Rice-Ramsperger-Kassel-Marcus theoretical prediction of high-pressure arrhenius parameters by nonlinear regression: application to silane and disilane decomposition

Journal Article · Thu Oct 22 00:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100306a043· OSTI ID:5678410

Roenigk, K F; Jensen, K F; Carr, R W

Arrhenius parameters are estimated for silane and disilane thermal decomposition reactions by direct regression of RRKM predictions on published static and shock-tube data. For silane decomposition, they find E/sub infinity/ = 57.4-61.1 kcal/mol and log A/sub infinity/ = 14.9-16.3, while for disilane they find E/sub infinity/ = 51.1-52.5 kcal/mol and log A/sub infinity/ = 15.2-16.2. The lower limiting values correspond to inclusion of negative temperature dependence in the collision efficiency, while the higher values correspond to inclusion of weak or negligible temperature dependence. The Arrhenium parameters for both silane and disilane decomposition differ substantially from previously published values. For silane, they predict preexponentials approximately an order of magnitude greater than the previous values for the same activation energy. For disilane, they find A/sub infinity/ is roughly an order of magnitude higher than the literature values and E/sub infinity/ is greater by more than 2 kcal/mol. Falloff curves for both silane and disilane decomposition are given. Implications of these results for the activation energy of SiH/sub 2/ insertion into H/sub 2/ and SiH/sub 4/ and for ..delta..H/sub f//sup 0/(SiH/sub 2/) are discussed.

• Research Organization: Univ. of Minnesota, Minneapolis
• OSTI ID: 5678410
• Journal Information: J. Phys. Chem.; (United States), Vol. 91:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SILANES
DECOMPOSITION
ARRHENIUS EQUATION
ENERGY TRANSFER
HIGH PRESSURE
MATHEMATICAL MODELS
REGRESSION ANALYSIS
SHOCK TUBES
TEMPERATURE DEPENDENCE
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
CHEMICAL REACTIONS
DATA
EQUATIONS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
MATHEMATICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
PHYSICAL PROPERTIES
SILICON COMPOUNDS
STATISTICS
400201* - Chemical & Physicochemical Properties