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Nonlinear Phenomena and Kinetic Mechanism of a Gaseous Branching Chain Process by the Example of Thermal Decomposition of Nitrogen Trichloride Read chapter Read first chapter

2017 | OriginalPaper | Chapter

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

Author : Nikolai M. Rubtsov

Published in: Key Factors of Combustion

Publisher: 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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previous chapter Nonlinear Phenomena and Kinetic Mechanism of a Gaseous Branching Chain Process by the Example of Thermal Decomposition of Nitrogen Trichloride
next chapter Electric Phenomena in Silanes Chlorination and Oxidation
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Metadata
Title
Nonlinear Effects in Silanes Oxidation and Chlorination in Gaseous Phase: Collecting a Puzzle
Author
Nikolai M. Rubtsov
Copyright Year
2017
Book
Key Factors of Combustion

Print ISBN: 978-3-319-45996-7

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

Copyright Year: 2017

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

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