Temperature-dependent kinetics study of the gas-phase reactions of OH with n- and i-propyl bromide.
An experimental, temperature-dependent kinetics study of the gas-phase reactions of hydroxyl radical with n-propyl bromide, OH+n-C3H7Br-->products (reaction 1), and i-propyl bromide, OH+i-C3H7Br-->products (reaction 2), has been performed over wide ranges of temperatures 297-725 and 297-715 K, respectively, and at pressures between 6.67 and 26.76 kPa by a pulsed laser photolysis/pulsed laser-induced fluorescence technique. Data sets of absolute bimolecular rate coefficients obtained in this study for reactions 1 and 2 demonstrate no correlation with pressure and exhibit positive temperature dependencies that can be represented with modified three-parameter Arrhenius expressions within their corresponding experimental temperature ranges: k1(T)=(1.32x10(-17))T1.95 exp(+25/T) cm3 molecule(-1) s(-1) for reaction 1 and k2(T)=(1.56x10(-24))T4.18exp(+922/T) cm3 molecule(-1) s(-1) for reaction 2. The present results, which extend the current kinetics data base of reactions 1 and 2 to high temperatures, are compared with those from previous works. On the basis of the present data and available data from previous studies, the following bimolecular rate coefficient temperature dependencies can be recommended for the purpose of kinetic modeling: k1(T)=(1.89x10(-19))T2.54exp(+301/T) cm3 molecule-1 s-1 for reaction 1 in a temperature range 210-725 K, and k2(T)=(2.83x10(-21))T3.1exp(+521/T) cm3 molecule(-1) s(-1) and k2(T)=(4.54x10(-24))T4.03exp(+860/T) cm3 molecule(-1) s(-1) for reaction 2 in temperature ranges 210-480 and 297-715 K, respectively.
Bryukov
Mikhail G
MG
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
Vidrine
Rebecca G
RG
Dellinger
Barry
B