The homogeneous gas-phase decomposition kinetics of methylsilane and methylsilane-d3 have been investigated by the comparative-rate-single-pulse shock-tube technique a t total pressures of 4700 torr in the 1125-1250 K temperature range. Three primary processes occur:CH:$iH3 -CH3SiH + HS (l), CH3SiH3 -CH4 + SiHz (2), and CH3SiH3 -CHa = SiH2 + H2 (3). The high-pressure rate constants for the primary processes in CH3SiH3 obtained by RRKM calculations are log ( k l + k s ) (s-l) = 15.2 -64,780 cal/@ and log kz (s-l) = 14.50
The kinetics and mechanism of the thermal decomposition of n-propylsilane have been studied by the single pulse shock tube-comparative rate technique a t pressures
The gas-phase decompositions of methylsilane and methylsilane-d3 have been investigated in a single-pulse shock tube at 4700 torr total pressure in the temperature range of 1125-1250
The static system pyrolysis of methylsilane ( T -700 K, PT -150 torr), pure and in the presence of ethylene, propylene, and acetylene, has been investigated. It is proposed that in the uninhibited system, the major products (silane and dimethylsilane) are produced by free radical processes, and that the free radicals are formed at the walls from methylsilylenes. In the presence of olefins, the free radicals are trapped to form methylsilane adducts. In acetylene, ,trapping of methylsilylenes prevents free radical production and eliminates the free radical produced products of the pure and the olefin inhibited systems. Rates of initiation correlate with rates of reactant loss in acetylene inhibited systems, and with rates of hydrogen formation in olefin inhibited systems. Rough estimates of primary dissociation process yields give for the 1,l-Hn elimination z 0.78, for the 1,2-H elimination 91,~ z 0.16, and for the methane elimination ~$ c H~ 0.06 at 700 K. Deuteration lowers initial step kinetics by about 15%.
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