The ionic work function and its role in estimating absolute electrode potentials.

The experimental determination of the ionic work function is briefly described. Data for the proton, alkali metal ions, and halide ions in water, originally published by Randles (Randles, J. E. B. Trans Faraday Soc. 1956, 52, 1573) are recalculated on the basis of up-to-date thermodynamic tables. These calculations are extended to data for the same ions in four nonaqueous solvents, namely, methanol, ethanol, acetonitrile, and dimethyl sulfoxide. The ionic work function data are compared with estimates of the absolute Gibbs energy of solvation obtained by an extrathermodynamic route for the same ions. The work function data for the proton are used to estimate the absolute potential of the standard hydrogen electrode in each solvent. The results obtained here are compared with those published earlier by Trasatti (Trasatti, S. Electrochim. Acta 1987, 32, 843) and more recently by Kelly et al. (Kelly, C. P.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2006, 110, 16066. Kelly, C. P.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2007, 111, 408). A comparison of the ionic work function with the absolute Gibbs solvation energy permits an estimation of the surface potential of the solvent. The results show that the surface potential of water is small and positive whereas the surface potential of the nonaqueous solvents considered is negative. The sign of the surface potential is consistent with the known structure of each solvent.