✦ LIBER ✦

Bond dissociation energies and radical heats of formation in CH3Cl, CH2Cl2, CH3Br, CH2Br2, CH2FCl, and CHFCl2

✍ Scribed by E. Tschuikow-Roux; S. Paddison

Publisher: John Wiley and Sons
Year: 1987
Tongue: English
Weight: 595 KB
Volume: 19
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550190103

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✦ Synopsis

An analysis of thermochemical and kinetic data on the bromination of the halomethanes CH, ,X,, (X = F, C1, Br; n = 1-31, the two chlorofluoromethanes, CH,FCI and CHFCl,, and CH,, shaws that the recently reported heats of formation of the radicals CH2C1, CHClz, CHBr2, and CFC12, and the C-H bond dissociation energies in the matching halomethanes are not compatible with the activation energies for the corresponding reverse reactions. From the observed trends in CH, and the other halomethanes, the following revised AH;z98 (R ) values have been derived: 4.H,"(CH2C1) = 29.1 -+ 1.0, A.H;(CHC12) = 23.5 t 1.2, AHf"(CH2Br) = 40.4 t 1.0, AHf"(CHBr2) = 45.0 * 2.2, and DSI,"(CFC12) = -21.3 5 2.4 kcal mol-l. The previously unavailable radical heat of formation, DSI,"(CHFCl) = -14.5 +-2.4 kcal mo1-' has also been deduced. These values are used with the heats of formation of the parent compounds from the literature to evaluate C-H and C-X bond dissociation energies in CH,

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