Abstract
The homogeneous gas-phase decomposition of methylgermane has been investigated by the comparative rate-single-pulse shock tube technique at 3100 torr of total pressure between 1050 and 1250 K. Three primary processes occur: CH/sub 3/GeH/sub 3/ ..-->.. CH/sub 3/GeH + H/sub 2/ (1), CH/sub 3/GeH/sub 3/ ..-->.. CH/sub 4/ + GeH/sub 2/ (2), and CH/sub 3/GeD/sub 3/ ..-->.. CH/sub 2/ = GeD/sub 2/ + HD (3). The overall decomposition rate constant in its pressure falloff regime is log k/sub 0/ (s/sup -1/) = 13.34 - 50,420 + - 3700 cal/theta, comprised of about 40% of reaction 1, and 30% each of reactions 2 and 3; and the high-pressure rate constants for the primary processes, obtained by RRKM calculations, are log k/sub 1/ (s/sup -1/) = 14.6 - 50,400 cal/theta, and log k/sub 2/ (s/sup -1/) = 14.9 - 51,600 cal/theta, and log k/sub 3/ (s/sup -1/) = 14.7 - 51,600 cal/theta. The decomposition of the primary product methylgermylene (CH/sub 3/GeH) to CH/sub 3/ and GeH radicals increases with increasing temperature with an activation energy of about 53 kcal, while the decomposition of germylene (GeH/sub 2/) to Ge and H/sub 2/ is fast and complete at shock temperatures.
Published Version
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