Abstract
This paper gives two empirical correlations of formation Gibbs energies of gaseous clusters ΔGfn as function of number of solvent molecules attached to the ion, n, and one correlation connecting the ΔGfn for each individual cluster with the total ΔGohydr value. The experimental ratios of ΔGf2/ΔGf1 and ΔGf3/ΔGf1 for both alkali metal and halide ions are on average equal to 0.75 and 0.5, respectively. ΔGfn values for n ≥ 4 are correlated with n as ΔGfn = [a/(n - 1)] ΔGf1 + b ΔGf1. For all available data on cluster energies and each individual cluster, the ΔGfn’s are straight-line functions of ΔGohydr. This well corresponds to another empirical rule stating that the Gibbs energies of transfer of ions between two solvents are often as well straight-line functions of ΔGohydr [J. Rais and T. Okada, J. Phys. Chem. A, 2000, 104, 7314]. Tentative models of the found behavior are proposed. A full data set of the gaseous cluster energies of formation based on inclusion of new, usually not used entries from the literature is provided.
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Rais, J., Okada, T. Three Empirical Correlations Connecting Gaseous Cluster Energies and Solvation Energies of Alkali Metal and Halide Ions. ANAL. SCI. 22, 533–538 (2006). https://doi.org/10.2116/analsci.22.533
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DOI: https://doi.org/10.2116/analsci.22.533