ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The temperature dependence of the rate coefficients for the OH radical reactions with toluene, benzene, o-cresol, m-cresol, p-cresol, phenol, and benzaldehyde were measured by the competitive technique under simulated atmospheric conditions over the temperature range 258-373 K. The relative rate coefficients obtained were placed on an absolute basis using evaluated rate coefficients for the corresponding reference compounds. Based on the rate coefficient k(OH + 2,3-dimethylbutane) = 6.2 × 10-12 cm3 molecule-1s-1, independent of temperature, the rate coefficient for toluene kOH = 0.79 × 10-12 exp[(614 ± 114)/T] cm3 molecule-1 s-1 over the temperature range 284-363 K was determined. The following rate coefficients in units of cm3 molecule-1 s-1 were determined relative to the rate coefficient k(OH + 1,3-butadiene) = 1.48 × 10-11 exp(448/T) cm3 molecule-1 s-1: o-cresol; kOH = 9.8 × 10-13 exp[(1166 ± 248)/T]; 301-373 K; p-cresol; kOH = 2.21 × 10-12 exp[(943 ± 449)/T]; 301-373 K; and phenol, kOH = 3.7 × 10-13 exp[(1267 ± 233)/T]; 301-373 K. The rate coefficient for benzaldehyde kOH = 5.32 × 10-12 exp[(243 ± 85)/T], 294-343 K was determined relative to the rate coefficient k(OH + diethyl ether) = 7.3 × 10-12 exp(158/T) cm3 molecule-1 s-1. The data have been compared to the available literature data and where possible evaluated rate coefficients have been deduced or updated. Using the evaluated rate coefficient k(OH + toluene) = 1.59 × 10-12 exp[(396 ± 105)/T] cm3 molecule-1 s-1, 213-363 K, the following rate coefficient for benzene has been determined kOH = 2.58 × 10-12 exp[(-231 ± 84)/T] cm3 molecule-1 s-1 over the temperature range 274-363 K and the rate coefficent for m-cresol, kOH = 5.17 × 10-12 exp[(686 ± 231)/T] cm3 molecule-1 s-1, 299-373 K was determined relative to the evaluated rate coefficient k(OH + o-cresol) = 2.1 × 10-12 exp[(881 ± 356)/T] cm3 molecule-1 s-1. The tropospheric lifetimes of the aromatic compounds studied were calculated relative to that for 1,1,1-triclorethane = 6.3 years at 277 K. The lifetimes range from 6 h for m-cresol to 15.5 days for benzene. © 1995 John Wiley & Sons, Inc.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550270307
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