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Reaction Rate Constants (reaction + rate_constant)
Selected AbstractsEstimation of Aqueous-Phase Reaction Rate Constants of Hydroxyl Radical with Phenols, Alkanes and AlcoholsMOLECULAR INFORMATICS, Issue 11-12 2009Ya-nan Wang Abstract A quantitative structure activity relationship (QSAR) model was developed for the aqueous-phase hydroxyl radical reaction rate constants (kOH) employing quantum chemical descriptors and multiple linear regressions (MLR). The QSAR development followed the OECD guidelines, with special attention to validation, applicability domain (AD) and mechanistic interpretation. The established model yielded satisfactory performance: the correlation coefficient square (R2) was 0.905, the root mean squared error (RMSE) was 0.139, the leave-many-out cross-validated QLMO2 was 0.806, and the external validated QEXT2 was 0.922 log units. The AD of the model covering compounds of phenols, alkanes and alcohols, was analyzed by Williams plot. The main molecular structural factors governing kOH are the energy of the highest occupied molecular orbital (EHOMO), average net atomic charges on hydrogen atoms (), molecular surface area (MSA) and dipole moment (,). It was concluded that kOH increased with increasing EHOMO and MSA, while decreased with increasing and ,. [source] Absolute rate constants for the gas-phase ozonolysis of isoprene and methylbutenolINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2004N. Klawatsch-Carrasco The reactions of the biogenic organic compounds isoprene and 2-methyl-3-buten-2-ol (MBO) with ozone have been investigated under controlled conditions for pressure (atmospheric pressure) and temperature (293 ± 2 K), using FTIR spectrometry. CO was added to scavenge hydroxyl radical formation during the ozonolysis experiments. Reaction rate constants were determined by absolute rate technique, by measuring both ozone and the organic compound concentrations. The measured values were k1 = (1.19 ± 0.09) × 10,17 cm3 molecule,1 s,1 for the reaction between ozone and isoprene and k2 = (8.3 ± 1.0) × 10,18 cm3 molecule,1 s,1 for the reaction between ozone and MBO. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 152,156 2004 [source] L -Cysteine Voltammetry at a Carbon Paste Electrode Bulk-Modified with Ferrocenedicarboxylic AcidELECTROANALYSIS, Issue 17 2007Jahan-Bakhsh Raoof Abstract The electrochemical behavior of L -cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH,8.00) in cyclic voltammetry, the oxidation of L -cysteine occurs at a potential about 200,mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, ,, and catalytic reaction rate constant, kh were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L -cysteine showed a linear dependent on the L -cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10,5 M,2.2×10,3 M and 1.5×10,5 M,3.2×10,3 M of L -cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3,) were determined as 2.6×10,5 M and 1.4×10,6 M by CV and DPV methods. [source] Solvent effects on kinetics of an aromatic nucleophilic substitution reaction in mixtures of an ionic liquid with molecular solvents and prediction using artificial neural networksINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2009Aziz Habibi-Yangjeh Kinetics of the reaction between 1-chloro-2,4-dinitrobenzene and aniline was studied in mixtures of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO4]) with methanol, chloroform, and dimethylsulfoxide at 25°C. Single-parameter correlations of log kA versus normalized polarity parameter (ENT), hydrogen-bond acceptor basicity (,), hydrogen-bond donor acidity (,), and dipolarity/polarizability (,*) of media do not give acceptable results. Multiparameter linear regression (MLR) of log kA versus the solvatochromic parameters demonstrates that the reaction rate constant increases with ENT, ,*, and , and decreases with , parameter. To predict accurately solvent effects on the rate constant, optimized artificial neural network with three inputs (including ,, ,*, and , parameters) was applied for prediction of the log kA values in the prediction set. It was found that properly selected and trained neural network could fairly represent the dependence of the reaction rate constant on solvatochromic parameters. Mean percent deviation of 5.023 for the prediction set by the MLR model should be compared with the value of 0.343 by the artificial neural network model. These improvements are due to the fact that the reaction rate constant shows nonlinear correlations with the solvatochromic parameters. