化学学报 ›› 1988, Vol. 46 ›› Issue (1): 82-84. 上一篇    下一篇

研究论文

用分子束研究.F(^2P)与CH3F和CH3Cl的化学反应

史济良;李方琳;蒋锡夔;邱元武;周士康;刘颂豪   

  1. 中国科学院上海有机化学研究所;中国科学院安徽光学精密机械研究所
  • 发布日期:1988-01-15

A molecular beam study of the reactions of fluorine atoms with CH3F and CH3Cl

SHI JILIANG;LI FANGLIN;JIANG XIKUI;QIU YUANWU;ZHOU SHIKANG;LIU SONGHAO   

  • Published:1988-01-15

近年来, 我们在研究含氟烯烃和烷烃的红外激光诱导氧化和氯化反应的基础上, 深入研究了红外激光诱导卤代烷烃的脱卤化氢并生成: CF2卡宾和:CFCF3卡宾的反应[1-4]以往的研究往往是根据反应产物推论反应机理, 认为在反应过程中存在着卡宾中间体,但在实验中未能直接检测到. Kakimoto[5,6]曾报道过在流动体系中测到了.F+CH3F和.F+CH3Cl反应中:CHF和:CHCl的激光荧光激发谱, 但没有讨论卡宾形成的机理.Hirota[7]在讨论.F+CH3F反应时, 认为:CHF可能由攫氢过程产生而对于.F+CH3Cl反应同时生成:CHF和:CHCl未做说明. 本实验中用扩散分子束代替了流动反应体系, 从而大大减少了产物和反应物气体分子间的猝灭过程, 获得了信噪比大而清晰的图谱, 由此确证了:CHF和:CHCl的存在, 说明了.F+CH3Cl反应中自由基攫氢过程和偶合反应过程共存的反应历程. 这一结论对红外激光诱导一碳卤代宾化学反应机理研究有重要参考意义.

关键词: 甲烷 P, 反应机理, 氟, 氯代烃, 碳烯, 游离基, 猝灭效应, 氟代烃, 自由基反应, 激光光谱法

The reactions of fluorine atoms with CH3F and CH3Cl have been investigated by mol. beam set-up and laser spectroscopy. In these systems, in addition to the hydrogen abstraction reactions, radical coupling reactions also occur. Furthermore, the chemiluminescence of HF has also been observed in these reactions. These results are valuable for the discussion of laser induced chem. reaction mechanism.

Key words: METHANE P, REACTION MECHANISM, FLUORINE, CHLOROHYDROCARBON, CARBENE, FREE RADICAL, QUENCHING EFFECTS, FLUOROHYDROCARBON, FREE RADICAL REACTION, LASER SPECTROMETRY

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