ION—WATER INTERACTION (“SALTING OUT”) IN NITROMETHANE AND THE FREE ENERGY OF TRANSFER OF SOME ELECTROLYTES TO PURE NITROMETHANE FROM NITROMETHANE SATURATED WITH WATER1

1963 ◽  
Vol 67 (9) ◽  
pp. 1757-1761 ◽  
Author(s):  
G. R. Haugen ◽  
H. L. Friedman
Keyword(s):  
Free Energy ◽  
Salting Out ◽  
Water Interaction ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer

Thermodynamics of transfer of Ph4C; scaled-particle theory and the Ph4As+/Ph4B− assumption for single ions

1979 ◽  
Vol 57 (15) ◽  
pp. 2004-2009 ◽  
Author(s):  
Michael H. Abraham ◽  
Asadollah Nasehzadeh
Keyword(s):  
Free Energy ◽  
Total Free Energy ◽  
Scaled Particle Theory ◽  
Free Energies ◽  
Particle Theory ◽  
Free Energy Of Transfer ◽  
Enthalpy And Entropy ◽  
Interaction Term ◽  
Energy Of Transfer ◽  
Entropy Of Transfer

Free energies of transfer of Ph4C from acetonitrile to 20 other solvents have been calculated from literature data. The contribution of the cavity term to the total free energy has been obtained from scaled-particle theory and Sinanoglu–Reisse–Moura Ramos theory. It is shown that there is little connection between the cavity term and the total free energy of transfer, and that there must be, in general, a large interaction term. If the latter is important for transfer of Ph4C, we argue that it must also be important for transfer of the ions Ph4As+ and Ph4B−. Previous suggestions that the interaction term is zero for transfer of these two ions are thus seen to be unreasonable. We also show, for six solvents, that the interaction term for Ph4C is very large in terms of enthalpy and entropy, and that scaled-particle theory seems not to apply to transfers of Ph4C between pure organic solvents.The free energy, enthalpy, and entropy of transfer of Ph4As+ = Ph4B− have been calculated by dividing the total transfer values into neutral and electrostatic contributions; reasonable agreement is obtained between calculated and observed values.

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