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 153,159, 2009 [source] Ultrasonic assisted alkali extraction of protein from defatted rice bran and properties of the protein concentratesINTERNATIONAL JOURNAL OF FOOD SCIENCE & TECHNOLOGY, Issue 9 2009Thutiyaporn Chittapalo Summary Alkaline extraction for the preparation of protein concentrate from rice bran was compared with a range of ultrasonic treatments. Results revealed that the extraction time decreased, and the reaction rate constant increased, with increasing ultrasonic power. The reaction rate constants were 0.0065, 0.0130, 0.0237 and 0.0924 at 40, 60, 80 and 100 W respectively. The defatted rice bran protein concentrate (DRBPC) using ultrasonication (100 W for 5 min) and conventional methods showed no significant difference in bulk densities (P > 0.05) but it had higher yield (%) and was lighter brown using ultrasonication (P , 0.05). The SEM showed that the residual rice bran after extracting protein using ultrasonication exhibited more damage than the conventional method. The functional properties of both samples were not significantly different (P > 0.05) in terms of foam and emulsifying stability. However, the water and oil absorption, foam capacity and emulsion activity were significantly different (P , 0.05). The nitrogen solubility index of both DRBPC samples gave similar profiles with the lowest solubility at pH 4,6. [source] Combustion of chlorinated hydrocarbons in catalyst-coated sintered metal fleece reactors,JOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 2-3 2003K Everaert Abstract Incinerators emit chlorinated hydrocarbons, such as polychlorinated benzenes (PCBz) and phenols (PCPh), polychlorinated biphenyls (PCB) and polychlorinated dibenzodioxins and furans (PCDD/F), as very dilute streams. High temperatures (>1000,°C) are required in traditional oxidizers. From an energy-saving perspective and to avoid de novo synthesis of PCDD/F, exhaust gas clean-up must be performed at low temperatures (250,350,°C). Catalytic combustion can be applied in this temperature range and different reactor layouts are used (eg monoliths, honeycomb). The present investigation uses a novel catalyst-coated sintered metal fleece. Thin metal fibers are sintered (non-woven) to fleece of various thickness, structure and porosity. V,Ti,W catalysts are examined. The paper will briefly review the catalyst coating method suitable to provide a structured fleece reactor with adequate characteristics. Experiments were carried out in the temperature range of 260,340,°C with various hydrocarbons injected in a carrier air stream. The experimental investigations demonstrated: (i) that the conversion of the hydrocarbons (volatile organic compounds, VOC) is independent of the oxygen concentration, corresponding to a zero-order dependence of the reaction rate; (ii) that the conversion of the hydrocarbons is a first-order reaction in the VOC; (iii) that the oxidation of the VOC proceeds to a greater extent with increasing temperature, with chlorine substitution enhancing the reactivity, and (iv) that the reaction rate constant follows an Arrhenius-dependence with activation energies between 37.3 and 58.4,kJ,mol,1. An assessment of the results leads to a model expression with kinetic reaction control. This model can be used in a scale-up strategy. © 2003 Society of Chemical Industry [source] Kinetics of Formation and Physicochemical Characterization of Thermally-Induced ,-Lactoglobulin AggregatesJOURNAL OF FOOD SCIENCE, Issue 5 2010R.N. Zúñiga Abstract:, The kinetics of heat denaturation and aggregation for ,-lactoglobulin dispersions (5% w/v) were studied at 3 pHs (6, 6.4, and 6.8) and at a heating temperature of 80 °C. Protein aggregates were characterized for hydrodynamic diameter, microstructure, and molecular weight by means of dynamic light scattering, transmission electron microscopy, and polyacrylamide gel electrophoresis, respectively. Concentration of native ,-lactoglobulin decreased with holding time and with a decrease in the pH. Apparent rate constants were calculated for ,-lactoglobulin denaturation applying the general kinetic equation solved for a reaction order of 1.5. Values of the apparent reaction rate constant,k,= 7.5, 6.3 and 5.6 × 10,3 s,1 were found for pH 6, 6.4, and 6.8, respectively. Decreasing the pH of the dispersions produced higher aggregate sizes. After a holding time of 900 s, average hydrodynamic diameters for ,-lactoglobulin aggregates at pH 6, 6.4, and 6.8 were 96, 49, and 42 nm, respectively. These results were confirmed by transmission electron microscopy images, where a shift in the size and morphology of aggregates was found, from large and spherical at pH 6 to smaller and linear aggregates at pH 6.8. ,-Lactoglobulin formed disulfide-linked intermediates (dimers, trimers, tetramers) and so on) which then formed high molecular weight aggregates. From the results obtained by DLS, TEM, and SDS-PAGE a mechanism for ,-lactoglobulin aggregation was proposed. This study shows that heat treatment can be used to produce protein aggregates with different sizes and morphologies to be utilized as ingredients in foods. [source] Effect of supercritical deposition synthesis on dibenzothiophene hydrodesulfurization over NiMo/Al2O3 nanocatalystAICHE JOURNAL, Issue 10 2009Mehrdad Alibouri Abstract The synthesis of two NiMo/Al2O3 catalysts by the supercritical carbon dioxide/methanol deposition (NiMo-SCF) and the conventional method of wet coimpregnation (NiMo-IMP) were conducted. The results of the physical and chemical characterization techniques (adsorption,desorption of nitrogen, oxygen chemisorption, XRD, TPR, TEM, and EDAX) for the NiMo-SCF and NiMo-IMP demonstrated high and uniform dispersed deposition of Ni and Mo on the Al2O3 support for the newly developed catalyst. The hydrodesulfurization (HDS) of fuel model compound, dibenzothiophene, was used in the evaluation of the NiMo-SCF catalyst vs. the commercial catalyst (NiMo-COM). Higher conversion for the NiMo-SCF catalyst was obtained. The kinetic analysis of the reaction data was carried out to calculate the reaction rate constant of the synthesized and commercial catalysts in the temperature rang of 543,603 K. Analysis of the experimental data using Arrhenius' law resulted in the calculation of frequency factor and activation energy of the HDS for the two catalysts. