
TY  - JOUR
A1  - Alexander, R 
A1  - Owensby, DA 
A1  - Parker, AJ 
A1  - Waghorne, WE 
T1  - Solvation of ions. XXII. Solvation of cations by hard N,N-dimethylformamide and soft N,N-dimethylthioformamide
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1974
VL  - 27
IS  - 5
SP  - 933
EP  - 941
KW  - 
UR  - https://doi.org/10.1071/CH9740933 
N2  - 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, &#916;Gtr(M+) = m&#916;Gtr(K+), is roughly obeyed by many cations for transfer to a variety of solvents. Deviations from this relationship, for example &#916;Gtr(Ag2+) to acetonitrile, &#916;Gtr (Ph4As+) to water and &#916;Gtr (Ag+) to N,N-dimethylthioformamide, allow specific solvation mechanisms to be detected. 
ER  -

