Journal of Physical Chemistry, Vol.98, No.28, 6995-7003, 1994
Unimolecular Decomposition of Methyltrichlorosilane - Rrkm Calculations
On the basis of reaction thermochemistry and estimates of Arrhenius A factors, it is expected that Si-C bond cleavage, C-H bond cleavage, and HCl elimination will be the primary channels for the unimolecular decomposition of methyltrichlorosilane. Using RRKM theory, we calculated rate constants for these three reactions. The calculations support the conclusion that these three reactions are the major decomposition pathways. Rate constants for each reaction were calculated in the high-pressure limit (800-1500 K) and in the falloff regime (1300-1500 K) for bath gases of both helium and hydrogen. These calculations thus provide branching fractions as well as decomposition rates. We also calculated bimolecular rate constants for the overall decomposition in the low-pressure limit. Interesting and surprising kinetic behavior of this system and the individual reactions is discussed. The reactivity of this chlorinated organosilane is compared to that of other organosilanes.
Keywords:CHEMICAL VAPOR-DEPOSITION;VIBRATIONALLY EXCITED MOLECULES;COLLISIONAL ENERGY-TRANSFER;FLEXIBLE TRANSITION-STATES;RANDOM-WALK MODEL;RECOMBINATION REACTIONS;SILICON-CARBIDE;RATE CONSTANTS;LOW-PRESSURES;H SYSTEM