Reactions of alkyl radicals. Part III. Relative rates of methylation and hydrogen abstraction by methyl radicals

1973 ◽  
pp. 484 ◽  
Author(s):  
Stephen J. Hammond ◽  
Gareth H. Williams
Keyword(s):  
Hydrogen Abstraction ◽  
Methyl Radicals ◽  
Alkyl Radicals

Hydrogen abstraction by methyl radicals in glasses

1984 ◽  
Vol 78 ◽  
pp. 175 ◽  
Author(s):  
Takahisa Doba ◽  
Keith U. Ingold ◽  
Willem Siebrand ◽  
Timothy A. Wildman
Keyword(s):  
Hydrogen Abstraction ◽  
Methyl Radicals

The homogeneous conversion of methane to higher hydrocarbons in the presence of ethylene in the temperature range 925–1023 K

1991 ◽  
Vol 69 (1) ◽  
pp. 37-42 ◽  
Author(s):  
Alain R. Bossard ◽  
Margaret H. Back
Keyword(s):  
Hydrogen Abstraction ◽  
Homogeneous System ◽  
Catalytic Reactions ◽  
The Other ◽  
Methyl Radicals ◽  
Temperature Range ◽  
Vinyl Radicals ◽  
Conversion Of Methane ◽  
Radical Distribution ◽  
Higher Hydrocarbons

Mixtures of ethylene and methane have been pyrolyzed in the temperature range 925–1023 K for the purpose of converting methane to higher hydrocarbons. Addition of methane to thermally-reacting ethylene increases the rate of formation of propylene but decreases the rates of formation of the other major products, ethane, acetylene, and butadiene. Hydrogen abstraction from methane is a major propagation reaction and causes a shift in the radical distribution from ethyl and vinyl radicals, the main radicals in the pyrolysis reactions of ethylene alone, to methyl radicals, which lead to the formation of propylene. At 1023 K with a pressure of ethylene of 6.5 Torr and of methane of 356 Torr, 1.5 mol of methane is converted to higher molecular weight products for every mole of ethylene reacted. The rate of conversion of methane in the homogeneous system is lower than in catalytic reactions but the product is entirely hydrocarbon and no methane is lost to carbon monoxide or carbon dioxide. Key words: methane, ethylene, kinetics, pyrolysis, fuels.

THE REACTIONS OF TRIFLUOROMETHYL RADICALS WITH PROPANE, n-BUTANE, AND ISOBUTANE

1956 ◽  
Vol 34 (2) ◽  
pp. 103-107 ◽  
Author(s):  
P. B. Ayscough ◽  
E. W. R. Steacie
Keyword(s):  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Methyl Radicals ◽  
Kcal Mole

A study of the reactions of trifluoromethyl radicals, produced by the photolysis of hexafluoroacetone, with propane, n-butane, and isobutane has been made. The rate constants of the hydrogen-abstraction reactions have been determined at temperatures between 27 °C and 119 °C and the activation energies found to be 6.5 ± 0.5, 5.1 ± 0.3, and 4.7 ± 0.3 kcal./mole respectively. These values are compared with those obtained for the reactions with methane and ethane, and with the corresponding reactions of methyl radicals.

Reactions of free radicals with aromatic compounds in the gaseous phase. II. Kinetics of the reaction of methyl radicals with phenol

1965 ◽  
Vol 18 (1) ◽  
pp. 20 ◽  
Author(s):  
MFR Mulcahy ◽  
DJ Williams
Keyword(s):  
Free Radicals ◽  
Gaseous Phase ◽  
Hydrogen Abstraction ◽  
High Reactivity ◽  
Phenoxy Radical ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Kinetics Of Formation ◽  
Phenolic Substances ◽  
Kinetics Of

Knowledge of the reactivity of phenols towards simple free radicals is needed to throw light on the behaviour of the phenolic substances involved in the pyrolysis of coal and other organic materials. In the present investigation the reaction between methyl radicals and phenol vapour has been studied a t total pressures from 0.5 to 3 cmHg and temperatures from 445 to 547°K, the concentrations of methyl radicals and phenol being varied from 2 × 10-12 to 4 × 10-11 and 1 × 10-8 to 8 × 10-7 mole cm-3 respectively. The main products identified by gas chromatography were methane and o- and p-cresol, together with a little anisole and 2,4- and 2,6-dimethylphenol. The cresols are produced via hydrogen abstraction Diagram followed by combination of a methyl radical at a ring position of the phenoxy radical either ortho or para to the oxygen atom, e.g. in the case of the para position: Diagram The kinetics can be explained by postulating (a) that the keto forms of the cresols (methylcyclohexadienones) formed initially by reaction (6) have a finite lifetime in the gaseous phase and (b) that these molecules, which contain a tertiary hydrogen atom α to a system of a carbonyl bond and two carbon-carbon double bonds, partly undergo hydrogen abstraction by methyl radicals before they are able to enolize: CH3· + (HCH3 = C6H4 = O → CH4 + CH3C6H4O· The mechanism is consistent with the kinetics of formation of methane, the distribu- tion of the free electron in the phenoxy radical, the formation of o- and p-cresols as major products, the kinetics of formation of the cresols, and the high reactivity of the intermediate product towards methyl radicals.

Mechanisms in metal-organic chemical vapour deposition

1990 ◽  
Vol 330 (1610) ◽  
pp. 183-193 ◽  
Keyword(s):  
Chemical Vapour Deposition ◽  
Vapour Deposition ◽  
Hydrogen Abstraction ◽  
Chemical Vapour ◽  
Morphological Characteristics ◽  
Current Status ◽  
Organic Chemical ◽  
Methyl Radicals ◽  
Carrier Gas ◽  
Metal Organic

The current status of our understanding of mechanistic details of GaAs growth by metal-organic chemical vapour deposition from various starting materials is reviewed. Despite a high level of recent activity in the study of precursor decomposition and reactivity there are still considerable gaps in our knowledge; for example, a clear differentiation between homogeneous (gas phase) and heterogenous (surfacecontrolled) processes is not yet possible. The decomposition of trimethylgallium in dihydrogen as carrier gas and the concomitant production of methane may occur by means of a radical process where hydrogen is abstracted by methyl radicals from the trimethylgallium rather than from the carrier gas. Triethylgallium on the other hand also offers the possibility of B-elimination as a facile pathway and this is reflected in the ratio ethene: ethane (3:1). In the presence of arsine there is a more facile pathway for hydrogen abstraction by alkyl radicals, giving rise in the case of triethylgallium and arsine to more ethane than ethene and in the case of trimethylgallium with arsine there is a difference in the reactivity to that found in studies of its decomposition in dihydrogen alone. Several workers have therefore deduced the participation of an intermediate adduct under growth conditions because arsine and trimethylgallium lower each others’ decomposition temperature significantly. However, it should be remembered that arsine is almost certainly a better donor of hydrogen to methyl radicals than is dihydrogen. Phenylarsine has been found to be a potentially useful alternative precursor to arsine for the preparation of epitaxial GaAs. Thin films with excellent electrical and morphological characteristics have been prepared. Phenylarsine decomposes in dihydrogen to yield benzene and arsine and in the presence of trimethylgallium and triethylgallium mechanisms similar to those found with trimethylgallium and triethylgallium with arsine are suggested. These appear not to involve the dihydrogen carrier gas.

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