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Stoichiometric Coefficient (stoichiometric + coefficient)
Selected AbstractsEfficient method of cyclic imides synthesis under ozone influence by the example of ,-caprolactam oxidation reactionHETEROATOM CHEMISTRY, Issue 7 2008Olga Alekseeva The process of ,-caprolactam oxidation by ozone in a CCl4 solution was investigated. Stoichiometric coefficient (1:1) and the mechanism of oxidation were identified. The composition and structure of the ozonolysis reaction products and the ozone attack on the caprolactam molecule were determined by IR and 1H NMR spectroscopy methods, as well as using thin-layer chromatography. It was found that the ozonolysis reaction is rather selective. The main reaction product,azepane-2,7-dione (Scharf et al., Angew Makromol Chem 1979, 79, 193),was formed with a yield of more than 90% and can be used as an intermediate during the production of commercially important antibiotics. Kinetics of the reaction obeyed the bimolecular law, the effective rate constant of the reaction in the CCl4 solution is equal to kr = 22.7 l/(mol s). The method of fast conversion of lactame to cycloimide under the ozone influence is reported. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:661,666, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20492 [source] Natural polyphenols as chain-breaking antioxidants during methyl linoleate peroxidationEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 8 2010Ivan Tichonov Abstract A technique based on monitoring oxygen consumption was applied to study 11 natural and model polyphenols (PP, QH2) as well as four typical monophenolics as a chain-breaking antioxidant during the controlled chain oxidation of methyl linoleate (ML) in bulk at 37°C. The antioxidant activities of QH2 were characterized by two parameters: the rate constant k1 for reaction of QH2 with the peroxy radical : (i) QH2,+,,,,,+,LOOH and the stoichiometric factor of inhibition, f, which shows how many kinetic chains may be terminated by one molecule of QH2. The rate constant k1 were reduced significantly by factor of 4 ,28 as compared to these determined during the oxidation of styrene in bulk; the effect was typically more pronounced for catechol derivatives than for pyrogallol derivatives. At the same time, f for QH2 was found to be close to two independent of the number of active OH groups, similar to that determined earlier during the inhibited oxidation of styrene. The formation of H bond between OH group of QH2 and carboxyl group of ML is suggested as a reason for reducing effect of ML on k1. Practical applications: This work reports rate constants for the reaction of lipid peroxyl radical with phenolics and stoichiometric coefficient of inhibition, which characterize the antioxidant activity (AOA) of 15 natural and model PP, QH2 during the controlled peroxidation of ML. The reactivity of PP, QH2 during the oxidation of ML is routinely lower than the reactivity during the oxidation of non-polar model hydrocarbons. This information may be useful to estimate the AOA of natural PP, QH2 in real systems of practical significance including plant oils, fats, food-stuffs, biological objects, and similar. [source] The chain-breaking antioxidant activity of phenolic compounds with different numbers of O-H groups as determined during the oxidation of styreneINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2009Ivan Tikhonov The technique based on monitoring oxygen consumption was applied to test 18 polyphenols (PP) and model phenolics as a chain-breaking antioxidant during the oxidation of styrene initiated by 2,2,-azobis(2,4-dimethylvaleronitril) at 37°C. The chain-breaking capability of PP was characterized by two parameters: the rate constant k1 for the reaction of antioxidants with the peroxy radical produced from styrene and the stoichiometric coefficient of inhibition, f, which shows how many kinetic chains are terminated by one molecule of PP. Rate constants k1 × 105 (in M,1 s,1) were found to be 10 (catechol), 27 (pyrogallol), 34 (3,6-di-tert-Bu-catechol), 4.3 (protocatechic acid), 12 (gallic acid), 15 (caffeic acid), <0.01 (chrysin), 1.3 (kaempferol), 19 (quercetin), 5.3 (baicalein), 16 (epicatechin), 32 (epigallocatechin), 9.0 (dihydroquercetin), 3.3 (resveratrol), and 16 (nordihydroguaiaretic acid). The value of k1 increases when going from one to two and three adjacent O-H groups in a benzene ring (catechol and pyrogallol derivatives, respectively). At the same