Kinetics of the gas-phase reaction of OH with chlorobenzene.
Kinetics of the gas-phase reaction of OH with chlorobenzene.
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DOI：
10.1021/jp9049186
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发表时间：
2009-10-01
期刊：
影响因子：
--
通讯作者：
Dellinger B
中科院分区：
文献类型：
--
作者：
Bryukov MG;Knyazev VD;Gehling WM Jr;Dellinger B
The kinetics of the reaction of hydroxyl radicals with chlorobenzene was studied experimentally using a pulsed laser photolysis/pulsed laser induced fluorescence technique over a wide range of temperatures, 298-670 K, and at pressures between 13.33 and 39.92 kPa. The bimolecular rate constants demonstrate different behavior at low and high temperatures. At room temperature, T = 298.8±1.5 K, the rate constant is equal to (6.02 ± 0.34)×10-13 cm3 molecule-1 s-1; at high temperatures (474 - 670 K), the rate constant values are significantly lower and have a positive temperature dependence that can be described by an Arrhenius expression k1(T ) = (1.01 ± 0.35)×10-11 exp[(-2490 ± 170 K)/T] cm3 molecule-1 s-1. This behavior is consistent with the low-temperature reaction being dominated by reversible addition and the high-temperature reaction representing abstraction and addition-elimination channels. The potential energy surface of the reaction was studied using quantum chemical methods and a transition state theory model was developed for all reaction channels. The temperature dependences of the high-temperature rate constants obtained in calculations using the method of isodesmic reactions for transition states (IRTS) and the CBS-QB3 method are in very good agreement with experiment, with deviations smaller than the estimated experimental uncertainties. The G3//B3LYP-based calculated rate constants are in disagreement with the experimental values. The IRTS-based model was used to provide modified Arrhenius expressions for the temperature dependences of the rate constant for the abstraction and addition-elimination (Cl replacement) channels of the reaction.
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影响因子：
4.4
作者：
Montgomery, JA;Frisch, MJ;Petersson, GA
通讯作者：
Petersson, GA
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
--
作者：
GONZALEZ, C;SCHLEGEL, HB
通讯作者：
SCHLEGEL, HB
影响因子：
2.9
作者：
Knyazev, VD
通讯作者：
Knyazev, VD
影响因子：
1.5
作者：
MULDER, P;LOUW, R
通讯作者：
LOUW, R