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Effect of metal-support interface on hydrogen permeation through palladium membranesAICHE JOURNAL, Issue 3 2009Ke Zhang Abstract Thin palladium membranes of different thicknesses were prepared on sol-gel derived mesoporous ,-alumina/,-alumina and yttria-stabilized zirconia/,-alumina supports by a method combining sputter deposition and electroless plating. The effect of metal-support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/,-Al2O3/,-Al2O3 membranes are significantly smaller than those for the Pd/YSZ/,-Al2O3 membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/,-Al2O3/,-Al2O3 membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd-Al alloy, than the Pd/YSZ/,-Al2O3 membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] The study of the creatine kinase in rat brain during ischemia by magnetization transfer and biochemical analysisJOURNAL OF NEUROCHEMISTRY, Issue 2003D. Dobrota Various methods are used to study the biochemical changes in the central nervous system under normal and pathological conditions. The magnetization transfer 31P magnetic resonance technique was used here to measure the creatine kinase (CK) reaction rate constant in vivo in rats with cerebral ischemia. The measurements indicated that the rate constant of the CK reaction was significantly reduced in the case of chronic brain ischemia in aged rats. The similar reduction of the creatine kinase activity was found in the ischemic rat brain homogenate measured by biochemical analysis. At the same time, corresponding conventional phosphorus magnetic resonance spectra showed negligible or no change in signal intensities of compounds containing macroergic phosphates. Acknowledgements: This work was supported by the Grant Category C and Comenius University Grant No. X/2003. [source] High-temperature kinetics of the homogeneous reverse water,gas shift reactionAICHE JOURNAL, Issue 5 2004F. Bustamante Abstract The high-temperature rate of reaction of the homogeneous, reverse water,gas shift reaction (rWGSR) has been evaluated in quartz reactors with rapid feed preheating under both low- and high-pressure conditions. The form of the power-law rate expression was consistent with the Bradford mechanism. The Arrhenius expressions for the reaction rate constant, corresponding to the empty reactor, were in very good agreement with the low-pressure results of Graven and Long, but yielded rate constants roughly four times greater than those obtained in our packed reactor and those reported by Kochubei and Moin and by Tingey. Reactor geometry was not responsible for these differences because computational fluid dynamics simulations revealed similar residence time distributions and comparable conversions when the same kinetic expression was used to model the rWGSR in each reactor. Most likely, the empty NETL reactor and the Graven and Long reactor did not attain an invariant value of the concentration of the chain carrier (H) at low reaction times, which led to an overestimation of the rate constant. Conversions attained in an Inconel® 600 reactor operating at comparable conditions were approximately two orders of magnitude greater than those realized in the quartz reactor. This dramatic increase in conversion suggests that the Inconel® 600 surfaces, which were depleted of nickel during the reaction, catalyzed the rWGSR. © 2004 American Institute of Chemical Engineers AIChE J, 50: 1028,1041, 2004 [source] Fabrication and Characterization of Cordierite/Zircon Composites by Reaction Sintering: Formation Mechanism of ZirconJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 6 2002En-Hai Sun The formation mechanism of ZrSiO4 in the cordierite-ZrO2 system was studied in the temperature range of 1250° to 1400°C by X-ray diffraction analysis and discussed by analyzing experimental data using some reported reaction models. Nuclei growth models were found to describe the reaction well, and a satisfactory fit was obtained by applying the Avrami equation to estimate the reaction rate constant ,. Different values of the time exponent m were obtained at different temperatures: 0.32 at 1250°C, 0.34 at 1300°C, 0.39 at 1350°C, and 0.49 at 1400°C. The results indicate that there is a progressive change in reaction mechanism. [source] Hydroxylation and Dehydroxylation Behavior of Silica Glass Fracture SurfacesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 6 2002Andrew S. D'Souza The hydroxylation and dehydroxylation behavior of amorphous silica fracture surfaces was studied using temperature-programmed static SIMS. The results show that vacuum heat treatments result in more extensive condensation of silanol groups on the silica