Abstract
The binding energy and number of anion-water interactions were investigated by infrared spectroscopy in aqueous CH2Cl2 solutions containing salts and cryptands. In these solutions the frequency of the bound OH vibration and the H-bond energy both correlate linearly (Badger-Bauer rule) and are of the same order of magnitude as those in water-organic H-bond acceptor systems. The frequency shift of the OH vibration and the H-bond energy both show an anion dependence which increases in the order:
to 340 cm−1 and 17.2 kJ-mol−1 of H-bonds, respectively, when compared to H2O-CH2Cl2 interactions. Anion-water H-bond energies agree with the results of computer simulations and heats of hydration. This indicates that an H-bond may be regarded as an interaction between an acid H-atom and a partial charge-whether the H-bond acceptor is formally charged or not (anion or organic base). The magnitude of water-anion interaction energies show a similar order as is found for water interactions.
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Kleeberg, H., Luck, W.A.P. Infrared study of anion-water interactions in dichloromethane. J Solution Chem 12, 369–381 (1983). https://doi.org/10.1007/BF00646391
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DOI: https://doi.org/10.1007/BF00646391