Kinetics and thermochemistry of the reaction Si(CH3)3 + HBr ⇌ Si(CH3)3H + Br: Determination of the (CH3)3Si-H bond energy

Ilia J. Kalinovski; D. Gutman; Lev N. Krasnoperov; A. Goumri; W. J. Yuan; Paul Marshall

doi:10.1021/j100089a031

Kinetics and thermochemistry of the reaction Si(CH₃)₃ + HBr ⇌ Si(CH₃)₃H + Br: Determination of the (CH₃)₃Si-H bond energy

Ilia J. Kalinovski, D. Gutman, Lev N. Krasnoperov, A. Goumri, W. J. Yuan, Paul Marshall

Chemistry and Environmental Science

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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) × 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) × 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 ΔH°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.

Original language	English (US)
Pages (from-to)	9551-9557
Number of pages	7
Journal	Journal of physical chemistry
Volume	98
Issue number	38
DOIs	https://doi.org/10.1021/j100089a031
State	Published - 1994

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General Engineering
Physical and Theoretical Chemistry

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@article{5d7b1f49610f499e9f418e4dfa9b8edb,

title = "Kinetics and thermochemistry of the reaction Si(CH3)3 + HBr ⇌ Si(CH3)3H + Br: Determination of the (CH3)3Si-H bond energy",

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) × 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) × 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 ΔH°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.",

author = "Kalinovski, {Ilia J.} and D. Gutman and Krasnoperov, {Lev N.} and A. Goumri and Yuan, {W. J.} and Paul Marshall",

year = "1994",

doi = "10.1021/j100089a031",

language = "English (US)",

volume = "98",

pages = "9551--9557",

journal = "Journal of physical chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "38",

}

TY - JOUR

T1 - Kinetics and thermochemistry of the reaction Si(CH3)3 + HBr ⇌ Si(CH3)3H + Br

T2 - Determination of the (CH3)3Si-H bond energy

AU - Kalinovski, Ilia J.

AU - Gutman, D.

AU - Krasnoperov, Lev N.

AU - Goumri, A.

AU - Yuan, W. J.

AU - Marshall, Paul

PY - 1994

Y1 - 1994

N2 - 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) × 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) × 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 ΔH°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.

AB - 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) × 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) × 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 ΔH°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.

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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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