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Absolute rate constants for the reactions between amino and alkyl radicals at 298 K
Author(s) -
Demissy M.,
Lesclaux R.
Publication year - 1982
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.550140102
Subject(s) - chemistry , radical , isopropyl , flash photolysis , alkyl , reaction rate constant , photochemistry , medicinal chemistry , organic chemistry , kinetics , physics , quantum mechanics
The absolute rate constants for the reactions of NH 2 radicals with ethyl, isopropyl, and t ‐butyl radicals have been measured at 298 K, using a flash photolysis–laser resonance absorption method. Radicals were generated by flashing ammonia in the presence of an olefin. A new measurement of the NH 2 extinction coefficient and oscillator strength at 597.73 nm was performed. The decay curves were simulated by adjusting the rate constants of both the reaction of NH 2 with the alkyl radical and the mutual interactions of alkyl radicals. The results are k (NH 2 + alkyl) = 2.5 (±0.5), 2.0 (±0.4), and 2.5 (±0.5) × 10 10 M −1 ·s −1 for ethyl, isopropyl, and t ‐butyl radicals, respectively. The best simulations were obtained when taking k (alkyl + alkyl) = 1.2, 0.6, and 0.65 × 10 10 M −1 ·s −1 for ethyl, isopropyl, and t ‐butyl radicals, respectively, in good agreement with literature values.