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The oxidation of methyl radicals at room temperature
Author(s) -
Parkes D. A.
Publication year - 1977
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.550090313
Subject(s) - neopentane , chemistry , radical , torr , mass spectrometry , analytical chemistry (journal) , reaction rate constant , kinetics , physics , molecule , thermodynamics , chromatography , organic chemistry , quantum mechanics
Using the technique of molecular modulation spectrometry, we have measured directly the rate constants of several reactions involved in the oxidation of methyl radicals at room temperature:k 1 is in the fall‐off pressure regime at our experimental pressures (20–760 torr) where the order lies between second and third and we obtain an estimate for the second‐orderlimit of (1.2 ± 0.6) × 10 −12 cm 3 /molec · sec, together with third‐order rate constants of (3.1 ± 0.8) × 10 −31 cm 6 /molec 2 · sec with N 2 as third body and (1.5 ± 0.8) × 10 −30 with neopentane;we cannot differentiate between k 2a and k 2c and we conclude k 2a + ( k 2c ) = (3.05 ± 0.8) × 10 −13 cm 3 /molec · sec and k 2b = (1.6 ± 0.4) × 10 −13 cm 3 /molec · sec;k 3 = (6.0 ± 1.0) × 10 −11 cm 3 /molec · sec.