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

scholarly journals The Born model can accurately describe electrostatic ion solvation

2020 ◽  
Vol 22 (43) ◽  
pp. 25126-25135
Author(s):  
Timothy T. Duignan ◽  
X. S. Zhao
Keyword(s):  
Oxygen Atom ◽  
Linear Response ◽  
Ion Solvation ◽  
Response Model ◽  
Free Energies ◽  
Born Model ◽  
Repulsion Force ◽  
Solvation Free Energies

The solvation free energies of ions in water are consistent with the Born linear response model if the centre on which the ion–water repulsion force acts is moved from the oxygen atom towards the hydrogens.

Solvation of ions. XXII. Solvation of cations by hard N,N-dimethylformamide and soft N,N-dimethylthioformamide

1974 ◽  
Vol 27 (5) ◽  
pp. 933 ◽  
Author(s):  
R Alexander ◽  
DA Owensby ◽  
AJ Parker ◽  
WE Waghorne
Keyword(s):  
Electrochemical Cell ◽  
Linear Free Energy Relationship ◽  
Free Energies ◽  
Univalent Cations ◽  
Liquid Junction Potential ◽  
Liquid Junction ◽  
Linear Free Energy ◽  
Solvation Of Ions ◽  
Solvation Mechanisms ◽  
Junction Potential

The free energies of transfer of some univalent cations from N,N-dimethylformamide to N,N- dimethylthioformamide at 25� are Li+, 64.0; Na+, 50.2; K+, 37.2; Cs+, 23.4; TI+, -4.2 and Ag+, - 87.0 kJ g-ion-1. The values are based on the assumption of negligible liquid junction potential in an electrochemical cell. Certain ones of these values can be interpreted in terms of general interactions of hard and soft cations with hard and soft basic solvents. A linear free energy relationship, ΔGtr(M+) = mΔGtr(K+), is roughly obeyed by many cations for transfer to a variety of solvents. Deviations from this relationship, for example ΔGtr(Ag2+) to acetonitrile, ΔGtr (Ph4As+) to water and ΔGtr (Ag+) to N,N-dimethylthioformamide, allow specific solvation mechanisms to be detected.

Solvation thermodynamics of ions: free energies in water, ammonia, and fused LiCl–KCl eutectic

1969 ◽  
Vol 47 (8) ◽  
pp. 1401-1410 ◽  
Author(s):  
James A. Plambeck
Keyword(s):  
Thermodynamic Data ◽  
Liquid Ammonia ◽  
Statistical Tests ◽  
Free Energies ◽  
Solvation Thermodynamics ◽  
Solvation Of Ions

Conventional free energies of solvation of ions are calculated from appropriate thermodynamic data in water, liquid ammonia, and fused LiCl–KCl eutectic. These are fitted to a modified Born-charging equation, whose origin and significance are discussed. Statistical tests are applied to certain aspects of the form of the equation. Parameters obtained from the equation can be used to calculate the free energies of solvation of single 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. XIX. Thermodynamic properties for transfer of single ions between protic and dipolar aprotic solvents

1974 ◽  
Vol 27 (3) ◽  
pp. 477 ◽  
Author(s):  
BG Cox ◽  
GR Hedwig ◽  
AJ Parker ◽  
DW Watts
Keyword(s):  
Thermodynamic Properties ◽  
Water Structure ◽  
Dimethyl Formamide ◽  
Aprotic Solvents ◽  
Free Energies ◽  
Enthalpy Changes ◽  
Solvation Of Ions ◽  
Anions And Cations ◽  
Solvent Molecules ◽  
Dipolar Aprotic Solvents

Standard molar free energies, enthalpies and entropies of transfer of some uni-univalent electrolytes from water to methanol, N-methylformamide, formamide, dimethyl sulphoxide, N,N-dimethyl- formamide, propylene carbonate, sulpholane, N-methylpyrrolidone and acetonitrile are presented. They have been divided into the corresponding thermodynamic properties for single ions by means of extrathermodynamic assumptions. Changes in the chemistry of anions on transfer from protic to dipolar aprotic solvents are mainly a function of enthalpy changes. There is a substantial loss of entropy on transferring both anions and cations from water to non-aqueous solvents. Entropies of transfer can be interpreted in terms of ordering and disordering solvent molecules and a uniquely extensive water structure. Evidence for solvation of the first and second kind in water is presented. Enthalpies of transfer from water are exothermic for cations but endothermic for many anions.

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