Enthalpy of Solvation Correlations for Gaseous Solutes Dissolved in Chloroform and 1,2-dichloroethane Based on the Abraham Model Page: 7
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temperature range of 283 K - 318 K. Enthalpies of solvation are temperature dependent,
and we did not want to introduce large errors in the database by including experimental
data far removed from 298 K. For several solutes there were multiple, independently
determined values. In such cases, we selected direct calorimetric data over indirect
values based on the temperature dependence of measured solubilities or infinite dilution
activity coefficients. Using the fore-mentioned criteria, we obtained 100 molar
enthalpies of solvation in chloroform and 88 molar enthalpies of solvation in 1,2-
dichloroethane for regression analysis. The experimental AHSol,CFM and AHSol,DCE
values are listed in Tables 1 and 2, respectively, along with the literature references.
For the analysis of the data, we use the two linear free energy equations of
Abraham et al. [69,70]. In Eqn. 10, the descriptor V is the McGowan volume.
SP= c+e -E+s -S+a A+b -B+ 1 L (9)
SP= c+e -E+s S+a A+b B +vV (10)
Most of our precious studies have dealt with partition processes related to the Gibbs
energy of transfer, where the dependent solute property, SP, would be either the
logarithm of the gas-to-liquid (Eqn. 9) or the logarithm of the water-to-organic solvent
(Eqn. 10) partition coefficient. The basic model can be used to correlate enthalpies of
solvation and enthalpies of solute transfer from one condensed phase to a second
condensed phase. Equations 1-3 correspond to the temperature derivative of the
respective gas-to-liquid partition coefficient correlation; i.e., AHsolv = R a In K/8 (1/T).
From a thermodynamic standpoint, the temperature derivative of the logarithm of the
water-to-organic solvent partition coefficient would be related to enthalpy of transfer
from water to the organic solvent, i.e., AHtrans = R 8 In P/8 (1/T). We have also reported
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Mintz, Christina; Burton, Katherine; Acree, William E. (William Eugene) & Abraham, M. H. (Michael H.). Enthalpy of Solvation Correlations for Gaseous Solutes Dissolved in Chloroform and 1,2-dichloroethane Based on the Abraham Model, article, September 15, 2007; [Amsterdam, Netherlands]. (digital.library.unt.edu/ark:/67531/metadc155628/m1/7/: accessed June 18, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.