Solvatochromic parameters Kamlet-Taft

The properties of organic liquids relevant to their use as solvating agents have also been reviewed [76]. The ability of liquids to solvate a solute species depends mainly on their polarity and polarizability properties, ability to hydrogen bond, and cohesive electron density. These molecular properties are best measured by the Kamlet-Taft solvatochromic parameters, and the square of Hildebrand s solubility parameter. 

FIGURE 9.7 Variation of Kamlet-Taft solvatochromic parameters for methanol/C02 mixtures as a function of added CO2 at 298 K and 17.2 MPa (A)n (dipolarity/polarizability, ( ) (H-bond acidity), and (T)/8 (H-bond basicity). (Adapted from Y. Cui, S. V. Olesik, Anal. Chem., 63 1812(1991).)... 

ENGINEERING, CHEMICALDATA CORRELATION] (Vol 9) Kamlet-Taft solvatochromic parameters... 

The oxidation of meta- and para-substituted anilines with imidazolium fluorochro-mate (IFC)18 and nicotinium dichromate (NDC),19 in several organic solvents, in the presence of p-toluenesulfonic acid (TsOH) is first order in the oxidant and TsOH and is zero order with respect to substrate. A correlation of rate data in different solvents with Kamlet-Taft solvatochromic parameters suggests that the specific solute-solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute-solvent complexation. The oxidation rates with NDC exhibited negative reaction constants, while the oxidation with IFC did not correlate well with any linear free energy relationships. 

A comprehensive research of a large number of benzofurazan nitro derivatives using UV spectroscopy and other physical-chemical methods has been carried out [777, 1006, 1007, 1106, 1107, 1229-1241], The frequencies of long-wave absorption bands of hydroxy- and aminosubstituted of nitrobenzofurazans greatly depend on the solvent nature [1106, 1107, 1230-1233, 1235, 1236], They are assigned to the bands of intramolecular charge transfer [1007, 1232], Correlation relationships between the wave number (v) and the Kamlet-Taft solvatochromic parameter (it ) are presented in the works cited ... 

INVESTIGATED SOLVENTS AND THEIR KAMLET-TAFT SOLVATOCHROMIC PARAMETERS (12,1. 124 ... 

One such methodology is the Kamlet-Taft Solvatochromic parameter approach. In this methodology, a solvent can be characterized by three parameters, tt, a measure of the polarity and polarizability of the fluid, a, the acidity or hydrogen bond donor capability and P, the hydrogen bond acceptor capability or basicity. Each of these parameters is determined from the shift in UV-visible absorbance of a series of select indicator species dissolved in the solvent. Rather than depending on the bulk properties of the fluid, as is the case with the cohesive energy approaches, the solvatochromic parameters are derived from the interactions between the indicator solute and the immediate solvent shell, in effect they are a measure of how a solute sees the solvent. In each case, the scale of values has been normalized to between 0.0 for cyclohexane... 

From the values of the Kamlet-Taft solvatochromic parameters (Table IV), R-134a is seen to behave as a moderately polar, weakly polarizable fluid with little or no basicity and weak acidity (of the order of dichloromethane). The negative value for P has been commented on previously (J) and may be an artifact of the original scale definition, the regression for which did not include heavily fluorinated species. In any case, the value suggests that R-134a is a poorer hydrogen bond acceptor than, for example, hydrocarbons. 

A subsequent multiple linear regression analysis [138] focused on the Kamlet-Taft solvatochromic parameters, employing transfer Gibbs energies and enthalpies AG°t and AH°r) for 26 solvents. Standard molar Gibbs energies of transfer for nine univalent and six divalent small cations correlated well with the Kamlet-Taft parameters via linear solvation energy relationships of the form... 

Here Rs is the excess molar refraction of the solute over that of an alkane with the same characteristic volume (Abraham et al. 1990) (not further specified). The Kamlet-Taft solvatochromic parameters of the solute (Kamlet et al. 1983) are n, the polarity/polarizibility, a the HB donation (electron pair acceptance) ability, and P the HB acceptance (electron pair donation) ability. The volume of the solute is represented by the Abraham-McGowan volumes Vx (Abraham and McGowan 1987), based on invariant atom and bond contributions. The parameters a and /9 pertain to the monomeric solutes (measured in dilute solutions thereof). The correlation coefficient for Eq. (1.21) for 408 solutes is 0.998 and the standard deviation is 0.15. 

The Kamlet-Taft solvatochromic parameters )t a, and p for a micellar medium are usually determined by measuring the spectroscopic parameters of certain probes using known correlation equations. The correlation equations are, however, obtained from studies in pure solvents. It is assumed that the correlation equation obtained for pure solvents is also valid for micellar media. Both absorption [14-17] and fluorescence [18,90] probes have been used for estimating values of a, p, and it for the micellar media. 

AF Lagalante, RL Hall, TJ Bruno. Kamlet-Taft solvatochromic parameters of tbe sub- and supercritical fluorinated ethane solvents. J Phys Chem B 102 6601, 1998. K Takahashi, K Abe, S Sawamura, CD Jonah. Spectroscopic study of 4-aminoben-zophenone in supercritical CF3H and CO2 local density and Onsager s reaction cavity radius. Chem Phys Lett 282 361, 1998. 

Table 15.4 shows the acid/base ratios of the van Oss-Good parameters from various sources, as compared to the acid/base ratio predicted from the Kamlet-Taft solvatochromic parameters. The latter parameters are used both in the original form and their normalized values from Lee. We notice that the newest sets of parameters are in better agreement with the water trends predicted from the Kamlet-Taft... 

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