The kinetics of oxidation of hydrocarbons in the gas phase. A theory of the low-temperature mechanism

1951 ◽  
Vol 10 ◽  
pp. 259 ◽  
Author(s):  
M. F. R. Mulcahy
Keyword(s):  
Low Temperature ◽  
Gas Phase ◽  
Kinetics Of Oxidation ◽  
Oxidation Of Hydrocarbons ◽  
Kinetics Of

Gas-Phase Kinetics of the N + C2N Reaction at Low Temperature

2015 ◽  
Vol 119 (13) ◽  
pp. 3194-3199 ◽  
Author(s):  
James W. Stubbing ◽  
Gianmarco Vanuzzo ◽  
Audrey Moudens ◽  
Jean-Christophe Loison ◽  
Kevin M. Hickson
Keyword(s):  
Low Temperature ◽  
Gas Phase ◽  
Gas Phase Kinetics ◽  
Kinetics Of

On the Low-Temperature Oxidation of Processed Peat

1997 ◽  
Vol 15 (2) ◽  
pp. 162-171 ◽  
Author(s):  
J.C. Jones
Keyword(s):  
Low Temperature ◽  
Low Temperature Oxidation ◽  
Temperature Oxidation ◽  
Kinetics Of Oxidation ◽  
The Difference ◽  
Kinetics Of

Small amounts of processed peat have been examined in a microcalorimeter. Kinetics of oxidation are different from those previously re ported for the same material using much larger samples. The difference is at least in part due to loss of volatiles during the initial conditioning of a sample in the microcalorimeter.

The kinetics of the catalytic oxidation over palladium of some alkanes and cycloalkanes

1976 ◽  
Vol 349 (1659) ◽  
pp. 523-534 ◽  
Keyword(s):  
Gas Phase ◽  
Surface Oxidation ◽  
Reaction Rates ◽  
Optimum Operating ◽  
Optimum Operating Temperature ◽  
Kinetics Of Oxidation ◽  
Low Concentrations ◽  
Diffusion Effects ◽  
Kinetics Of

Measurements have been made of the kinetics of oxidation over palladium of the C 1 to C 4 alkanes, cyclopropane and cyclohexane in the temperature range 588-873 K by means of a microcalorimetric bead technique. With an initially reduced and degassed catalyst, reaction rates for the alkanes increase from C 1 to C 4 , while butane, cyclopropane and cyclohexane are of comparable reactivity. The rates of oxidation of the alkanes are significantly increased when the catalyst is preheated in oxygen, and cyclo­propane oxidation is markedly enhanced by this procedure. Reactions are inhibited by gas-phase diffusion effects, particularly at higher tempera­tures; there is thus apparent inhibition by oxygen. All the reactions are preceded by the surface oxidation of the catalyst, this latter process having an activation energy of 176 ± 18 kJ mol -1 . Reaction appears to involve the interaction of hydrocarbon from the gas phase with palladium oxide, followed by the rapid desorption of carbon dioxide and the slower desorption of water. Large concentrations of water vapour cause a loss of catalytic activity, probably due to the formation of palladium hydroxide. When the bead system is used for the detection of low concentrations of hydrocarbons, the optimum operating temperature lies between 793 and 723 K, decreasing as the hydrocarbons become more reactive. The most significant single factor governing response is the heat of combustion, so that this method is most sensitive for the determination of high molecular mass hydrocarbons.

The kinetics of oxidation of benzaldehyde. I

1953 ◽  
Vol 216 (1124) ◽  
pp. 10-29 ◽  
Keyword(s):  
Benzene Solution ◽  
Point Of View ◽  
Peroxide Formation ◽  
Kinetics Of Oxidation ◽  
Oxidation Of Hydrocarbons ◽  
Complicated Manner ◽  
Short Period ◽  
The Relationship ◽  
Kinetics Of ◽  
Dibenzoyl Peroxide

For the study of the mechanism of oxidation of hydrocarbons and other organic compounds it is desirable to find systems suitable for kinetic study in which the mechanism of peroxide formation is not complicated by autocatalysis. The oxidation of benzaldehyde in benzene solution in the absence of light has been examined from this point of view. It was found that in the absence of catalysts and inhibitors consistently reproducible rates of oxidation are to be obtained only with special precautions in the preparation and handling of the materials. For a short period after the beginning of the reaction, the amount of peroxide in the solution corresponds closely to the oxygen taken up. There is no sign of autocatalysis. The reaction, on the contrary, is self-inhibiting. The rate of oxidation is extremely sensitive to the presence of inhibitors, the effect of 10~e mole /?-naphthol/mole solution being easily detected. The reaction is catalyzed by dibenzoyl peroxide according to the relationship ρ = ρ u + k [ Bz 2 O 2 ]1/2 , P and pu being the initial rates in the presence and absence of dibenzoyl peroxide respectively and k a constant. Two conclusions are drawn from this result: (i) in the peroxide catalyzed reaction the chains are terminated by mutual interaction and (ii) the mechanism of the uncatalyzed dark reaction involves different chain carriers from those of the catalyzed reaction. In the presence of dibenzoyl peroxide both reactions take place simultaneously but independently. The oxidation is also catalyzed, though in a rather more complicated manner, by Pyrex glass.

Gas-Phase Kinetics of the Hydroxyl Radical Reaction with Allene: Absolute Rate Measurements at Low Temperature, Product Determinations, and Calculations

2012 ◽  
Vol 116 (45) ◽  
pp. 10871-10881 ◽  
Author(s):  
Julien Daranlot ◽  
Kevin M. Hickson ◽  
Jean-Christophe Loison ◽  
Raphaël Méreau ◽  
Françoise Caralp ◽  
...  
Keyword(s):  
Low Temperature ◽  
Hydroxyl Radical ◽  
Gas Phase ◽  
Radical Reaction ◽  
Absolute Rate ◽  
Gas Phase Kinetics ◽  
Kinetics Of
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