Solvation of ions—enthalpies, entropies and free energies of transfer

1976 ◽  
Vol 21 (9) ◽  
pp. 671-679 ◽  
Author(s):  
A.J. Parker
Keyword(s):  
Free Energies ◽  
Free Energies Of Transfer ◽  
Solvation Of Ions

Solvation of ions. Some applications. III. Solutions of copper(I) salts in water containing ligands

1977 ◽  
Vol 30 (8) ◽  
pp. 1661 ◽  
Author(s):  
AJ Parker ◽  
DA Clarke ◽  
RA Couche ◽  
G Miller ◽  
RI Tilley ◽  
...  
Keyword(s):  
Free Energies ◽  
Molar Excess ◽  
Free Energies Of Transfer ◽  
Reduction Potentials ◽  
Solvation Of Ions

Solutions of copper(II) and copper(I) sulphate in water containing acetonitrile have applications in the hydrometallurgy of copper. The potentials (n.h.e.) of the Cu+/Cu; the Pt/Cu2+, Cu+, and the Cu2+/Cu electrodes in water containing a large molar excess of various copper(I) bases and various counter-anions have been measured. Free energies of transfer of copper(I) ions from water to water containing the bases are calculated. ΔGtr(Cu+) at 25�C becomes less exoenergetic for water containing the bases in the following order: CN- >> S2O32- > Me2NCHS > KI > NH3 > C5H5N > KBr > KCl > C3H5OH ≥ MeCN, CO, C2H4 > C3H6. The reduction potentials of CuSO4/Cu2SO4 in acidic saturated copper(II) sulphate solutions and a range of Cu2SO4 concentrations in acetonitrile- water mixtures show that CuSO4/MeCN/H2O is a powerful oxidant, comparable in strength to acidic iron(III) sulphate in water. Acetonitrile is the preferred base for the processing of copper by way of solutions of copper(I) sulphate.

Solvation of ions. XXVI. Free energies of transfer of ions to multi-site solvents and solvent mixtures

1978 ◽  
Vol 31 (6) ◽  
pp. 1181 ◽  
Author(s):  
AJ Parker ◽  
WE Waghorne
Keyword(s):  
Solvent Mixtures ◽  
Free Energies ◽  
Free Energies Of Transfer ◽  
Solvation Of Ions ◽  
Solvent Transfer

The free energies of solvent transfer of Ag+, K+, Cl-, Br-, I- and ClO4- from acetonitrile to glycolonitrile, 3-hydroxypropionitrile and mixtures of 2,2,2-trifluoroethanol or water with acetonitrile are reported. ��� The anion-solvating properties of a series of hydroxylic solvents decrease by 24 kJ mol-1 in the order CF3CH2OH > CNCH2OH > CNCH2CH2OH > CH3OH > CH3CH2OH; Ag+-solvating properties decrease by 70 kJ mol-1 in the order CH3CN > HOCH2CH2CN > HOCH2CN > CH3CH2OH > CF3CH2OH; and the K+- solvating properties decrease by 27 kJ mol-1 in the order CH3CN > HOCH2CH2CN ≈ CH3OH ≈ HOCH2CN ≈ CH3CH2OH > CF3CH2OH. It is not possible to make more than qualitative generalizations as to the ion-solvating properties of solvent mixtures if only the solvating properties of the pure components are known. Multi-site solvents like CNCH2OH are compared with related equimolar mixtures, like CH3CN/HOH, in their ability to solvate ions.

scholarly journals Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

2012 ◽  
Vol 137 (12) ◽  
pp. 124101 ◽  
Author(s):  
Jaydeep P. Bardhan ◽  
Pavel Jungwirth ◽  
Lee Makowski
Keyword(s):  
Response Model ◽  
Free Energies ◽  
Solvation Of Ions
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