glass fracture surface as compared to fumed silica (Cabosil). This is attributed to differences in the distribution of silanol groups on the two silica surfaces. The rehydration kinetics of the dehydroxylated silica fracture surfaces showed two distinct reaction rates,an initial rapid increase in the silanol concentration, followed by a slower rehydration for longer dosing times. The slower rehydration reaction was shown to follow first-order reaction kinetics with the reaction rate constant, suggesting hydrolysis of strained siloxane bonds on three-membered silicate ring structures. The much faster initial rehydration is attributed to the hydrolysis of extremely strained siloxane bonds in two-membered, edge-shared tetrahedral rings. The effect of the dehydration time and temperature (i.e., thermal history of the surface) on the rehydration kinetics is also discussed. [source] Examination of intermediate species in GaN metal-organic vapor-phase epitaxy by selective-area growthPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 7-8 2010Masakazu Sugiyama Abstract The major reactive intermediate species of GaN has been deduced and its surface reaction rate constant has been obtained through the analysis of multi-scale growth-rate profiles both in the reactor-scale and in the micrometer-scale that were obtained by selective-area growth. Usually, it is difficult to explore surface reaction kinetics, especially for metal-organic vapour phase epitaxy (MOVPE), because of mass-transfer-limited kinetics. This multi-scale analysis, however, has clarified that a single precursor, a gas-phase reaction product between (CH3)3Ga and NH3, leads to the growth of GaN with a surface reaction probability of approximately 0.4 at 1400 K which is a typical growth temperature of GaN. Contribution of higher-order polymers was not significant in growth rate, but they seemed to be a cause of degraded surface morphology. A lumped reaction model of GaN MOVPE was proposed that led to reasonable agreement between a simulated growth-rate profile in the reactor-scale and a corresponding measured profile, which would lead to improved design of reactors and growth conditions. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Isotopologue fractionation during N2O production by fungal denitrificationRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 24 2008Robin L. Sutka Identifying the importance of fungi to nitrous oxide (N2O) production requires a non-intrusive method for differentiating between fungal and bacterial N2O production such as natural abundance stable isotopes. We compare the isotopologue composition of N2O produced during nitrite reduction by the fungal denitrifiers Fusarium oxysporum and Cylindrocarpon tonkinense with published data for N2O production during bacterial nitrification and denitrification. The fractionation factors for bulk nitrogen isotope values for fungal denitrification were in the range ,74.7 to ,6.6,. There was an inverse relationship between the absolute value of the fractionation factors and the reaction rate constant. We interpret this in terms of variation in the relative importance of the rate constants for diffusion and enzymatic reduction in controlling the net isotope effect for N2O production during fungal denitrification. Over the course of nitrite reduction, the ,18O values for N2O remained constant and did not exhibit a relationship with the concentration characteristic of an isotope effect. This probably reflects isotopic exchange with water. Similar to the ,18O data, the site preference (SP; the difference in ,15N between the central and outer N atoms in N2O) was unrelated to concentration during nitrite reduction and, therefore, has the potential to act as a conservative tracer of production from fungal denitrification. The SP values of N2O produced by F. oxysporum and C. tonkinense were 37.1,±,2.5, and 36.9,±,2.8,, respectively. These SP values are similar to those obtained in pure culture studies of bacterial nitrification but quite distinct from SP values for bacterial denitrification. The large magnitude of the bulk nitrogen isotope fractionation and the ,18O values associated with fungal denitrification are distinct from bacterial production pathways; thus multiple isotopologue data holds much promise for resolving bacterial and fungal production. Our work further provides insight into the role that fungal and bacterial nitric oxide reductases have in determining site preference during N2O production. Copyright © 2008 John Wiley & Sons, Ltd. [source] Relationship between sound pressure and reaction rate in sonochemical reactionTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 4 2009Yasuhiko Takuma Abstract Relationship between sound pressure in a sonochemical reactor and degradation rate of organic compounds, p -chlorophenol and p -nitrophenol, was investigated. Reaction rates were analyzed as first-order reaction. As a result, linear relationship was shown for each compound. Slope indicating the first reaction rate constant was remarkably affected by the position of the reaction flask. The sound pressure profile was measured and the relationship between the averaged pressure in a flask and the rate constant was shown. The