Kinetics of the reactions of Cl*(2P(1/2)) and Cl(2P(3/2)) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K.
Kinetics of the reactions of Cl*(2P(1/2)) and Cl(2P(3/2)) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K.
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295 K 下 Cl*(2P(1/2)) 和 Cl(2P(3/2)) 原子与 CH3OH、C2H5OH、n-C3H7OH 和 i-C3H7OH 反应的动力学。
DOI：
10.1021/jp050055t
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
T. Wallington
中科院分区：
文献类型：
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作者：
F. Taketani;Kenshi Takahashi;Y. Matsumi;T. Wallington
采用激光闪光光解/激光诱导荧光（FP-LIF）技术研究了标题反应。两个自旋轨道状态，Cl*（2 P（1/2））和Cl（2 P（3/2）），使用LIF分别在135.2和134.7 nm处检测到。测定的反应速率常数如下（单位：cm 3分子（-1）s（-1））：K（Cl（2P（3/2））+CH3OH）=（5.35 +/- 0.24）x 10（-11），k（Cl（2P（3/2））+C2H5OH）=（9.50 +/- 0.85）× 10（-11），k（Cl（2P（3/2））+n-C3H7OH）=（1.71 +/- 0.11）× 10（-10），和k（Cl（2P（3/2））+i-C3H7OH）=（9.11 +/- 0.60）× 10（-11）。Cl*（2 P（1/2））在与CH 3OH、C2 H5 OH、n-C3 H7 OH和i-C3 H7 OH碰撞中的总去除的测量速率常数为：分别为（1.95 +/- 0.13）x 10（-10）、（2.48 +/- 0.18）x 10（-10）、（3.13 +/- 0.18）x 10（-10）和（2.84 +/- 0.16）x 10（-10）;引用的误差为两个标准差。虽然自旋-轨道激发的Cl*（2 P（1/2））原子比Cl（2 P（3/2））具有2.52 kcal/mol的能量，但Cl*（2 P（1/2））与CH 3OH、C2 H5 OH、n-C3 H7 OH和i-C3 H7 OH的化学反应速率仅为相应Cl（2 P（3/2））原子反应的60-90%。在环境条件下，自旋-轨道激发的Cl* 原子分别对CH 3OH，C2 H5 OH，n-C3 H7 OH和i-C3 H7 OH的热化Cl原子的反应性的0.5%，0.5%，0.4%和0.7%负责。
The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm3 molecule(-1) s(-1)): k(Cl(2P(3/2))+CH3OH) = (5.35 +/- 0.24) x 10(-11), k(Cl(2P(3/2))+C2H5OH) = (9.50 +/- 0.85) x 10(-11), k(Cl(2P(3/2))+n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(2P(3/2))+i-C3H7OH) = (9.11 +/- 0.60) x 10(-11). Measured rate constants for total removal of Cl*(2P(1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-10), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(2P(1/2)) atoms have 2.52 kcal/mol more energy than Cl(2P(3/2)), the rates of chemical reaction of Cl*(2P(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(2P(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.