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Direct rate measurements of the combination and disproportionation of vinyl radicals

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100365a040· OSTI ID:6879226
 [1];  [2]
  1. National Institute of Standards and Technology, Gaithersburg, MD (USA)
  2. Dept. of Energy, Washington, DC (USA)
The rates of removal of vinyl radicals (C{sub 2}H{sub 3}) by means of combinations and disproportionation reactions have been directly measured at room temperature. Vacuum-ultraviolet (vacuum-UV) flash photolysis of divinylmercury was used to generate vinyl radicals, and vacuum-UV absorption kinetic spectroscopy was used to monitor the time history of vinyl radicals through their absorption at 1647.1 {angstrom}. The absolute rate constant for vinyl radical decay was determined to be 1.0 {times} 10{sup {minus}10} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. A ratio of 4.7 for the combination/disproportionation rate constants was measured by gas chromatographic analysis of the final reaction products. Absorption coefficients for the vinyl radical absorption in the 1,650-{angstrom} region were redetermined. The absolute rate constants for combination and disproportionation are then 8.2 {times} 10{sup {minus}11} and 1.8 {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, respectively.
OSTI ID:
6879226
Journal Information:
Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:2; ISSN 0022-3654; ISSN JPCHA
Country of Publication:
United States
Language:
English