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Generation of ground electronic state haloalkyl radicals in the gas phase
Author(s) -
Holmes B. E.,
Paisley S. D.,
Rakestraw D. J.,
King E. E.
Publication year - 1986
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 - 10.1002/1097-4601(198606)18:6<639::aid-kin550180604>3.0.co;2-m
Subject(s) - chemistry , halide , radical , photodissociation , mercury (programming language) , photochemistry , bond cleavage , reaction rate constant , gas phase , ground state , iodine , decomposition , inorganic chemistry , kinetics , catalysis , organic chemistry , atomic physics , physics , quantum mechanics , computer science , programming language
Gaseous haloalkyl radicals were prepared by the photolysis of iodohaloalkanes in Pyrex vessels containing mercury (I) halides. Cleavage of the carbon‐iodine bond gave mercury (II) halide and a radical which was subsequently shown to react on the ground state electronic energy surface. The usefulness of this method for chemical activation rate constant studies is illustrated by measurement of unimolecular rate constants for decomposition of CH 2 ClCH 2 Cl and CF 3 CH 3 . Possible mechanisms for photodecomposition of iodoalkanes in the presence of mercury (I) halides are discussed.