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Modeling the gas-phase thermochemistry of organosulfur compounds

Aäron Vandeputte (UGent) , Maarten Sabbe (UGent) , Marie-Françoise Reyniers (UGent) and Guy Marin (UGent)
(2011) CHEMISTRY-A EUROPEAN JOURNAL. 17(27). p.7656-7673
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
Key to understanding the involvement of organosulfur compounds in a variety of radical chemistries, such as atmospheric chemistry, polymerization, pyrolysis, and so forth, is knowledge of their thermochemical properties. For organosulfur compounds and radicals, thermochemical data are, however, much less well documented than for hydrocarbons. The traditional recourse to the Benson group additivity method offers no solace since only a very limited number of group additivity values (GAVs) is available. In this work, CBS-QB3 calculations augmented with 1D hindered rotor corrections for 122 organosulfur compounds and 45 organosulfur radicals were used to derive 93 Benson group additivity values, 18 ring-strain corrections, 2 non-nearest-neighbor interactions, and 3 resonance corrections for standard enthalpies of formation, standard molar entropies, and heat capacities for organosulfur compounds and organosulfur radicals. The reported GAVs are consistent with previously reported GAVs for hydrocarbons and hydrocarbon radicals and include 77 contributions, among which 26 radical contributions, which, to the best of our knowledge, have not been reported before. The GAVs allow one to estimate the standard enthalpies of formation at 298 K, the standard entropies at 298 K, and standard heat capacities in the temperature range 300-1500 K for a large set of organosulfur compounds, that is, thiols, thioketons, polysulfides, alkylsulfides, thials, dithioates, and cyclic sulfur compounds. For a validation set of 26 organosulfur compounds, the mean absolute deviation between experimental and group additively modeled enthalpies of formation amounts to 1.9 kJmol(-1). For an additional set of 14 organosulfur compounds, it was shown that the mean absolute deviations between calculated and group additively modeled standard entropies and heat capacities are restricted to 4 and 2 Jmol(-1) K(-1), respectively. As an alternative to Benson GAVs, 26 new hydrogen-bond increments are reported, which can also be useful for the prediction of radical thermochemistry.
Keywords
CHEMICAL THERMODYNAMIC PROPERTIES, BOND-DISSOCIATION ENERGIES, AB-INITIO MO, SUPPORTED HYDROTREATING CATALYSTS, ORGANIC SULFUR-COMPOUNDS, GROUP ADDITIVE VALUES, COMPLETE BASIS-SET, THERMAL-DECOMPOSITION, DIMETHYL DISULFIDE, C-H, ab initio calculations, group additivity, radicals, sulfur, thermochemistry

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Citation

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Chicago
Vandeputte, Aäron, Maarten Sabbe, Marie-Françoise Reyniers, and Guy Marin. 2011. “Modeling the Gas-phase Thermochemistry of Organosulfur Compounds.” Chemistry-a European Journal 17 (27): 7656–7673.
APA
Vandeputte, Aäron, Sabbe, M., Reyniers, M.-F., & Marin, G. (2011). Modeling the gas-phase thermochemistry of organosulfur compounds. CHEMISTRY-A EUROPEAN JOURNAL, 17(27), 7656–7673.
Vancouver
1.
Vandeputte A, Sabbe M, Reyniers M-F, Marin G. Modeling the gas-phase thermochemistry of organosulfur compounds. CHEMISTRY-A EUROPEAN JOURNAL. 2011;17(27):7656–73.
MLA
Vandeputte, Aäron, Maarten Sabbe, Marie-Françoise Reyniers, et al. “Modeling the Gas-phase Thermochemistry of Organosulfur Compounds.” CHEMISTRY-A EUROPEAN JOURNAL 17.27 (2011): 7656–7673. Print.
@article{1853844,
  abstract     = {Key to understanding the involvement of organosulfur compounds in a variety of radical chemistries, such as atmospheric chemistry, polymerization, pyrolysis, and so forth, is knowledge of their thermochemical properties. For organosulfur compounds and radicals, thermochemical data are, however, much less well documented than for hydrocarbons. The traditional recourse to the Benson group additivity method offers no solace since only a very limited number of group additivity values (GAVs) is available. In this work, CBS-QB3 calculations augmented with 1D hindered rotor corrections for 122 organosulfur compounds and 45 organosulfur radicals were used to derive 93 Benson group additivity values, 18 ring-strain corrections, 2 non-nearest-neighbor interactions, and 3 resonance corrections for standard enthalpies of formation, standard molar entropies, and heat capacities for organosulfur compounds and organosulfur radicals. The reported GAVs are consistent with previously reported GAVs for hydrocarbons and hydrocarbon radicals and include 77 contributions, among which 26 radical contributions, which, to the best of our knowledge, have not been reported before. The GAVs allow one to estimate the standard enthalpies of formation at 298 K, the standard entropies at 298 K, and standard heat capacities in the temperature range 300-1500 K for a large set of organosulfur compounds, that is, thiols, thioketons, polysulfides, alkylsulfides, thials, dithioates, and cyclic sulfur compounds. For a validation set of 26 organosulfur compounds, the mean absolute deviation between experimental and group additively modeled enthalpies of formation amounts to 1.9 kJmol(-1). For an additional set of 14 organosulfur compounds, it was shown that the mean absolute deviations between calculated and group additively modeled standard entropies and heat capacities are restricted to 4 and 2 Jmol(-1) K(-1), respectively. As an alternative to Benson GAVs, 26 new hydrogen-bond increments are reported, which can also be useful for the prediction of radical thermochemistry.},
  author       = {Vandeputte, A{\"a}ron and Sabbe, Maarten and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keyword      = {CHEMICAL THERMODYNAMIC PROPERTIES,BOND-DISSOCIATION ENERGIES,AB-INITIO MO,SUPPORTED HYDROTREATING CATALYSTS,ORGANIC SULFUR-COMPOUNDS,GROUP ADDITIVE VALUES,COMPLETE BASIS-SET,THERMAL-DECOMPOSITION,DIMETHYL DISULFIDE,C-H,ab initio calculations,group additivity,radicals,sulfur,thermochemistry},
  language     = {eng},
  number       = {27},
  pages        = {7656--7673},
  title        = {Modeling the gas-phase thermochemistry of organosulfur compounds},
  url          = {http://dx.doi.org/10.1002/chem.201002422},
  volume       = {17},
  year         = {2011},
}

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