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The hydration of 15-crown-5 (15C5) and 18-crown-6 (18C6) in aqueous solutions has been studied by FTIR-ATR spectroscopy. A model of decomposition of the O−H stretching band of water into four components, accounting for bound and bulk water in the solutions, has been employed in the analysis of the spectra. The dependencies of the relative areas and peak wavenumbers of the resolved components on concentration reveal similarities and differences in the hydration of the two crown ethers. The number of water molecules influenced by the hydration is ca. 18−20 for 18C6 solutions and ca . 12−15 for 15C5 solutions at sufficiently high dilutions. The immediate hydration shell for both crown ethers consists of 4−5 water molecules directly H-bonded to the crown ring. The most probable hydration structure around 18C6 is composed of two bridging water molecules and two other water molecules singly bound to the ring, while, due to differences in its conformational structure, 15C5 is hydrated mostly by singly H-bonded water molecules.
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Nickolov et al. (1999) studied this question.
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