Kinetic Study of the Temperature Dependence of OH-Initiated Oxidation of n-Dodecane.

Abstract

Reaction rate constants for the reaction of n-dodecane with hydroxyl radicals were measured as a function of temperature between 283 and 303 K, using the relative rate method in the CESAM chamber (French acronym for "experimental multiphasic atmospheric simulation chamber"). The rate constants obtained at 283, 293, and 303 K are (1.27 ± 0.31) × 10-11, (1.33 ± 0.34) × 10-11, and (1.27 ± 0.40) × 10-11 cm3 molecule-1 s-1, respectively. Rate constants measured were in excellent agreement with the few available data in the literature over the studied temperature range (283-340 K). Rate constants estimated by the structure-activity relationship and transition state theory methods agreed with our experimental data within 14%. From these data combined with previous literature measurement, the following Arrhenius expression, kDDC+OH = (9.77 ± 6.19) × 10-11 × exp[(-595 ± 5580)/T] cm3 molecule-1 s-1, was found to be valid over a temperature range (283-340 K) of the tropospheric interest.