Journal of the Chemical Society - Faraday Transactions p. 1725 - 1730 (1996)
Update date:2022-08-28
Topics:
Stoyanov, Evgenii S.
Chesalov, Yurii A.
This work presents the results of IR spectroscopic studies of the molecular states of alkali-metal (Li, Na, K, Cs) acetates in glacial acetic acid. The associates M(Ac·nHAc)·pHAc (I) have been shown to form with n ≈ 8-9 and varying number p of the outersphere HAc molecules, depending on the salt concentration. The anion Ac·nHAc- is symmetrical about the central fragment O-H?-O with a very strong H-bond. The anion negative charge is located mainly on this fragment and on the two nearest O?-H-O fragments. The first coordination sphere of M+ comprises only oxygen atoms from the O-H?-O group and from the anion's terminal C=O groups. Associates I form a microvolume of structurized liquid phase which can be considered as a prototype of liquid-crystalline lamellar or ribbon-like structures produced by alkali acid soaps. When water is added, H2O molecules hydrate both anions and cations, M+, equalizing the polarizing influence of the latter on the anion. For hydrated salts the radius of the ordered liquid-phase microvolume around the cation M+ increases. On the whole, water addition produces a similar effect on the composition and structure of associates I as it does with liquid-crystalline water-free alkali acid soaps.
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