The Effect of Solvent Polarity on Chemical Systems

The effect of solvent polarity on chemical systems including reaction rates and equilibria can be quite significant. In general, it is necessary to consider the relative polarities of the reactants and products. In equilibria, a polar solvent will favour the more polar species. A good example is the keto-enol tautomerization of ethyl acetoacetate shown in Figure 1.9. The keto tautomer is more polar than the enol tautomer and therefore the equilibrium lies to the left in polar media such as water Table 1.11. 

There are two cases to consider when predicting the effect of solvent polarity on copolymerization propagation kinetics (1) the solvent polarity is dominated by an added solvent and polarity is thus independent of the comonomer feed ratio, or (2) the solvent polarity does depend on the comonomer feed ratio, as it would in a bulk copolymerization. In the first case, the effect on copolymerization kinetics is simple. The monomer reactivity ratios (and additional reactivity ratios, depending on which copolymerization model is appropriate for that system) would vary from solvent to solvent, but, for a given copolymerization system they would be constant as a function of the monomer feed ratios. Assiuning of course that there were no additional types of solvent effect present, these copolymerization systems could be described by their appropriate base model (such as the terminal model or the explicit or implicit penultimate models), depending on the chemical structine of the monomers. 

The effect of molecular interactions on the distribution coefficient of a solute has already been mentioned in Chapter 1. Molecular interactions are the direct effect of intermolecular forces between the solute and solvent molecules and the nature of these molecular forces will now be discussed in some detail. There are basically four types of molecular forces that can control the distribution coefficient of a solute between two phases. They are chemical forces, ionic forces, polar forces and dispersive forces. Hydrogen bonding is another type of molecular force that has been proposed, but for simplicity in this discussion, hydrogen bonding will be considered as the result of very strong polar forces. These four types of molecular forces that can occur between the solute and the two phases are those that the analyst must modify by choice of the phase system to achieve the necessary separation. Consequently, each type of molecular force enjoins some discussion. 

Several workers have attempted to use the common ion technique to depress [Pn+] and thus to achieve a monoeidic Pn+A system, as was done so successfully for anionic systems. However, because generally the solvents used for cationic polymerisations are much more polar, the KD of the chain-carriers and of the common-ion salts are considerably greater than in the anionic systems. Therefore the electro-chemical situation is likely to be complicated by triple ion formation and the effects of ionic strength on the KD and on the rate-constants, so that any results obtained by extrapolations to infinite ionic strength need to be scrutinised most carefully. 

Apart from the chemical effects of solvent as hydrogen donor, being heterogeneous systems, an important role of solvent is to provide appropriate reaction sites on the balance of solvent interactions with base polymer and growing graft chain. For the study of solvent effects, AM is not an adequate monomer since it is scarcely soluble in non-polar solvents. Instead, acrylic acid(AA) was employed and photografting was conducted as shown in Figure 8. 

Saito 7) measured the sound velocity in well-characterized CA solutions with a Pierce type ultrasonic interferometer with high accuracy and determined s. Figure 26 shows the relation between s,, of CA whole polymer solutions and e of the solvent at 25 °C 7). While the dependence of Sq on e differs depending on < F>, s, , except for C A(2.46)-acetone increases with increasing polarity of the solvent in a similar manner as the chemical shifts of the O-acetyl and hydroxyl groups. In Fig. 27, the effects of on Sq for CA-DMAc and CA-dimethylsulfoxide (DMSO) solutions at 25 °C are shown. In both systems, Sq has a maximum at F 2.5 7). 

The understanding and reliable prediction of the influence of the solute-solvent interactions on the nonlinear optical properties of molecular systems is a significant issue for a width range of theoretical and experimental areas of studies. In this review, it was shown that the simple two-state approximations combined with tlie solvatochromic methods are an effective tools in prediction tlie direction of tlie changes of molecular nonlinear responses as a function of solvent polarity. This methodology based on the description of the solvent effects at the molecular level should be treated as a supporting for the most sophisticated quantum chemical approaches. 

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