By measuring the A−(H2O)n−1 + H2O = A−(H2O)n equilibria in the gas phase and their temperature dependence, the equilibrium constants and ΔHn, n–1 and ΔSn, n–1 for some of the hydrates of NO2−, NO3−, CN−, and OH− were determined. Available thermochemical data are used for the evaluation of the total heats of hydration of the above ions. The total heats of hydration were then compared with the ΔH1,0. Relative to the total hydration energies the ΔH1,0 of the above ions were found larger than the ΔH1,0 of the halide ions.An approximate linear correlation was found to exist between ΔH1,0 of negative ions and the heterolytic bond dissociation energy D(A−–H+). With this relationship independent estimates for the electron affinities of NO2 and NO3 could be obtained.The ΔHn, n–1 of OH− were found in essential agreement with earlier measurements from this laboratory and in disagreements with recent measurements (Friedman) which gave much higher values.