relation was found to be remarkably different between the two. The threshold values were observed as 67kPa for p -chlorophenol and 22kPa for p -nitrophenol, respectively. From these results, it was shown that nature of compounds affects the dependency on sound pressure. On a étudié la relation entre les vitesses de dégradation des composés organiques, le p-chlorophénol et le p-nitrophénol, et la pression acoustique dans une réaction sonochimique. Les premières constantes de vitesse de réaction se sont avérées fortement influencée par la position de la cellule de réaction dans notre installation. Le profil de pression acoustique dans l'installation a été mesuré et la relation entre la pression moyennée dans la cellule et la constante de vitesse a été déterminée. On a trouvé que la relation était significativement différente entre les deux composés et que les valeurs seuils étaient de 100,kPa pour le p-chlorophénol. On a montré également que la nature des composés avait une influence sur leur dépendance à la pression acoustique. [source] Investigation of the stereodynamics of tris-(, -diimine),transition metal complexes by enantioselective dynamic MEKCELECTROPHORESIS, Issue 2 2009Sabrina Bremer Abstract Enantiomerization of octahedral tris(, -diimine),transition metal complexes was investigated by enantioselective dynamic MEKC. Varying both the transition metal ion (Fe2+, Fe3+, and Ni2+) and the bidentate diimine ligand (1,10-phenanthroline and 2,2,-bipyridyl), the enantiomer separations were performed either in a 100,mM sodium tetraborate buffer (pH 9.3) or in a 100,mM sodium tetraborate/sodium dihydrogenphosphate buffer (pH 8.0) both containing sodium cholate as chiral surfactant. The unified equation of dynamic chromatography was employed to determine apparent reaction rate constants from the electropherograms showing distinct plateau formation. Apparent activation parameters ,H, and ,S, were calculated from temperature-dependent measurements between 10.0 and 35.0°C in 2.5,K steps. It was found that the nature of the central metal ion and the ligand strongly influence the enantiomerization barrier. Surprisingly, complexes containing the 2,2,-bipyridyl ligand show highly negative activation entropies between ,103 and ,116,J (K,mol),1 while the activation entropy of tris(1,10-phenanthroline) complexes is positive indicating a different mechanism of interconversion. Furthermore, it was found that the Ni2+ complexes are stereostable under the conditions investigated here making them a lucent target as enantioselective catalysts. [source] Reaction kinetics for the degradation of phenol and chlorinated phenols using Fenton's reagentENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 1 2006Asim K. De Abstract Fenton's reaction is an advanced treatment technology often used for the removal of hazardous and refractory organic compounds from industrial wastewaters. It can effectively be used to degrade phenol and chlorophenols. The initial contaminant concentrations as well as the concentration of hydrogen peroxide and ferrous ions in aqueous solution have a significant effect on the effective degradation of contaminants. For a particular concentration of initial substrate in solution there should be an optimum level of ferrous ion concentration in the reaction medium. Based on experimental observations, a probable mechanism for Fenton's degradation kinetics has been proposed and a rate equation developed. From the rate expression, OH· radical reaction rate constants for the degradation of three compounds,phenol and o- and p-chlorophenols,in Fenton reaction were calculated to have values of 2.53 × 107, 2.38 × 107, and 2.45 × 107 m3 mol,1 s,1, respectively. © 2005 American Institute of Chemical Engineers Environ Prog, 2005 [source] Development and validation of a congener-specific photodegradation model for polybrominated diphenyl ethersENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2008Xia Zeng Abstract With the phaseout of the manufacture of some polybrominated diphenyl ether (PBDE) formulations, namely penta-brominated diphenyl ether (BDE) and octa-BDE, and the continued use of the deca-BDE formulation, it is important to be able to predict the photodegradation of the more highly brominated congeners. A model was developed and validated to predict the products and their relative concentrations from the photodegradation of PBDEs. The enthalpies of formation of the 209 PBDE congeners were calculated, and the relative reaction rate constants were obtained. The predicted reaction rate constants for PBDEs show linear correlation with previous experimental results. Because of their large volume use, their presence in the environment, and/or importance in the photodegradation of the deca-BDE formulation, BDE-209, BDE-184, BDE-100, and BDE-99 were chosen for further ultraviolet photodegradation experiments in isooctane. The photodegradation model successfully predicted the products of the photochemical reactions of PBDEs in experimental studies. A gas chromatography retention time model for PBDEs was developed using a multiple linear regression analysis and, together with the photodegradation model and additional PBDE standards, provided a way to identify