Experimental and computational study of diethyl sulfide pyrolysis and mechanism

Document Type

Article

Publication Date

1-1-2009

Abstract

The pyrolysis of diethyl sulfide (C2H5SC 2H5), a simulant for mustard chemical warfare agents, was studied in a turbulent flow reactor with extractive gas composition analysis by GC/MS and FTIR. Experiments were performed at approximately atmospheric pressure for four different temperatures between 630 and 740°C with maximum residence times between 0.06 and 0.08 s. Temperature and species profiles were obtained on the centerline of the reactor. The mixing characteristics in the reactor were determined by using carbon monoxide as a tracer. 80% destruction of diethyl sulfide was observed for the experiment at the temperature of 740°C and the residence time of 0.06 s. The following species were quantified: diethyl sulfide, ethylene, methane, ethane, acetylene, carbon disulfide, and thiophene. In addition, ethanethiol, methyl thiirane CH3-(Cy-CH- CH2-S), ethyl methyl disulfide, and diethyl disulfide were identified but not quantified. A light yellow solid containing sulfur condensed in sampling probes. Thermochemical properties for all species and a detailed mechanism were developed for modeling the reaction system. Thermodynamic and kinetic parameters were based on density functional theory and ab initio calculations using isodesmic work reactions for enthalpies. Kinetic parameters for chemical activation and unimolecular dissociation reactions were determined with multi frequency quantum RRK analysis for k(E) and master equation for fall-off. Important reactions were identified by sensitivity analysis and reaction pathway analysis of the mechanism. Model predictions show overall good agreement with experiment. © 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Identifier

61849164434 (Scopus)

Publication Title

Proceedings of the Combustion Institute

External Full Text Location

https://doi.org/10.1016/j.proci.2008.06.176

ISSN

15407489

First Page

469

Last Page

476

Issue

1

Volume

32 I

Grant

W911NF0410120

Fund Ref

Army Research Office

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