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Association reactions of atoms and radicals
Author(s) -
Pilling Michael J.
Publication year - 1989
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.550210406
Subject(s) - chemistry , extrapolation , radical , thermodynamics , limiting , atmospheric temperature range , master equation , range (aeronautics) , reaction rate constant , computational chemistry , kinetics , quantum mechanics , mathematical analysis , organic chemistry , physics , mechanical engineering , materials science , mathematics , engineering , composite material , quantum
The pressure and temperature dependences of association reactions involving atoms and/or radicals is discussed and illustrated by reference to the reactions CH 3 + CH 3 → C 2 H 6 , CH 3 + O 2 → CH 3 O 2 , CH 3 + H → CH 4 , and H + C 2 H 4 → C 2 H 5 . Recent experimental measurements of the rate coefficients, k ([M], T ) are described, particular attention being paid to experiments designed to measure the rate coefficient over wide ranges of pressure and temperature. Methods of fitting the experimental data, to obtain estimates of the limiting rate coefficients, k 0 and k ∞ , and to permit extrapolation to regions beyond the experimental range, are discussed. These methods include the Troe factorization technique, a combination of master equation and variational RRKM theory, and recent calculations by Wagner and Wardlaw using the technique developed by Wardlaw and Marcus to describe loose transition states.