Interpretation of free energies of transfer and solute partial molar volumes in mixed solvents using Kirkwood–Buff theory

1988 ◽  
Vol 84 (5) ◽  
pp. 1387 ◽  
Author(s):  
Kenneth E. Newman
Keyword(s):  
Mixed Solvents ◽  
Partial Molar Volumes ◽  
Free Energies ◽  
Molar Volumes ◽  
Free Energies Of Transfer

Ionization of ethylene glycol in isodielectric acetonitrile + ethylene glycol mixtures at 25 °C

1979 ◽  
Vol 57 (18) ◽  
pp. 2470-2475 ◽  
Author(s):  
Kumardev Bose ◽  
Kiron K. Kundu
Keyword(s):  
Free Energy ◽  
Ethylene Glycol ◽  
Mixed Solvents ◽  
Solvent Composition ◽  
Free Energies ◽  
Emf Measurements ◽  
Free Energies Of Transfer ◽  
Mixed Systems

The autoprotolysis constants (Ksm) of ethylene glycol in isodielectric acetonitrile + ethylene glycol mixtures have been determined at 25 °C from emf measurements on the cell[Formula: see text]From these values, those of δΔG0, the free energy of ionization of ethylene glycol in these mixed solvents relative to that in pure glycol, have been computed. The nature of variation of δΔG0 with solvent composition has been compared with that in two other mixed systems: water + ethylene glycol and methanol + 1,2-propanediol and the intrinsic differences between the solvation characteristics of the various solvents have been pointed out. The standard free energies of transfer of the glycoxide ion, ΔGt0(OEg−), from pure glycol to acetonitrile + glycol mixtures have also been estimated using ΔGt0(H+) values obtained earlier. The glycoxide ion is increasingly desolvated as the acetonitrile content of the solvent increases, as indicated by increasingly positive values of ΔGt0(OEg−). This behaviour has been compared with those of ΔGt0(H+) and ΔGt0(Cl−) determined previously.

scholarly journals Determination of partial molar volumes from free energy perturbation theory

2015 ◽  
Vol 17 (13) ◽  
pp. 8407-8415 ◽  
Author(s):  
Jonah Z. Vilseck ◽  
Julian Tirado-Rives ◽  
William L. Jorgensen
Keyword(s):  
Free Energy ◽  
Partial Molar Volumes ◽  
Free Energy Perturbation ◽  
Benzene Derivatives ◽  
Free Energies ◽  
Pressure Derivative ◽  
Molar Volumes ◽  
Elevated Pressures ◽  
Energy Perturbation

Free Energy Perturbation calculations are employed to determine free energies of solvation (ΔGsolv) for benzene and benzene-derivatives at elevated pressures. Absolute and relative partial molar volumes are determined as the pressure derivative of ΔGsolv.

Determination of absolute transfer free energies of hydroxyl ion from water to aqueous 2-methoxy ethanol

1981 ◽  
Vol 59 (7) ◽  
pp. 1153-1159 ◽  
Author(s):  
Abhijit Bhattacharya ◽  
Asim K. Das ◽  
Kiron K. Kundu
Keyword(s):  
Ethylene Glycol ◽  
Mixed Solvents ◽  
Aqueous Mixtures ◽  
Free Energies ◽  
Free Energies Of Transfer ◽  
Hydroxyl Ion ◽  
Relative Stabilization ◽  
Solvent Systems ◽  
Reference Electrolyte

Absolute standard free energies of transfer ΔGt0 of OH− from water to aqueous mixtures of 2-methoxy ethanol (ME) have been evaluated at 298.15 K by combining the apparent transfer free energies of the lyate ion that were obtained from the standard emf's of the double cell:[Formula: see text]and that from the autoionization constants of these mixed solvents determined by use of the cell comprising H2– and Ag–AgCl electrodes. The required ΔGt0 values of K+ and H+ were determined earlier using the well-known tetraphenyl arsonium tetraphenyl boride (TATB) reference electrolyte method. These values and their non-Born type contributions in particular, are found to be increasingly positive in water-rich compositions, indicating that the relative stabilization of OH− and the acidity of the mixed solvents decrease with increasing cosolvent composition. These, when compared with those in aqueous mixtures of ethylene glycol and 1,2-dimethoxy ethane, are found to lie intermediate between the latter solvent systems conforming to what is expected from the structural and electronic features of the cosolvents.

scholarly journals Volumetric, viscometric and refractive index behavior of amino acids in aqueous glycerol at different temperatures

2007 ◽  
Vol 72 (5) ◽  
pp. 495-512 ◽  
Author(s):  
A. Ali ◽  
S. Khan ◽  
F. Nabi
Keyword(s):  
Amino Acids ◽  
Mixed Solvents ◽  
Partial Molar Volumes ◽  
State Theory ◽  
Apparent Molar Volumes ◽  
Ternary Mixtures ◽  
Refractive Indices ◽  
Glycerol Solution ◽  
Molar Volumes ◽  
B Coefficients

Densities, ?, viscosities, ? and refractive indices, n D, of solutions of some amino acids (glycine, DL-alanine, DL-? -amino- n-butyric acid, L-valine and L-leucine) in the concentration range 0.02 to 0.10 m in 5 % (v/v) aqueous glycerol were determined at 298.15, 303.15, 308.15 and 313.15 K. These experimental data were used to calculate the apparent molar volumes, ? v, the infinite dilution apparent molar volumes, ? v 0, the partial molar volumes of transfer, ? v 0 (tr), of the amino acids from aqueous to aqueous glycerol solution, as well as the viscosity A and B coefficients of the Jones-Dole equation of the amino acids. The free energies of activation of viscous flow, ??1 0# and ?? 2 0# per mole of solvent and solute, respectively, were obtained by application of the transition-state theory to the B coefficient data and the corresponding activation enthalpy, ?H*, and entropy, ?S*, were also determined. The ? v 0, B coefficients and ?? 2 0# were found to vary linearly with increasing number of carbon atoms in the alkyl chain of the amino acids, and they were split into contributions from the zwitterionic end groups (NH3 +, COO-) and methylene (CH2) groups of the amino acids. The experimental values of the refractive indices, n D, were used to calculate the molar refractive indices, R D, of the amino acids + aqueous glycerol ternary mixtures. The results were interpreted in the light of the solute-solvent and solute-solute interactions in the mixed solvents.

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