploring molecular transitions such as the unfolding and refolding of a protein. However, the quantification of bi-directional transitions and near-equilibrium phenomena poses unique challenges, and is often limited by the detection resolution and long-term stability of the instrument. We have developed unique optical tweezers methods that address these problems, including an interference-based method for high-resolution 3D bead tracking (˜1 nm laterally, ˜0.3 nm vertically, at > 100 Hz), and a continuous autofocus system that stabilizes the trap height to within 1-2 nm longterm [1,2]. We have used our instruments to quantify the force-dependent unfolding and refolding kinetics of single protein domains (e.g. spectrin in collaboration with E. Evans). These single-molecule studies are presented, together with the accompanying probabilistic analysis that we have developed. References: 1. W.P. Wong, V. Heinrich, E. Evans, Mat. Res. Soc. Symp. Proc., 790, P5.1-P5.10 (2004). 2. V. Heinrich, W.P. Wong, K. Halvorsen, E. Evans, Langmuir, 24, 1194-1203 (2008).

  3. Energy resolution and efficiency of phonon-mediated kinetic inductance detectors for light detection

    SciTech Connect

    Cardani, L.; Colantoni, I.; Coppolecchia, A.; Cruciani, A.; Vignati, M.; Bellini, F.; Casali, N.; Cosmelli, C.; Di Domizio, S.; Castellano, M. G.; Tomei, C.

    2015-08-31

    The development of sensitive cryogenic light detectors is of primary interest for bolometric experiments searching for rare events like dark matter interactions or neutrino-less double beta decay. Thanks to their good energy resolution and the natural multiplexed read-out, Kinetic Inductance Detectors (KIDs) are particularly suitable for this purpose. To efficiently couple KIDs-based light detectors to the large crystals used by the most advanced bolometric detectors, active surfaces of several cm{sup 2} are needed. For this reason, we are developing phonon-mediated detectors. In this paper, we present the results obtained with a prototype consisting of four 40 nm thick aluminum resonators patterned on a 2 × 2 cm{sup 2} silicon chip, and calibrated with optical pulses and X-rays. The detector features a noise resolution σ{sub E} = 154 ± 7 eV and an (18 ± 2)% efficiency.

  4. Kinetic study of the hydrogen oxidation reaction on sub-stoichiometric titanium oxide-supported platinum electrocatalyst in acid solution

    NASA Astrophysics Data System (ADS)

    Babić, B.; Gulicovski, J.; Gajić-Krstajić, Lj.; Elezović, N.; Radmilović, V. R.; Krstajić, N. V.; Vračar, Lj. M.

    The kinetics and mechanism of the hydrogen oxidation reaction were studied in 0.5 mol dm -3 HClO 4 solution on an electrode based on titanium oxide with Magneli phase structure-supported platinum electrocatalyst applied on rotation Au disk electrode. Pt catalyst was prepared by impregnation method from 2-propanol solution of Pt(NH 3) 2(NO 2) 2 and sub-stoichiometric titanium oxide powder. Sub-stiochiometric titanium oxide support was characterized by X-ray diffraction and BET techniques. The synthesized catalyst was analyzed by TEM technique. Based on Tafel-Heyrovsky-Volmer mechanism the corresponding kinetic equations were derived to describe the hydrogen oxidation current-potential behavior on RDE over the entire potential region. The polarization RDE curves were fitted with derived polarization equations according to proposed model. The fitting shows that the HOR on Pt proceeds most likely via the Tafel-Volmer (TV) pathway in the lower potential region, while the Heyrovsky-Volmer (HV) pathway is operative in the higher potential region. It is pointed out that Tafel equation that has been frequently used for the kinetics analysis in the HOR, can not reproduce the polarization curves measured with high mass-transport rates. Polarization measurements on RDE revealed that the Pt catalyst deposited on titanium suboxide support showed equal specific activity for the HOR compared to conventional carbon-supported Pt fuel cell catalyst.

  5. Surface oxidation energetics and kinetics on MoS2 monolayer

    NASA Astrophysics Data System (ADS)

    KC, Santosh; Longo, Roberto C.; Wallace, Robert M.; Cho, Kyeongjae

    2015-04-01

    In this work, surface oxidation of monolayer MoS2 (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS2 shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS2 surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS2 surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS2 monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale.

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

    PubMed

    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. PMID:26426294

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

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

    2014-01-01

    In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated. PMID:24682678

  9. Enzymatic kinetic resolution of primary allenic alcohols. Application to the total synthesis and stereochemical assignment of striatisporolide A.

    PubMed

    Deska, Jan; Bäckvall, Jan-E

    2009-09-01

    Crude Porcine pancreatic lipase was successfully used for the kinetic resolution of axially chiral primary allenic alcohols providing very high enantioselectivities with E values above 200. This simple access to optically active allenes was applied to the total synthesis of the fungal metabolite (-)-striatisporolide A, allowing its unambiguous stereochemical assignment. PMID:19675888

  10. Kinetic resolution of axially chiral 2,2'-dihydroxy-1,1'-biaryls by palladium-catalyzed alcoholysis.

    PubMed

    Aoyama, Hiroshi; Tokunaga, Makoto; Kiyosu, Junya; Iwasawa, Tetsuo; Obora, Yasushi; Tsuji, Yasushi

    2005-08-01

    Palladium-diamine complexes catalyzed kinetic resolution of axially chiral 2,2'-dihydroxy-1,1'-biaryls by alcoholysis of vinyl ethers. The reaction proceeded with high selectivity for various kinds of biaryls. This process is applicable to not only binaphthols but also biphenols, which have been considered to be difficult for the enantioselective synthesis by known catalytic methods. PMID:16045319

  11. Exploring crystallization kinetics in natural rhyolitic melts using high resolution CT imagery of spherulites

    NASA Astrophysics Data System (ADS)

    Clow, T. W.; Befus, K. S.; Gardner, J. E.

    2014-12-01

    Little of our understanding of crystallization kinetics has been directly derived from studies of natural samples. We examine crystallization of rhyolitic melts by quantifying spherulite sizes and number densities in obsidian collected from Yellowstone caldera using high-resolution x-ray computed tomography (CT) imagery. Spherulites are spherical to ellipsoidal masses of intergrown alkali feldspar and quartz in a radiating, fibrous structure. They are thought to form in response to relatively rapid crystallization of melt in response to large amounts of undercooling. Recent research using compositional gradients that form outside of spherulites has suggested that they nucleate at 700 to 500 ˚C and their growth slows exponentially until it eventually ceases at ~400 ˚C. By quantifying spherulite textures, and using those temperature constraints, we derive new kinetic information regarding crystallization in natural rhyolitic systems. We find that spherulites range from 0.2 to 12.3 mm in diameter, and are 0.004 to 49.5 mm3 in volume. Such values generate number densities of 70 to 185 spherulites cm-3. Histograms of size display positively skewed distributions indicating small spherulites are far more abundant than larger ones. Those distributions imply nucleation rates change as a function of temperature. At higher temperatures where the melt is undercooled by 400-500 ˚C, nucleation is rare and growth is favored. With decreasing temperature, nucleation rates increase rapidly until cold enough temperatures are reached that diffusion limits crystallization and causes it to cease (undercoolings of ~650 ˚C). Assuming a cooling rate for the host obsidian of 10-5 ˚C s-1, then overall spherulite nucleation rates are 0.01 to 0.03 spherulites cm-3 hour-1.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Dissolution kinetics of spent petroleum catalyst using sulfur oxidizing acidophilic microorganisms.

    PubMed

    Mishra, Debaraj; Ahn, Jong G; Kim, Dong J; Roychaudhury, G; Ralph, David E

    2009-08-15

    Bioleaching studies of spent petroleum catalyst were carried out using sulfur oxidizing, Acidithiobacillus species. Leaching studies were carried out in two-stage, in the first stage bacteria were grown and culture filtrate was used in the second stage for leaching purpose. XRD analysis of spent petroleum catalyst showed oxides of V, Fe and Al and sulfides of Mo and Ni. The leaching kinetics followed dual rate, initial faster followed by slower rate and equilibrium could be achieved within 7 days. The leaching rate of Ni and V were high compared to Mo. The low Mo leaching rate may be either due to formation of impervious sulfur layer or refractoriness of sulfides or both. The leaching kinetics followed 1st order rate. Using leaching kinetics, rate equations for dissolution process for different metal ions were evaluated. The rate determining step observed to be pore diffusion controlled. PMID:19286311

  15. Atypical kinetic behavior of chloroperoxidase-mediated oxidative halogenation of polycyclic aromatic hydrocarbons.

    PubMed

    Aburto, Jorge; Correa-Basurto, Jose; Torres, Eduardo

    2008-12-01

    We have identified an atypical kinetic behavior for the oxidative halogenation of several polycyclic aromatic hydrocarbons (PAHs) by chloroperoxidase (CPO) from Caldariomyces fumago. This behavior resembles the capacity of some members of the P450 family to simultaneously recognize several substrate molecules at their active sites. Indeed, fluorometric studies showed that PAHs exist in solution as monomers and pi-pi dimers that interact to different extents with CPO. The dissociation constants of dimerization were evaluated for every single PAH by spectrofluorometry. Furthermore, docking studies also suggest that CPO might recognize either one or two substrate molecules in its active site. The atypical sigmoidal kinetic behavior of CPO in the oxidative halogenation of PAHs is explained in terms of different kinetic models for non-heteroatomic PAHs (naphthalene, anthracene and pyrene). The results suggest that the actual substrate for CPO in this study was the pi-pi dimer for all evaluated PAHs. PMID:18823932

  16. Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

    NASA Astrophysics Data System (ADS)

    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.

  17. Nitrite-Driven Nitrous Oxide Production Under Aerobic Soil Conditions: Kinetics and Biochemical Controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

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

    EPA Science Inventory

    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...

  19. Nitrite-driven nitrous oxide production under aerobic soil conditions: Kinetics and biochemical controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

  20. Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

    ERIC Educational Resources Information Center

    Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

    2008-01-01

    A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

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

    SciTech Connect

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

    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.

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

    NASA Astrophysics Data System (ADS)

    Marchand, M.; Fiquet, O.; Brothier, M.

    2013-06-01

    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 UC2 chemical phase is progressively oxidised into U3O8 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.

  3. Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures

    NASA Astrophysics Data System (ADS)

    Padilla, Rafael; Aracena, Alvaro; Ruiz, Maria C.

    2012-10-01

    Roasting of enargite (Cu3AsS4) in the temperature range of 648 K to 898 K (375 °C to 625 °C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:

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

    NASA Astrophysics Data System (ADS)

    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.

  5. The kinetics of the oxidation of pyrite by ferric ions and dissolved oxygen: An electrochemical study

    SciTech Connect

    Holmes, P.R.; Crundwell, F.K.

