Concerning the distant polar interaction in free energies of transfer. An explanation and an estimation procedure

1991 ◽  
Vol 69 (12) ◽  
pp. 1893-1903 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Free Energy ◽  
Hydrogen Bonding ◽  
Estimation Procedure ◽  
Free Energies ◽  
Polar Interaction ◽  
Free Energies Of Transfer ◽  
Polar Groups ◽  
Polyfunctional Compounds ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer

For polyfunctional compounds, free energies of transfer from gas to aqueous solution require corrections for the interactions of polar groups (Distant Polar Interactions). These corrections can be made with very few adjustable parameters by using a model of the solvation process assuming hydrogen bonding is the major source of the effect on free energy of transfer for polar groups, and that hydrogen bonding is perturbed by polar effects, measured by Taft σ*. Parameters evaluated for polyfluoro, polychloro, and polybromo compounds successfully predicted the free energies of transfer for mixed polyhalogen compounds. Preliminary parameters have been evaluated for ethers, amines, phenyl groups, nitriles, and esters. Key words: free energy of transfer, distant polar interaction, hydrogen bonding, solvation.

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.

Comparison of the free energy of transfer of electrolytes, measured with cells without transference, with the sum of the free energies of the corresponding cations and anions with the Owen-cell on standard conditions

1983 ◽  
Vol 36 (10) ◽  
pp. 1997 ◽  
Author(s):  
K Schwabe ◽  
W Hoffmann ◽  
C Queck
Keyword(s):  
Free Energy ◽  
Free Energies ◽  
Liquid Junction Potential ◽  
Liquid Junction ◽  
Ph Values ◽  
Liquid Junction Potentials ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer ◽  
Very High ◽  
Junction Potential

The comparison of S2ΔS1G°tr(E1) with the sum of the values for the corresponding cation and anion S2ΔS1G°tr(Ct+)~S2ΔS1G°tr(X-) (measured) with Owen cells, gained by double extrapolation and by the assumption that the liquid junction potential at 1→0 may be neglected) gives values which differ by not more than ±5%. Most of the investigated acids allow the conclusion that the pH values, measured in cells with transference, and having the same electrodes, give good information on the acidity of the organic solvent and its water mixtures, referred to the standard state in water. That means that the pH, changed to the same H+ concentration in the solvent compared with that in water, is essentially an effect of the free energy of transfer of the hydrogen ion and not of very high liquid junction potentials.

Solvation in hydroorganic media—I. Gibbs free energy of transfer for RbCl from cationic glass electrode measurements

1976 ◽  
Vol 21 (6) ◽  
pp. 425-430 ◽  
Author(s):  
R. Smits ◽  
D.L. Massart ◽  
J. Juillard ◽  
J.-P. Morel
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Glass Electrode ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer

Microemulsion as Model to Predict Free Energy of Transfer of Electrolyte in Solvent Extraction

2021 ◽  
pp. 1-36
Author(s):  
Simon Gourdin-Bertin ◽  
Jean-François Dufrêche ◽  
Magali Duvail ◽  
Thomas Zemb
Keyword(s):  
Free Energy ◽  
Solvent Extraction ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer

The Gibbs free energy of transfer of the alkali perrhenates and perchlorates between pure water and pure nitromethane

1968 ◽  
Vol 72 (13) ◽  
pp. 4549-4554 ◽  
Author(s):  
Gilbert R. Haugen ◽  
Harold L. Friedman
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Pure Water ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer

Solvation in hydroorganic media—II. Gibbs free energy of transfer for HCl and comparison between Rb+ and H+ ions

1976 ◽  
Vol 21 (6) ◽  
pp. 431-436 ◽  
Author(s):  
R. Smits ◽  
D.L. Massart ◽  
J. Juillard ◽  
J.-P. Morel
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Free Energy Of Transfer ◽  
Energy Of Transfer
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