Solutes solute-solvent interactions

VI International Symposium on Solute-Solute-Solvent Interactions, 1982, Minoo, Osaka (as Secretary General. Chairman Professor Nobuyuki Tanaka of Tohoku University)... 

L. A. Woolf, Insights into solute-solute-solvent interactions from transport property measurements with particular reference to methanol-water mixtures and their constituents. Pure Appl. Chem., 57 (1985), 1083. 

Enderby, J. E. In Proceedings of the 7th International Symposium on Solute-Solute-Solvent Interactions, Reading, U.K., July 15-19, 1985. 

U. Mayer, Ions and Molecules in Solution, A collection of invited papers presented at the session lectures and microsymposia during the 6th International Symposium on Solute-Solute-Solvent Interactions, Minoo, Japan, 4-10 July 1982 (eds N. Tanaka, H. Ohtaki and R. Tamamushi) Studies in Physical and Theoretical Chemistry, vol. 27, 219, Elsevier Science Publishers B.V., Amsterdam U. Mayer, V. Gutmann and W. Gerger, Monatsh. Chem., 1975, 106, 1235. 

Micro-Symposium on the Double Layer, International Conference Solute-Solute-Solvent Interactions, Florence, Italy, May (1980), /. Electroanal. Chem. 123, 81 (1981). 

Acknowledgments. Professor L. Blum (University of Puerto Rico), Dr. E. Johnson (ORNL), and Dr. R. E. Meyer (ORNL) critically read the manuscript interaction with them has been fruitful and very rewarding. We want to thank the Italian CRRNSM for a grant used for some of the calculations presented here and done at the Computer Centre of the University of Palermo (Italy). Finally, we want to thank the organization committee of the Fifth I.U.P.A.C International Symposium on Solute-Solute-Solvent Interactions for inviting this paper. 

In conclusion it is worth noting that the question of the role of the solute-solute-solvent interactions with participation of metal complexes is of particular importance and it is not yet solved. In view of this the focusing of the efforts of many workers on it is justified. 

D. Yordanov and D. Shopov, Proc. II Inti. Symp. Solute-Solute-Solvent Interactions, Leuven, p. 225 (1974). 

In conformity with the general title of this Symposium, on Solute-Solute-Solvent Interactions , we have provided here examples from work performed in our laboratory on solute-solvent, solute-solute, and solute-solute-solvent interactions. These interactions involving charged groups are fundamental to a better knowledge of important phenomena such as anion activation, ion-binding by proteins, phase-transfer catalysis, and the mechanism of enzymatic action. 

International Symposium on Solute-Solute-Solvent Interactions, 5th, Florence, Italy, 1980. 

A part of the proceedings of the Fifth International Symposium on Solute—Solute—Solvent Interactions, held June 2—6, 1980, in Florence, Italy... 

From June 2nd to 5th 1980, the Vth International Symposium on Solute-Solute-Solvent Interactions was held in Florence, Italy. Owing to the large range of interests included in the program and to their interdisciplinary nature, a number of microsymposia on specific subjects were organized, in addition to plenary lectures, session lectures and poster sessions. The abstracts of the Conference were published in Inorganics Chimica Acta as a special publication and as an appendix to the issue of June 1980. 

Vibrational effects on optical rotation may be predicted by zero-point vibrational correction as developed by Ruud et al. however, solvent effects remain an important issue to be addressed and may be considered one of the most important sources of deviations between experimental and calculated data. In solutions, solute-solvent interactions play an important role in conformer populations of flexible molecules. In the case of rigid molecules, solvent polarization effects may be the leading cause of deviations. To date, the use of the polarizable continuum model (PCM) seems to be the best alternative to predicting solvent effects on [q ]d nevertheless, it should be used with caution because the results for carbon tetrachloride, benzene, and chloroform showed poor agreement with observed data. ... 

The solute-solvent interaction in equation A2.4.19 is a measure of the solvation energy of the solute species at infinite dilution. The basic model for ionic hydration is shown in figure A2.4.3 [5] there is an iimer hydration sheath of water molecules whose orientation is essentially detemiined entirely by the field due to the central ion. The number of water molecules in this iimer sheath depends on the size and chemistry of the central ion ... 

Specific solute-solvent interactions involving the first solvation shell only can be treated in detail by discrete solvent models. The various approaches like point charge models, siipennoleciilar calculations, quantum theories of reactions in solution, and their implementations in Monte Carlo methods and molecular dynamics simulations like the Car-Parrinello method are discussed elsewhere in this encyclopedia. Here only some points will be briefly mentioned that seem of relevance for later sections. 

Considering, for simplicity, only electrostatic interactions, one may write the solute-solvent interaction temi of the Hamiltonian for a solute molecule surrounded by S solvent molecules as... 

Kramers solution of the barrier crossing problem [45] is discussed at length in chapter A3.8 dealing with condensed-phase reaction dynamics. As the starting point to derive its simplest version one may use the Langevin equation, a stochastic differential equation for the time evolution of a slow variable, the reaction coordinate r, subject to a rapidly statistically fluctuating force F caused by microscopic solute-solvent interactions under the influence of an external force field generated by the PES F for the reaction... 

RRKM fit to microcanonical rate constants of isolated tran.s-stilbene and the solid curve a fit that uses a reaction barrier height reduced by solute-solvent interaction [46],... 

Aguilar M A and Olivares del Valle F J 1989 Solute-solvent interactions. A simple procedure for constructing the solvent capacity for retaining a molecular solute Ohem. Rhys. 129 439-50... 

Schroeder J 1996 The role of solute-solvent interactions in the dynamics of unimolecular reactions in compressed solvents J. Phys. Condens. Matters 9379... 

The variation of chemical shifts as a function of dilution could be accounted for only qualitatively (235) because of the large diversity of solute-solvent interactions resulting from the nature and the shape of the solvent molecule (Table 1-34). 

Q are the absorbance and wavenumber, respectively, at the peak (center) of the band, p is the wavenumber, and y is the half width of the band at half height. Liquid band positions ate usually shifted slightly downward from vapor positions. Both band positions and widths of solute spectra are affected by solute—solvent interactions. Spectra of soHd-phase samples are similar to those of Hquids, but intermolecular interactions in soHds can be nonisotropic. In spectra of crystalline samples, vibrational bands tend to be sharper and may spHt in two, and new bands may also appear. If polarized infrared radiation is used, both crystalline samples and stressed amorphous samples (such as a stretched polymer film) show directional effects (28,29). 

The solvophobic model of Hquid-phase nonideaHty takes into account solute—solvent interactions on the molecular level. In this view, all dissolved molecules expose microsurface area to the surrounding solvent and are acted on by the so-called solvophobic forces (41). These forces, which involve both enthalpy and entropy effects, are described generally by a branch of solution thermodynamics known as solvophobic theory. This general solution interaction approach takes into account the effect of the solvent on partitioning by considering two hypothetical steps. Eirst, cavities in the solvent must be created to contain the partitioned species. Second, the partitioned species is placed in the cavities, where interactions can occur with the surrounding solvent. The idea of solvophobic forces has been used to estimate such diverse physical properties as absorbabiHty, Henry s constant, and aqueous solubiHty (41—44). A principal drawback is calculational complexity and difficulty of finding values for the model input parameters. 

As long as the normalization condition given by Eq. (5) is satisfied, an arbitrary offset constant may be added to W(X) without affecting averages in Eq. (3). The absolute value of the PMF is thus unimportant. For convenience, it is possible to choose the value of the free energy W(X) relative to a reference system from which the solute-solvent interactions are absent. The free energy W(X) may thus be expressed as... 

---