    2000-01-01

    The dissolution of pyrite is important in the geochemical cycling of iron and sulphur, in the formation of acid mine drainage, and in the extraction of metals by bacterial leaching. Many researchers have studied the kinetics of dissolution, and the rate of dissolution has often been found to be half-order in ferric ions or oxygen. Previous work has not adequately explained the kinetics of dissolution of pyrite. The dissolution of pyrite is an oxidation-reduction reaction. The kinetics of the oxidation and reduction half-reactions was studied independently using electrochemical techniques of voltammetry. The kinetics of the overall reaction was studied by the electrochemical technique of potentiometry, which consisted of measuring the mixed potential of a sample of corroding pyrite in solutions of different compositions. The kinetics of the half reactions are related to the kinetics of the overall dissolution reaction by the condition that there is no accumulation of charge. This principle is used to derive expressions for the mixed potential and the rate of dissolution, which successfully describe the mixed potential measurements and the kinetics of dissolution reported in the literature. It is shown that the observations of half-order kinetics and that the oxygen in the sulphate product arises from water are both a direct consequence of the electrochemical mechanism. Thus it is concluded that the electrochemical reaction steps occurring at the mineral-solution interface control the rate of dissolution. Raman spectroscopy was used to analyze reaction products formed on the pyrite surface. The results indicated that small amounts of polysulphides form on the surface of the pyrite. However, it was also found that the mixed (corrosion) potential does not change over a 14-day leaching period. This indicates that even though polysulphide material is present on the surface, it does not influence the rate of the reactions occurring at the surface. Measurement of the

  6. The influence of transition metal oxides on the kinetics of Li2O2 oxidation in Li-O2 batteries: high activity of chromium oxides.

    PubMed

    Yao, Koffi P C; Lu, Yi-Chun; Amanchukwu, Chibueze V; Kwabi, David G; Risch, Marcel; Zhou, Jigang; Grimaud, Alexis; Hammond, Paula T; Bardé, Fanny; Shao-Horn, Yang

    2014-02-14

    Reducing the energy loss associated with Li2O2 electrochemical oxidation is paramount to the development of efficient rechargeable lithium-oxygen (Li-O2) batteries for practical use. The influence of a series of perovskites with different eg filling on the kinetics of Li2O2 oxidation was examined using Li2O2-prefilled electrodes. While LaCrO3 is inactive for oxygen evolution upon water oxidation in alkaline solution, it was found to provide the highest specific current towards Li2O2 oxidation among all the perovskites examined. Further exploration of Cr-based catalysts showed that Cr nanoparticles (Cr NP) with an average particle size of 40 nm, having oxidized surfaces, had comparable surface area activities to LaCrO3 but much greater mass activities. Unlike Pt/C and Ru/C that promote electrolyte oxidation in addition to Li2O2 oxidation, no evidence of enhanced electrolyte oxidation was found for Cr NP relative to Vulcan carbon. X-ray absorption spectroscopy at the O K and Cr L edge revealed a redox process of Cr(3+) ↔ Cr(6+) on the surface of Cr NP upon Li2O2 oxidation, which might be responsible for the enhanced oxidation kinetics of Li2O2 and the reduced charging voltages of Li-O2 batteries. PMID:24352578

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

    SciTech Connect

    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.

  8. Kinetic analysis for ammonia decomposition in supercritical water oxidation of sewage sludge

    SciTech Connect

    Goto, Motonobu; Shiramizu, Daisuke; Kodama, Akio; Hirose, Tsutomu

    1999-11-01

    Supercritical water oxidation was applied to the destruction of municipal excess sewage sludge. The reaction was carried out in a batch reactor with hydrogen peroxide as an oxidant in the temperature range of 723--823 K. Ammonia and acetic acid are found to be refractory intermediates in supercritical water oxidation of organic wastes. Ammonia concentration produced during the reaction was measured as a function of reaction time. The dynamic data were analyzed by a first-order kinetics. The reaction rate constant coincides with those reported in the literature.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. PMID:26419340

  11. Influence of hydrogen oxidation kinetics on hydrogen environment embrittlement

    NASA Technical Reports Server (NTRS)

    Walter, R. J.; Kendig, M. W.; Meisels, A. P.

    1992-01-01

    Results are presented from experiments performed to determine the roles of hydrogen absorption and hydrogen electron transfer on the susceptibility of Fe- and Ni-base alloys to ambient-temperature hydroen embrittlement. An apparent independence is noted between hydrogen environment embrittlement and internal hydrogen embrittlement. The experiments were performed on Inconel 718, Incoloy 903, and A286. The electrochemical results obtained indicate that Inconel 718 either adsorbs hydrogen more rapidly and/or the electrochemical oxidation of the adsorbed hydrogen occurred more rapidly than in the other two materials.

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

    SciTech Connect

    Contescu, Cristian I; Burchell, Timothy D; Mee, Robert

    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.

  13. Chemoenzymatic Dynamic Kinetic Resolution: A Powerful Tool for the Preparation of Enantiomerically Pure Alcohols and Amines

    PubMed Central

    2015-01-01

    Chemoenzymatic dynamic kinetic resolution (DKR) constitutes a convenient and efficient method to access enantiomerically pure alcohol and amine derivatives. This Perspective highlights the work carried out within this field during the past two decades and pinpoints important avenues for future research. First, the Perspective will summarize the more developed area of alcohol DKR, by delineating the way from the earliest proof-of-concept protocols to the current state-of-the-art systems that allows for the highly efficient and selective preparation of a wide range of enantiomerically pure alcohol derivatives. Thereafter, the Perspective will focus on the more challenging DKR of amines, by presenting the currently available homogeneous and heterogeneous methods and their respective limitations. In these two parts, significant attention will be dedicated to the design of efficient racemization methods as an important means of developing milder DKR protocols. In the final part of the Perspective, a brief overview of the research that has been devoted toward improving enzymes as biocatalysts is presented. PMID:25730714

  14. Chemoenzymatic dynamic kinetic resolution: a powerful tool for the preparation of enantiomerically pure alcohols and amines.

    PubMed

    Verho, Oscar; Bäckvall, Jan-E

    2015-04-01

    Chemoenzymatic dynamic kinetic resolution (DKR) constitutes a convenient and efficient method to access enantiomerically pure alcohol and amine derivatives. This Perspective highlights the work carried out within this field during the past two decades and pinpoints important avenues for future research. First, the Perspective will summarize the more developed area of alcohol DKR, by delineating the way from the earliest proof-of-concept protocols to the current state-of-the-art systems that allows for the highly efficient and selective preparation of a wide range of enantiomerically pure alcohol derivatives. Thereafter, the Perspective will focus on the more challenging DKR of amines, by presenting the currently available homogeneous and heterogeneous methods and their respective limitations. In these two parts, significant attention will be dedicated to the design of efficient racemization methods as an important means of developing milder DKR protocols. In the final part of the Perspective, a brief overview of the research that has been devoted toward improving enzymes as biocatalysts is presented. PMID:25730714

  15. Dynamic Kinetic Resolution Enabled by Intramolecular Benzoin Reaction: Synthetic Applications and Mechanistic Insights.

    PubMed

    Zhang, Guoxiang; Yang, Shuang; Zhang, Xiaoyan; Lin, Qiqiao; Das, Deb K; Liu, Jian; Fang, Xinqiang

    2016-06-29

    The highly enantio-, diastereo-, and regioselective dynamic kinetic resolution of β-ketoesters and 1,3-diketones was achieved via a chiral N-heterocyclic carbene catalyzed intramolecular cross-benzoin reaction. A variety of tetralone derivatives bearing two contiguous stereocenters and multiple functionalities were liberated in moderate to excellent yields and with high levels of stereoselectivity (>95% ee and >20:1 dr in most cases). In addition, the excellent regioselectivity control for aryl/alkyl 1,3-diketones, and the superior electronic differentiation of 1,3-diarylketones were highlighted. Moreover, a set of new mechanistic rationale that differs with the currently widely accepted understanding of intramolecular benzoin reactions was established to demonstrate the superior preference of benzoin over aldol transformation: (1) A coexistence of competitive aldol and benzoin reactions was detected, but a retro-aldol-irreversible benzoin process performs a vital role in the generation of predominant benzoin products. (2) The most essential role of an N-electron-withdrawing substituent in triazolium catalysts was revealed to be accelerating the rate of the benzoin transformation, rather than suppressing the aldol process through reducing the inherent basicity of the catalyst. PMID:27270409

  16. Dynamic kinetic resolution of secondary alcohols combining enzyme-catalyzed transesterification and zeolite-catalyzed racemization.

    PubMed

    Zhu, Yongzhong; Fow, Kam-Loon; Chuah, Gaik-Khuan; Jaenicke, Stephan

    2007-01-01

    Hydrophobic zeolite beta containing low concentrations of Zr or Al was found to be a good catalyst for the racemization of 1-phenylethanol. The formation of styrene as a side product could be minimized by reducing the metal concentration in the zeolite beta. Combined with an immobilized lipase from Candida antarctica, the dynamic kinetic resolution of 1-phenylethanol to the (R)-phenylethylester can be achieved with high yield and selectivity. The reaction was best conducted in toluene as solvent at 60 degrees C, with higher temperatures leading to a loss in the enantioselectivity of the formed ester. By using high-molecular-weight acyl-transfer reagents, such as vinyl butyrate or vinyl octanoate, a high enantiomeric excess of the product esters of 92 and 98 %, respectively, could be achieved. This is attributed to a steric effect: the bulky ester is less able to enter the pore space of the zeolite catalyst where the active sites for racemization are localized. Close to 100 % conversion of the alcohol was achieved within 2 h. If the more common acyl donor, isopropenyl acetate, was used, the enantiomeric excess (ee) of the formed ester was only 67 %, and the reaction was considerably slower. PMID:17004277

  17. Oxidation kinetics of coated silicon carbide fiber-reinforced silicon carbide (SiC/SiC)

    SciTech Connect

    Fox, D.S.

    1994-12-31

    Silicon carbide fiber-reinforced silicon carbide (SiC/SiC) was exposed for 100 hours to dry, flowing oxygen. Oxidation kinetics were determined via thermogravimetric analysis at 981{degrees}, 1204{degrees} and 1316{degrees}C (1800{degrees}, 2200{degrees} and 2400{degrees}F). The effectiveness of three external coating systems applied for oxidation protection is discussed. In all cases, weight gains were observed, and the pyrolytic carbon interface layer remained intact. A CVD SiC external coating is the most promising due to low oxidation kinetics resulting from solid silica formation. A borosilicate glass was observed on the surface of two of the materials that have boron-containing coatings.

  18. Detailed kinetic modeling study of n-pentanol oxidation

    DOE PAGESBeta

    Heufer, K. Alexander; Sarathy, S. Mani; Curran, Henry J.; Davis, Alexander C.; Westbrook, Charles K.; Pitz, William J.

    2012-09-28

    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 detailedmore » 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. In addition, 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.« less

  19. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1975-01-01

    The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

  20. OH- Initiated Heterogeneous Oxidation of Saturated Organic Aerosols in the Presence of SO2: Uptake Kinetics and Product Identification.

    NASA Astrophysics Data System (ADS)

    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. Study of the oxidation of W(110) by full-solid-angle photoelectron diffraction with chemical state and time resolution

    SciTech Connect

    Ynzunza, R. X.; Palomares, F. J.; Tober, E. D.; Wang, Z.; Morais, J.; Denecke, R.; Daimon, H.; Chen, Y.; Hussain, Z; Liesengang, J.; Van Hove, M. A.; Fadley, C. S.

    1997-04-01

    The brightness of third-generation synchrotron radiation from beamline 9.3.2 at the Advanced Light Source has been combined with the high-intensities and energy resolutions possible with its advanced photoelectron spectrometer/diffractometer experimental station in order to study the time dependence of the oxidation of the W(110) surface. This has been done via chemical-state-resolved core-level photoelectron spectroscopy and diffraction. This system has been studied previously by other methods such as LEED and STM, but several questions remain as to the basic kinetics of oxidation and the precise adsorption structures involved. By studying the decay and growth with time of various peaks in the W 4f{sub 7/2} photoelectron spectra, it should be possible to draw quantitative conclusions concerning the reaction kinetics involved. The authors have also measured full-solid-angle photoelectron diffraction patterns for the two oxygen-induced W states, and these should permit fully defining the different structures involved in this oxidation process.

