Determination of the transfer thermodynamic functions for some monovalent ions from water to N,N-dimethylthioformamide, and for some anions from water to methanol, dimethyl sulfoxide, acetonitrile and pyridine, and standard electrode potentials of some M+/M(s) couples in N,N-dimethylthioformamide

1994 ◽  
Vol 90 (15) ◽  
pp. 2223 ◽  
Author(s):  
Halina D. Inerowicz ◽  
Wei Li ◽  
Ingmar Persson
Keyword(s):  
Dimethyl Sulfoxide ◽  
Thermodynamic Functions ◽  
Electrode Potentials ◽  
Monovalent Ions ◽  
Standard Electrode Potentials

Determination of Basicities of Organic Solvents and Absolute Electrode Potentials (E0-Values) of Monovalent Ions in Organic Solvents based on Absolute Values of Gibbs Energies of Solvation of Single Ions

2004 ◽  
Vol 218 (5) ◽  
pp. 515-550 ◽  
Author(s):  
Ranjana Bhattacharyya ◽  
S. C. Lahiri
Keyword(s):  
Organic Solvents ◽  
Gibbs Energies ◽  
Electrode Potentials ◽  
Induced Dipole ◽  
Single Scale ◽  
Monovalent Ions ◽  
Born Equation ◽  
The Absolute ◽  
Single Standard

AbstractSingle ion Gibbs energies of monovalent ions in fourteen solvents (water, methanol, NMF, PC, ethanol, n-propanol, iso-propanol, n-butanol, t-butanol, ethylene glycol, acetone, THF, 1,4-dioxan, acetonitrile) with or without (ion–dipole, ion–induced dipole, ion–quadrupole) interactions were determined. The basicity of the solvents was determined from the absolute values of ΔG0solvation(H+) or ΔG0solution(H+) based on single standard state utilising the modified Born equation suggested by Lahiri. The method involves no arbitrary assumptions. A single scale for the absolute electrode potentials (E0 values) has been determined based on calculated Gibbs energies of solvation or solution of single ions. Appropriation of Gibbs energies of solvation of electrolytes into single ion values is not possible. Gibbs energies of formation of electrolytes in solvents must be taken into consideration. Stabilisation energies of electrolytes (MX) in solvents akin to lattice energies in solids were determined.

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