Solvent polarity relationships

C. M. Hansen, in Macromolectdar Solutions Solvent-Polarity Relationships in Polymers, Proceedings of the Symposium, American Chemical Society, New York, 1981, edited by R. B. Seymour and G. A. Stahl (Pergamon, New York, 1982), p. 1 Org. Coat. Plast. Chem. 45, 227 (1981). 

The merocyanine dye mentioned above shows solvatochromism, which means that the absorption band maximum of the quinoid form (D form) is sensitive to solvent polarity [40,41]. In Fig. 3, the absorption maximum of the solvatochromic band for M-Mc (a low molecular weight merocyanine analog) is plotted against the dielectric constant of 1,4-dioxane/water mixtures [42]. With the relationship... 

The rate constants in organic reaction in a solvent generally reflect the solvent effect. Various empirical measures of the solvent effect have been proposed and correlated with the reaction rate constant [5]. Of these, some measures have a linear relation to the solubility parameter of the solvent. The logarithms of kj and k2/ki were plotted against the solubility parameter of toluene, NMP and DMSO[6] in Fig. 2. As shown in Fig.2, the plots satisfied the linear relationship. The solvent polarity is increased by the increase of solubility parameter of the solvent. It may be assumed that increase of unstability and solvation of Ci due to the increase of solvent polarity make the dissociation reaction of Ci and the reaction between Ci and COisuch as SNi by solvation[7] easier, respectively, and then, k2/ki and ks increases as increasing the solubility parameter as shown in Fig. 2. 

Dimers (73) and (74) were formed in approximately equal amounts in all cases, although, as in the cases of 2-cyclopentenone and 2-cyclohexenone, the relative amount of (72) (either cis-syn-cis or cis-anti-cis) was found to vary substantially with solvent polarity. As in 2-cyclopentenone, this increase in the rate of head-to-head dimerization was attributed to stabilization of the increase in dipole moment in going to the transition state leading to (72) in polar solvents. It is thought that the solvent effect in this case is not associated with the state of aggregation since a plot of Stem-Volmer plot and complete quenching with 0.2 M piperylene indicate that the reaction proceeds mainly from the triplet manifold. However, the rates of formation of head-to-head and head-to-tail dimers do not show the same relationship when sensitized by benzophenone as in the direct photolysis. This effect, when combined with different intercepts for head-to-head and head-to-tail dimerizations quenched by piperylene in the Stem-Volmer plot, indicates that two distinct excited triplet states are involved with differing efficiencies of population. The nature of these two triplets has not been disclosed. 

Grathwohl (1990) found a relationship between sorption capacity and the the atomic H/O ratio of NOM. Similarly, there is a good relationship between log Koc and the polarity index (PI) of SOM, defined as the (0+N)/C ratio (DePaolis and Kukkonen 1997 Rutherford et al. 1992 Xing 1997 Xing et al. 1994a). The effect of SOM polarity on sorption of organic compounds is consistent with the well-known theory of solvent polarity on solute solubility. In studying the influence of SOM composition... 

No particular relationship between solvent polarity and the observed change is apparent. Rader notes that the experimental conditions are such that no appreciable intramolecular hydrogen-bonding occurs between methanol molecules, presumably ruling out the possibility that the change arises from solvent induced variation of the self-association equilibrium. Differences in solvent-solute association are still a possible interaction mechanism. 

Solvent polarity was found to effect the rate of polymerization (Table I). For the three solvents studied, an essentially linear relationship (R=0.970) was observed between Rp and dielectric constant. 

Parameters of the Kamlet-Taft solvatochromic relationship. These parameters measure the contributions to overall solvent polarity of the hydrogen bond donor, the hydrogen bond acceptor, and the dipolarity/polarizability properties of solvents. 

Nuclear magnetic resonance studies on meso-ionic l,2,4-triazol-3-ones (200) were used to examine their relationship to the alternative l,3,4-oxadiazol-2-imine structure (153). The effect of solvent polarity upon the ultraviolet spectrum of anhydro-3-hydroxy-1,4-diphenyl-1,2,4-triazolium hydroxide (200, R = = Ph, R = H) has been discussed... 

