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Kinetic study of the reaction of OH with H/sub 2/ and D/sub 2/ from 250 to 1050/sup 0/K

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j150617a018· OSTI ID:6255674
Absolute rate coefficients for the reactions OH + H/sub 2/ ..-->.. H/sub 2/O + H (k/sub 1/) and OH + D/sub 2/ ..-->.. DHO + D (k/sub 2/) have been measured between 250 and 1050/sup 0/K by using the flash photolysis-resonance fluorescence technique. The adaptation of the flash photolysis-resonance fluorescence technique to high-temperature studies is described. The measured values of k/sub 1/ and k/sub 2/ exhibit non-Arrhenius behavior. k/sub 1/ and k/sub 2/ are best described by three-parameter functions, k/sub 1/(T) = (4.12 x 10/sup -19/)T/sup 2/ /sup 44/ exp(-1281/T) cm/sup 3/ molecule/sup -1/ s/sup -1/ and k/sub 2/(T) = (4.37 x 10/sup -15/)T/sup 1/ /sup 18/ exp(-2332/T) cm/sup 3/ molecule/sup -1/ s/sup -1/ over the entire temperature range 250 to 1050/sup 0/K. Alternatively, at low temperatures k/sub 1/ and k/sub 2/ can be described by Arrhenius expressions, k/sub 1/(T) = (4.9 +- 0.5) x 10/sup -12/ exp(-(1.99 +- 0.34) x 10/sup 3//T) cm/sup 3/ molecule/sup -1/ s/sup -1/ for 250 < T < 400/sup 0/K and k/sub 2/(T) = 1.21 +- 0.52) x 10/sup -11/ exp(-(2.67 +- 0.15) x 10/sup 3//T) cm/sup 3/ molecule/sup -1/ s/sup -1/ for 250 < T < 470/sup 0/K. The results are compared with theoretical calculations based on an ab initio potential energy surface for reaction 1.
Research Organization:
Georgia Inst. of Tech., Atlanta
OSTI ID:
6255674
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:17; ISSN JPCHA
Country of Publication:
United States
Language:
English