Solvation State and Selective Solvation of D-Sorbitol in Water-Dimethylformamide Medium of Varying Composition

K.A. Ignat'eva*, A.A. Chernov**, A.V. Rubanov***, F.V. Devyatov****

Kazan Federal University, Kazan, 420008 Russia

E-mail: *ToKlara@yandex.ru, **sbchernov@mail.ru, ***arubanov@rambler.ru, ****fedor.devyatov@kpfu.ru

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Abstract

The solvation state of D-sorbitol has been determined in water-dimethylformamide (DMF) system (from 0 to 10 m.p.) using the method of polarimetry. The composition and formation constants of        D-sorbitol – water – DMF heterosolvates have been obtained. The molar parts of D-sorbitol in heterosolvates have been found. It has been revealed that DMF acts as a selective solvent when its content is minimum (not higher than 0.7 m.p.), which is consistent with its higher nucleophilicity compared to water. If DMF concentration is higher than 0.7 m.p., there is inversion in solvation selectivity with water becoming a selective solvent. Under the experimental conditions, 12 water molecules in hydration shells were substituted with 6 DMF molecules. The substitution sequence of water molecules has been suggested.

Keywords: D-sorbitol, resolvation, selective solvation, aqueous-organic solvent, dimethylformamide, dipolar aprotic solvent, water, polarimetry, thermodynamical characteristics

Figure captions

Fig. 1. 3D model of D-sorbitol molecule in vacuum [3].

Fig. 2. Dependence of the molar optical rotation angle [αm]λt on the composition of binary solvent in     D-sorbitol – water – DMF system (T = 298 K, λ = 366 nm). Сs – molar concentration of DMF, Cw – molar concentration of water in mixed solvent, С(Srb) = 0.2000 mole/l, cuvette length l – 2 dm.

Fig. 3. Dependence of Srb(H2O)n(DMFA)m heterosolvates accumulation parts in the water – DMF binary solvent on DAS molar part; numbering of the forms is the same as in Table 1.

Fig. 4. To selective solvation of D-sorbitol in the binary solvent: dependence of Х2' on Х20; dash-and-dot line designates the absence of solvation selectivity.

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For citation: Ignat'eva K.A., Chernov A.A., Rubanov A.V., Devyatov F.V. Solvation state and selective solvation of D-sorbitol in water-dimethylformamide medium of varying composition. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2016, vol. 158, no. 2, pp. 187–196. (In Russian)

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