Abstract
Intrinsic ionic heats of transport q * (ion) and ionic heats of transport Q * (ion) have been evaluated for 53 aqueous ions at infinite dilution at 25°C using the reduction rule proposed by the authors and the limiting laws of Agar, and of Helfand and Kirkwood without electrophoretic terms. q * (ion) have been found to correlate linearly with the standard ionic entropies of hydration for the 38 ions investigated. The correlation yields three distinctive proportionality constants indicating that the ions may be divided into three distinctive groups. Although the sign of Q * (ion) is not definite, all values of q * (ion) are positive. For 17 ions Q * (ion) are in good agreement with TS * (ion). Here, S * (ion) is the ‘absolute’ standard ionic entropy of transport which can be obtained from potentiometric measurements on cells. The values of S * (ion) were determined by Agar, and recently by Lin and coworkers.
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