Formation of silylgermane by a silylene insertion reaction in the infrared photochemistry of monosilane-monogermane mixtures
The infrared photodecomposition at 944.2 cm/sup -1/ of silane-germane mixtures has been studied over a pressure range of 24-46 torr and over a temperature range of 295-356 K. The products observed are hydrogen, disilane, silylgermane, trace amounts of trisilane, and solid polymeric material. Digermane formation was not observed. The primary photodecomposition of SiH/sub 4/ is to SiH/sub 2/ + H/sub 2/; this is followed by insertion of SiH/sub 2/ into an Si-H bond of SiH/sub 4/ or a Ge-H bond of GeH/sub 4/ to form Si/sub 2/H/sub 6/ or SiH/sub 3/GeH/sub 3/, respectively. On the basis of these studies, the competitive rates of SiH/sub 3/GeH/sub 3/ and Si/sub 2/H/sub 6/ formation as a function of temperature and those in the literature relative to the absolute rate of insertion of SiH/sub 2/ into SiH/sub 4/, the value k/sub 2/ = 10/sup 10.4+/-0.5/ exp(-10.7 +/- 5.3 x 10/sup 3/ J/RT) L mol/sup -1/ s/sup -1/ for the specific reaction rate of insertion of SiH/sub 2/ into a Ge-H bond of germane is derived. 30 references, 4 figures.
- Research Organization:
- Pennsylvania State Univ., University Park
- OSTI ID:
- 5816282
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:25; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
ACTIVATION ENERGY
ARRHENIUS EQUATION
CARBON DIOXIDE LASERS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ENERGY
EQUATIONS
EXPERIMENTAL DATA
GAS LASERS
GERMANIUM COMPOUNDS
GERMANIUM HYDRIDES
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
QUANTITY RATIO
REACTION KINETICS
SILANES
SILICON COMPOUNDS
SYNTHESIS