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Theoretical study of the thermal decomposition of dimethyl disulfide

Aäron Vandeputte UGent, Marie-Françoise Reyniers UGent and Guy Marin UGent (2010) JOURNAL OF PHYSICAL CHEMISTRY A. 114(39). p.10531-10549
abstract
Despite its use in a wide variety of industrially important thermochemical processes, little is known about the thermal decomposition mechanism of dimethyl disulfide (DMDS). To obtain more insight, the radical decomposition mechanism of DMDS is studied theoretically and a kinetic model is developed accounting for the formation of all the decomposition products observed in the experimental studies available in literature. Thermochemical data and rate coefficients are obtained using the high-level CBS-QB3 composite method. Among five methods tested (BMK/6-311G(2d,d,p), MPW1PW91/6-311G(2d,d,p), G3, G3B3, and CBS-QB3), the CBS-QB3 method was found to reproduce most accurately the experimental standard enthalpies of formation for a set of 17 small organosulfur compounds and the bond dissociation energies for a set of 10 sulfur bonds. Enthalpies of formation were predicted within 4 kJ mol(-1) while the mean absolute deviation on the bond dissociation enthalpies amounts to 7 kJ mol(-1). From the theoretical study, a new reaction path is identified for the formation of carbon disulfide via dithiirane (CH2S2). A reaction mechanism was constructed containing 36 reactions among 25 species accounting for the formation of all the decomposition products reported in literature. High-pressure limit rate coefficients for the 36 reactions in the reaction mechanism are presented. The kinetic model is able to grasp the experimental observations. With the recombination of thiyl radicals treated as being in the low-pressure limit, the experimentally reported first-order rate coefficients for the decomposition of DMDS are reproduced within 1 order of magnitude, while the observed product selectivities of most compounds are reproduced satisfactory. Simulations indicate that at high conversions most of the carbon disulfide forms according to the newly identified reaction path involving the formation of dithiirane.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
AB-INITIO MO, DENSITY-FUNCTIONAL GEOMETRIES, GROUP ADDITIVITY, THERMOCHEMICAL PROPERTIES, TRANSITION-STATE THEORY, BOND-DISSOCIATION ENTHALPIES, GAS-PHASE THERMOLYSIS, SUPPORTED HYDROTREATING CATALYSTS, VARIABLE REACTION COORDINATE, REACTION-RATE PREDICTION
journal title
JOURNAL OF PHYSICAL CHEMISTRY A
J. Phys. Chem. A
volume
114
issue
39
pages
10531 - 10549
Web of Science type
Article
Web of Science id
000282210000008
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
2.732 (2010)
JCR rank
8/31 (2010)
JCR quartile
2 (2010)
ISSN
1089-5639
DOI
10.1021/jp103357z
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1081472
handle
http://hdl.handle.net/1854/LU-1081472
date created
2010-12-01 16:00:30
date last changed
2017-03-09 12:38:52
@article{1081472,
  abstract     = {Despite its use in a wide variety of industrially important thermochemical processes, little is known about the thermal decomposition mechanism of dimethyl disulfide (DMDS). To obtain more insight, the radical decomposition mechanism of DMDS is studied theoretically and a kinetic model is developed accounting for the formation of all the decomposition products observed in the experimental studies available in literature. Thermochemical data and rate coefficients are obtained using the high-level CBS-QB3 composite method. Among five methods tested (BMK/6-311G(2d,d,p), MPW1PW91/6-311G(2d,d,p), G3, G3B3, and CBS-QB3), the CBS-QB3 method was found to reproduce most accurately the experimental standard enthalpies of formation for a set of 17 small organosulfur compounds and the bond dissociation energies for a set of 10 sulfur bonds. Enthalpies of formation were predicted within 4 kJ mol(-1) while the mean absolute deviation on the bond dissociation enthalpies amounts to 7 kJ mol(-1). From the theoretical study, a new reaction path is identified for the formation of carbon disulfide via dithiirane (CH2S2). A reaction mechanism was constructed containing 36 reactions among 25 species accounting for the formation of all the decomposition products reported in literature. High-pressure limit rate coefficients for the 36 reactions in the reaction mechanism are presented. The kinetic model is able to grasp the experimental observations. With the recombination of thiyl radicals treated as being in the low-pressure limit, the experimentally reported first-order rate coefficients for the decomposition of DMDS are reproduced within 1 order of magnitude, while the observed product selectivities of most compounds are reproduced satisfactory. Simulations indicate that at high conversions most of the carbon disulfide forms according to the newly identified reaction path involving the formation of dithiirane.},
  author       = {Vandeputte, A{\"a}ron and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {1089-5639},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY A},
  keyword      = {AB-INITIO MO,DENSITY-FUNCTIONAL GEOMETRIES,GROUP ADDITIVITY,THERMOCHEMICAL PROPERTIES,TRANSITION-STATE THEORY,BOND-DISSOCIATION ENTHALPIES,GAS-PHASE THERMOLYSIS,SUPPORTED HYDROTREATING CATALYSTS,VARIABLE REACTION COORDINATE,REACTION-RATE PREDICTION},
  language     = {eng},
  number       = {39},
  pages        = {10531--10549},
  title        = {Theoretical study of the thermal decomposition of dimethyl disulfide},
  url          = {http://dx.doi.org/10.1021/jp103357z},
  volume       = {114},
  year         = {2010},
}

Chicago
Vandeputte, Aäron, Marie-Françoise Reyniers, and Guy Marin. 2010. “Theoretical Study of the Thermal Decomposition of Dimethyl Disulfide.” Journal of Physical Chemistry A 114 (39): 10531–10549.
APA
Vandeputte, Aäron, Reyniers, M.-F., & Marin, G. (2010). Theoretical study of the thermal decomposition of dimethyl disulfide. JOURNAL OF PHYSICAL CHEMISTRY A, 114(39), 10531–10549.
Vancouver
1.
Vandeputte A, Reyniers M-F, Marin G. Theoretical study of the thermal decomposition of dimethyl disulfide. JOURNAL OF PHYSICAL CHEMISTRY A. 2010;114(39):10531–49.
MLA
Vandeputte, Aäron, Marie-Françoise Reyniers, and Guy Marin. “Theoretical Study of the Thermal Decomposition of Dimethyl Disulfide.” JOURNAL OF PHYSICAL CHEMISTRY A 114.39 (2010): 10531–10549. Print.