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Infrared study of anion-water interactions in dichloromethane

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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:

$$ClO_4^ - {\text{ }}<< {\text{ NO}}_{\text{3}}^ - \lesssim I^ -< {\text{ SCN}}^ - {\text{ }}< {\text{ }}Cl^{ - {\text{ }}} \lesssim CO_3^2 {\text{ }} \lesssim F^ -$$

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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Authors and Affiliations

  1. Department of Physical Chemistry, University of Marburg, FRG

    Hubertus Kleeberg & Werner A. P. Luck

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  1. Hubertus Kleeberg
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  2. Werner A. P. Luck
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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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