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Rate constants for the bimolecular self‐reaction of cyano‐substituted alkyl radicals in solution
Author(s) -
Korth H. G.,
Lommes P.,
Sicking W.,
Sustmann R.
Publication year - 1983
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.550150306
Subject(s) - chemistry , radical , hydrogen atom abstraction , reaction rate constant , photochemistry , kinetics , electron paramagnetic resonance , alkyl , spectroscopy , organic chemistry , nuclear magnetic resonance , physics , quantum mechanics
Cyano‐substituted methyl radicals (cyanomethyl–hand 2‐cyano‐2‐propyl radicals) and syn ‐and anti ‐1‐cyano‐allyl radicals were generated, and their recombination kinetics in solution were investigated between −50 and +50°C by time‐resolved electron‐spin‐resonance spectroscopy. The comparison of the activation energies for recombination with the activation energies of the solution viscosities proves that the dimerizations of the radicals are diffusion controlled with rate constants on the order of 10 8 –10 9 M −1 ·s −1 . In the case of cyanomethyl radicals an additional pseudo‐first‐order process, hydrogen abstraction, was detected and analyzed kinetically. Product analyses support the kinetic measurements.