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Absolute rate coefficients for methyl radical reactions by laser photolysis, time-resolved infrared chemiluminescence: CD/sub 3/ + HX. -->. CD/sub 3/H + X(X = Br, I)

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100277a046· OSTI ID:6013233
Absolute rate coefficients are reported for the room temperature reactions of deuterated methyl radicals with HI and HBr, CD/sub 3/ + HI (HBr) ..-->.. CD/sub 3/H + I(Br). Excimer laser photolysis of CD/sub 3/I is used to generate methyl radicals, and time-resolved infrared chemiluminescence from the CH stretch of the CD/sub 3/H products is detected to follow the time evolution of the reaction. The rate constants obtained in this manner are (7.7 +/- 0.7) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ for CD/sub 3/ + HI and (4.7 +/- 0.4) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ for CD/sub 3/ + HBr. These rate constants are considerably greater than earlier, indirectly measured values and indicate that the activation energy for these light-atom transfer reactions is lower than previously believed. 53 references, 3 figures, 2 tables.
Research Organization:
National Bureau of Standards, Boulder, CO
OSTI ID:
6013233
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:5; ISSN JPCHA
Country of Publication:
United States
Language:
English