unknown products from PBDE photodegradation experiments. Based on the results of the photodegradation experiments, as well as the model predictions, it appears that the photodegradation of PBDEs is a first-order reaction and, further, that the rate-determining step is the stepwise loss of bromine. Our results suggest that, based on photodegradation, over time, BDE-99 will remain the most abundant penta-BDE, while BDE-49 and BDE-66 will increase greatly and will be comparable in abundance to BDE-47. [source] Kinetics and mechanism of myristic acid and isopropyl alcohol esterification reaction with homogeneous and heterogeneous catalystsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2008Tuncer Yalçinyuva The reaction of myristic acid (MA) and isopropyl alcohol (IPA) was carried out by using both homogeneous and heterogeneous catalysts. For a homogeneously catalyzed system, the experimental data have been interpreted with a second order, using the power-law kinetic model, and a good agreement between the experimental data and the model has been obtained. In this approach, it was assumed that a protonated carboxylic acid is a possible reaction intermediate. After a mathematical model was proposed, reaction rate constants were computed by the Polymath* program. For a heterogeneously catalyzed system, interestingly, no pore diffusion limitation was detected. The influences of initial molar ratios, catalyst loading and type, temperature, and water amount in the feed have been examined, as well as the effects of catalyst size for heterogeneous catalyst systems. Among used catalysts, p -toluene sulfonic acid (p -TSA) gave highest reaction rates. Kinetic parameters such as activation energy and frequency factor were determined from model fitting. Experimental K values were found to be 0.54 and 1.49 at 60°C and 80°C, respectively. Furthermore, activation energy and frequency factor at forward were calculated as 54.2 kJ mol,1 and 1828 L mol,1 s,1, respectively. © 2008 Wiley Periodicals, Inc. 40: 136,144, 2008 [source] Kinetics for the gas-phase reactions of OH radicals with the hydrofluoroethers CH2FCF2OCHF2, CHF2CF2OCH2CF3, CF3CHFCF2OCH2CF3, and CF3CHFCF2OCH2CF2CHF2 at 268,308 KINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2003L. Chen Rate constants were determined for the reactions of OH radicals with the hydrofluoroethers (HFEs) CH2FCF2OCHF2(k1), CHF2CF2OCH2CF3 (k2), CF3CHFCF2OCH2CF3(k3), and CF3CHFCF2OCH2CF2CHF2(k4) by using a relative rate method. OH radicals were prepared by photolysis of ozone at UV wavelengths (>260 nm) in 100 Torr of a HFE,reference,H2O,O3,O2,He gas mixture in a 1-m3 temperature-controlled chamber. By using CH4, CH3CCl3, CHF2Cl, and CF3CF2CF2OCH3 as the reference compounds, reaction rate constants of OH radicals of k1 = (1.68) × 10,12 exp[(,1710 ± 140)/T], k2 = (1.36) × 10,12 exp[(,1470 ± 90)/T], k3 = (1.67) × 10,12 exp[(,1560 ± 140)/T], and k4 = (2.39) × 10,12 exp[(,1560 ± 110)/T] cm3 molecule,1 s,1 were obtained at 268,308 K. The errors reported are ± 2 SD, and represent precision only. We estimate that the potential systematic errors associated with uncertainties in the reference rate constants add a further 10% uncertainty to the values of k1,k4. The results are discussed in relation to the predictions of Atkinson's structure,activity relationship model. The dominant tropospheric loss process for the HFEs studied here is considered to be by the reaction with the OH radicals, with atmospheric lifetimes of 11.5, 5.9, 6.7, and 4.7 years calculated for CH2FCF2OCHF2, CHF2CF2OCH2CF3, CF3CHFCF2OCH2CF3, and CF3CHFCF2OCH2CF2CHF2, respectively, by scaling from the lifetime of CH3CCl3. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 239,245, 2003 [source] Constrained least squares methods for estimating reaction rate constants from spectroscopic dataJOURNAL OF CHEMOMETRICS, Issue 1 2002Sabina Bijlsma Abstract Model errors, experimental errors and instrumental noise influence the accuracy of reaction rate constant estimates obtained from spectral data recorded in time during a chemical reaction. In order to improve the accuracy, which can be divided into the precision and bias of reaction rate constant estimates, constraints can be used within the estimation procedure. The impact of different constraints on the accuracy of reaction rate constant estimates has been investigated using classical curve resolution (CCR). Different types of constraints can be used in CCR. For example, if pure spectra of reacting absorbing species are known in advance, this knowledge can be used explicitly. Also, the fact that pure spectra of reacting absorbing species are non-negative is a constraint that can be used in CCR. Experimental data have been obtained from UV-vis spectra taken in time of a biochemical reaction. From the experimental data, reaction rate constants and pure spectra were estimated with and without implementation of constraints in CCR. Because only the precision of reaction rate constant estimates could be investigated using the experimental data, simulations were set up that were similar to the experimental data in order to additionally investigate the bias of reaction rate constant estimates. From the results of the simulated