DOI: 10.1002/kin.550111104. Kinetics and mechanism of the silane decomposition

Kinetics and mechanism of the silane decomposition

10.1002/kin.550111104

Crossref journal-article

Wiley

International Journal of Chemical Kinetics (311)

Abstract

AbstractThe homogeneous gas‐phase decomposition kinetics of silane has been investigated using the single‐pulse shock tube comparative rate technique (T = 1035–1184˚K, Ptotal ≈︁ 4000 Torr). The initial reaction of the decomposition SiH4 \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm SiH}_{\rm 4} \mathop \to \limits^1 {\rm SiH}_{\rm 2} + {\rm H}_{\rm 2} $\end{document} SiH2 + H2 is a unimolecular process in its pressure fall‐off regime with experimental Arrhenius parameters of logk1 (sec−1) = 13.33 ± 0.28–52,700 ± 1400/2.303RT. The decomposition has also been studied at lower temperatures by conventional methods. The results confirm the total pressure effect, indicate a small but not negligible extent of induced reaction, and show that the decomposition is first order in silane at constant total pressures. RRKM‐pressure fall‐off calculations for four different transition‐state models are reported, and good agreement with all the data is obtained with a model whose high‐pressure parameters are logA1 (sec−1) = 15.5, E1(∞) = 56.9 kcal, and ΔE0±0(1) = 55.9 kcal. The mechanism of the decomposition is discussed, and it is concluded that hydrogen atoms are not involved. It is further suggested that silylene in the pure silane pyrolysis ultimately reacts with itself to give hydrogen: 2SiH2 → (Si2H4)* → (SiH3SiH)* → Si2H2 + H2. The mechanism of H ⟷ D exchange absorbed in the pyrolysis of SiD4‐hydrocarbon systems is also discussed.

Bibliography

Newman, C. G., Oâneal, H. E., Ring, M. A., Leska, F., & Shipley, N. (1979). Kinetics and mechanism of the silane decomposition. International Journal of Chemical Kinetics, 11(11), 1167â1182. Portico.

Authors 5

C. G. Newman (first)
H. E. O'neal (additional)
M. A. Ring (additional)
F. Leska (additional)
N. Shipley (additional)

References 26 Referenced 152

10.1021/ja00486a058
10.1021/ja01292a036
{'key': 'e_1_2_1_4_2', 'first-page': '1', 'article-title': 'Investigations on Silanes with Light and Heavy Hydrogen', 'volume': '3', 'author': 'Stockland K.', 'year': '1950', 'journal-title': 'K. Nor. Vidensk. Selsk. Skr.'} / K. Nor. Vidensk. Selsk. Skr. / Investigations on Silanes with Light and Heavy Hydrogen by Stockland K. (1950)
10.1098/rspa.1966.0189
10.1021/ja00719a015
10.1021/j100644a001
10.1063/1.1679522
{'key': 'e_1_2_1_9_2', 'first-page': '2136', 'volume': '43', 'author': 'Varma R. D.', 'year': '1965', 'journal-title': 'Can. J. Chem.'} / Can. J. Chem. by Varma R. D. (1965)
10.1021/ja00882a014
10.1002/kin.550080302
{'key': 'e_1_2_1_11_3', 'first-page': '917', 'year': '1972', 'journal-title': 'Chem. Lett.'} / Chem. Lett. (1972)
10.1021/ja00512a018
10.1021/ja00419a055
10.1021/ja00752a033
10.1021/j100491a022
10.1016/0022-1902(65)80125-7
R.Ditchfield M. A.Jensen andJ. N.Murrell J. Chem. Soc. A 1674(1967). (10.1039/J19670001674)
10.1021/ic50066a033
10.1021/ja50001a034
10.1063/1.1725353
10.1021/ja01280a040
10.1021/ja00821a009
10.1063/1.1696193
10.1002/kin.550020406
10.1021/j100789a036
C. G.Newman Ph.D. thesis San Diego State University 1979.

Dates

Type	When
Created	20 years, 8 months ago (Dec. 28, 2004, 12:23 p.m.)
Deposited	1 year, 10 months ago (Oct. 18, 2023, 2:27 p.m.)
Indexed	4 weeks ago (Aug. 7, 2025, 4:32 p.m.)
Issued	45 years, 10 months ago (Nov. 1, 1979)
Published	45 years, 10 months ago (Nov. 1, 1979)
Published Online	20 years, 10 months ago (Oct. 19, 2004)
Published Print	45 years, 10 months ago (Nov. 1, 1979)

Funders 0

None

BibTeX

@article{Newman_1979, title={Kinetics and mechanism of the silane decomposition}, volume={11}, ISSN={1097-4601}, url={http://dx.doi.org/10.1002/kin.550111104}, DOI={10.1002/kin.550111104}, number={11}, journal={International Journal of Chemical Kinetics}, publisher={Wiley}, author={Newman, C. G. and O’neal, H. E. and Ring, M. A. and Leska, F. and Shipley, N.}, year={1979}, month=nov, pages={1167–1182} }

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