Correlation of Partial Molar Heats of Transfer at Infinite Dilution by a Linear Solvation Energy Relationship

Solution calorimetry of organic nonelectrolytes as a tool for investigation of intermolecular interactions

“…Despite the parameters in Eqns (1) and (2) are used to describe data on Gibbs energies of solvation and solution, these equations were also used for solvation enthalpies. [23,24,[27][28][29][30][31][32][33] It was confirmed that the LSER approach is quite good for the description of calorimetric data.…”

“…Parameter p H 2 reflects 'polarity/polarizability' of a solute, [12,24,[35][36][37] while the product sp H 2 is a measure of the dipolar and inductive interactions between the solute and the solvent. [24] Owing to the above-mentioned reason this parameter must contain the contribution of dispersion interactions. Indeed, this parameter is based on the solvent pà parameter of Kamlet, Taft, and Abboud, which was derived to be free from specific interactions.…”

“…Over the last few decades most solvation studies made use of the linear solvation-energy relationships (LSER) formulated by Kamlet, Taft, and Abboud. [6][7][8][9] More recently, this approach was widely used predominantly in the works of Abraham et al [10][11][12][13][14][15][16][17][18][19][20][21][22][23] and Carr et al [24,25] According to this approach, the thermodynamic parameter (TP) of solvation or transfer depends on a number of solute parameters (Eqns (1) and (2)):…”

“…where V X is the McGowan characteristic volume, [26] which, along with log L 16 (Ostwald coefficient of solute in hexadecane), defines the contributions into TP of cavity formation and general dispersion interaction; [12] p H 2 relates to the ability of solute to dipole and induction interactions with solvent; R 2 is the excess molar refraction; [10] d 2 is an empirical correction factor which compensates for the impossibility of describing electrostatic interactions by a single parameter (0 for aliphatic compounds, 0.5 for polychlorinated aromatic compounds, and 1 for any other aromatic compound); [24] Sa H 2 and Sb H 2 are the apparent acidity and basicity of solute. [11] The first three terms of Eqns (1) and (2) relate to nonspecific solvation and the latter two to specific solute-solvent interaction.…”

Compilation and Correlation of Limiting Activity Coefficients of Nonelectrolytes in Water

“…The LSER concept has since been expanded and applied successfully to both solvent and solute systems for a variety of purposes including correlations of octanolwater partition coefficients (Abraham, 1993), retention in gas-liquid chromatography Abraham et al, 1974Abraham et al, , 1987aAbraham et al, ,b, 1990, and correlation of partial molar heats of transfer (Sherman et al, 1995). The model we have developed assumes that the solute's π*, R, , and molar volume contribute linearly and independently to the log of the solute's Henry's constant.…”