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气相反应 CH3 + HO2 的动力学。

Kinetics of the gas phase reaction CH3 + HO2.

机构信息

Department of Chemistry and Environmental Science, New Jersey Institute of Technology, University Heights, Newark, New Jersey 07102, USA.

出版信息

J Phys Chem A. 2013 Apr 11;117(14):2916-23. doi: 10.1021/jp4000889. Epub 2013 Apr 1.

Abstract

Reaction of methyl radicals with hydroperoxy radicals, CH3 + HO2 → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy at 295 K and 1 bar (He). Photolysis of N2O/H2O2/CH4/H2O/He mixtures at 193.3 nm (ArF excimer laser) was used to simultaneously produce methyl radicals and hydroperoxy radicals in reactions of electronically excited oxygen atoms O((1)D) with CH4 and OH radicals with H2O2, respectively. Temporal profiles of CH3 and HO2 were recorded via absorption at 216.4 and 224 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The measured rate constant of reaction 1 is k1 = (3.7 ± 1.8 × 10(-11) cm(3) molecule(-1) s(-1) (295 K, 1 bar, He).

摘要

甲基自由基与过氧自由基反应,CH3 + HO2 → 产物 (1),在 295 K 和 1 巴(氦气)下使用脉冲激光光解结合瞬态紫外可见吸收光谱进行了研究。通过在 193.3nm(ArF 准分子激光)下用光解 N2O/H2O2/CH4/H2O/He 混合物,分别用光解电子激发态氧原子 O((1)D)与 CH4 的反应和 OH 自由基与 H2O2 的反应,同时产生甲基自由基和过氧自由基。通过在 216.4nm 和 224nm 处的吸收,记录了 CH3 和 HO2 的时间曲线。通过在分子氧存在下基于臭氧形成的准确原位化学发光法,确定了反应器内光解光的绝对强度。反应 1 的测量速率常数为 k1 = (3.7 ± 1.8 × 10(-11) cm(3) molecule(-1) s(-1) (295 K, 1 bar, He)。

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