TY - JOUR
T1 - Theoretical derivation for reaction rate constants of H abstraction from thiophenol by the H/O radical pool
AU - Batiha, Marwan
AU - Altarawneh, Mohammednoor
AU - Al-Harahsheh, Mohammad
AU - Altarawneh, Ibrahem
AU - Rawadieh, Saleh
N1 - Funding Information:
This study has been funded and supported by a grant of computing time from the Australian Centre of Advanced Computing and Communications (ac3).
PY - 2011/9/1
Y1 - 2011/9/1
N2 - Reaction and activation energy barriers are calculated for the H abstraction reactions (C6H5SH+X→C6H5S+XH, X=H, OH and HO2) at the BB1K/GTLarge level of theory. The corresponding reactions with H2S and CH3SH are also investigated using the G3B3 and CBS-QB3 methods in order to demonstrate the accuracy of BB1K functional in finding activation barriers for hydrogen atom transfer reactions. Arrhenius parameters for the title reactions are fitted in the temperature range of 300K-2000K. The calculated reaction enthalpies are in good agreement with their corresponding experimental reaction enthalpies. It is found that H abstraction by OH radicals from the thiophenol molecule proceed in a much slower rate in reference to the analogous phenol molecule. ΔfH298o of thiophenoxy radical is calculated to be 63.3kcal/mol. Kinetic parameters presented herein should be useful in describing the decomposition rate of thiophenol; i.e., one of the major aromatic sulfur carriers, at high temperatures.
AB - Reaction and activation energy barriers are calculated for the H abstraction reactions (C6H5SH+X→C6H5S+XH, X=H, OH and HO2) at the BB1K/GTLarge level of theory. The corresponding reactions with H2S and CH3SH are also investigated using the G3B3 and CBS-QB3 methods in order to demonstrate the accuracy of BB1K functional in finding activation barriers for hydrogen atom transfer reactions. Arrhenius parameters for the title reactions are fitted in the temperature range of 300K-2000K. The calculated reaction enthalpies are in good agreement with their corresponding experimental reaction enthalpies. It is found that H abstraction by OH radicals from the thiophenol molecule proceed in a much slower rate in reference to the analogous phenol molecule. ΔfH298o of thiophenoxy radical is calculated to be 63.3kcal/mol. Kinetic parameters presented herein should be useful in describing the decomposition rate of thiophenol; i.e., one of the major aromatic sulfur carriers, at high temperatures.
KW - BB1K functional
KW - Oil shale
KW - Reaction rate constant
KW - Thiophenol
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U2 - 10.1016/j.comptc.2011.05.015
DO - 10.1016/j.comptc.2011.05.015
M3 - Article
AN - SCOPUS:84555218050
SN - 2210-271X
VL - 970
SP - 1
EP - 5
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
IS - 1-3
ER -