Acetonitrile transfer activity coefficients

A Bronsted fl]t value of 0.5 and occh value of 1.31 have been calculated for deprotonation reactions of (3,5-dinitrophenyl)nitromethane promoted by substituted benzoate ions and of substituted (3-nitro-, 4-nitro- and 3,5-dinitro-)phenyhiitro-methanes promoted by benzoate ion, respectively, in methanol.146 The intrinsic rate constants are (2.0-6.3)x 104 tunes lower than for the same reactions in acetonitrile solution, and this has been attributed to commensurate reduction of strength of the hydrogen bond between the carbon acid and benzoate ion in the imbalanced transition state. The transfer activity coefficient (logMyAN) from methanol to acetonitrile solution have been calculated for (// -nitrophenyl)nitromcthyl anion (3.6) and (m-nitrophenyl)-nitromethane (—1.0). 

These several assumptions do not lead to the same conclusions. For example, transfer activity coefficients obtained by the tetraphenylarsonium tetraphenyl borate assumption differ in water and polar aprotic solvents by up to 3 log units from those based on the ferrocene assumption. From data compiled by Kratochvil and Yeager on limiting ionic conductivities in many organic solvents, it is clear that no reference salt can serve for a valid comparison of all solvents. For example, the tetraphenylarsonium and tetraphenyl borate ions have limiting conductivities of 55.8 and 58.3 in acetonitrile. Krishnan and Friedman concluded that the solvation enthalpy of... 

X 10 , where AN, DMF, and DMSO stand for acetonitrile, dimethylformamide, and dimethyl sulfoxide. The value for yJ Ag+) about 20, and for about 250. Acetonitrile solvates many ions more weakly than does water, and their resulting high reactivity is reflected in large transfer activity coefficients. In contrast, the transfer activity coefficient for silver ions in acetonitrile is small, about 1.3 x 10. For hydrogen ions in pyridine, Mukherjee gives a value of about 1.4 x 10. Values such as these have led to useful correlations and qualitative predictions. 

The meaning to be attached to pH values obtained in different solvents and under different conditions needs interpretation. For example, solutions of pH 5 in the three solvents water, ethanol, and acetonitrile do not denote the same acidity (acidity defined as a measure of the tendency for protons to be donated to basic substances). In view of what is known about transfer activity coefficients (Section 4-1), an acetonitrile solution of pH 5 is far more acidic (higher absolute activity) than an ethanol solution of pH 5 and, in turn, one in ethanol is more acidic than one in water. The significant point is that a solution of, say, pH 5 in a given solvent has an acidity 10 times the acidity of another solution of pH 6 in that same solvent. A single universal scale of pH for all solvents does not exist instead there is a different scale for every solvent of differing composition. To denote pH values in nonaqueous solvents, the... 

It is a serious drawback that it is not possible to determine the transfer activity coefficient of the proton (or of any other single-ion species) directly by thermodynamic methods, because only the values for both the proton and its counterion are obtained. Therefore, approximation methods are used to separate the medium effect on the proton. One is based on the simple sphere-in-continuum model of Born, calculating the electrostatic contribution of the Gibb s free energy of transfer. This approach is clearly too weak, because it does not consider solvation effects. Different ex-trathermodynamic approximation methods, unfortunately, lead not only to different values of the medium effect but also to different signs in some cases. Some examples are given in the following log yH+ for methanol -1-1.7 (standard deviation 0.4) ethanol -1-2.5 (1.8), n-butanol -t-2.3 (2.0), dimethyl sulfoxide -3.6 (2.0), acetonitrile -1-4.3 (1.5), formic acid -1-7.9 (1.7), NH3 -16. From these data, it can be seen that methanol has about the same basicity as water the other alcohols are less basic, as is acetonitrile. Di-... 

M.K. Chantooni, Jr. and I.M. Kolthoff, Acid-base equilibria in methanol, acetonitrile, and dimethyl sulfoxide in acids and salts of oxalic acid and homologs, fumaric and o-phthalic acids. Transfer activity coefficients of acids and ions, J. Phys. Chem. 79 (1975), pp. 1176-1182. 

Experiments under the restrictions of classical thermoelectrochemistry in open cells with moderate temperature variation addressed, to some extent, also the conditions in the bulk electrolyte solution and the properties of ions. Potentiometric measurements in aqueous solutions of hydrogen and potassium bromides yielded the temperature dependence of activity coefficients of important ions [58]. As mentioned in Chap. 2, all electrolyte solutions tend to approach the ideal state with increasing temperature. The conductance of various electrolytes has been studied in dependence on temperature [59-66]. Solvents studied were propanol [59], propylene carbonate [60, 64], dimethoxyethane [65], primary alcohols and acetonitrile [62]. Conductance values were used to determine transference numbers of ions in non-aqueous solution [62]. Salt melts of sodium and caesium halides also have been studied [66]. Theoretical considerations were subject of [63]. 

Not only does anion-1 differ from the molecular anions of acetonitrile in its absorption properties, but its dynamic properties are also anomalous. While anion-2 has normal mobility, anion-1 is a high-mobility anion whose room temperature diffusion coefficient is more than three times higher than that of solute ions and anion-2 [30]. The activation energy for this migration is just 3.2 kJ/mol while the value for normal ions (including anion-2) is 7.6 kJ/mol [30]. Electron-transfer reactions that involve anion-1... 

---