  2. Impact of Biodiesel on the Oxidation Kinetics and Morphology of Diesel Particulate

    SciTech Connect

    Strzelec, Andrea; Toops, Todd J; Daw, C Stuart

    2011-01-01

    We compare the oxidation characteristics of four different diesel particulates generated with a modern light-duty engine. The four particulates represent engine fueling with conventional ultra-low sulfur diesel (ULSD), biodiesel, and two intermediate blends of these fuels. The comparisons discussed here are based on complementary measurements implemented in a laboratory micro-reactor, including temperature programmed desorption and oxidation, pulsed isothermal oxidation, and BET surface area. From these measurements we have derived models that are consistent with the observed oxidation reactivity differences. When accessible surface area effects are properly accounted for, the oxidation kinetics of the fixed carbon components were found to consistently exhibit an Arrhenius activation energy of 113 6 kJ/mol. Release of volatile carbon from the as-collected particulate appears to follow a temperaturedependent rate law.

  3. The impact of the initial state on the kinetics of oxidation ion- modified fuel cladding alloy E110

    NASA Astrophysics Data System (ADS)

    Kalin, B. A.; Volkov, N. V.; Valikov, R. A.; Yashin, A. S.; Yakutkina, T. V.

    2016-04-01

    The paper examines the impact of the initial state (the presence of impurities, surface preparation), and surface alloying on the kinetics of the oxidation of fuel cladding alloy E110. The studies concluded that the use of ionic polishing instead of traditional chemical polishing helps to reduce the rate of oxidation of zirconium alloys. Also studied the effect of alloying elements introduced in the surface layers of claddings by ion mixing on the kinetics of the oxidation of the alloy E110.

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

    PubMed

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

    2016-02-16

    Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH2Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems. PMID:26789138

  5. Influence of recrystallization on phase separation kinetics of oxide dispersion strengthened Fe Cr Al alloy

    SciTech Connect

    Capdevila, C.; Miller, Michael K; Pimentel, G.; Chao, J.

    2012-01-01

    The effect of different starting microstructures on the kinetics of Fe-rich ({alpha}) and Cr-rich ({alpha}') phase separation during aging of Fe-Cr-Al oxide dispersion strengthened (ODS) alloys has been analyzed with a combination of atom probe tomography and thermoelectric power measurements. The results revealed that the high recrystallization temperature necessary to produce a coarse grained microstructure in Fe-base ODS alloys affects the randomness of Cr-atom distributions and defect density, which consequently affect the phase separation kinetics at low annealing temperatures.

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

    SciTech Connect

    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.

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

    PubMed

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

    2009-12-01

    The present study aimed to examine the effects of a prior 1-hour continuous exercise bout (CONT) at an intensity (Fat(max)) that elicits the maximal fat oxidation (MFO) on the fat oxidation kinetics during a subsequent submaximal incremental test (IncrC). Twenty moderately trained subjects (9 men and 11 women) performed a graded test on a treadmill (Incr), with 3-minute stages and 1-km.h(-1) increments. Fat oxidation was measured using indirect calorimetry and plotted as a function of exercise intensity. A mathematical model (SIN) including 3 independent variables (dilatation, symmetry, and translation) was used to characterize the shape of fat oxidation kinetics and to determine Fat(max) and MFO. On a second visit, the subjects performed CONT at Fat(max) followed by IncrC. After CONT performed at 57% +/- 3% (means +/- SE) maximal oxygen uptake (Vo(2max)), the respiratory exchange ratio during IncrC was lower at every stage compared with Incr (P < .05). Fat(max) (56.4% +/- 2.3% vs 51.5% +/- 2.4% Vo(2max), P = .013), MFO (0.50 +/- 0.03 vs 0.40 +/- 0.03 g.min(-1), P < .001), and fat oxidation rates from 35% to 70% Vo(2max) (P < .05) were significantly greater during IncrC compared with Incr. However, dilatation and translation were not significantly different (P > .05), whereas symmetry tended to be greater in IncrC (P = .096). This study showed that the prior 1-hour continuous moderate-intensity exercise bout increased Fat(max), MFO, and fat oxidation rates over a wide range of intensities during the postexercise incremental test. Moreover, the shape of the postexercise fat oxidation kinetics tended to have a rightward asymmetry. PMID:19632694

  8. Kinetics of low-temperature CO oxidation on Au(111)

    NASA Astrophysics Data System (ADS)

    Thuening, Theodore; Walker, Joshua; Adams, Heather; Furlong, Octavio; Tysoe, Wilfred T.

    2016-06-01

    The oxidation of carbon monoxide on oxygen-modified Au(111) surfaces is studied using a combination of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). TPD reveals that CO desorbs in two states with the low-temperature state have a peak temperature between ~ 130 and 150 K, and the higher-temperature state having a peak temperature that varies from ~ 175 to ~ 220 K depending on the initial oxygen and CO coverages. Infrared spectroscopy indicates that the low-temperature CO desorption state is predominantly associated with CO adsorbed on Auδ + sites, while the higher-temperature states are due to CO on Au0 sites. No additional vibrational features are detected indicating that CO reacts directly with adsorbed atomic oxygen on gold to form CO2. Estimates of the activation energy for CO2 formation suggest that they are in the same range and found for supported gold catalysts at reaction temperature below ~ 300 K.

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

    PubMed

    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. PMID:24569272

  10. Estimation of Sintering Kinetics of Oxidized Magnetite Pellet Using Optical Dilatometer

    NASA Astrophysics Data System (ADS)

    Sandeep Kumar, T. K.; Viswanathan, Neelakantan Nurni; Ahmed, Hesham M.; Andersson, Charlotte; Björkman, Bo

    2015-04-01

    The quality of magnetite pellet is primarily determined by the physico-chemical changes the pellet undergoes as it makes excursion through the gaseous and thermal environment in the induration furnace. Among these physico-chemical processes, the oxidation of magnetite phase and the sintering of oxidized magnetite (hematite) and magnetite (non-oxidized) phases are vital. Rates of these processes not only depend on the thermal and gaseous environment the pellet gets exposed in the induration reactor but also interdependent on each other. Therefore, a systematic study should involve understanding these processes in isolation to the extent possible and quantify them seeking the physics. With this motivation, the present paper focusses on investigating the sintering kinetics of oxidized magnetite pellet. For the current investigation, sintering experiments were carried out on pellets containing more than 95 pct magnetite concentrate from LKAB's mine, dried and oxidized to completion at sufficiently low temperature to avoid sintering. The sintering behavior of this oxidized pellet is quantified through shrinkage captured by Optical Dilatometer. The extent of sintering characterized by sintering ratio found to follow a power law with time i.e., Kt n . The rate constant K for sintering was determined for different temperatures from isothermal experiments. The rate constant, K, varies with temperature as and the activation energy ( Q) and reaction rate constant ( K') are estimated. Further, the sintering kinetic equation was also extended to a non-isothermal environment and validated using laboratory experiments.

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

    PubMed

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

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (±0.5) × 10(9) and 3.1 (±0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation. PMID:26299576

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

    PubMed Central

    Hanson, Thomas E.; Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Hess, Daniel

    2013-01-01

    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. PMID:24391629

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

    PubMed

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

    2016-06-01

    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. PMID:27187246

  14. High resolution mapping of oxygen reduction reaction kinetics at polycrystalline platinum electrodes.

    PubMed

    Chen, Chang-Hui; Meadows, Katherine E; Cuharuc, Anatolii; Lai, Stanley C S; Unwin, Patrick R

    2014-09-14

    The scanning droplet-based technique, scanning electrochemical cell microscopy (SECCM), combined with electron backscatter diffraction (EBSD), is demonstrated as a powerful approach for visualizing surface structure effects on the rate of the oxygen reduction reaction (ORR) at polycrystalline platinum electrodes. Elucidating the effect of electrode structure on the ORR is of major interest in connection to electrocatalysis for energy-related applications. The attributes of the approach herein stem from: (i) the ease with which the polycrystalline substrate electrode can be prepared; (ii) the wide range of surface character open to study; (iii) the possibility of mapping reactivity within a particular facet (or grain), in a pseudo-single-crystal approach, and acquiring a high volume of data as a consequence; (iv) the ready ability to measure the activity at grain boundaries; and (v) an experimental arrangement (SECCM) that mimics the three-phase boundary in low temperature fuel cells. The kinetics of the ORR was analyzed and a finite element method model was developed to explore the effect of the three-phase boundary, in particular to examine pH variations in the droplet and the differential transport rates of the reactants and products. We have found a significant variation of activity across the platinum substrate, inherently linked to the crystallographic orientation, but do not detect any enhanced activity at grain boundaries. Grains with (111) and (100) contributions exhibit considerably higher activity than those with (110) and (100) contributions. These results, which can be explained by reference to previous single-crystal measurements, enhance our understanding of ORR structure-activity relationships on complex high-index platinum surfaces, and further demonstrate the power of high resolution flux imaging techniques to visualize and understand complex electrocatalyst materials. PMID:25072300

  15. Kinetics of the Oxidation of Bismuthinite in Oxygen-Nitrogen Atmospheres

    NASA Astrophysics Data System (ADS)

    Padilla, Rafael; Villa, Ricardo; Ruiz, Maria C.; Reddy, Ramana G.

    2011-10-01

    Bismuth is present in copper concentrates mainly as the mineral bismuthinite (Bi2S3). In some cases of smelting of concentrates, a substantial amount of bismuth can lead to contaminated copper cathodes. Thus, understanding the behavior of Bi2S3 at high temperatures is crucial to assessing the potential of bismuth removal in the pyrometallurgical process. Therefore, the oxidation of bismuthinite in mixtures of oxygen-nitrogen atmospheres was investigated using a thermogravimetric analysis technique. The results indicate that the oxidation process occurs through the following consecutive reactions: {{First stage: }}{{Bi}}_{ 2} {{S}}_{ 3} ( {{s,l}} ) + 3{{O}}2 ( {{g}} ) = 2{{Bi}}( {{l}} ) + 3{{SO}}_{ 2} ( {{g}} ) {{Second stage: }}2{{Bi}}( {{l}} ) + 3/2{{O}}2 ( {{g}} ) = {{Bi}}2 {{O}}3 ( {{s,l}} ) The kinetics of the oxidation of bismuthinite (first stage) was studied, and the model ln(1 - X) = -kapp t describes the kinetics of this reaction well. The bismuthinite oxidation dependence on oxygen partial pressure was of 0.9 order, and the intrinsic kinetic constants were obtained in the temperature range of 873 K to 1273 K (600 °C to 1000 °C), which were used to determine the activation energy of 91 kJ/mol. The results indicate that the oxidation of bismuthinite is a process controlled by chemical reactions. From this study, it can be concluded that the removal of bismuth from the Bi2S3-containing concentrates through a mechanism involving gaseous bismuth compounds is not feasible during an oxidizing roasting and/or smelting of concentrates containing Bi2S3.

  16. Dynamic Kinetic Resolution of Biaryl Lactones via a Chiral Bifunctional Amine Thiourea-Catalyzed Highly Atropo-enantioselective Transesterification.

