Premium
Abstraction of chlorine atoms from chloromethanes by the cyclohexyl radical
Author(s) -
Katz M. G.,
Horowitz A.,
Rajbenbach L. A.
Publication year - 1975
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550070203
Subject(s) - chemistry , arrhenius equation , chlorine , radical , chlorine atom , halogen , bromine , reaction rate constant , medicinal chemistry , kinetics , activation energy , organic chemistry , alkyl , physics , quantum mechanics
The kinetics of chlorine atom abstraction from the chloromethanes (CM)CCl 4 , CHCl 3 , and CH 2 Cl 2 by radiolytically generated cyclohexyl radicals has been studied in the liquid phase by a competitive method. The halogen abstraction data have been put on an absolute basis by comparing the rates of the metathetical reactions with the known rate of addition of cyclohexyl radicals to C 2 Cl 4 . The following Arrhenius parameters were obtained: TextCM log A (CM)/ A (C 2 Cl 4) E (CM) E (C 2 Cl 4 )(kcal/mole) log A (CM)(1./mole·sec) E (CM) (kcal/mole) Temperaure Range(°K)CCl 4 0.72±0.02 −1.42±0.05 9.40±0.08 5.88±0.15 333–453 CHCl 3 0.77±0.06 2.86±0.01 9.45±0.12 10.16±0.11 392–492 CH 2 Cl 2 0.56±0.12 6.37±0.27 9.42±0.18 13.67 ± 0.37 463–543The error limits are the standard deviations from least mean square Arrhenius plots. The possible application of the Evans–Polanyi relationship to chlorine atom abstraction reaction from CM is considered.