Solvents, interactive

Viscosity additives are aliphatic polymers of high molecular weight whose main chain is flexible. It is known that in a poor solvent, interactions between the elements making up the polymer chain are stronger than interactions between the solvent and the chain (Quivoron, 1978), to the point that the polymer chain adopts a ball of yarn configuration. The macromolecules in this configuration occupy a small volume. The viscosity of a solution being related to the volume occupied by the solute, the effect of polymers on the viscosity in a poor solvent will be small. 

In polymer solutions and blends, it becomes of interest to understand how the surface tension depends on the molecular weight (or number of repeat units, IV) of the macromolecule and on the polymer-solvent interactions through the interaction parameter, x- In terms of a Hory lattice model, x is given by the polymer and solvent interactions through... 

As described at the end of section Al.6.1. in nonlinear spectroscopy a polarization is created in the material which depends in a nonlinear way on the strength of the electric field. As we shall now see, the microscopic description of this nonlinear polarization involves multiple interactions of the material with the electric field. The multiple interactions in principle contain infomiation on both the ground electronic state and excited electronic state dynamics, and for a molecule in the presence of solvent, infomiation on the molecule-solvent interactions. Excellent general introductions to nonlinear spectroscopy may be found in [35, 36 and 37]. Raman spectroscopy, described at the end of the previous section, is also a nonlinear spectroscopy, in the sense that it involves more than one interaction of light with the material, but it is a pathological example since the second interaction is tlirough spontaneous emission and therefore not proportional to a driving field... 

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 ... 

The McMillan-Mayer theory offers the most usefiil starting point for an elementary theory of ionic interactions, since at high dilution we can incorporate all ion-solvent interactions into a limitmg chemical potential, and deviations from solution ideality can then be explicitly coimected with ion-ion interactions only. Furthemiore, we may assume that, at high dilution, the interaction energy between two ions (assuming only two are present in the solution) will be of the fomi... 

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... 

Abstract. A smooth empirical potential is constructed for use in off-lattice protein folding studies. Our potential is a function of the amino acid labels and of the distances between the Ca atoms of a protein. The potential is a sum of smooth surface potential terms that model solvent interactions and of pair potentials that are functions of a distance, with a smooth cutoff at 12 Angstrom. Techniques include the use of a fully automatic and reliable estimator for smooth densities, of cluster analysis to group together amino acid pairs with similar distance distributions, and of quadratic progrmnming to find appropriate weights with which the various terms enter the total potential. For nine small test proteins, the new potential has local minima within 1.3-4.7A of the PDB geometry, with one exception that has an error of S.SA. 

Our potential is a sum of smooth surface potentials that model amino acid-solvent interactions and of smooth pair potentials that model amino acid-amino acid interactions. As in [24], we take as essential only the Ca atoms. 

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). 

The nature of solute-solute and solute-solvent interactions is dependent on the solvent environment. Solvent influences the hydrogen-bonding pattern, solute surface area, and hydrophilic and hydrophobic group exposures. 

At the beginning of this section we enumerated four ways in which actual polymer molecules deviate from the model for perfectly flexible chains. The three sources of deviation which we have discussed so far all lead to the prediction of larger coil dimensions than would be the case for perfect flexibility. The fourth source of discrepancy, solvent interaction, can have either an expansion or a contraction effect on the coil dimensions. To see how this comes about, we consider enclosing the spherical domain occupied by the polymer molecule by a hypothetical boundary as indicated by the broken line in Fig. 1.9. Only a portion of this domain is actually occupied by chain segments, and the remaining sites are occupied by solvent molecules which we have assumed to be totally indifferent as far as coil dimensions are concerned. The region enclosed by this hypothetical boundary may be viewed as a solution, an we next consider the tendency of solvent molecules to cross in or out of the domain of the polymer molecule. 

A good solvent is the technical as well as descriptive term used to identify a solvent which tends to increase coil dimensions. Since this is a consequence of thermodynamically favorable polymer-solvent interactions, good solvents also dissolve polymers more readily in the first place. 

In parallel with item (3), the contribution of all solvent interactions to the total energy is A) z0iN[02Wi2 + (1 - 02)wn]. 

Many ceUulosic derivatives form anisotropic, ie, Hquid crystalline, solutions, and cellulose acetate and triacetate are no exception. Various cellulose acetate anisotropic solutions have been made using a variety of solvents (56,57). The nature of the polymer—solvent interaction determines the concentration at which hquid crystalline behavior is initiated. The better the interaction, the lower the concentration needed to form the anisotropic, birefringent polymer solution. Strong organic acids, eg, trifluoroacetic acid are most effective and can produce an anisotropic phase with concentrations as low as 28% (58). Trifluoroacetic acid has been studied with cellulose triacetate alone or in combination with other solvents (59—64) concentrations of 30—42% (wt vol) triacetate were common. 

Gelatin stmctures have been studied with the aid of an electron microscope (23). The stmcture of the gel is a combination of fine and coarse interchain networks the ratio depends on the temperature during the polymer-polymer and polymer-solvent interaction lea ding to bond formation. The rigidity of the gel is approximately proportional to the square of the gelatin concentration. Crystallites, indicated by x-ray diffraction pattern, are beUeved to be at the junctions of the polypeptide chains (24). 

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). 

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