Kinetic and Spectroscopic Studies of the Reaction of CF2 with H2 in Shock Waves.
Kinetic and Spectroscopic Studies of the Reaction of CF2 with H2 in Shock Waves.
复制标题
CF2 与 H2 在冲击波中反应的动力学和光谱研究。
DOI：
10.1021/acs.jpca.7b05859
复制
发表时间：
2017
期刊：
影响因子：
--
通讯作者：
J. Troe
中科院分区：
文献类型：
--
作者：
C. Cobos;G. Knight;L. Sölter;E. Tellbach;J. Troe
通过监测紫外吸收信号，研究了冲击波作用下CF2与H2的反应。CF2是由C2 F4（或c-C3 F6）的热分解制备的。发现在2000 K附近反应CF2 + H2 → CHF + HF的速率常数接近1011 cm 3 mol-1 s-1，与逆反应CHF + HF → CF2 + H2的早期信息和模型平衡常数一致。动力学研究伴随着光谱调查。在1000 K附近测量了C2 F4在190和220 nm之间的吸收截面，并与文献中的室温值进行了比较。同样，在210和300 nm之间测量了2000 K附近CF2的吸收截面，并与室温数据进行了比较。在反应过程中记录了额外的叠加吸收信号，并通过它们的时间依赖性和采用时间依赖性密度泛函理论的量子化学计算来确定。一个以前未知的吸收光谱CHF自由基附近200 nm的确定和其波长依赖性。在190和300 nm之间的进一步强吸收归因于CH 2F和CF自由基。在较长的波长，达到510 nm的吸收，被假定产生的C2自由基形成在反应的后期阶段。
The reaction of CF2 with H2 was studied in shock waves by monitoring UV absorption signals. CF2 was prepared by thermal dissociation of C2F4 (or of c-C3F6). The rate constant of the reaction CF2 + H2 → CHF + HF near 2000 K was found to be close to 1011 cm3 mol-1 s-1, consistent with earlier information on the reverse reaction CHF + HF → CF2 + H2 and a modeled equilibrium constant. The kinetic studies were accompanied by spectroscopic investigations. Absorption cross sections of C2F4 between 190 and 220 nm were measured near 1000 K and compared with room-temperature values from the literature. Likewise, absorption cross sections of CF2 near 2000 K were measured between 210 and 300 nm and compared with room-temperature data. Additional superimposed absorption signals were recorded during the reaction and identified by their time dependence and by quantum-chemical calculations employing time-dependent density functional theory. A previously unknown absorption spectrum of CHF radicals near 200 nm was identified and its wavelength dependence determined. Further strong absorptions between 190 and 300 nm were attributed to CH2F and CF radicals. Absorptions at longer wavelengths, reaching up to 510 nm, were postulated to arise from C2 radicals formed at later stages of the reaction.
CH2F2 I初级过程解离的冲击波和理论模拟研究
DOI：
10.1021/acs.jpca.7b05854
发表时间：
2017
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
C. J. Cobos;Hintzer;L. Sölter;E. Tellbach;A. Thaler;J. Troe
通讯作者：
J. Troe
CH2F2 II 二次反应解离的冲击波和理论模型研究
DOI：
10.1021/acs.jpca.7b05857
发表时间：
2017
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
C. J. Cobos;G. Knight;L. Sölter;E. Tellbach;J. Troe
通讯作者：
J. Troe