The gas‐phase decomposition of methylsilane. Part III. Kinetics

Sawrey, B. A.; O’Neal, H. E.; Ring, M. A.; Coffey, Dewitt

doi:10.1002/kin.550160106

Cited by 31 publications

(16 citation statements)

References 13 publications

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“…This can be interpreted in terms of a normal deuterium isotope rate effect for methylsilane of about 10-20%. This is also in fairly good agreement with our shock-tube results [2].…”

Section: Primary Dissociation Process Observationssupporting

confidence: 90%

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The gas‐phase decomposition of methylsilane. Part II. Mechanisms of decomposition under static system conditions

Sawrey

O’Neal

Ring

1984

Int J of Chemical Kinetics

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The static system pyrolysis of methylsilane ( T -700 K, PT -150 torr), pure and in the presence of ethylene, propylene, and acetylene, has been investigated. It is proposed that in the uninhibited system, the major products (silane and dimethylsilane) are produced by free radical processes, and that the free radicals are formed at the walls from methylsilylenes. In the presence of olefins, the free radicals are trapped to form methylsilane adducts. In acetylene, ,trapping of methylsilylenes prevents free radical production and eliminates the free radical produced products of the pure and the olefin inhibited systems. Rates of initiation correlate with rates of reactant loss in acetylene inhibited systems, and with rates of hydrogen formation in olefin inhibited systems. Rough estimates of primary dissociation process yields give for the 1,l-Hn elimination z 0.78, for the 1,2-H elimination 91,~ z 0.16, and for the methane elimination ~$ c H~ 0.06 at 700 K. Deuteration lowers initial step kinetics by about 15%.

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“…This can be interpreted in terms of a normal deuterium isotope rate effect for methylsilane of about 10-20%. This is also in fairly good agreement with our shock-tube results [2].…”

Section: Primary Dissociation Process Observationssupporting

confidence: 90%

“…111 [3]) in the high-pressure region were found to be in good agreement with Neudorfl and Strausz, giving log h , (s-l) = 15.29 -65,015 ca1/2.303RT…”

Section: Introductionsupporting

confidence: 72%

The gas‐phase decomposition of methylsilane. Part II. Mechanisms of decomposition under static system conditions

Sawrey

O’Neal

Ring

1984

Int J of Chemical Kinetics

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“…From shock tube pyrolysis studies, O'Neal and Ring and coworkers [12] [16,17]. This gives where the uncer-Ϫ1 E (1) ϭ 59 Ϯ 12 kJ mol a tainty largely comes from the experimental value for E a (Ϫ 1) but also from the uncertain temperature correction (from 1200 to 298 K).…”

Section: ϯ05mentioning

confidence: 97%

“…Previous estimates of E a (1)/kJ mol Ϫ1 were 42 [11] and 80 [12] from experiment (and thermochemistry) and 115 [18] and 87 [19] from ab initio theoretical calculations. Unfortunately, there is no information to estimate E a (2).…”

Section: ϫ1 ϫ1mentioning

confidence: 99%

“…This reaction may be regarded as a benchmark for C 9 H bond insertion, and since intramolecular C 9 H insertion by silylenes is known to occur [11], it seemed worthy of re-examination. Moreover, from other considerations this reaction is thought to have an activation barrier lying between 42 and 80 kJ Ϫ1 mol [11,12], and therefore an attempt to study it at elevated 10 molecule s this molecule has the potential for Si 9 C bond as well as C 9 H bond insertion.…”

Section: Introductionmentioning

confidence: 99%

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Communication:The insertion of silylene in C?H bonds; rate constant limits and the energy barrier

Becerra¹,

Walsh²

1999

Int. J. Chem. Kinet.

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The technique of laser flash photolysis has been used to set limits on the rate constants for the bimolecular reactions of SiH 2 with methane (CH 4 ) and tetramethylsilane (SiMe 4 ) at both ambient and elevated temperatures (ca 600 K). These limits show that the energy barriers to insertion reactions of SiH 2 in the C9 H bonds of CH 4 are at least 45(Ϯ6) kJ and in the C9 H and/or Si 9 C bonds of SiMe 4 are at least 23(Ϯ6) kJ The best Ϫ1 Ϫ1 mol mol . thermochemical estimate of the activation energy for is 59(Ϯ12) kJ Reasons Ϫ1SiH ϩ CH mol .2 4for the greatly diminished reactivity of SiH 2 with C9H as compared with Si 9 H bonds are discussed.

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Si/C Phases from the IR Laser-induced Decomposition of Silacyclobutane and 1,3-Disilacyclobutane

Bastl¹,

Bürger²,

Fajgаr³

et al. 1996

Appl. Organometal. Chem.

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CO2 laser‐induced infrared multiphoton decomposition (IRMPD) and SF6 photosensitized decomposition (LPD) of silacyclobutane (SCB) and 1,3‐disilacyclobutane (DSCB) in the gas phase results in the very efficient deposition of Si/C/H and SiC materials, and it is inferred that the process is dominated by formation of transient silene; silene rearrangement to methylsilylene; silene and methylsilylene dehydrogenation; and polymerization of SiCHn (n < 4) species. The deposits are sensitive to oxygen. Decomposition and SiC formation are favoured with IRMPD experiments conducted with high‐energy fluxes. The laser technique is promising for low‐temperature chemical vapour deposition of amorphous SiC.

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The gas‐phase decomposition of methylsilane. Part III. Kinetics

Cited by 31 publications

References 13 publications

The gas‐phase decomposition of methylsilane. Part II. Mechanisms of decomposition under static system conditions

The gas‐phase decomposition of methylsilane. Part II. Mechanisms of decomposition under static system conditions

Communication:The insertion of silylene in C?H bonds; rate constant limits and the energy barrier

Si/C Phases from the IR Laser-induced Decomposition of Silacyclobutane and 1,3-Disilacyclobutane

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