data it is concluded that the use of constraints does not result self-evidently in an improvement in the accuracy of rate constant estimates. Guidelines for using constraints are given. Copyright © 2002 John Wiley & Sons, Ltd. [source] Time-dependent quantum study of H(2S) + FO(2,) , OH(2,) + F(2P) reaction on the 13A, and 13A, statesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 14 2010Fahrettin Gogtas Abstract The dynamics of the H(2S) + FO(2,) , OH(2,) + F(2P) reaction on the adiabatic potential energy surface of the 13A, and 13A, states is investigated. The initial state selected reaction probabilities for total angular momentum J = 0 have been calculated by using the quantum mechanical real wave packet method. The integral cross sections and initial state selected reaction rate constants have been obtained from the corresponding J = 0 reaction probabilities by means of the simple J -Shifting technique. The initial state-selected reaction probabilities and reaction cross section do not manifest any sharp oscillations and the initial state selected reaction rate constants are sensitive to the temperature. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010 [source] Nitration of nitrobenzene at high-concentrations of sulfuric acid: Mass transfer and kinetic aspectsAICHE JOURNAL, Issue 3 2010M. Rahaman Abstract This article reports studies on mass transfer and kinetics of nitration of nitrobenzene at high concentrations of sulfuric acid in a batch reactor at different temperatures. The effects of concentration of sulfuric acid, speed of stirring, and temperature on mass transfer coefficient were investigated. The kinetics of nitration under homogenized conditions was studied at different sulfuric acid concentrations at these temperatures. The reaction rate constants were determined. The variation of rate constant with sulfuric acid concentration was explained by the Mc function. The activation energies of the reactions were determined from the Arrhenius plots. The regimes of the reactions were determined using the values of the mass transfer coefficients and the reaction rate constants. A model was developed for simultaneous mass transfer and chemical reaction in the aqueous phase. The yields of the three isomers of dinitrobenzene were determined, and the variation of isomer distribution with sulfuric acid concentration and temperature was analyzed. This work demonstrates that more than 90% conversion of nitrobenzene is possible at high-sulfuric acid concentrations resulting in high yield of the product even at moderate temperatures and at low speeds of stirring. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Gas-phase ion chemistry in the ternary silane,propyne,phosphine systemJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 6 2004Lorenza Operti Abstract The gas-phase ion chemistry of propyne,phosphine and silane,propyne,phosphine mixtures was studied by ion trap mass spectrometry. For the binary mixture, the effect of different partial pressures of the reagents on the yield of C and P-containing ions was evaluated. Reaction sequences and rate constants were determined and reaction efficiencies were calculated from comparison of experimental and collisional rate constants. In the ternary silane,propyne,phosphine systems, the reaction pathways leading to formation of SimCnPpHq+ ions were determined and the rate constants of the most important steps were measured. For some ion species, selected by double isolation procedures (MS/MS), the low ion abundances prevented determination of the reaction rate constants. Si, C and P-containing ions are mainly produced in reactions of SimPpHq+ ions with propyne, while the reactivity of the SimCnHq+ ions towards PH3 and of the CnPpHq+ ions towards SiH4 is very low. The formation of hydrogenated SiCP ions is interesting for their possible role as precursors of amorphous silicon carbides doped with phosphorus, obtained in a single step, by deposition from properly activated silane,propyne,phosphine mixtures. Copyright © 2004 John Wiley & Sons, Ltd. [source] Reactions of gaseous ions.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2001Editor's Note: The following paper is the first in a series that describes the gas phase reactions of positive ions derived from compounds such as methane and ethylene with other gas phase molecules to produce secondary ions. These very careful experiments formed the basis of chemical ionization, one of the ionization techniques that revolutionized mass spectrometry at that time and a technique still very much in use today. At elevated pressures in a mass spectrometer ion source reactions occur between certain ions and the neutral species present. We have studied the various secondary ions formed in methane and ethylene at elevated pressures and have determined the reactions by which they are formed and the rates of these reactions. The rates are all extremely fast. The reaction rates have been treated by classical collision theory and it has been shown that to a fair approximation the cross-sections and reaction rate constants can be predicted from a simple balance of rotational and polarization forces. [Reprinted from J. Am. Chem. Soc. 1957; 79: 