Solvation of ions. XXII. Solvation of cations by hard N,N-dimethylformamide and soft N,N-dimethylthioformamide
Alexander, R., Owensby, D.A., Parker, A.J. and Waghorne, W.E. (1974) Solvation of ions. XXII. Solvation of cations by hard N,N-dimethylformamide and soft N,N-dimethylthioformamide. Australian Journal of Chemistry, 27 (5). pp. 933-941.
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The free energies of transfer of some univalent cations from N,N-dimethylformamide to N,N- dimethylthioformamide at 25º 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.
|Publication Type:||Journal Article|
|Publisher:||Commonwealth Scientific and Industrial Research Organization Publishing|
|Copyright:||© CSIRO 1974|
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