TY - JOUR
T1 - Theoretical study on thermochemical parameters and pKa values for fluorinated isomers of toluene
AU - Zanganeh, Jafar
AU - Altarawneh, Mohammednoor
AU - Saraireh, Ibrahim
AU - Namazi, Samira
AU - Zanganeh, Javad
N1 - Funding Information:
This study has been supported by a grant of computing time from the National Computational Infrastructure (NCI) , Australia. (Project ID: De3).
PY - 2013/5/1
Y1 - 2013/5/1
N2 - Despite the prominent importance of fluorinated isomers of toluene in environmental and industrial applications, robust data pertinent to their thermochemistry is rather scarce. Thermochemical properties, in terms of standard entropies, heat capacities, standard enthalpies of formation, Gibbs free energies of formation and solvation energies are calculated herein for all fluorinated isomers of toluene. Estimated barriers for the internal rotation of the methyl group are in accord with experimental measurements available for a few congeners. Very exoergic values for Δ. fG298o indicates a thermodynamic tendency toward the formation of highly fluorinated congeners. Solvation of all isomers in water at ambient conditions incurs a trivial exoergicity. Profiles for internal rotations obtained from partial optimisation reasonably match corresponding profiles obtained via automatic recognition for barriers of rotations based on Pitzer-Gwinn tables. Calculated p. Ka values reveal a very weak acidic character; especially for lower fluorinated congeners.
AB - Despite the prominent importance of fluorinated isomers of toluene in environmental and industrial applications, robust data pertinent to their thermochemistry is rather scarce. Thermochemical properties, in terms of standard entropies, heat capacities, standard enthalpies of formation, Gibbs free energies of formation and solvation energies are calculated herein for all fluorinated isomers of toluene. Estimated barriers for the internal rotation of the methyl group are in accord with experimental measurements available for a few congeners. Very exoergic values for Δ. fG298o indicates a thermodynamic tendency toward the formation of highly fluorinated congeners. Solvation of all isomers in water at ambient conditions incurs a trivial exoergicity. Profiles for internal rotations obtained from partial optimisation reasonably match corresponding profiles obtained via automatic recognition for barriers of rotations based on Pitzer-Gwinn tables. Calculated p. Ka values reveal a very weak acidic character; especially for lower fluorinated congeners.
KW - DFT
KW - Energy of solvation
KW - PKa
KW - Pitzer-Gwinn tables
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U2 - 10.1016/j.comptc.2013.02.003
DO - 10.1016/j.comptc.2013.02.003
M3 - Article
AN - SCOPUS:84874711741
SN - 2210-271X
VL - 1011
SP - 21
EP - 29
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -