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在 294-714 K 的温度和 1-100 巴的压力范围内研究了 CH3 + OH 的反应。

Reaction CH3 + OH studied over the 294-714 K temperature and 1-100 bar pressure ranges.

机构信息

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

出版信息

J Phys Chem A. 2012 Aug 30;116(34):8661-70. doi: 10.1021/jp305070c. Epub 2012 Aug 17.

Abstract

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 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 results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).

摘要

甲基自由基与羟基自由基的反应,CH(3) + OH → 产物 (1),在 294-714 K 的温度和 1-100 巴的压力范围内(浴气体为 He)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。甲基自由基通过在 193.3nm 处光解丙酮产生。羟基自由基通过在 193.3nm 处光解 N(2)O 产生的电子激发氧原子 O((1)D)与 H(2)O 反应生成。通过使用氙弧灯和光谱仪在 216.4nm 处记录 CH(3)的吸收时间曲线;通过在约 308nm 处使用直流放电 H(2)O/Ar 低压共振灯的瞬态吸收监测 OH 自由基。反应器内光解光的绝对强度通过基于分子氧存在下臭氧形成的准确原位光化学法确定。这项研究的结果表明,在所研究的压力和温度范围内,反应 1 的速率常数与压力无关,并且具有轻微的负温度依赖性,k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1)。

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