Liquid-phase reactions of CCl/sub 3/ radicals with trimethylsilane and triethylsilane. [Gamma rays]
The ..gamma..-radiation-induced chain reactions in liquid solution of silane (R'/sub 3/SiH) in CCl/sub 4/-c-C/sub 6/H/sub 12/(RH) mixtures were investigated over the temperature range 303-423 K for R' = Me and 335-423 K for R' = Et. In both systems the main products are R'/sub 3/SiCl, CHCl/sub 3/, and RCl. By kinetic analyses of product distribution, the rate constants of hydrogen abstraction from the two silanes by CCl/sub 3/ radicals were competitively determined vs. hydrogen abstraction from cyclohexane. The relative rate constants combined with the known Arrhenius parameters of the reference systems gave the following Arrhenius parameters for the reaction CCl/sub 3/ + R'/sub 3/SiH ..-->.. CHCl/sub 3/ + R'/sub 3/Si: log A/sub 4/ (L mol/sup -1/s/sup -1/) = 8.49 and E/sub 4/ = 8.70 kcal mol/sup -1/ when R' = Me, and log A/sub 4/ = 8.62 and E/sub 4/ = 8.06 when R' = Et. These results indicate that alkyl-substituted silanes are considerably more reactive than Cl/sub 3/SiH in the H-atom transfer reactions with CCl/sub 3/ radicals. This observation is rationalized in terms of the polar effects of the alkyl substituents.
- Research Organization:
- Soreq Nuclear Research Center, Yavne, Israel
- OSTI ID:
- 6873524
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Journal Issue: 20 Vol. 84:20; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400600* -- Radiation Chemistry
ALKANES
ARRHENIUS EQUATION
CARBON TETRACHLORIDE
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CYCLOALKANES
CYCLOHEXANE
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
EQUATIONS
FLUIDS
GAMMA RADIATION
HALOGENATED ALIPHATIC HYDROCARBONS
HIGH TEMPERATURE
HYDROCARBONS
IONIZING RADIATIONS
KINETICS
LIQUIDS
MEDIUM TEMPERATURE
MIXTURES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
REACTION KINETICS
SILICON COMPOUNDS