For reviews of solvent polarity scales, see Abraham Grellier Abboud Doherty Taft Can. J. Chem. 1988,66. 2673-2686 Kamlet Abboud Taft Prog. Phys. Org. Chem. 1981,13,485-630 Shorter Correlation Analysis of Organic Reactivity Wiley New York, 1982, pp. 127-172 Reichardt, Ref. 386 Reichardt Dimroth, Ref. 386 Abraham Prog. Phys. Org. Chem. 1974, II, I -87 Koppel Palm, in Chapman Shorter Advances in Linear Free Energy Relationships, Plenum New York, 1972, pp. 203 280 Ref. 384. See also Chastrette Carrclto Tetrahedron 1962,38, 1615 Chastrette Rajzmann Chanon Purcell J. Am. Chem. Soc. 1965,107, 1. 

The major usable variable controlling k is solvent polarity. While temperature and column polarity also effect retention times, they do not show the same direct, linear relationship for all peaks and are usually classed under the separation factor (a). 

The Kamlet-Taft u polarity/polarizability scale is based on a linear solvation energy relationship between the n it transition energy of the solute and the solvent polarity ( 1). The Onsager reaction field theory (11) is applicable to this type of relationship for nonpolar solvents, and successful correlations have previously been demonstrated using conventional liquid solvents ( 7 ). The Onsager theory attempts to describe the interactions between a polar solute molecule and the polarizable solvent in the cybotatic region. The theory predicts that the stabilization of the solute should be proportional to the polarizability of the solvent, which can be estimated from the index of refraction. Since carbon dioxide is a nonpolar fluid it would be expected that a linear relationship... 

The effective correlation times for an approximately isotropic motion, tr, ranged from 40.3 ps in methanol to 100.7 ps in acetic acid for 5a, and from 61.6 ps to 180.1 ps for 5b in the same solvents. Neither solvent viscosity nor dielectric constant bore any direct relationship to the correlation times found from the overall motion, and attempts to correlate relaxation data with parameters (other than dielectric constant) that reflect solvent polarity, such as Kosover Z-values, Win-stein y-values, and the like, were unsuccessful.90 Based on the maximum allowed error of 13% in the tr values derived from the propagation of the experimental error in the measured T, values, the rate of the overall motion for either 5a or 5b in these solvents followed the order methanol N,N-dimethylformamide d2o < pyridine < dimethyl sulfoxide. This sequence appears to reflect both the solvent viscosity and the molecular weight of the solvated species. On this basis, and assuming that each hydroxyl group is hydrogen-bonded to two molecules of the solvent,137 the molecular weights of the solvated species are as follows in methanol 256, N,N-dimethylformamide 364, water 144, pyridine 496, and dimethyl sulfoxide 312. 

The hydrogenation of j3-octalone (XII) in a number of neutral solvents over a palladium catalyst gave mixtures of the cis- and tra s-j3-decalones. Initial examination of these product ratios showed no correlation between the dielectric constant of the solvent and the amount of cis-j3-decalone (XIIII) obtained. When the solvents were separated into protic and aprotic categories, however, a direct relationship between product stereochemistry and solvent polarity in each series became apparent, as shown by the data given in Tables II and III (24). 

Table 42 gives an overview of annular tautomerism data for azoles in the gas phase and in solution or crystals. In the gas phase the stability of alternative tautomers largely depends on their relative aromaticities. In Section 2 A.4.2.2 it was noted that 1,2-relationships between pyrrole- and pyridine-type nitrogen atoms favor aromaticity (Figure 21) and this is consistent with the relative stabilities of triazole and tetrazole tautomers in the gas phase (Table 42) <2010T2695>. In solution (and crystals) other factors such as solvent polarity, hydrogen bonding, and temperature become important and the relative stabilities can be reversed. Polar solvents tend to stabilize the tautomer with the largest dipole moment and this probably accounts for the observation of both 2H-1,2,3-triazole (p = 0.12D) and H-1,2,3-triazole (p = 4.55D) in...

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