Chain Propagation in the Oxidation of Alkyl Radicals

Fish, A.

doi:10.1021/ba-1968-0076.ch031

Cited by 31 publications

(6 citation statements)

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“…Since atomic oxygen-n-butane reaction acts only as a chaininitiating reaction, a mechanism must be written to explain the large differences between the observed and calculated rates. The suggested mechanism is similar to that proposed by Fish (1968) This mechanism makes hydroxyl radicals the principal chain-propagating free radicals. Since rate constants between OH and hydrocarbons are quite large (Greiner, 1967), the disappearance of «-butane can be easily explained.…”

Section: Resultssupporting

confidence: 75%

Oxidation of n-butane by the photolysis of nitrogen dioxide

Bufalini¹,

Gay²,

Kopczynski³

1971

Environ. Sci. Technol.

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Section: Resultssupporting

confidence: 75%

Oxidation of n-butane by the photolysis of nitrogen dioxide

Bufalini¹,

Gay²,

Kopczynski³

1971

Environ. Sci. Technol.

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“…(i) Certains travaux soulignent la prCpondCrance de l'iso-mCrisation des radicaux alcoylperoxy qui avait Ct C plus spCcialement dtveloppte par Fish (5). Cette interpritation peut etre reprisentte par le mCcanisme symbolique ci-dessous oh RH reprksente l'alcane de dCpart, R. le radical alcoyle qui en dtrive par arrachement d'hydrogbne, R02.…”

Section: Introduction Gkneralites Sur L'oxydation Des Alcanesunclassified

“…1. SchCma mkcanistique gknkralisC de l'oxydation des alcanes d'aprbs la mise au point de Fish (5). Knox (7) suggere qu'en dCbut de rCaction, c'est H 0 2 -, radical sClectif et relativement peu rCactif, qui arrache l'atome d'hydrogbne ?…”

Section: Introduction Gkneralites Sur L'oxydation Des Alcanesunclassified

Étude chimique et cinétique de l'oxydation homogène en phase gazeuse d'alcanes légers. I. Isobutane

Vogin¹,

Baronnet²,

Scacchi³

1989

Can. J. Chem.

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A literature survey on the homogeneous gas-phase oxidation of light alkanes shows that despite a rather high number of papers there are still, even in the case of isobutane, an important number of unresolved questions, which makes the writing of a reaction scheme rather difficult. To obtain more reliable experimental data, we have studied the homogeneous gas-phase oxidation of isobutane in a conventional static system, at 310 and 340 °C and subatmospheric pressure. This investigation is chiefly aimed at identifying and measuring the major primary products of the reaction. A chain radical scheme based on the primary products and on estimation of the rate constants of the elementary steps by the methods of Thermochemical Kinetics is put forward to interpret our experimental results. Two major reaction routes appear, one corresponding to the formation of isobutene and the other to the formation of isobutene oxide. The conclusions of the present investigation and suggestions for further developments are also mentioned. Keywords: oxidation, chemical kinetics, reaction mechanism, isobutane.

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“…During the hydrocarbon oxidation, peroxy radicals and various intermediate oxygenated compounds are formed, until transformation into the final products, i.e., water and CO 2 . Knox et al, followed by Fish, carried out the first low-temperature oxidation of alkanes. , The detailed kinetic models have undergone major improvement. , The oxidation chemistry of hydrocarbons in the reservoir conditions was expected to be in accordance with the low-temperature kinetic model (600–900 K), but the model needed to be upgraded to take the high pressure (1–100 MPa) into account and the particularly low temperature (<500 K) of a petroleum reservoir. In a previous study, these modifications were considered (i.e., some new reactions were added to the literature kinetic model and some kinetic parameters were optimized) in the primary mechanism of the oxidation of n -octane .…”

Section: Introductionmentioning

confidence: 99%

“…Knox et al, followed by Fish, carried out the first low-temperature oxidation of alkanes. 13,14 The detailed kinetic models have undergone major improvement. 15,16 The oxidation chemistry of hydrocarbons in the reservoir conditions was expected to be in accordance with the low-temperature kinetic model (600−900 K), but the model needed to be upgraded to take the high pressure (1−100 MPa) into account and the particularly low temperature (<500 K) of a petroleum reservoir.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of n-Alkane (n-C₈H₁₈) under Reservoir Conditions in Response to Gas Mixture Injection (CO₂/O₂): Understanding Oxygenated Compound Distribution

et al. 2016

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CO 2 geosequestration [carbon capture and storage (CCS)] and enhanced oil recovery (EOR) by CO 2 injection in hydrocarbon-depleted reservoirs could limit the CO 2 atmospheric accumulation. In the case of CO 2 capture by oxy-combustion, the main annex gas associated with CO 2 is O 2 . O 2 that remains in the flue gas for injection can induce the oxidation of the hydrocarbons contained in the reservoirs. The effect of O 2 must be studied in terms of benefit and/or risk for CCS or EOR. To investigate the mechanism of hydrocarbon oxidation, it is essential to analyze the distributions of the formed oxygenated compounds. That is why experiments have been performed with a model compound (n-octane) in a closed reactor under high pressure at different temperatures and with different oxygen concentrations. The product distribution suggests two pathways of n-alkane oxidation, with (i) the preservation of the aliphatic chain length of the initial n-alkane, which generates oxygenated products with the same number of carbon, and (ii) the breakdown processes of the initial n-alkane, which generates lowmolecular-weight oxygenated products. The new understanding of the mechanism of n-alkane oxidation could be incorporated into the detailed kinetic model of our previous study, which is specific to the reservoir conditions.

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Chain Propagation in the Oxidation of Alkyl Radicals

Cited by 31 publications

References 0 publications

Oxidation of n-butane by the photolysis of nitrogen dioxide

Oxidation of n-butane by the photolysis of nitrogen dioxide

Étude chimique et cinétique de l'oxydation homogène en phase gazeuse d'alcanes légers. I. Isobutane

Oxidation of n-Alkane (n-C₈H₁₈) under Reservoir Conditions in Response to Gas Mixture Injection (CO₂/O₂): Understanding Oxygenated Compound Distribution

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Chain Propagation in the Oxidation of Alkyl Radicals

Cited by 31 publications

References 0 publications

Oxidation of n-butane by the photolysis of nitrogen dioxide

Oxidation of n-butane by the photolysis of nitrogen dioxide

Étude chimique et cinétique de l'oxydation homogène en phase gazeuse d'alcanes légers. I. Isobutane

Oxidation of n-Alkane (n-C8H18) under Reservoir Conditions in Response to Gas Mixture Injection (CO2/O2): Understanding Oxygenated Compound Distribution

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Oxidation of n-Alkane (n-C₈H₁₈) under Reservoir Conditions in Response to Gas Mixture Injection (CO₂/O₂): Understanding Oxygenated Compound Distribution