Formation of HCOH + H 2 through the reaction CH 3 + OH. Experimental evidence for a hitherto undetected product channel

In an extension of our earlier studies at lower temperatures [4,5] the title reaction was measured directly in a flow reactor at temperatures of 600 and 700 K. The pressure of 0.65 mb was chosen that low in order to reduce the contribution of the stabilization channel. OH was used in an excess over CH 3 . Both reactants along with the reaction products were monitored by mass spectrometry. CH 3 profiles served as the major observable quantity for the extraction of rate data. This had to be done by using computer simulation since it was impossible to work under pseudo‐first‐order conditions. The obtained total rate coefficients were divided into channel rate coefficients by means of branching ratios as determined by the mass spectrometric measurement of the reaction products. For CH 3 + OH, this led to a rate coefficient, k 1a into the stabilization channel, and another one, k 1e + f referring to the sum of two H 2 ‐eliminating channels yielding the biradical HCOH and to a minor extent H 2 CO. These latter channels have not been measured before. In order to distinguish between them we switched over from OH to OD to getso that the biradical and/or aldehyde channels could be determined by their by‐products H 2 and HD, respectively. The use of OD makes it also possible to measure the channelthrough its by‐product, HDO. A comparison of the rate coefficients of both systems, i.e., CH 3 + OH and CH 3 + OD, indicates that within our error limits no significant isotope effect takes place. For the rate coefficient into the HCOH channel, we arrive at a preliminary Arrhenius expression in units of cm, molec, and s:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1{\rm e}} \,\, = \,\,9.1 \times 10^{ - 11} \,{\rm exp}\left({{{ - 15000} \mathord{\left/ {\vphantom {{ - 15000} T}} \right. \kern-\nulldelimiterspace} T}} \right) $$\end{document} . The H 2 CO channel could not be detected at our lower temperature rendering us with a rate coefficient at 700 K:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1{\rm f}} \left({700\,{\rm K}} \right)\,\, = \,\,1.7 \times 10^{ - 12} $$\end{document} . Since simulation is needed for the deduction of the total rate coefficients as well as of the branching ratios, an uncertainty factor of 1.5 has to be attributed to these numbers. © 1995 John Wiley & Sons, Inc.