Abstract
Abstract Isotopically diluted HDO in D2O + acetonitrile (AN) + Zn(ClO4)2 system have been investigated by near-infrared spectroscopy at 25°C. Measurements were carried out in the range of the first overtone of 2υ3(OH) stretching vibration and of υ3(OH) + υ3(OD) combination vibration bands of HDO at selected D2O + AN mixture compositions. Spectral results infinitely diluted solutions, in respect to HDO and Zn(ClO4)2, were interpreted. Spectra of HDO molecules affected by the solute and its respective hydration numbers were determined. Changes of the 2υ3(OH) band caused by Zn(ClO4)2 were transformed into changes of enthalpy of hydrogen bonds of water, using the Badger-Bauer rule. The results were discussed in the light of respective calorimetric data. It was stated that with the increase of AN content in the mixture, Zn(ClO4)2 becomes more and more effective in strengthening the structure of water in respect to the situation in the mixture and also in pure water. Preferential hydration of Zn(II) have been inferred from that. The obtained results are justified by the microheterogenic structure of water + AN mixture and cooperation of hydrogen bonds stimulated by the presence of Zn(II) in solution.
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