Experimental and theoretical studies of the reaction of atomic oxygen with silane

Ding, Luying; Marshall, Paul

doi:10.1063/1.464513

Cited by 26 publications

(29 citation statements)

References 37 publications

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“…Details of the kinetic apparatus have been given elsewhere [16][17][18]. Briefly, SO 2 diluted in Ar bath gas flowed through a stainless steel reaction cell.…”

Section: Methodsmentioning

confidence: 99%

A kinetic study of the reaction of atomic oxygen with SO2

Naidoo

Goumri

Marshall

2005

Proceedings of the Combustion Institute

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The effective second-order rate constant for O + SO 2 (+Ar) fi SO 3 (+Ar) has been measured by pulsed laser-photolysis with resonance fluorescence detection of atomic oxygen under pseudo-first-order conditions. The pressure dependence was determined at five temperatures in the range 290-840 K. The results obtained at pressures up to 880 mbar reveal fall-off behavior. With an estimated broadening parameter F c , Troe fits to the measurements yield the low-pressure limit k 0 = 9.5 · 10 À23 T À3 exp (À2400/T) cm 6 molecule À2 s À1 and the high-pressure limit k 1 = 6.1 · 10 À13 exp (À850/T) cm 3 molecule À1 s À1. An RRKM extrapolation of the present k 0 values yields k 0 = 6.7 · 10 À21 T À3.6 exp (À2610/T) cm 6 molecule À2 s À1 , which is in good accord with several literature values over 220-2500 K. At low temperatures, k 0 shows a positive activation energy rationalized in terms of a barrier of 15.9 kJ mol À1, and k 0 reaches a maximum at around 750 K. Our expression for k 1 is in order-of-magnitude accord with values used to model a flow reactor and indicates a small pre-exponential factor. This may reflect the probability of triplet-singlet transitions in the spin-forbidden addition reaction and/or a tight transition state.

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“…Details of the kinetic apparatus have been given elsewhere [16][17][18]. Briefly, SO 2 diluted in Ar bath gas flowed through a stainless steel reaction cell.…”

Section: Methodsmentioning

confidence: 99%

A kinetic study of the reaction of atomic oxygen with SO2

Naidoo

Goumri

Marshall

2005

Proceedings of the Combustion Institute

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“…The six best estimates of kl from Table 2 are plotted in Arrhenius form in Figure 1. A linear fit, where each point was weighted by the inverse variance, yields k l ( T ) = (6.7 f 2.0) X lo-'' X exp(-1030 f 100 K/T) cm3 molecule-' s-' (6) with E, = 8.6 f 0.8 kJ mol-'. Thequoted uncertainties represent f 2 u for A and E,.…”

Section: -12mentioning

confidence: 99%

“…The present data also extend the kinetic database for alkyl-substituted silanes and are discussed in the context of recent measurements on O(3P) reactions with triethylsilane and triisopropylsilane.I* Recently it was shown that k2 could be closely reproduced by combination of ab initio Gaussian-2 theory, which approximates QCISD(T)/6-31 l+G(3df,2p)//MP2/6-3lG* energies,I3 witha transition state theory (TST) analysis. 6 Here the analogous transition state for kl is too large to analyze at the same level of theory, so we assess the relative energetics of the transition states 0 Abstract published in Advance ACS Abstracts, March IS, 1994.…”

Section: Introductionmentioning

confidence: 99%

Investigations of the Reaction of Trimethylsilane with O(3P) Atoms

Misra¹,

Ding²,

Marshall³

et al. 1994

J. Phys. Chem.

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The reaction O(,PJ) + (CH&SiH -products (1) has been investigated by the discharge/fast-flow method with mass spectrometric detection (DF-MS) over 298-773 K and by the flash photolysis/resonance fluorescence (FP-RF) technique over 293-549 K. The rate constants from both methods are in close accord and may be summarized by kl(T) = 5.6 X lo-" exp(-1005 K/7') cm3 molecule-' s-l for 290-770 K. There is reasonable agreement with previous room-temperature studies. kl is larger than k2 for 0 + SiH4 (2), similar to results for triethylsilane and triisopropylsilane [Buchta, Chr.; Stucken, D.-V.; Vollmer, J.-T.; Wagner, H. Gg. Z. Phys.Chem. Neue Folge, to be published], and tri-alkylation is seen to increase the reactivity of the Si-H bonds by similar amounts largely independent of the nature of the alkyl group. This silane activation occurs through lowering the energy barrier to abstraction to form O H + (CH3)3Si*. Ab initio analysis of this pathway at the MP2/6-31G*//HF/3-21G(*) level of theory gives relative energies for the transition states of reactions 1 and 2 that agree well with experiment.

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“…The laser photolysis apparatus and general operating procedures have been described elsewhere [10][11][12][13]. Briefly, mixtures of H2S and CS2 diluted in Ar bath gas flowed slowly through a heated, stainless steel reaction cell.…”

Section: Experimental Methods and Resultsmentioning

confidence: 99%