Gas-phase oxidations of hydrocarbons

McKay, Gordon

doi:10.1016/0360-1285(77)90010-7

Cited by 19 publications

(3 citation statements)

References 145 publications

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“…Most of this work has been reviewed by McKay (1977), Pollard. (1977), Benson (1976Benson ( , 1981Benson ( , 1982, Minkoff and Tipper (1962), and Lewis and Von Elbe (1961).…”

Section: Introductionmentioning

confidence: 99%

The Oxidation of Propane at Low and Transition Temperatures

Wilk

Cernansky

Cohen

1986

Combustion Science and Technology

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An experimental study of the oxidation of propane in the temperature range 563-743 K was carried out using a static reactor. The oxidation mechanism was found to undergo a transition from a low temperature reaction regime ( T < 600 K) t o that of a n intermediate temperature regime (T > 650 K) separated by a region of negative temperature coefficient (600-650 K). In the lower temperature regime alkylperoxy radicals are formed and become the dominant radical species. These can react in several ways, the most important of which leads to the formation of hydroperoxides. Hydroperoxides were determined to be the main chain branching intermediates responsible for the acceleration of the reaction and for the formation of cool flames. At the intermediate temperatures hydroperoxyl radicals are dominant and lead to hydrogen peroxide. which is the main branching intermediate in this regime. These conclusions are based in large measure upon the hydrocarbon products formed which consist mainly of oxygenated species at the lower temperatures and lower alkanes and alkenes at the intermediate temperatures. The negative temperature coefficient and the change in mechanism are due to the competition between reactions involving the addition of OZ to the alkyl radical forming the alkylperoxy radical and reactions involving the abstraction of hydrogen from the alkyl radical by Oz to form the conjugate alkene and the hydroperoxyl radical. The effect of increasing the reaction vessel surface-tovolume ratio was t o enhance heterogeneous termination, resulting in longer reaction times. Comparison of the reaction products from vessels with different surface-to-volume ratios showed there t o be n o significant effect of surface on the main reaction paths of the mechanism. Some aspects of the mechanism at these temperatures are compared to those in the high temperature regime (T > 1000 K).

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“…Most of this work has been reviewed by McKay (1977), Pollard. (1977), Benson (1976Benson ( , 1981Benson ( , 1982, Minkoff and Tipper (1962), and Lewis and Von Elbe (1961).…”

Section: Introductionmentioning

confidence: 99%

The Oxidation of Propane at Low and Transition Temperatures

Wilk

Cernansky

Cohen

1986

Combustion Science and Technology

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“…Deep understanding on the combustion reaction mechanism of hydrocarbon is an urgent scientific goal [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17], and investigations on the reactions of reactive species such as hydrocarbon radicals can provide significant insights into combustion, hydrocarbon synthesis, interstellar space, and atmospheric chemistry. The reactivity of radicals which is very different from closed-shell molecules is extremely important in the reactions, e.g., between oxygen and hydrocarbon radicals.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrocarbon radicals are common intermediates in many chemical processes, and reactions of them with oxygen are important elementary steps in the atmospheric processes and combustion of hydrocarbons [1][2][3][4][5]. Deep understanding on the combustion reaction mechanism of hydrocarbon is an urgent scientific goal [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17], and investigations on the reactions of reactive species such as hydrocarbon radicals can provide significant insights into combustion, hydrocarbon synthesis, interstellar space, and atmospheric chemistry.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study on the reaction mechanism of O2 with C4H9• radical

Gong

2011

J Mol Model

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Ab initio calculations have been performed using the complete basis set model (CBS-QB3) to study the reaction mechanism of butane radical (C(4)H(9)•) with oxygen (O(2)). On the calculated potential energy surface, the addition of O(2) to C(4)H(9)• forms three intermediates barrierlessly, which can undergo subsequent isomerization or decomposition reaction leading to various products: HOO• + C(4)H(8), C(2)H(5)• + CH(2)CHOOH, OH• + C(3)H(7)CHO, OH• + cycle-C(4)H(8)O, CH(3)• + CH(3)CHCHOOH, CH(2)OOH• + C(3)H(6). Five pathways are supposed in this study. After taking into account the reaction barrier and enthalpy, the most possible reaction pathway is C(4)H(9)• + O(2) → IM1 → TS5 → IM3 → TS6 → IM4 → TS7 → OH• + cycle-C(4)H(8)O.

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Deoxygenation, Deaeration and Degassing: A Survey and Evaluation of Methods

Luyckx

Ceulemans

1987

Bulletin des Soc Chimique

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and classified according to their working principles. Consideration of these working principles reveals some inherent limitations of certain techniques and it may be concluded that the different methods complement each other in a number of aspects. Proton spin-lattice relaxation time measurements and polarographic analyses are used for evaluation of different deoxygenation methods.It is concluded that for most purposes the different methods yield satisfactory results if applied properly and within the inherent limitations of the techniques. When the presence of oxygen is very critical and its concentration must be reduced to very small amounts, a combination of methods appears advisable.Techniques for the removal of dissolved gases from liquids are reviewed

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Gas-phase oxidations of hydrocarbons

Cited by 19 publications

References 145 publications

The Oxidation of Propane at Low and Transition Temperatures

The Oxidation of Propane at Low and Transition Temperatures

A theoretical study on the reaction mechanism of O2 with C4H9• radical

Deoxygenation, Deaeration and Degassing: A Survey and Evaluation of Methods

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