Activity of Real Electrolyte Solutions

The thermodynamic properties of real electrolyte solutions can be described by various parameters the solvent s activity Oq, the solute s activity the mean ion activities a+, as well as the corresponding activity coefficients. Two approaches exist for determining the activity of an electrolyte in solution (1) by measuring the solvent s activity and subsequently converting it to electrolyte activity via the thermodynamic Gibbs-Duhem equation, which for binary solutions can be written as 

The solvent s activity can be determined by measuring the saturation vapor pressure above the solution. Such measurements are rather tedious and their accuracy at concentrations below 0.1 to 0.5M is not high enough to produce reliable data therefore, this method is used only for concentrated solutions. The activity can also be determined from the freezing-point depression or boiling-point elevation of the solution. These temperature changes must be ascertained with an accuracy of about 0.0001 K, which is quite feasible. This method is used primarily for solutions with concentrations not higher than 1M. 

Direct measurements of solute activity are based on studies of the equilibria in which a given substance is involved. The parameters of these equilibria (the distribution coefficients, equilibrium constants, and EMF of galvanic cells) are determined at different concentrations. Then these data are extrapolated to very low concentrations, where the activity coincides with concentration and the activity coefficient becomes unity. 

Electrochemical Cell Without Transference Assume that we want to determine the activities of HCl solutions of various concentrations. We assemble a galvanic cell with hydrogen and calomel electrode  

FIGURE 7.3 Extrapolation of experimental data for the determination of activity coefficients. 

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