Kinetic study of the gas-phase reaction of OH with Br2.
Kinetic study of the gas-phase reaction of OH with Br2.
复制标题
OH 与 Br2 气相反应的动力学研究。
DOI：
10.1021/jp061038m
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
Knyazev,VadimD
中科院分区：
文献类型：
--
作者：
Bryukov,MikhailG;Dellinger,Barry;Knyazev,VadimD
An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed by using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297−766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A nonlinear least-squares fit with two floating parameters of the temperature-dependentk1(T) data set using an equation of the formk1(T) =ATnyields the recommended expressionk1(T) = (1.85 × 10-9)T-0.66cm3molecule-1s-1for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated with use of quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled by using the RRKM method on the basis of the calculated PES.
