K.A. Ignat'eva*, A.A. Chernov**, A.V. Rubanov***, F.V. Devyatov****
Kazan Federal University, Kazan, 420008 Russia
E-mail: *ToKlara@yandex.ru, **email@example.com, ***firstname.lastname@example.org, ****email@example.com
Full text PDF
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
Fig. 1. 3D model of D-sorbitol molecule in vacuum .
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.
- Fialkov Yu.Ya. Control of Chemical Processes by Means of Solvents. Leningrad, Khimiya, 1990. 240 p. (In Russian)
- Balk R.W., Somsen G. Preferential solvation and hydrophobic hydration of polyols in mixtures of water and N,N-dimethylformamide. J. Phys. Chem., 1985, vol. 89, no. 23, pp. 5093–5097.
- Lerbret A., Mason P. E., Venable R. M., Cesaro A., Saboungi M.-L., Pastor R.W., Brady J.W. Molecular dynamics studies of the conformation of sorbitol. Carbohydr. Res., 2009, vol. 344, no. 16, pp. 2229–2235. doi: 10.1016/j.carres.2009.08.003.
- Brady J.W., Schmidt R.K. The role of hydrogen bonding in carbohydrates: molecular dynamics simulations of maltose in aqueous solution. J. Phys. Chem., 1993, vol. 97, no. 4, pp. 958–966.
- Gutmann V. Coordination Chemistry in Non-Aqueous Solutions. New York, Wien, Springer Verlag, 1968. 268 p.
- Physical Chemistry of Organic Solvents Systems. Covington A.K., Dickinson T. (Eds.). London, New York, Plenum Press, 1973. 823 p.
- Reihardt H. Solvents and Solvent Effects in Organic Chemistry. Moscow, Mir, 1991. 763 p. (In Russian)
- Fialkov Yu.Ya., Zhitomirskii A.N., Tarasenko Yu.A. Physical Chemistry of Non-Aqueous Solutions. Leningrad, Khimiya, 1973. 376 p. (In Russian)
- Sal'nikov Yu.I., Glebov A.N., Devyatov F.V. Polynuclear Complexes in Solutions. Kazan, Izd. Kazan. Univ., 1989. 288 p. (In Russian)
- Devyatov F.V., Nepryakhin A.E., Mustafina A.R., Sal'nikov Yu.I. Aqua-bypolar aprotic solvent associates based on PMR data. Zh. Fiz. Khim., 1990, vol. 64, no. 3, pp. 853 – 864. (In Russian)
- Brewster J. Spiral model of optical activity. Izbrannye problemyi stereokhimii [Selected Problems of Stereochemistry]. Sokolov V.I. (Ed.). Moscow, Mir, 1970, pp. 217–283.
- Devyatov F.V., Safina V.F., Sal'nikov Yu.I., Nozdrina O.A. Selective solvation of cations and proton donors in the water-dipolar aprotic solvent mixtures. Russ. J. Coord. Chem., 1998, vol. 24, no. 7, pp. 521–524.
- Thomas A.B., Rochow E.G. Conductance studies of organometalic chlorides of group IYB and hydrogen chloride in N,N-dimethylformamide. Some observations about the purification of the solvent. J. Am. Chem. Soc., 1957, vol. 79, no. 8, pp. 1843–1848.
- Becker H.G., Berger W., Domschke G. Organikum. Organisch-Chemisches Grundpraktikum. Transl., 2 vol. Moscow, Mir, 1979, 442 p. (In Russian)
- Shcherbakova E.S., Goldshtein I.P., Gur'yanova E.N. Methods for mathematical processing of results from the physicochemical studies of complex compounds. Usp. Khim., 1978, vol. 47, no. 12, pp. 2134–2159. (In Russian)
- Shcherbakova E.S., Bugaevskii A.A., Karpov I.K., Kumok V.N., Mar'yanov B.M., Nikishina L.E. Mathematical Questions in Studying Chemical Equilibria. Tomsk, Izd. Tomsk. Univ., 1978. 232 p. (In Russian)
- Krestov G.A., Afanas'ev V.N., Agafonov A.V. Complex Formation in Non-Aqueous Solutions. Moscow, Nauka, 1989. 256 p. (In Russian)
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)
The content is available under the license Creative Commons Attribution 4.0 License.