    PubMed

    Yu, Chenguang; Huang, He; Li, Xiangmin; Zhang, Yueteng; Wang, Wei

    2016-06-01

    A solution to the unmet synthetic challenge of achieving highly atropo-enantioselective transesterification of Bringmann's lactones has been realized, employing a chiral bifunctional amine thiourea as promoter. The synergistic activation of the lactones and alcohols/phenols by the respective thiourea and amine groups is crucial for achieving the highly enantioselective, high-yielding dynamic kinetic resolution process. This protocol gives highly optically pure, axially chiral biaryl compounds with a broad substrate scope under mild reaction conditions. PMID:27218264

  17. Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

    PubMed

    Shinozawa, Toru; Terasaki, Shou; Mizuno, Shota; Kawatsura, Motoi

    2016-07-01

    We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value. PMID:27276556

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

    SciTech Connect

    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.

  19. Oxidation kinetics of common Kilka (Clupeonella cultiventris caspia) oil in presence of bene oils' unsaponifiable matter.

    PubMed

    Pazhouhanmehr, Samaneh; Farhoosh, Reza; Sharif, Ali; Esmaeilzadeh Kenari, Reza

    2016-01-01

    The oxidation mechanisms and kinetics of the purified common Kilka (Clupeonella cultiventris caspia) triacylglycerols (PKO) as affected by 1-1.5% (w/w) of unsaponifiable matters of bene kernel (UKO) and hull (UHO) oils were studied and compared with that of 100 mg/kg of butylated hydroxytoluene (BHT) and α-tocopherol in the Rancimat test at 50-70 °C. There were good correlations between the oxidative stability index (OSI) and time required to reach a 50%-increase in PV (t50). The frequency factor (A) and activation energy (Ea) were correlated well with the values of entropy and enthalpy, respectively. The values of free energy of activation (ΔG(++)) could describe the values of t50 or OSI well. Kinetic data indicated that the UKO with higher contents of tocopherols and tocotrienols, and terpenoid compounds was more effective than the UHO on the PKO stability. PMID:26213034

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

    SciTech Connect

    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.

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

    SciTech Connect

    Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K.

    2010-05-15

    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. (author)

  2. [Degradation kinetics of ozone oxidation on landfill leachate rejected by RO treatment].

    PubMed

    Zheng, Ke; Zhou, Shao-Qi; Sha, Shuang; Yang, Mei-Mei

    2011-10-01

    This study kinetically investigated landfill leachate rejected by reverse osmosis (RO) oxidation degradation by ozonation. Initial pH, ozone dosage, temperature and initial COD had significant impact on the oxidation rate. The results demonstrated that for the removal efficiencies of COD 67.6% under the conditions of 8.0 pH, 5.02 g/h ozone dosage, 303K temperature. The empirical kinetic equation of ozonation degradation for landfill leachate under the conditions of 2.0-8.0 pH, 2.53-6.90 g/h ozone dosage, 934-4 037 mg/L initial COD, 283-323 K temperature fitted well with the experimental data(R2 0.969-0.996), with low activation energy E(a) = 1.43 x1094) J x mol(-1). PMID:22279910

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

    NASA Technical Reports Server (NTRS)

    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. Oxidation rate of graphitic matrix material in the kinetic regime for VHTR air ingress accident scenarios

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    Data on oxidation rates of matrix-grade graphite in the kinetically-controlled temperature regime of graphite oxidation are needed for safety analysis of High Temperature Gas Cooled Reactors and Very High Temperature Reactors. In this work, the oxidation rate of graphitic matrix material GKrS was measured thermogravimetrically for various oxygen concentrations and with temperatures from 873 to 1873 K. A semi-empirical Arrhenius rate equation was also developed for this temperature range. The activation energy of the graphitic material is found to be about 111.5 kJ/mol. The order of reaction was found to be about 0.89. The surface of oxidized GKrS was characterized by Scanning Electron Microscopy, Electron Dispersive Spectroscopy, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy.

  5. One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates.

    PubMed

    Trujillo, Madia; Alvarez, Beatriz; Radi, Rafael

    2016-01-01

    The oxidation of biothiols participates not only in the defense against oxidative damage but also in enzymatic catalytic mechanisms and signal transduction processes. Thiols are versatile reductants that react with oxidizing species by one- and two-electron mechanisms, leading to thiyl radicals and sulfenic acids, respectively. These intermediates, depending on the conditions, participate in further reactions that converge on different stable products. Through this review, we will describe the biologically relevant species that are able to perform these oxidations and we will analyze the mechanisms and kinetics of the one- and two-electron reactions. The processes undergone by typical low-molecular-weight thiols as well as the particularities of specific thiol proteins will be described, including the molecular determinants proposed to account for the extraordinary reactivities of peroxidatic thiols. Finally, the main fates of the thiyl radical and sulfenic acid intermediates will be summarized. PMID:26329537

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

    PubMed

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

    2014-09-01

    Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. PMID:24997929

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

    NASA Astrophysics Data System (ADS)

    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 the oxidation of methyl tert-butyl ether (MTBE) by potassium permanganate.

    PubMed

    Damm, Jochen H; Hardacre, Christopher; Kalin, Robert M; Walsh, Kayleen P

    2002-08-01

    The occurrence of the fuel oxygenate methyl tert-butyl ether (MTBE) in the environment has received considerable scientific attention. The pollutant is frequently found in the groundwater due to leaking of underground storage tanks or pipelines. Concentrations of more than several mg/L MTBE were detected in groundwater at several places in the US and Germany in the last few years. In situ chemical oxidation is a promising treatment method for MTBE-contaminated plumes. This research investigated the reaction kinetics for the oxidation of MTBE by permanganate. Batch tests demonstrated that the oxidation of MTBE by permanganate is second order overall and first order individually with respect to permanganate and MTBE. The second-order rate constant was 1.426 x 10(-6) L/mg/h. The influence of pH on the reaction rate was demonstrated to have no significant effect. However, the rate of MTBE oxidation by potassium permanganate is 2-3 orders of magnitude lower than of other advanced oxidation processes. The slower rates of MTBE oxidation by permanganate limit the applicability of this process for rapid MTBE cleanup strategies. However, permanganate oxidation of MTBE has potential for passive oxidation risk management strategies. PMID:12230210

  9. High-temperature oxidation kinetics of Zircaloy-4 in oxygen/argon mixtures

    NASA Astrophysics Data System (ADS)

    Uetsuka, H.; Hofmann, P.

    1989-11-01

    The reaction kinetics of Zircaloy-4 in a gas mixture of oxygen and argon was determined by isothermal oxidation tests of cladding tube specimens at temperatures from 1173 to 1773 K for times between 120 and 3600 s. The reaction obeyed a cubic rate law at 1173 K, but a parabolic rate law at temperatures above 1273 K. A discontinuity in the temperature dependence of the parabolic rate constants was observed between 1273 and 1373 K, which may be attributed to an allotropic phase transformation of the ZrO 2 reaction layer. The equations describing the parabolic rate law constants for the mass increase, the ZrO 2 oxide layer growth and the growth of the combined layer of ZrO 2 and oxygen-stabilized alpha-Zr(O) were determined. No significant difference was found between the oxidation rates obtained in the present study and those obtained in Zircaloy-4/steam oxidation experiments. Changing the oxygen concentration in the gas mixture from 10 to 100 vol% did not affect the oxidation kinetics of Zircaloy-4.

  10. Kinetics of the oxidative degradation of formaldehyde with electrogenerated hypochlorite ion

    SciTech Connect

    Do, J.S.; Yeh, W.C.; Chao, I.Y.

    1997-02-01

    Aldehydes pose a potential problem in waste waters coming from a variety of process industry sources and must be treated before industrial waste waters can be discharged. The mechanisms and kinetics of the anodic oxidation of chloride ion on SnO{sub 2}-PdO-RuO{sub 2}-TiO{sub 2}/Ti (SPR) anode and the oxidation of formaldehyde with hypochlorite ion were studied, and the new kinetic data based on theoretical analysis were evaluated in this investigation. The reaction order of the anodic oxidation of chloride ion on SPR was unity. Also, the oxidation of formaldehyde with hypochlorite ion was second order in formaldehyde and first order in hypochlorite ion. Furthermore, the activation energy was evaluated as 37.9 kJ/mol. Formaldehyde was degraded from 3,000 to 279 ppm, and the degradation fraction was 90.7% when the electrolysis time was 111 min. A model calculation of the in situ oxidative degradation of formaldehyde with electrogenerated hypochlorite ion correlated well with experimental results.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Kinetics of the electrochemical oxidation of 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum

    NASA Astrophysics Data System (ADS)

    Vedenyapina, M. D.; Simakova, A. P.; Platonov, M. M.; Terent'ev, A. O.; Skundin, A. M.; Vedenyapin, A. A.

    2013-03-01

    The electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane (1,2,4,5-tetraoxane) from 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum electrode in a cell with separated and unseparated cathode and anode space in an aprotic solvent is conducted. The kinetics of electrochemical oxidation of 1,1-bis(hydroperoxy)-4-methylcyclohexane is studied. The current yield of the reaction is determined.

  13. Mass-transfer limitations for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor.

    PubMed

    Xiu, G H; Jiang, L; Li, P

    2001-07-01

    A mathematical model has been developed for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor in which the enzyme-catalyzed reaction (the irreversible uni-uni competitive Michaelis-Menten kinetics is chosen as an example) was coupled with intraparticle diffusion, external mass transfer, and axial dispersion. The effects of mass-transfer limitations, competitive inhibition of substrates, deactivation on the enzyme effective enantioselectivity, and the optical purity and yield of the desired product are examined quantitatively over a wide range of parameters using the orthogonal collocation method. For a first-order reaction, an analytical solution is derived from the mathematical model for slab-, cylindrical-, and spherical-enzyme supports. Based on the analytical solution for the steady-state resolution process, a new concise formulation is presented to predict quantitatively the mass-transfer limitations on enzyme effective enantioselectivity and optical purity and yield of the desired product for a continuous steady-state kinetic resolution process in a fixed-bed reactor. PMID:11353408

  14. 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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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. 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.

  17. Z-Selective Hydrothiolation of Racemic 1,3-Disubstituted Allenes: An Atom-Economic Rhodium-Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Pritzius, Adrian B; Breit, Bernhard

    2015-12-21

    A Z-selective rhodium-catalyzed hydrothiolation of 1,3-disubstituted allenes and subsequent oxidation towards the corresponding allylic sulfones is described. Using the bidentate 1,4-bis(diphenylphosphino)butane (dppb) ligand, Z/E-selectivities up to >99:1 were obtained. The highly atom-economic desymmetrization reaction tolerates functionalized aromatic and aliphatic thiols. Additionally, a variety of symmetric internal allenes, as well as unsymmetrically disubstituted substrates were well tolerated, thus resulting in high regioselectivities. Starting from chiral but racemic 1,3-disubstituted allenes a dynamic kinetic resolution (DKR) could be achieved by applying (S,S)-Me-DuPhos as the chiral ligand. The desired Z-allylic sulfones were obtained in high yields and enantioselectivities up to 96 % ee. PMID:26418035

  18. Adsorption kinetics of plasma proteins on ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles.

    PubMed

    Jansch, M; Stumpf, P; Graf, C; Rühl, E; Müller, R H

    2012-05-30

    In this study the kinetics of plasma protein adsorption onto ultrasmall superparamagnetic iron oxide (USPIO) particles have been analyzed and compared to previously published kinetic studies on polystyrene particles (PS particles), oil-in-water nanoemulsions and solid lipid nanoparticles (SLNs). SPIO and USPIO nanoparticles are commonly used as magnetic resonance imaging (MRI) enhancers for tumor imaging as well as in drug delivery applications. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) has been used to determine the plasma protein adsorption onto the citrate/triethylene glycol-stabilized iron oxide surface. The results indicate that the existence of a Vroman effect, a displacement of previously adsorbed abundant proteins, such as albumin or fibrinogen, respectively, on USPIO particles has to be denied. Previously, identical findings have been reported for oil-in-water nanoemulsions. Furthermore, the protein adsorption kinetics differs dramatically from that of other solid drug delivery systems (PS, SLN). More relevant for the in vivo fate of long circulating particles is the protein corona after several minutes or even hours. Interestingly, the patterns received after an incubation time of 0.5 min to 240 min are found to be qualitatively and quantitatively similar. This leads to the assumption of a long-lived ("hard") protein corona around the iron oxide nanoparticles. PMID:22342465

  19. Development and validation of a model for the chemical kinetics of graphite oxidation

    NASA Astrophysics Data System (ADS)

    El-Genk, Mohamed S.; Tournier, Jean-Michel P.