2419.] Copyright © 1957 by the American Chemical Society and reprinted by permission of the copyright owner. [source] Quantification of the water/lipid affinity of melatonin and a pinoline derivative in lipid modelsJOURNAL OF PINEAL RESEARCH, Issue 4 2007Jamila Mekhloufi Abstract:, This study assessed the location of melatonin (N-acetyl-5-methoxytryptamine) and of a pinoline derivative (GWC22) [6-ethyl-1-(3-methoxyphenyl)-2-propyl-1,2,3,4-tetrahydro-beta-carboline], when present in lipid assemblies such as linoleate micelles, phosphatidylcholine liposomes or low density lipoproteins (LDL). The efficiency of radical scavenging by these compounds is highly dependent on their partitioning between the lipidic and aqueous phases. We determined the proportion of melatonin or GWC22 in the aqueous and lipid phases of each system (concentrations of the antioxidants ranging between 3 × 10,5 and 10,4 m) by assaying melatonin or GWC22 by HPLC/UV detection, or by fluorescence for melatonin in micelles. Our results show that melatonin and GWC22 were preferentially located in the aqueous phase of micelles (68.4% and 59.0%, respectively), whereas only 30.5% of melatonin and 39.0% of GWC22 were found in the lipid phase. By contrast, in phosphatidylcholine liposomes, both compounds were essentially present in the lipid phase (73.5% for melatonin and 79.1% for GWC22, versus 25.9% and 19.5% in the aqueous phase, respectively). In the case of LDL, 99.9% of the melatonin added was found in the methanol/water extracting phase containing phospholipids, unesterified cholesterol and apolipoprotein B100. The partitioning of melatonin and GWC22 in linoleate micelles gave new insights on the marked protective effect of GWC22 towards radiation-induced lipid peroxidation and allowed us to determine more accurately the lower limit values of the reaction rate constants of the two molecules studied with lipid peroxyl radicals, i.e. k(LOO,+melatonin) , 9.0 × 104m,1s,1 and k(LOO,+GWC22) , 3.5 × 105m,1s,1. [source] Oxidation and Volatilization of Silica Formers in Water VaporJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 8 2003Elizabeth J. Opila At high temperatures, SiC and Si3N4 react with water vapor to form a SiO2 scale. SiO2 scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming SiO2 and the other removing SiO2, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved. After steady state is achieved, the oxide found on the surface is a constant thickness, and recession of the underlying material occurs at a linear rate. The steady-state oxide thickness, the time to achieve steady state, and the steady-state recession rate can be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate also can be determined from parameters that describe a water-vapor-containing environment. Accordingly, maps have been developed to show these steady-state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of SiO2 formers in water-vapor-containing environments, such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4. [source] New Approach in Modeling of Metallocene-Catalyzed Olefin Polymerization Using Artificial Neural NetworksMACROMOLECULAR THEORY AND SIMULATIONS, Issue 3 2009Mostafa Ahmadi Abstract A new approach for the estimation of kinetic rate constants in olefin polymerization using metallocene catalysts is presented. The polymerization rate has been modeled using the method of moments. An ANN has been used and trained to behave like the mathematical model developed before, so that it gets polymerization rate at different reaction times and predicts reaction rate constants. The network was trained using modeling results in desired operational window. The polymerization rates were normalized to make the network work independent of operational conditions. The model has also been applied to real polymerization rate data and the predictions were satisfactory. This model is specially useful in comparing different new metallocene catalysts. [source] Estimation of Aqueous-Phase Reaction Rate Constants of Hydroxyl Radical with Phenols, Alkanes and AlcoholsMOLECULAR INFORMATICS, Issue 11-12 2009Ya-nan Wang Abstract A quantitative structure activity relationship (QSAR) model was developed for the aqueous-phase hydroxyl radical reaction rate constants (kOH) employing quantum chemical descriptors and multiple linear regressions (MLR). The QSAR development followed the OECD guidelines, with special attention to validation, applicability domain (AD) and mechanistic interpretation. The established model yielded satisfactory performance: the correlation coefficient square (R2) was 0.905, the root mean squared error (RMSE) was 0.139, the leave-many-out cross-validated QLMO2 was 0.806, and the external validated QEXT2 was 0.922 log units. The AD of the model covering compounds of phenols, alkanes and alcohols, was analyzed by Williams plot. The main molecular structural factors governing kOH are the energy of the highest occupied molecular orbital (EHOMO), average net atomic charges on hydrogen atoms (), molecular surface area (MSA) and dipole moment (,). It was concluded that kOH increased with increasing EHOMO and MSA, while decreased with increasing and ,. [source] | ||||||||||||||||||||||||||||||||||