The decomposition kinetics of disilane and the heat of formation of silylene

Martin, J. G.; Ring, M. A.; O’Neal, H. E.

doi:10.1002/kin.550190805

Cited by 53 publications

(38 citation statements)

References 16 publications

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“…The value k 6 was taken from [54] in which the pressure dependence of this rate constant was obtained by RRKM calculations for the case of undiluted silane. To use these data in our conditions we took into account the collision efficiency of argon relative to silane [56]. Note that the initial rate of silane con-␤ ϭ 0.2 sumption must be close to double the rate of reaction (6) because reaction (6) is accompanied by fast reaction (7).…”

Section: Kinetic Modelingmentioning

confidence: 99%

Studying of silane thermal decomposition mechanism

Onischuk

Strunin

Ushakova

et al. 1998

Int. J. Chem. Kinet.

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The mechanism of silane thermal decomposition is investigated in a flow reactor. The time dependencies of silane consumption and disilane formation were compared with those parameters of solid product (aerosol particles) such as concentration, total hydrogen content in solid product, and fraction of hydrogen contained in solid product as polyhydride groups (SiH 2 ) n . Silane loss and gaseous product formation were analyzed using a mass spectrometer. The hydrogen content in solid product was analyzed by the methods of IR-spectroscopy and hydrogen evolution. Based on a simple kinetic scheme we qualitatively explained the experimental dependencies of silane conversion and disilane formation, the effective activation energy of the decomposition process, and the amount of polyhydride groups in the solid product on reaction time and initial silane concentration.

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Section: Kinetic Modelingmentioning

confidence: 99%

Studying of silane thermal decomposition mechanism

Onischuk

Strunin

Ushakova

et al. 1998

Int. J. Chem. Kinet.

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“…Martin, Ring and O'Neal reexamined the pyrolysis of Si 2 H 6 (equation 3) in a static reactor and found both the high-pressure A-factor (10 15.6 to 10 16.0 s 1 ) and E a (51.2 kcal mol 1 ) to be higher than previously determined 12 . Walsh argued in 1988 that the A-factors for the disilanes Me n H 3 n SiSiH 3 were all higher than the previous experimentally based estimates (with the exception of Me 2 HSiSiH 3 ) 13 . Walsh's higher suggested activation parameters for MeH 2 SiSiH 3 were very close to those subsequently found (log A D 15.6 suggested versus 15.53š0.…”

Section: A Thermolysis Of Polysilanesmentioning

confidence: 77%

Silylenes

Gaspar¹,

West²

2009

Patai's Chemistry of Functional Groups

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Introduction Generation of Silylenes Reactions of Silylenes Theoretical Calculations Spectroscopic Characterization of Silylenes Kinetics of Silylene Reactions Silylene–Transition Metal Complexes Special Topics Speculations on the Future of Silylene Chemistry

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“…2 The ES decomposition was studied over a 53 K range (695-748 K) using reactant mixtures of ethylsilane and tetramethylsilane (TMS). The latter served as an internal analytical GC standard and as a third-body bath gas.…”

Section: Methodsmentioning

confidence: 99%

Mechanism of the Thermal Decomposition of Ethylsilane

Jardine¹,

O’Neal²,

Ring³

et al. 1995

J. Phys. Chem.

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Products and kinetics of the thermal decomposition of ethylsilane, under static system conditions, are reported. Both neat and propylene-inhibited reactions follow silylene chain mechanisms. Modeling fits to product yield and reactant loss data establish approximate values for the rate constants of the ethylsilylene decomposition to ethylene and silylene (kz * 2 x lo6 s-I) and the ethylsilylene isomerization to vinylsilane (ks 5 x lo2 s-l), both at 723 K. RRKh4 and thermochemical analyses of these results yield values for the high-pressure activation energy of the ethylsilylene decomposition (EtSiH -C2& + SiH2) of E2 = 25.0 kcal/mol and a heat of formation for ethylsilylene of AHdEtSiH) = 47.7 f 2.5 kcal/mol. An enthalpy group additivity for the methylene group in organosilanes and organosilylenes of AHf[C-(H2)(C)(Si)] = -1.3 f 2 kcal/mol is deduced as well as the activation energy of the isomerization of ethylsilylene to vinylsilane (EtSiH -.CHz-CHSiH3) of E8 = 35.6 f 2 kcal/mol. 2 8

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The decomposition kinetics of disilane and the heat of formation of silylene

Abstract: The static system decomposition kinetics of disilane (Si,H, A SiH, + SiH,, 538-587 K and 10-500 Torr), are reported. Reaction rate constants are weakly pressure dependent. and best fits of the data are realized with RHKM fall-off calculations using IogA,,.

Cited by 53 publications

References 16 publications

Studying of silane thermal decomposition mechanism

Studying of silane thermal decomposition mechanism

Silylenes

Mechanism of the Thermal Decomposition of Ethylsilane

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