    2011-04-01

    A model of the chemical kinetics and primary reactions of graphite oxidation is developed and successfully validated for pyrolytic carbon thin films. The model uses Gaussian distributions of the activation energies for adsorption and desorption and the measured active surface area (ASA) as a function of burn-off. The activation energies distributions and the pre-exponential rate coefficients for the four elementary oxidation kinetics reactions in the model are obtained from the reported measurements of the gases yields and adsorbed oxygen using a multi-parameter optimization algorithm. The model calculates the production rates of CO and CO 2 and the gasification rate as functions of temperature and oxygen partial pressure, and its predictions are in excellent agreement with reported experimental measurements. Results for pyrolytic carbon thin films show that when the oxygen pressure is kept constant, the gasification rate depends on both temperature and ASA until a full burn-off is reached. By contrast, in a depleting oxygen environment, only partial burn-off is possible; gasification ceases following the consumption of the free oxygen in the enclosure. This model represents the first phase in an ongoing effort to develop a model for predicting the oxidation kinetics of nuclear graphite following a massive air ingress in high temperature reactors.

  20. Total organic carbon disappearance kinetics for the supercritical water oxidation of monosubstituted phenols

    SciTech Connect

    Martino, C.J.; Savage, P.E.

    1999-06-01

    Supercritical water oxidation (SCWO) is a process technology for destroying organic compounds present in aqueous waste streams. The authors oxidized phenols bearing single -CH{sub 3}, -C{sub 2}H{sub 5}, -COCH{sub 3}, -CHO, -OH, -OCH{sub 3}, and -NO{sub 2} substituents in supercritical water at 460 C and 25.3 MPa. The observed effects of the concentrations of total organic carbon (TOC) and oxygen on the global disappearance rates for TOC were correlated by using power-law rate expressions. This kinetics study revealed that the rate of TOC disappearance is more sensitive to the oxygen concentration than is the rate of reactant disappearance. Additionally, the rate of TOC disappearance is always slower than the rate of reactant disappearance, with the ratio of these rates ranging from 0.10 to 0.65 for the different phenols at the conditions studied. The rates of TOC disappearance during SCWO of these substituted phenols varied by nearly 2 orders of magnitude, showing significant effects from both the identity and location of the substituent. These substituent effects are greater for TOC disappearance kinetics than for reactant disappearance kinetics. Additionally, all of the substituted phenols exhibit faster TOC disappearance rates than does phenol. Accordingly, phenol is a good worst case model compound for SCWO studies. The pronounced substituent effects for TOC disappearance rates indicate that the oxidation of a common refractory intermediate is not an important feature of the SCWO networks for these phenols at the conditions studied.

  1. Chemistry of Al in Oxidizer Medium: From Shock Initiation to Post Detonation Kinetics

    NASA Astrophysics Data System (ADS)

    Chaudhuri, Santanu; Losada, Martin; Fotovati, Shahryar

    2013-06-01

    Reactive materials, propellants, and thermites are often constructed from Al/oxidizer composites. Al/oxidizer composites are also considered for self-sustaining reactions for deep space applications to reduce the need for carrying oxygen. In particular, Al/Teflon, Al/I2O5 and Al/RDX composites will be discussed as representative Al in oxidizer systems. Results of post-detonation kinetics using transition state theory and master equation based RRKM theory will be compared including discussion on some unresolved theoretical issues in collision theories and basis set effects in predicting the temperature/pressure-dependent kinetics. For Al/Teflon system, the RRKM theory calculated fall-off curves show a significant pressure dependence of rate constant in wide range of 0-1 MPa pressures at elevated temperatures. For Al/I2O5 systems, incorporation of spin-orbit coupling in DFT with various standard and augmented basis sets is important. A mechanism for generation of I2 and O2 during the reaction will be proposed. Finally, describing shock initiation reactions inside a condensed phase Al/RDX composites for a combustion reaction or detonation is currently a challenge for theoretical chemistry and chemical dynamics community. Especially, exact theoretical treatment for kinetics of reactants in confined hot-spots under high-pressure/temperature conditions is lacking. A new collision theoretical approach and reactive embedding possiblityies will be discussed as alternative to reactive force field based simulations of hot-spot growth.

  2. Oxidation kinetics of cyclophosphamide and methotrexate by ozone in drinking water.

    PubMed

    Garcia-Ac, Araceli; Broséus, Romain; Vincent, Simon; Barbeau, Benoit; Prévost, Michèle; Sauvé, Sébastien

    2010-05-01

    This study investigates the aqueous degradation by ozone of two target cytostatic drugs, cyclophosphamide and methotrexate. A column switching technique for on-line solid phase extraction (SPE) coupled to electro-spray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was used for the simultaneous detection of the trace contaminants. The second-order kinetic rate constants for the reaction of cyclophosphamide with molecular ozone and hydroxyl radicals were determined in bench-scale experiments at pH 8.10. The molecular ozone oxidation kinetics was studied in buffered ultrapure water and compared to the oxidation kinetics in natural water from a municipal drinking water treatment plant in the province of Quebec (Canada). For cyclophosphamide, the degradation rate constant with molecular ozone in ultrapure water was low (k(O3)=3.3+/-0.2M(-1)s(-1)) and the extent of oxidation was linearly correlated to the ozone exposure. The impact of water quality matrix on oxidation efficacy was not significant during direct ozone reaction (k(O3) =2.9+/-0.3M(-1)s(-1)). The rate constant with hydroxyl radicals was higher at 2.0 x 10(9) M(-1)s(-1). Methotrexate reacted quickly with molecular ozone at dosages typically applied in drinking water treatment (k(O3)>3.6 x 10(3)M(-1)s(-1)). Overall, the results confirmed that organic compounds reactivity with ozone was dependent of their chemical structure. Ozone was very effective against methotrexate but high oxidant concentration x contact time (CT) values were required to completely remove cyclophosphamide from drinking water. Further studies should be conducted in order to identify the ozonation by-products and explore the impact of ozone on their degradation and toxicity. PMID:20403630

  3. Kinetics of plastoquinol oxidation by the Q-cycle in leaves.

    PubMed

    Laisk, Agu; Oja, Vello; Eichelmann, Hillar

    2016-06-01

    Electrochromic shift measurements confirmed that the Q-cycle operated in sunflower leaves. The slow temporarily increasing post-pulse phase was recorded, when ATP synthase was inactivated in the dark and plastoquinol (PQH(2)) oxidation was initiated by a short pulse of far-red light (FRL). During illumination by red light, the Q-cycle-supported proton arrival at the lumen and departure via ATP synthase were simultaneous, precluding extreme build-up of the membrane potential. To investigate the kinetics of the Q-cycle, less than one PQH(2) per cytochrome b(6)f (Cyt b(6)f) were reduced by illuminating the leaf with strong light pulses or single-turnover Xe flashes. The post-pulse rate of oxidation of these PQH2 molecules was recorded via the rate of reduction of plastocyanin (PC(+)) and P700(+), monitored at 810 and 950 nm. The PSII-reduced PQH(2) molecules were oxidized with multi-phase overall kinetics, τ(d)=1, τ(p)=5.6 and τ(s)=16 ms (22 °C). We conclude that τ(d) characterizes PSII processes and diffusion, τ(p) is the bifurcated oxidation of the primary quinol and τ(s) is the Q-cycle-involving reduction of the secondary quinol at the n-site, its transport to the p-site, and bifurcated oxidation there. The extraordinary slow kinetics of the Q-cycle may be related to the still unsolved mechanism of the "photosynthetic control." PMID:27056771

  4. Oxidation kinetics of some nickel-based superalloy foils and electronic resistance of the oxide scale formed in air. Part 1

    SciTech Connect

    England, D.M.; Virkar, A.V.

    1999-09-01

    Haynes 230, Inconel 625, Inconel 718, and Hastelloy X foil specimens were oxidized in air for several thousand hours in the temperature range of 800--1,100 C. The oxidation kinetics of alloys studied obeyed the parabolic rate law. Haynes 230 exhibited the slowest oxidation kinetics of the alloys studied. X-ray diffraction, scanning electron microscopy, and electron probe microanalysis (EPMA) were the principal characterization tools employed. Chromium oxide, Cr{sub 2}O{sub 3}, was the predominant oxide phase in the oxide scale of all alloys studied. Manganese chromate was also detected in the oxide scales of Haynes 230, Hastelloy X, and Inconel 625. EPMA showed that the concentration of Mn in the oxide scale was much higher than in the alloy, indicating selective oxidation of Mn. The electronic resistance of the oxide scale was measured in air at temperatures up to 800 C on samples oxidized in air for up to several thousand hours. The oxide scale on Haynes 230 exhibited the lowest area-specific resistance, consistent with its slower oxidation kinetics.

  5. High temperature X-ray diffraction study of the oxidation products and kinetics of uranium-plutonium mixed oxides.

    PubMed

    Strach, Michal; Belin, Renaud C; Richaud, Jean-Christophe; Rogez, Jacques

    2014-12-15

    The oxidation products and kinetics of two sets of mixed uranium-plutonium dioxides containing 14%, 24%, 35%, 46%, 54%, and 62% plutonium treated in air were studied by means of in situ X-ray diffraction (XRD) from 300 to 1773 K every 100 K. The first set consisted of samples annealed 2 weeks before performing the experiments. The second one consisted of powdered samples that sustained self-irradiation damage. Results were compared with chosen literature data and kinetic models established for UO2. The obtained diffraction patterns were used to determine the temperature of the hexagonal M3O8 (M for metal) phase formation, which was found to increase with Pu content. The maximum observed amount of the hexagonal phase in wt % was found to decrease with Pu addition. We conclude that plutonium stabilizes the cubic phases during oxidation, but the hexagonal phase was observed even for the compositions with 62 mol % Pu. The results indicate that self-irradiation defects have a slight impact on the kinetics of oxidation and the lattice parameter even after the phase transformation. It was concluded that the lattice constant of the high oxygen phase was unaffected by the changes in the overall O/M when it was in equilibrium with small quantities of M3O8. We propose that the observed changes in the high oxygen cubic phase lattice parameter are a result of either cation migration or an increase in the miscibility of oxygen in this phase. The solubility of Pu in the hexagonal phase was estimated to be below 14 mol % even at elevated temperatures. PMID:25412433

  6. Statistical model for grain boundary and grain volume oxidation kinetics in UO{sub 2} spent fuel

    SciTech Connect

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

    1989-09-01

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

  7. Kinetics of the Oxidation of Reduced Cu,Zn-Superoxide Dismutase by Peroxymonocarbonate

    PubMed Central

    Ranguelova, Kalina; Ganini, Douglas; Bonini, Marcelo G.; London, Robert E.; Mason, Ronald P.

