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The temperature coefficient of the rates in the system Cl + CH4 ⇆ CH3 + HCl, thermochemistry of the methyl radical

✍ Scribed by Shawn P. Heneghan; Peter A. Knoot; Sidney W. Benson

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
578 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

The bimolecular rate constant for the title reaction has been measured by very-low-pressure reactor techniques a t 233 < T K < 338. The equilibrium constant has also been measured between 253 and 338 K. Our rate constants are in excellent agreement with recent measurements using very different techniques and reaction conditions, and the general agreement probably makes this one of the most accurately measured rate constants. Transition state models of the reaction rule out a bent TS in favor of a TS with colinear Cl-H--C bonds. The curvature at higher temperatures (>350 K) is quantitatively accounted for by transition state theory analysis. Tunneling is shown not to play a role. The measured values of K1 allow an experimental value of So (CH3) to be fixed to only f2.4 e.u. However, using known values of So for all species gives AH; 298(CHr) = 35.1 f 0.1 kcal/mol in excellent agreement with other measured values.

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