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Recombination of methyl radicals. 1. New data between 1175 and 1750 K in the falloff region

Journal Article · · Journal of Physical Chemistry
DOI:https://doi.org/10.1021/jp951217w· OSTI ID:199404
;  [1];  [2]
  1. Argonne National Lab., IL (United States)
  2. Earlham College, Richmond, IN (United States)

The rate coefficient for the recombination of methyl radicals, CH{sub 3} + CH{sub 3} {yields} C{sub 2}H{sub 6}, was measured in incident shock-wave experiments on azomethane (0.12-1.3%) in argon. Methyl radicals were detected at 46294 cm{sup -1} (215.94 nm in air) by the tunable-laser flash absorption technique. Postshock pressures between 114 and 230 kPa (1.13-2.27 atm) produced buffer gas concentrations between 5.4 x 10{sup 18} and 1.1 x 10{sup 19} cm{sup -3}. The cross section for optical absorption, the rate of dissociation of azomethane, and the rate coefficient of the recombinational reaction were determined simultaneously by least-squares analysis of methyl absorption profiles. The rate coefficient for the dissociation of azomethane from 850 to 1430 K is k{sub dis}(T) = 2.22 x 10{sup 39}T{sup -7.99} exp[C@-25920/T(K)] s{sup -1}. The temperature- dependent rate of recombination at 1.2 atm compares favorably with previous measurements. In terms of the phenomenological three-parameter equation of Kooji and the asymmetric Lorentzian broadening function of Gilbert et al., the recombination data from 296 to 1800 K is described by the equation given here. 37 refs., 6 figs., 3 tabs.

OSTI ID:
199404
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 3 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English