    2012-01-01

    Kinetic evidence is reported for the role of the peroxymonocarbonate, HOOCO2−, as an oxidant for reduced Cu,Zn-superoxide dismutase-Cu(I) (SOD1) during the peroxidase activity of the enzyme. The formation of this reactive oxygen species results from the equilibrium between hydrogen peroxide and bicarbonate. Recently, peroxymonocarbonate has been proposed to be a key substrate for reduced SOD1 and has been shown to oxidize SOD1-Cu(I) to SOD1-Cu(II) much faster than H2O2. We have reinvestigated the kinetics of the reaction between SOD1-Cu(I) and HOOCO2− by using conventional stopped-flow spectrophotometry and obtained a second-order rate constant of k = 1600 ± 100 M−1s−1 for SOD1-Cu(I) oxidation by HOOCO2−. Our results demonstrate that peroxymonocarbonate oxidizes SOD1-Cu(I) to SOD1-Cu(II) and is in turn reduced to the carbonate anion radical. It is proposed that the dissociation of His61 from the active site Cu(I) in SOD-Cu(I) contributes to this chemistry by facilitating the binding of larger anions, such as peroxymonocarbonate. PMID:22569304

  8. Oxidation of chlorinated ethenes by heat-activated persulfate: kinetics and products.

    PubMed

    Waldemer, Rachel H; Tratnyek, Paul G; Johnson, Richard L; Nurmi, James T

    2007-02-01

    In situ chemical oxidation (ISCO) and in situ thermal remediation (ISTR) are applicable to treatment of groundwater contaminated with chlorinated ethenes. ISCO with persulfate (S2O8(2-)) requires activation, and this can be achieved with the heat from ISTR, so there may be advantages to combining these technologies. To explore this possibility, we determined the kinetics and products of chlorinated ethene oxidation with heat-activated persulfate and compared them to the temperature dependence of other degradation pathways. The kinetics of chlorinated ethene disappearance were pseudo-first-order for 1-2 half-lives, and the resulting rate constants-measured from 30 to 70 degrees C--fit the Arrhenius equation, yielding apparent activation energies of 101 +/- 4 kJ mol(-1) for tetrachloroethene (PCE), 108 +/- 3 kJ mol(-1) for trichloroethene (TCE), 144 +/- 5 kJ mol(-1) for cis-1,2-dichloroethene (cis-DCE), and 141 +/- 2 kJ mol(-1) for trans-1,2-dichloroethene (trans-DCE). Chlorinated byproducts were observed, but most of the parent material was completely dechlorinated. Arrhenius parameters for hydrolysis and oxidation by persulfate or permanganate were used to calculate rates of chlorinated ethene degradation by these processes over the range of temperatures relevant to ISTR and the range of oxidant concentrations and pH relevant to ISCO. PMID:17328217

  9. Influence of Dihydrogen and Water Vapor on the Kinetics of CO Oxidation over Au/Alumina

    SciTech Connect

    Calla,J.; Davis, R.

    2005-01-01

    Alumina-supported Au nanoparticles were prepared by a deposition-precipitation method using HAuCl{sub 4} and a thermal treatment in He. X-ray absorption spectroscopy at the Au L{sub III} edge revealed that the Au particles were predominantly metallic with an average size of 1.2 nm. The kinetics of CO oxidation were measured with various amounts of co-fed H2O in the presence and absence of H2. Co-feeding H2O significantly increased the rate of CO oxidation, with rates similar to that observed during selective CO oxidation in H2. The order of reaction with respect to CO decreased from 0.32 to 0.18 by the addition of water vapor. In contrast, the O2 order increased from 0.36 to 0.48 in the presence of H2O. The temperature dependence of the rate changes with water concentration. Although values of the kinetic parameters determined in the presence of H2 were different from those in the presence of co-fed H{sub 2}O, the general trends were similar. These results suggest that the presence of H{sub 2}O or H{sub 2} and O{sub 2} have similar promotional effects during CO oxidation on Au/Al{sub 2}O{sub 3}.

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

    PubMed

    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. PMID:23046696

  11. Surface oxidation energetics and kinetics on MoS{sub 2} monolayer

    SciTech Connect

    KC, Santosh; Longo, Roberto C.; Wallace, Robert M.; Cho, Kyeongjae

    2015-04-07

    In this work, surface oxidation of monolayer MoS{sub 2} (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS{sub 2} shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS{sub 2} surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS{sub 2} surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS{sub 2} monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale.

  12. Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

    USGS Publications Warehouse

    Power, L.E.; Arai, Y.; Sparks, D.L.

    2005-01-01

    Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

  13. Oxide Transformation in Cr-Mn-Prealloyed Sintered Steels: Thermodynamic and Kinetic Aspects

    NASA Astrophysics Data System (ADS)

    Hryha, Eduard; Nyborg, Lars

    2014-04-01

    The main obstacle for utilization of Cr and Mn as alloying elements in powder metallurgy is their high oxygen affinity leading to oxidation risk during powder manufacturing, handling, and especially during further consolidation. Despite the high purity of the commercially available Cr- and Mn-prealloyed iron powder grades, the risk of stable oxide formation during the sintering process remains. Thermodynamic and kinetic simulation of the oxide formation/transformation on the former powder surface during heating and sintering stages using thermodynamic modeling tools (Thermo-Calc and HSC Chemistry) was performed. Simulation is based on the results from the analysis of amount, morphology, and composition of the oxide phases inside the inter-particle necks in the specimens from interrupted sintering trials utilizing advanced analysis tools (HRSEM + EDX and XPS). The effect of the processing parameters, such as sintering atmosphere composition, temperature profile as well as graphite addition on the possible scenarios of oxide reduction/formation/transformation for Fe-Cr-Mn-C powder systems, was evaluated. Results indicate that oxide transformation occurs in accordance with the thermodynamic stability of oxides as follows: Fe2O3 → FeO → Fe2MnO4 → Cr2FeO4 → Cr2O3 → MnCr2O4 → MnO/MnSiO x → SiO2. Spinel MnCr2O4 was identified as the most stable oxide phase at applied sintering conditions up to 1393 K (1120 °C). Controlled conditions during the heating stage minimize the formation of stable oxide products and produce oxide-free sintered parts.

  14. Kinetics of Mn(II) oxidation by Leptothrix discophora SS1

    NASA Astrophysics Data System (ADS)

    Zhang, Jinghao; Lion, Leonard W.; Nelson, Yarrow M.; Shuler, Michael L.; Ghiorse, William C.

    2002-03-01

    The kinetics of Mn(II) oxidation by the bacterium Leptothrix discophora SS1 was investigated in this research. Cells were grown in a minimal mineral salts medium in which chemical speciation was well defined. Mn(II) oxidation was observed in a bioreactor under controlled conditions with pH, O 2, and temperature regulation. Mn(II) oxidation experiments were performed at cell concentrations between 24 mg/L and 35 mg/L, over a pH range from 6 to 8.5, between temperatures of 10°C and 40°C, over a dissolved oxygen range of 0 to 8.05 mg/L, and with L. discophora SS1 cells that were grown in the presence of Cu concentrations ranging from zero to 0.1 μM. Mn(II) oxidation rates were determined when the cultures grew to stationary phase and were found to be directly proportional to O 2 and cell concentrations over the ranges investigated. The optimum pH for Mn(II) oxidation was approximately 7.5, and the optimum temperature was 30°C. A Cu level as low as 0.02 μM was found to inhibit the growth rate and yield of L. discophora SS1 observed in shake flasks, while Cu levels between 0.02 and 0.1 μM stimulated the Mn(II) oxidation rate observed in bioreactors. An overall rate law for Mn(II) oxidation by L. discophora as a function of pH, temperature, dissolved oxygen concentration (D.O.), and Cu concentration is proposed. At circumneutral pH, the rate of biologically mediated Mn(II) oxidation is likely to exceed homogeneous abiotic Mn(II) oxidation at relatively low (≈μg/L) concentrations of Mn oxidizing bacteria.

  15. Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

    NASA Astrophysics Data System (ADS)

    Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Davis, James A.

    2006-02-01

    The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m 2 g -1) and reductively extractable iron contents (18-26 μmol m -2), but with varying total manganese contents (0.5-3.5 μmol m -2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the

  16. Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

    USGS Publications Warehouse

    Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

    2006-01-01

    The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the

  17. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface

    NASA Astrophysics Data System (ADS)

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-01

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  18. Thermal oxidation of single-crystal silicon carbide - Kinetic, electrical, and chemical studies

    NASA Technical Reports Server (NTRS)

    Petit, J. B.; Neudeck, P. G.; Matus, L. G.; Powell, J. A.

    1992-01-01

    This paper presents kinetic data from oxidation studies of the polar faces for 3C and 6H SiC in wet and dry oxidizing ambients. Values for the linear and parabolic rate constants were obtained, as well as preliminary results for the activation energies of the rate constants. Examples are presented describing how thermal oxidation can be used to map polytypes and characterize defects in epitaxial layers grown on low tilt angle 6H SiC substrates. Interface widths were measured using Auger electron spectroscopy (AES) with Ar ion beam depth profiling and variable angle spectroscopic ellipsometry (VASE) with effective medium approximation (EMA) models. Preliminary electrical measurements of MOS capacitors are also presented.

  19. Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

    NASA Astrophysics Data System (ADS)

    Kamble, Vinayak; Umarji, Arun

    2015-03-01

    Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide - carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size ˜7 nm and ˜95 m2/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO2 thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors.

  20. Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

    SciTech Connect

    Kamble, Vinayak Umarji, Arun

    2015-03-15

    Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide – carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size ∼7 nm and ∼95 m{sup 2}/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO{sub 2} thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors.

  1. Kinetics of switch grass pellet thermal decomposition under inert and oxidizing atmospheres.

    PubMed

    Chandrasekaran, Sriraam R; Hopke, Philip K

    2012-12-01

    Grass pellets are a renewable resource that have energy content similar to that of wood. However, the higher ash and chlorine content affects combustion. Thermal degradation analysis of a fuel is useful in developing effective combustion. Thermogravimetric analysis (TGA) of the thermal degradation of grass pellets under inert (nitrogen) and oxidizing (air) atmospheres was conducted. Non-isothermal conditions were employed with 4 different heating rates. Kinetic parameters (activation energy and pre-exponential factors) were estimated using the iso-conversional method. Both pyrolysis and oxidative atmospheric thermal degradation exhibited two major loss process: volatilization of cellulose, hemicelluloses and lignin and burning or slow oxidation of the residual char. The activation energy and pre-exponential factors were high for the oxidizing environment. During pyrolysis, major decomposition occurred with 40% to 75% conversion of the mass to gas with an activation energy of 314 kJ/mol. In air the decomposition occurred with 30% to 55% conversion with an activation energy of 556 kJ/mol. There was a substantial effect of heating rate on mass loss and mass loss rate. The TG shifted to higher temperature ranges on increasing the heating rate. In both pyrolyzing and oxidizing conditions, average combustion and devolatilization rates increased. Enhanced combustion takes place with higher activation energy in oxidizing atmosphere compared to the inert atmosphere due to presence of air. PMID:23026316

  2. Oxidation Kinetics and Textures for Natural and Synthetic MORB Glasses and Subliquidus Melts: RBS Analyses

    NASA Astrophysics Data System (ADS)

    Burgess, K.; Cooper, R. F.; Cherniak, D. J.

