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Kinetics of the gas phase reaction of hydroxyl radicals with ethane, benzene, and a series of halogenated benzenes over the temperature range 234–438 K

✍ Scribed by Timothy J. Wallington; Douglas M. Neuman; Michael J. Kurylo

Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
738 KB
Volume
19
Category
Article
ISSN
0538-8066

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✦ Synopsis

Absolute rate constants for the gas phase reactions of OH radicals with ethane ( k , ) . benzene ( k L ) , fluorobenzene ( k 3 i , chlorobenzene ( k 4 ) , bromobenzene ( h , ) , iodobenzene (kc;), and hexafluorobenzene (k,i have been measured over the temperature range 234-438 K using the flash photolysis resonance fluorescence technique. The rate constants measured a t room temperature (296 K), a t total pressures of argon diluent between 25 and 50 Torr, were (in units of cm3 molecule-' s I): k , = (2.30 2 0.261, k , = (12.9 -+ 1.4). k , = (6.31 i 0.811, k , = (7.41 2 0.941, k , = (9.15 2 0.97), k6 = (13.2 t 1.6). and k 1 = I 1.61 t 0.241, respectively. The indicated errors are our estimate of 95% confidence limits and include two standard deviations from the least-squares analysis together with an allowance for any possible systematic errors in the measurements. At elevated temperatures and under pseudo-first-order reaction conditions, non-exponential hydroxyl radical decays were observed for benzene and the monosubstituted halo-aromatics. For ethane and hexafluorobenzene, exponential decays were observed over the complete temperature range and the data were fit by the Arrhenius expressions: k , = ( 8 . 4 i 3.1) x 10 l 2 exp[(-lO50 t 1 0 0 i / T I a n d h: = (1.3 -+ 0 . 3 ) x 10 I' exp[( -610 2 8 0 ) / T 1. respectively. The results are compared with previous literature data and the mechanistic implications are discussed.

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