Effects of some salts on H2O as probed by a thermodynamic signature of glycerol: towards understanding the Hofmeister effects (VII).

The generality of the Hofmeister effects has been questioned of late, and doubts have been cast over their importance in understanding the specific ion effects on the chemistry and physics of biopolymers in aqueous solutions. Recent experimental evidence from modern non-linear spectroscopies points mostly to the direct interaction between the ion and the biopolymer in question that is more important for understanding the Hofmeister effects. On the other hand, our own contribution by higher order thermodynamical studies indicated that the effects of ions on H2O itself may not be denied all together. Namely, we devised a methodology whereby the effect of an ion on H2O is characterized by two orthogonal indices, hydrophobicity and hydrophilicity, by using a third order thermodynamic signature of hydrophobic 1-propanol (1P) as a probe, the 1P-probing methodology. The results indicated that the common anion ranking could be understood in terms of two indices, hydrophobicity and hydrophilicity of an individual ion. In the present work, we make an attempt at probing the effects of the same ions on H2O by a typical hydrophile, glycerol (abbreviated as Gly in this article). Compared with the results of the 1P-probing methodology, we seek to determine how hydrophiles would react to the subtle modification of H2O caused by the presence of an ion, since biopolymers are large amphiphiles with hydrophobic and hydrophilic surfaces. The results indicate that the Gly-probe is much less sensitive than the 1P-probe. We suggest therefore that it is the hydrophobic moieties of biopolymers that mainly give more conspicuous response to the modified H2O by the presence of an ion.