    2007-12-01

    Fe and ionic Mg effects oxidation at higher temperatures, giving way to kinetic domination of ionic Ca at lower temperatures. Specific results will be presented. We are initiating transmission electron microscopy studies to characterize the compositions and distributions of internally-nucleated ferrites. Cook, G.B. and R.F. Cooper, Amer. Mineral. 85, 397-406 (2000).

  3. Kinetics and mechanism of oxidation of vanadium(2+) by molecular oxygen and hydrogen peroxide

    SciTech Connect

    Rush, J.D.; Bielski, B.H.J.

    1985-12-04

    The reaction between hexaaquovanadium (II) and molecular oxygen has been studied by the stopped-flow method in 0.12M perchloric acid and in solutions containing 0.1M sulfate ion. The kinetics and stoichiometry of the reactions are consistent with a general oxidation mechanism for divalent transition-metal ions proposed by Ochiai. The reaction was found to proceed by parallel pathways resulting in a V(II)-dependent stoichiometry. At concentrations < 0.005 M V(II), one molecule of VO2 was produced per molecule of O2 consumed. At V(II) concentrations greater than 0.1 M, no free peroxide was formed and two vanadyl ions, VOS , are the intermediate reaction products. A mechanism involving a V(II)-dependent equilibrium between a mononuclear vanadium(III) peroxide and a dinuclear vanadium(III) peroxide intermediate explain the reported results. The kinetic parameters of the reaction have been determined and are reported.

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

    NASA Astrophysics Data System (ADS)

    Gelß, Patrick; Matera, Sebastian; Schütte, Christof

    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 RuO2(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.

  5. Application of Electrode Methods in Studies of Nitric Oxide Metabolism and Diffusion Kinetics

    PubMed Central

    Liu, Xiaoping; Zweier, Jay L.

    2012-01-01

    Nitric oxide (NO) has many important physiological roles in the body. Since NO electrodes can directly measure NO concentration in the nM range and in real time, NO electrode methods have been generally used in laboratories for measuring NO concentration in vivo and in vitro. This review focuses on the application of electrode methods in studies of NO diffusion and metabolic kinetics. We have described the physical and chemical properties that need to be considered in the preparation of NO stock solution, discussed the effect of several interfering factors on the measured curves of NO concentration that need to be eliminated in the experimental setup for NO measurements, and provided an overview of the application of NO electrode methods in measuring NO diffusion and metabolic kinetics in solution and in biological systems. This overview covers NO metabolism by oxygen (O2), superoxide, heme proteins, cells and tissues. Important conclusions and physiological implication of these studies are discussed. PMID:23730264

  6. Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

    PubMed

    Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

    2015-10-01

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

  7. Gas-Phase Oxidation Kinetics and Organic Aerosol Products of Ethanolamine

    NASA Astrophysics Data System (ADS)

    Borduas, N.; Abbatt, J.; Murphy, J. G.

    2012-12-01

    Ethanolamine is currently the solvent of choice in carbon capture and storage technology (CCS) which aims to reduce CO2 emissions to the atmosphere in coal powered pilot plants. CCS technology represents an unprecedented large scale application of ethanolamine and little is known of its fate if it was unintentionally released into the atmosphere. Relative kinetic experiments were conducted in a 1m3 smog chamber using online proton-transfer-reaction mass spectrometry. The kinetics of oxidation with hydroxyl radicals from light and dark sources converge to a value of (7.6 ± 1.1) x 10-11 cm3 molec-1 s-1. The reaction of ethanolamine with ozone was determined to be (1.05 ± 0.08) x 10-18 cm3 molec-1 s-1. We find that ethanolamine has a short lifetime in the atmosphere and readily deposits onto wall and particle surfaces, as observed by considerable formation of organonitrogen aerosol products. An investigation into the oxidation product formation using a combination of reagent ions with online chemical ionization mass spectrometry approaches lead to the detection of higher order products. The formation of these high molecular weight products is simultaneous with the oxidation of ethanolamine and implies substantial organic aerosol chemistry.

  8. Oxidation and combustion of the n-hexene isomers: a wide range kinetic modeling study

    SciTech Connect

    Mehl, M; Vanhove, G; Pitz, W J; Ranzi, E

    2008-03-12

    A detailed chemical kinetic mechanism has been developed to study the oxidation of the straight-chain isomers of hexene over a wide range of operating conditions. The main features of this detailed kinetic mechanism, which includes both high and low temperature reaction pathways, are presented and discussed with special emphasis on the main classes of reactions involved in alkene oxidation. Simulation results have been compared with experimental data over a wide range of operating conditions including shock tube, jet stirred reactor and rapid compression machine. The different reactivities of the three isomers have been successfully predicted by the model. Isomerization reactions of the hexenyl radicals were found to play a significant role in the chemistry and interactions of the three n-hexene isomers. A comparative reaction flux analysis is used to verify and discuss the fundamental role of the double bond position in the isomerization reactions of alkenyl radicals, as well as the impact of the allylic site in the low and high temperature mechanism of fuel oxidation.

  9. The kinetic isotopic effect, bridge ligand, and mechanisms of oxidation of alkanes in solutions

    SciTech Connect

    Rudakov, E.S

    1982-10-01

    The purpose of this article was to call attention to a new and striking fact: the kinetic isotopic effect of hydrogen (KIE) in oxidative homolysis, in a first approximation, is independent of the central atom-oxidizing agent M/sup n/ and is determined exclusively by the bridge ligand, which is a quantitative criterion for the selection of the bridge. Most of the data were obtained recently in a study of the first step of the oxidation of alkanes in sulfuric acid and aqueous media by reagents which, as has been suggested, include sulfate (OSO/sub 2/O-) or oxo (O=) bridges. The structures of the reagents were selected considering data on the kinetics, selectivity, and KIE. For the reactions of RH with CF/sub 3/-COOH, HOCl(Cl/sub 2/ + H/sub 2/O), H/sub 2/SO/sub 5/ (H/sub 2/O/sub 2/-90% H/sub 2/SO/sub 4/) and HNO/sub 3/-Pt/sup IV/-Cl/sup -/-H/sub 2/O, structures with OH bridges were assumed. The values of the KIE are the same for tert- and sec-C-H bonds; the reproducibility is usually within +/- 15%.

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

    SciTech Connect

    Bertone, P.C.

    1986-01-01

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

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

    PubMed

    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. PMID:25914926

  12. Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

    NASA Technical Reports Server (NTRS)

    Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

    1974-01-01

    Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.

  13. Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

    PubMed

    González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

    2014-07-15

    The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively. PMID:24941285

  14. Zinc oxide nanowire gamma ray detector with high spatiotemporal resolution

    NASA Astrophysics Data System (ADS)

    Mayo, Daniel C.; Nolen, J. Ryan; Cook, Andrew; Mu, Richard R.; Haglund, Richard F.

    2016-03-01

    Conventional scintillation detectors are typically single crystals of heavy-metal oxides or halides doped with rare-earth ions that record the recombination of electron-hole pairs by photon emission in the visible to ultraviolet. However, the light yields are typically low enough to require photomultiplier detection with the attendant instrumental complications. Here we report initial studies of gamma ray detection by zinc oxide (ZnO) nanowires, grown by vapor-solid deposition. The nanowires grow along the c-axis in a wurtzite structure; they are typically 80 nm in diameter and have lengths of 1- 2 μm. The nanowires are single crystals of high quality, with a photoluminescence (PL) yield from band-edge exciton emission in the ultraviolet that is typically one hundred times larger than the PL yield from defect centers in the visible. Nanowire ensembles were irradiated by 662 keV gamma rays from a Cs-137 source for periods of up to ten hours; gamma rays in this energy range interact by Compton scattering, which in ZnO creates F+ centers that relax to form singly-charged positive oxygen vacancies. Following irradiation, we fit the PL spectra of the visible emission with a sum of Gaussians at the energies of the known defects. We find highly efficient PL from the irradiated area, with a figure of merit approaching 106 photons/s/MeV of deposited energy. Over a period of days, the singly charged O+ vacancies relax to the more stable doubly charged O++ vacancies. However, the overall defect PL returns to pre-irradiation values after about a week, as the vacancies diffuse to the surface of these very thin nanowires, indicating that a self-healing process restores the nanowires to their original state.

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

    SciTech Connect

    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.

  16. Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid.

    PubMed

    Horiguchi, Kosaku; Yamamoto, Eri; Saito, Kodai; Yamanaka, Masahiro; Akiyama, Takahiko

    2016-06-01

    Asymmetric synthesis of tetrahydrobenzodiazepines was achieved by transfer hydrogenation of dihydrobenzodiazepines with benzothiazoline having a hydrogen-bonding donor substituent by means of a newly synthesized chiral phosphoric acid. This method was applicable to various racemic dihydrobenzodiazepines to give the corresponding products in good yields with excellent diastereoselectivities and enantioselectivities taking advantage of the dynamic kinetic resolution. Furthermore, the effect of bulky substituent at 3,3'-position on the catalyst and hydrogen-bonding donor substituent on benzothiazoline was fully elucidated by the theoretical study. PMID:27150449

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

    PubMed

    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). PMID:21700312

  18. Chemical Kinetic Study of Toluene Oxidation Under Premixed and Nonpremixed Conditions

    SciTech Connect

    Costa, I D; Bozzelli, J W; Seiser, R; Pitz, W J; Westbrook, C K; Chen, C -; Fournet, R; Seshadri, K; Battin-Leclerc, F; Billaud, F

    2003-12-10

    A study was performed to elucidate the chemical-kinetic mechanism of combustion of toluene. A detailed chemical-kinetic mechanism for toluene was improved by adding a more accurate description of the phenyl + O{sub 2} reaction channels, toluene decomposition reactions and the benzyl + O reaction. Results of the chemical kinetic mechanism are compared with experimental data obtained from premixed and non-premixed systems. Under premixed conditions, predicted ignition delay times are compared with new experimental data obtained in shock tube. Also, calculated species concentration histories are compared to experimental flow reactor data from the literature. Under non-premixed conditions, critical conditions of extinction and autoignition were measured in strained laminar flows in the counterflow configuration. Numerical calculations are performed using the chemical-kinetic mechanism at conditions corresponding to those in the experiments. Critical conditions of extinction and autoignition are predicted and compared with the experimental data. Comparisons between the model predictions and experimental results of ignition delay times in shock tube, and extinction and autoignition in non-premixed systems show that the chemical-kinetic mechanism predicts that toluene/air is overall less reactive than observed in the experiments. For both premixed and non-premixed systems, sensitivity analysis was used to identify the reaction rate constants that control the overall rate of oxidation in each of the systems considered. Under shock tube conditions, the reactions that influence ignition delay time are H + O{sub 2} chain branching, the toluene decomposition reaction to give an H atom, and the toluene + H abstraction reaction. The reactions that influence autoignition in non-premixed systems involve the benzyl + HO{sub 2} reaction and the phenyl + O{sub 2} reaction.

