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Methyl‐radical association studied by time‐resolved mass spectroscopy
Author(s) -
Truby Frank K.,
Rice James K.
Publication year - 1973
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.550050502
Subject(s) - chemistry , torr , dissociation (chemistry) , photodissociation , kinetics , analytical chemistry (journal) , flash photolysis , spectroscopy , mass spectrometry , reaction rate constant , photochemistry , thermodynamics , chromatography , physics , quantum mechanics
Time‐resolved mass spectroscopy has been utilized to study the kinetics of methylradical association. The rate coefficient for the association process was determined by following the time dependence of ethane formation after flash photolysis of CH 3 I in the presence of N 2 . The net rate coefficient for the process 2CH 3 (+M) → C 2 H 6 (+M) has a high‐pressure limit of (4.0 ± 0.3) × 10 −11 cm 3 molecule −1 sec −1 at 313°K. This rate coefficient has found to be insensitive to the third‐body number densities for pressures ranging from 13 Torr down to below 0.5 Torr, indicating that the lifetime for dissociation of the intermediate C 2 H 6 * species is greater than 2 × 10 −7 sec at 313°K for a gas pressure of 0.5 Torr.