Thermochemical kinetics, 2nd. Ed., Sidney W. Benson, Wiley Interscience, 320 pp., $22.50, New York, 1976
About: This article is published in Aiche Journal.The article was published on 1977-07-01. It has received 89 citations till now.
Citations
More filters
TL;DR: The most recent review and evaluation of Atkinson [J. Phys. Chem. Ref. Data, 26, No. 3 (1997) and as mentioned in this paper concerning the gas phase reactions of alkanes and alkenes (including isoprene and monoterpenes) leading to their first generation products are reviewed and evaluated for tropospheric conditions.
Abstract: Literature data (through mid-1996) concerning the gas-phase reactions of alkanes and alkenes (including isoprene and monoterpenes) leading to their first generation products are reviewed and evaluated for tropospheric conditions. The recommendations of the most recent IUPAC evaluation [J. Phys. Chem. Ref. Data, 26, No. 3 (1997)] are used for the ⩽C3 organic compounds, unless more recent data necessitates reevaluation. The most recent review and evaluation of Atkinson [J. Phys. Chem. Ref. Data, Monograph 2, 1 (1994)] concerning the kinetics of the reactions of OH radicals, NO3 radicals, and O3 is also updated for these two classes of volatile organic compounds.
1,228 citations
TL;DR: In this article, a detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated with a test set at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation was developed.
Abstract: Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated b...
279 citations
TL;DR: The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations, giving a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps.
Abstract: The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3–)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the...
235 citations
TL;DR: In this article, an experimental and modeling study of low-temperature oxidation of toluene was performed in a continuous flow stirred tank reactor with carbon-containing products analyzed by gas chromatography under the following experimental conditions.
Abstract: This paper describes an experimental and modeling study of the oxidation of toluene The low-temperature oxidation was studied in a continuous flow stirred tank reactor with carbon-containing products analyzed by gas chromatography under the following experimental conditions: temperature from 873 to 923 K, 1 bar, fuel equivalence ratios from 045 to 091, concentrations of toluene from 14 to 17%, and residence times ranging from 2 to 13 s corresponding to toluene conversion from 5 to 85% The ignition delays of toluene–oxygen–argon mixtures with fuel equivalence ratios from 05 to 3 were measured behind reflected shock waves for temperatures from 1305 to 1795 K and at a pressure of 87 ± 07 bar A detailed kinetic mechanism has been proposed to reproduce our experimental results, as well as some literature data obtained in other shock tubes and in a plug flow reactor The main reaction paths have been determined by sensitivity and flux analyses © 2004 Wiley Periodicals, Inc Int J Chem Kinet 37: 25–49, 2005
192 citations
01 Jan 2000
TL;DR: In this paper, the reaction between H2 and O2 was studied in a reflected shock tube apparatus between temperatures of 1662 - 2097 K and pressures of 400 - 570 torr with Kr as the diluent gas, and experimental and ab initio theoretical results both indicated that the process, H2 + O2 -> H + HO2, is the most probable reaction.
Abstract: : The reaction between H2 and O2 has been studied in a reflected shock tube apparatus between temperatures of 1662 - 2097 K and pressures of 400 - 570 torr with Kr as the diluent gas. O atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]sub t under conditions of low [H2]sub 0 so that most secondary reactions were negligible. Hence, the observed [O]sub t was the direct result of the rate controlling reaction between H2 and O2. Three different reactions were considered, but experimental and ab initio theoretical results both indicated that the process, H2 + O2 -> H + HO2, is the most probable reaction. After rapid HO2 dissociation, O atoms are then instantaneously produced by H + O2 -> O + OH. Using the ab initio result, conventional transition state theoretical calculations (CTST) with tunneling corrections give the expression k(th/1) = 1.288 X 10(-18) T(2.4328) exp(-26,926 K/T) cu cm molecule(-1) s(-1), applicable between 400 and 2300 K. This theoretical result agrees with the present experimental determinations and those at lower temperature, derived from earlier work on the reverse reaction.
112 citations
Cites background from "Thermochemical kinetics, 2nd. Ed., ..."
..., 10 12 cm3 molecule 1 s 1) for four-center or tight transition states, respectively [27], but much higher values, A2 1 10 8 or A3 3 10 11 cm3 molecule 1 s 1, are required to explain the data....
[...]