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2017 | OriginalPaper | Buchkapitel

2. Nonlinear Effects in Silanes Oxidation and Chlorination in Gaseous Phase: Collecting a Puzzle

verfasst von : Nikolai M. Rubtsov

Erschienen in: Key Factors of Combustion

Verlag: Springer International Publishing

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Abstract

It has been found that the time delay τ of thermal ignition of dichlorosilane—chlorine mixtures occur in the presence of more than 4 % of propylene; the consumption of inhibitor leads to ignition, in which absorption spectrum of dichlorosilylene radicals is detected along with the emission of SiHCl (A¹B₁–X¹A₁). The inhibiting effect is due to the fast reactions of propylene with silylenes as chain carriers. In the presence of both inhibitor and of more than 45 % inert additive (sulfur hexafluoride) the dependence of τ on the concentration of deactivator undergoes drastic change. Thus, deactivation processes have marked influence on the flammability. Experimental data are in agreement with calculations based on the generalized kinetic model of the branched-chain process including chain termination via both inhibitor and deactivator. It is shown that non-thermal flame propagation is inherent both to monosilane and dichlorosilane oxidation. Deactivating properties of an inert additive influence on the velocities of non-thermal flame propagation in the case of dichlorosilane oxidation. That may be the evidence of participation of excited particles in nonlinear branching reaction. An electron-vibration structure of the UV spectrum of a long-lived intermediate is detected during oxidation of SiH₄ and SiH₂Cl₂. This product is common to both reactions and exhibits the same promoting effect on them. It is shown that the formation of this promoting compound in the course of a branched chain reaction provides non-thermal flame propagation in reacting mixtures outside of the thermal ignition region.

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Titel: Nonlinear Effects in Silanes Oxidation and Chlorination in Gaseous Phase: Collecting a Puzzle
verfasst von: Nikolai M. Rubtsov
Verlag: Springer International Publishing
Buch: Key Factors of Combustion
Print ISBN: 978-3-319-45996-7

Electronic ISBN: 978-3-319-45997-4

Copyright-Jahr: 2017
DOI: https://doi.org/10.1007/978-3-319-45997-4_2

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