  19. Kinetic control by limiting glutaredoxin amounts enables thiol oxidation in the reducing mitochondrial intermembrane space

    PubMed Central

    Kojer, Kerstin; Peleh, Valentina; Calabrese, Gaetano; Herrmann, Johannes M.; Riemer, Jan

    2015-01-01

    The mitochondrial intermembrane space (IMS) harbors an oxidizing machinery that drives import and folding of small cysteine-containing proteins without targeting signals. The main component of this pathway is the oxidoreductase Mia40, which introduces disulfides into its substrates. We recently showed that the IMS glutathione pool is maintained as reducing as that of the cytosol. It thus remained unclear how equilibration of protein disulfides with the IMS glutathione pool is prevented in order to allow oxidation-driven protein import. Here we demonstrate the presence of glutaredoxins in the IMS and show that limiting amounts of these glutaredoxins provide a kinetic barrier to prevent the thermodynamically feasible reduction of Mia40 substrates by the IMS glutathione pool. Moreover, they allow Mia40 to exist in a predominantly oxidized state. Consequently, overexpression of glutaredoxin 2 in the IMS results in a more reduced Mia40 redox state and a delay in oxidative folding and mitochondrial import of different Mia40 substrates. Our findings thus indicate that carefully balanced glutaredoxin amounts in the IMS ensure efficient oxidative folding in the reducing environment of this compartment. PMID:25392302

  20. Effects of preconditioning the rhizosphere of different plant species on biotic methane oxidation kinetics.

    PubMed

    Ndanga, Éliane M; Lopera, Carolina B; Bradley, Robert L; Cabral, Alexandre R

    2016-09-01

    The rhizosphere is known as the most active biogeochemical layer of the soil. Therefore, it could be a beneficial environment for biotic methane oxidation. The aim of this study was to document - by means of batch incubation tests - the kinetics of CH4 oxidation in rhizosphere soils that were previously exposed to methane. Soils from three pre-exposure to CH4 zones were sampled: the never-before pre-exposed (NEX), the moderately pre-exposed (MEX) and the very pre-exposed (VEX). For each pre-exposure zone, the rhizosphere of several plant species was collected, pre-incubated, placed in glass vials and submitted to CH4 concentrations varying from 0.5% to 10%. The time to the beginning of CH4 consumption and the CH4 oxidation rate were recorded. The results showed that the fastest CH4 consumption occurred for the very pre-exposed rhizosphere. Specifically, a statistically significant difference in CH4 oxidation half-life was found between the rhizosphere of the VEX vegetated with a mixture of different plants and the NEX vegetated with ryegrass. This difference was attributed to the combined effect of the preconditioning level and plant species as well as to the organic matter content. Regardless of the preconditioning level, the oxidation rate values obtained in this study were comparable to those reported in the reviewed literature for mature compost. PMID:27177464

  1. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans.

    PubMed

    Lizama, H M; Suzuki, I

    1989-11-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 muM Fe per min per FeS(2) percent pulp density for the spontaneous pyrite dissolution, 10 muM Fe per min per mM Fe for the indirect leaching with Fe, 90 muM O(2) per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 muM O(2) per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The K(m) values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a K(i) value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe production from Fe plus pyrite. PMID:16348054

  2. Wet oxidation of an azo dye: Lumped kinetics in batch and mixed flow reactors

    SciTech Connect

    Donlagic, J.; Levec, J.

    1999-12-01

    Oxidation of a dilute aqueous solution of a model azo dye pollutant (Orange II) was studied in batch and continuous well-mixed (CSTR) reactors. Both reactors operate at 200--250 C, and total pressures up to 50 bar and at oxygen partial pressure from 10 to 30 bar. The model pollutant concentrations were in a range between 100 and 1,000 mg/L, which may be found in industrial wastewaters. The dye oxidation undergoes parallel-consecutive reaction pathways, in which it first decomposes thermally and oxidatively to aromatic intermediates and via organic acids to the final product carbon dioxide. To develop a kinetic equation capable of predicting organic carbon reduction, all organic species present in solution were lumped by total organic carbon (TOC). The lumped oxidation rate in batch reactor exhibited second-order behavior, whereas in the CSTR is was found linearly proportional to its TOC concentration. The lump behavior in batch reactor was dominated by the refractory low molecular mass aliphatic acids formed during the oxidation.

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

    SciTech Connect

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

    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.

  4. Heterogeneous oxidation of folpet and dimethomorph by OH radicals: A kinetic and mechanistic study

    NASA Astrophysics Data System (ADS)

    Al Rashidi, M.; Chakir, A.; Roth, E.

    2014-01-01

    This study investigates the heterogeneous OH oxidation of folpet and dimethomorph, two fungicides identified in the atmosphere of the Champagne-Ardenne region. Kinetic experiments were conducted in the relative mode, using terbuthylazine as a reference compound. The experimental method employed makes use of a simulation chamber coupled to a GC/MS analytical system. Meanwhile, the identification of (4-chlorophenyl)(3,4-dimethoxyphenyl)methanone (CPMPM), a degradation product of the OH oxidation of dimethomorph, is achieved using SPME/GC/MS. Moreover, a degradation mechanism of dimethomorph is proposed, and the heterogeneous OH reactivity of CPMPM is evaluated. The obtained OH reaction rate constants (cm3 molecule-1 s-1) are: kZ-dimethomorph = (2.0 ± 1.2) 10-14, kE-dimethomorph = (1.7 ± 1.2) 10-14, kFolpet = (1.6 ± 0.9) 10-13 and kCPMPM = (1.9 ± 1.0) 10-12. The implicated tropospheric life-times are up to 2 months, which shows that the investigated pesticides are relatively persistent towards oxidation removal processes. CPMPM, the identified product of OH oxidation of dimethomorph, is less persistent with a life time of only 6 days relative to heterogeneous oxidation by OH radicals.

  5. Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process.

    PubMed

    Fan, Yan; Ji, Yuefei; Kong, Deyang; Lu, Junhe; Zhou, Quansuo

    2015-12-30

    Sulfamethazine (SMZ) is widely used in livestock feeding and aquaculture as an antibiotic agent and growth promoter. Widespread occurrence of SMZ in surface water, groundwater, soil and sediment has been reported. In this study, degradation of SMZ by heat-activated persulfate (PS) oxidation was investigated in aqueous solution. Experimental results demonstrated that SMZ degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing concentration of PS and temperature. Radical scavenging tests revealed that the predominant oxidizing species was SO4·(-) with HO playing a less important role. Aniline moiety in SMZ molecule was confirmed to be the reactive site for SO4·(-) attack by comparison with substructural analogs. Nontarget natural water constituents affected SMZ removal significantly, e.g., Cl(-) and HCO3(-) improved the degradation while fulvic acid reduced it. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). 6 products derived from sulfonamide S--N bond cleavage, aniline moiety oxidation and Smiles-type rearrangement were identified, and transformation pathways of SMZ oxidation were proposed. Results reveal that heat-activated PS oxidation could be an efficient approach for remediation of water contaminated by SMZ and related sulfonamides. PMID:26151383

  6. Kinetics and Mechanism of Oxidation of Methimazole by Chlorite in Slightly Acidic Media.

    PubMed

    Chipiso, Kudzanai; Simoyi, Reuben H

    2016-06-01

    The kinetics and mechanism of the oxidation of methimazole (1-methyl-3H-imidazole), MMI, by chlorite in mildly acidic environments were studied. It is a complex reaction that gives oligo-oscillations in chlorine dioxide concentrations in excess chlorite conditions. The stoichiometry is strictly 2:1, with the sulfur center being oxidized to sulfate and the organic moiety being hydrolyzed to several indeterminate species. In excess MMI conditions over chlorite, the sulfinic acid and sulfonic acid were observed as major intermediates. The sulfenic acid, which was observed in the electrochemical oxidation of MMI, was not observed with chlorite oxidations. Initial reduction of chlorite produced HOCl, an autocatalytic species in chlorite oxidations. HOCl rapidly reacts with chlorite to produce chlorine dioxide, which, in turn, reacts rapidly with MMI to produce more chlorite. The reaction of chlorine dioxide with MMI is competitive, in rate, with the chlorite-MMI and HOCl-ClO2(-) reactions. This explains the oligo-oscillations in ClO2 concentrations. PMID:27126471

  7. A kinetic approach to the catalytic oxidation of mercury in flue gas

    SciTech Connect

    Albert A. Presto; Evan J. Granite; Andrew Karash; Richard A. Hargis; William J. O'Dowd; Henry W. Pennline

    2006-10-15

    Four mercury oxidation catalysts were tested in a packed bed reactor in the presence of flue gas generated by the NETL 500 lb/h coal combustor. The four catalysts tested were Ir, Ir/HCl, Darco FGD activated carbon, and Thief/HCl. The Thief/HCl and Darco converted the highest percentage of the inlet mercury; however, the high conversion in these experiments was aided by larger catalyst loadings than in the Ir and Ir/HCl experiments. We propose a method for analyzing mercury oxidation catalyst results in a kinetic framework using the bulk reaction rate for oxidized mercury formation normalized by either the catalyst mass or surface area. Results reported for fractional mercury oxidation are strongly influenced by the specific experimental conditions and are therefore difficult to translate from experiment to experiment. The catalyst-normalized results allow for more quantitative analysis of mercury oxidation catalyst data and are the first step in creating a predictive model that will allow for efficient scaling up from laboratory-scale to larger-scale studies. 34 refs., 1 fig., 3 tabs.

  8. Kinetic spectrophotometric method for the determination of silymarin in pharmaceutical formulations using potassium permanganate as oxidant.

    PubMed

    Rahman, N; Khan, N A; Azmi, S N H

    2004-02-01

    A new simple and sensitive kinetic spectrophotometric method for the determination of silymarin in pure form and in pharmaceutical formulations is described. The method is based on the oxidation of the drug with potassium permanganate at pH 7.0 +/- 0.2. The reaction is followed spectrophotometrically by measuring the decrease in the absorbance at 530 nm. The calibration graph is linear in the range of 18-50 microg x m(-1). The method has been successfully applied to the determination of silymarin in pharmaceutical formulations. Statistical comparison of the results with the reference method shows excellent agreement and indicates no significant difference in accuracy and precision. PMID:15025178

  9. Carbon kinetic isotope effect accompanying microbial oxidation of methane in boreal forest soils

    NASA Astrophysics Data System (ADS)

    Reeburgh, W. S.; Hirsch, A. I.; Sansone, F. J.; Popp, B. N.; Rust, T. M.

    1997-11-01

    Atmospheric methane (CH 4) oxidation occurs in soils at sites in the Bonanza Creek L.T.E.R. near Fairbanks, Alaska, USA, at rates ⩽2 mg CH 4 m -2 d -1; the maximum CH 4 oxidizing activity is located in loess at a depth of ˜15 cm. Methane, carbon dioxide, and stable isotope (δ 13C-CH 4, δ 13C-CO 2) depth distributions were measured at two sites: South facing Aspen (AS2) and North facing Black Spruce (BS2). The combined effects of diffusion and oxidation are similar at both sites and result in a CH 4 concentration decrease (1.8-0.1 ppm) and a δ 13C-CH 4 increase (-48% to -43%) from the soil surface to 60-80 cm depth. Isotope flux ratio and diffusion-consumption models were used to estimate the kinetic isotope effect (KIE); these results agree with the observed top-to-bottom difference in δ 13C-CH 4, which is the integrated result of isotope fractionation due to diffusion and oxidation. The KIE for CH 4 oxidation determined from these measurements is 1.022-1.025, which agrees with previous KIE determinations based on changes in headspace CH 4 concentration and δ 13C-CH 4 over time. A much lower soil respiration rate in the North facing Black Spruce soils is indicated by fivefold lower Soil CO 2 concentrations. The similarity in CH 4 oxidation at the two sites and the differences in inferred soil respiration at the two sites suggest that soil CH 4 oxidation and soil respiration are independent processes. The soil organic matter responsible for the CO 2 flux has a δ 13C estimated to be -27 to -28%.

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

    NASA Astrophysics Data System (ADS)

    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