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Thermodynamic parameters including acid dissociation constants for bromochlorophenols (BCPs)
Journal article   Open access   Peer reviewed

Thermodynamic parameters including acid dissociation constants for bromochlorophenols (BCPs)

A. Saeed, M. Altarawneh, G. Hefter and B.Z. Dlugogorski
Journal of Chemical & Engineering Data, Vol.61(1), pp.160-172
2016
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Abstract

This contribution reports standard gas-phase enthalpies of formation (ΔfH°298), entropies (S°298), and heat capacities (Cp°(T)) for all plausible 64 bromochlorophenols (BCPs) at the M062X meta hybrid level using a polarized basis set of 6-311+G(d,p). Isodesmic work reactions served to calculate the standard enthalpies of formation for all bromochlorophenol molecules and several bromochlorophenoxy radicals. Standard entropies and heat capacities comprise correction terms due to the treatment of O-H bonds as hindered rotors. Values of the bond dissociation enthalpies (BDHs) of O-H bonds, calculated for a selected series of bromochlorophenols, vary slightly with the change in the pattern and degree of halogenation of the phenyl ring. A thermodynamic cycle facilitated the estimation of pKa values, based on the calculated solvation and gas-phase deprotonation energies. We estimated the solvation energies of 19 out of 64 BCPs and their respective anions based on the integral equation formalism polarizable continuum model using optimized structures in the aqueous phase. Values of pKa decrease significantly from around 9 for monohalogenated to around 3 for pentahalogenated phenols.

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Chemistry, Multidisciplinary
Engineering, Chemical
Thermodynamics
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Chemistry
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