Kinetics and Thermochemistry of the Reaction Si(CH₃)₃ + HBr ⇋ Si(CH₃)₃H + Br: Determination of the (CH₃)₃Si-H Bond Energy

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Article on kinetics and thermochemistry of the reaction Si(CH₃)₃ + HBr ⇋ Si(CH₃)₃H + Br and determination of the (CH₃)₃Si-H bond energy.

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7 p.

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Kalinovski, Ilia J.; Gutman, D.; Krasnoperov, Lev N.; Goumri, Abdellatif; Yuan, W. J. & Marshall, Paul September 1994.

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Article on kinetics and thermochemistry of the reaction Si(CH₃)₃ + HBr ⇋ Si(CH₃)₃H + Br and determination of the (CH₃)₃Si-H bond energy.

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7 p.

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Abstract: The reaction Si(CH₃)₃ + HBr → Si(CH₃)₃H + Br (1) has been investigated using flash photolysis/photoionization mass spectrometry detection of Si(CH₃)₃ and flash photolysis/resonance fluorescence spectroscopy detection of Br. The measured rate constants are k₁ = (1.06 ± 0.13) x 10⁻¹¹ exp((6.14 ± 0.31) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹ for T = 296-702 K and k₁ = (8.1 ± 2.0) x 10⁻¹² exp((5.12 ± 0.72) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹ for T = 289-515 K, respectively. The 1σ uncertainties represent precision only. Combination with k₋₁ data and analysis by second and third law methods yields ∆H˚₂₉₈ = -31.1 kJ mol⁻¹ for (1), with accuracy limits of about ± 2.0 kJ mol⁻¹. The results imply an Si-H bond dissociation enthalpy of 397.4 ± 2 kJ mol⁻¹ and an enthalpy of formation for trimethylsilyl of 16.4 ± 6.0 kJ mol⁻¹.

Reprinted with permission from the Journal of Physical Chemistry. Copyright 1994 American Chemical Society.

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  • Journal of Physical Chemistry, 1994, Washington D.C.: American Chemical Society, pp. 9551-9557

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  • Publication Title: Journal of Physical Chemistry
  • Volume: 98
  • Issue: 38
  • Page Start: 9551
  • Page End: 9557
  • Pages: 7
  • Peer Reviewed: Yes

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  • September 1994

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  • April 25, 2015, 8:59 p.m.

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Kalinovski, Ilia J.; Gutman, D.; Krasnoperov, Lev N.; Goumri, Abdellatif; Yuan, W. J. & Marshall, Paul. Kinetics and Thermochemistry of the Reaction Si(CH₃)₃ + HBr ⇋ Si(CH₃)₃H + Br: Determination of the (CH₃)₃Si-H Bond Energy, article, September 1994; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc503272/: accessed August 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.