ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Part I: Kinetic data for the static system silane pyrolysis (from 640-703 K, 60-400 torr) are presented. For conversion from 3-30%, first-order kinetics are obtained, with silane loss rates equal to half the hydrogen formation rates. At conversions greater than 40%, rate inhibition attributable to the back reaction of hydrogen with silylene occurs. Overall reaction rates are not surface sensitive, but disilane and trisilane yield maxima under some conditions are. A nonchain mechanism capable of describing quantitatively all stages of the silane pyrolysis is proposed. Post 1.0% initiation is both homogeneous (gas phase) and heterogeneous (on the walls), and reaction intermediates are silylenes and disilenes. Free radicals are not involved at any stage of the reaction. Rate data at high conversions and with added hydrogen provide kinetics for the addition of silylene to hydrogen [reaction (-1)1] relative to its addition to silane [reaction (2)]: k-1,/k2 = 10-0.65 × e-3200 cal/RT. With E2 = 1300 cal, this gives a high pressure activation energy for silylene insertion into hydrogen of E-1 = 8200 cal.Part II: An analysis is made of each rate constant of the silane mechanism and the modeling results are compared with experimental results. Agreement is excellent. It is concluded that the dominant sink reaction for silylene intermediates is 1,2 - H2 elimination from disilane (followed by Si2H4 polymerization and wall deposition). The model is in accord with slow isomerization between disilene and silylsilylene and near exclusive 1,2 - H2 elimination from Si2H6. It is also concluded that disilene is about 10 kcal/mol more stable than silylsilylene and that the activation energy for isomerization of silylsilylene to disilene is greater than 26 kcal/mol.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550171003
Permalink
