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Kinetic and thermochemical parameters of chlorine atom transfer reactions from CF 3 Cl, CF 3 CF 2 Cl, CF 2 ClCF 2 Cl, and CF 2 ClCFCl 2 in gas phase
Author(s) -
Taccone R. A.,
Salinovich O.,
Staricco E. H.
Publication year - 1989
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.550210504
Subject(s) - chemistry , halogen , arrhenius equation , chlorine , chlorine atom , radical , bond dissociation energy , dissociation (chemistry) , isotopes of chlorine , bromine , standard enthalpy change of formation , kinetic energy , atom (system on chip) , standard enthalpy of formation , activation energy , medicinal chemistry , organic chemistry , alkyl , physics , quantum mechanics , computer science , embedded system
The following reactions:were studied over the temperature ranges 533–687 K, 563–663 K, and 503–613 K for the forward reactions respectively and over 683–763 K, for the back reaction. Arrhenius parameters for chlorine atom transfer were determined relative to the combination of the attacking radicals. The ΔH r °(1) = −3.95 ± 0.45 kcal mol −1 was calculated and from this value the ΔH∮(C 2 F 5 Cl) = −2.66.3 ± 2.5 kcal mol −1 and D(C 2 F 5 ‐Cl) = 82.0 ± 1.2 kcal mol −1 were obtained. Besides, the ΔH r °(2) was estimated leading to D(CF 2 ClCF 2 Cl) = 79.2 ± 5 Kcal mol −1 . The bond dissociation energies and the heat of formation are compared with those of the literature. The effect of the halogen substitutents as well as the importance of the polar effects for halogen transfer processes are discussed.