time, two O-H groups in metaposition in a A-ring of flavonoids actually do not participate in the inhibition. For the majority of PP, f is near to 2 independent of the number of OH groups. The correlation of k1 with the structure of PP and the OH bond dissociation enthalpy has been discussed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 92,100, 2009 [source] Bacterial energetics, stoichiometry, and kinetic modeling of 2,4-Dinitrotoluene biodegradation in a batch respirometerENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2004Chunlong Zhang Abstract A stoichiometric equation and kinetic model were developed and validated using experimental data from batch respirometer studies on the biodegradation of 2,4-dinitrotoluene (DNT). The stoichiometric equation integrates bacterial energetics and is revised from that in a previous study by including the mass balance of phosphorus (P) in the biomass. Stoichiometric results on O2 consumption, CO2 evolution, and nitrite evolution are in good agreement with respirometer data. However, the optimal P requirement is significantly higher than the stoichiometrically derived P, implying potentially limited bioavailability of P and the need for buffering capacity in the media to mitigate the adverse pH effect for optimal growth of DNT-degrading bacteria. An array of models was evaluated to fit the O2/CO2 data acquired experimentally and the DNT depletion data calculated from derived stoichiometric coefficients and cell yield. The deterministic, integrated Monod model provides the goodness of fit to the test data on DNT depletion, and the Monod model parameters (Ks, X0, ,max, and Y) were estimated by nonlinear regression. Further analyses with an equilibrium model (MINTEQ) indicate the interrelated nature of medium chemical compositions in controlling the rate and extent of DNT biodegradation. Results from the present batch respirometer study help to unravel some key factors in controlling DNT biodegradation in complex remediation systems, in particular the interactions between acidogenic DNT bacteria and various parameters, including pH and P, the latter of which could serve as a nutrient, a buffer, and a controlling factor on the bioavailable fractions of minerals (Ca, Fe, Zn, and Mo) in the medium. [source] Formation and decay of the ABTS derived radical cation: A comparison of different preparation proceduresINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2002Carola Henriquez Bleaching of a preformed solution of the blue-green radical cation 2,2,-azinobis (3-ethylbenzothizoline-6-sulfonic acid) (ABTS+·) has been extensively used to evaluate the antioxidant capacity of complex mixtures and individual compounds. The reaction of the preformed radical with free-radical scavengers can be easily monitored by following the decay of the sample absorbance at 734 nm. The ABTS radical cation can be prepared employing different oxidants. Results obtained using MnO2 as oxidant show that the presence of manganese ions increases the rate of [ABTS]+· autobleaching in a concentration-dependent manner. The radicals can also be obtained by oxidizing ABTS with 2,2, -azobis(2-amidinopropane)hydrochloride (AAPH) or peroxodisulfate (PDS). The oxidation by AAPH takes place with a large activation energy and a low reaction order in ABTS. The data support a mechanism in which the homolysis of AAPH is the rate-limiting step, followed by the reaction of ABTS with the peroxyl radicals produced after the azocompound thermolysis. On the other hand, the low activation energy measured employing PDS, as well as the kinetic law, are compatible with the occurrence of a bimolecular reaction between the oxidant and ABTS. Regarding the use of ABTS-based methodologies for the evaluation of free radical scavengers, radical cations obtained employing AAPH as oxidant can be used only at low temperatures, conditions where further decomposition of the remaining AAPH is minimized. The best results are obtained with ABTS derived radicals generated in the reaction of PDS with an ABTS/PDS concentration ratio equal (or higher) to two. However, even with radicals prepared by this procedure, stoichiometric coefficients considerably larger than two are obtained for the consumption of the radical cation employing tryptophane or p -terbutylphenol as reductants. This casts doubts on the use of ABTS-based procedures for the estimation of antioxidant capacities. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 659,665, 2002 [source] | |||||||||||||