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The reactions of methyl radicals with chloromethanes

✍ Scribed by Kenneth V. Macken; Howard W. Sidebottom

Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
745 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis

The reactions of methyl radicals with CC14 and CC13Br have been reinvestigated in the gas phase over a wide range of temperatures and pressures using both the photolysis of acetone and the pyrolysis of di-tertiary butyl peroxide (dtBP) as the methyl radical sources. The results are in essential agreement with previous work; however, these new studies provide evidence that a t higher pressures the major source of HCl in the reactions is due to methyl radical attack on CH3CC13, formed via the combination of methyl and trichloromethyl radicals.

From these investigations Arrhenius parameters for the reactions

(2)

have been determined:

Pyrolysis of dtBP in the presence of relatively high-pressure mixtures of CCl4 and CClsBr resulted in no enhanced methane formation, since, under these conditions, the only termination product is CzC16, and the HC1 precursor CHsCC13 is not formed. A competitive technique has been used in which dtBP was pyrolysed in the gas phase in the presence of high-pressure mixtures of CCl3Br and a chloromethane. Arrhenius parameters were obtained for the reactions (19) CHy + CH4-,Cln + CH4 + CH3-,Cln* (11.6 f 0.2 kca) RT k ~~( c H ~c I ) = 109.'*0.' expl/mol.sec (9.0 f i : kca) l/mol-sec k1$I(CH2C12j = iOs.8*o.4 exp -

and the results were used to provide information on the importance of polar effects for hydrogen abstraction from halogenated methanes.

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