Abstract
Electromotive force measurements were made of cells of the type glycerol at 5°, 15°, 25°, 35°, and 45°C and also in 10 w/o glycerol at 25°C. The cell has been used to calculate, (a) the standard emf, (b) the mean molal activity coefficients of , (c) the primary medium effect, (d) the relative partial molal enthalpy, and (e) the standard thermodynamic functions (δG°t, δS°t, and δH°t) for the transfer of from the aqueous standard state to the standard state in the respective mixed solvents. The electrostatic part of the total free energy, entropy, and enthalpy of transfer has been computed using Born's model. The nonelectrostatic contribution (the chemical effect) of the thermodynamic quantities has been evaluated by subtracting the electrostatic contributions from the total values. The values of E°m obtained by a theoretically justified polynomial curve fitting technique have been expressed as a function of temperature. The significance of these results in relation to the acid‐base behavior and the breakdown of the structure of water is discussed.
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