Reactions of cyanogen radical with alkanes and an explanation for negative temperature dependence of rate constants

Rao, Sreedhara V and Chandra, AK (1995) Reactions of cyanogen radical with alkanes and an explanation for negative temperature dependence of rate constants. In: Chemical Physics, 192 (3). pp. 247-254.

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Abstract

Reactions of cyanide radicals with alkanes have been investigated by ab initio methods. It is found that the potential energy surface for reaction of CN with a primary C-H bond in methane has a small positive barrier while reactions of CN with a secondary and a tertiary C-H bond in alkanes are barrierless at the correlated level. A simple explanation for the obtained negative temperature dependence of rate constants for reactions of CN with a secondary and a tertiary C-H bond in alkanes are given in terms of the collision theory of bimolecular reactions. It is shown that for barrierless reactions the negative temperature dependence of the rate constants is attributed to the variation of the pre-exponential factor with temperature.

Item Type:	Journal Article
Publication:	Chemical Physics
Publisher:	Elsevier Science
Additional Information:	Copyright of this article belongs to Elsevier Science.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	24 May 2011 07:06
Last Modified:	24 May 2011 07:06
URI:	http://eprints.iisc.ac.in/id/eprint/37875

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