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Elucidation of the Water–DMSO Mixing Process Based on an IR Study

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Abstract

The IR spectra of water–DMSO mixtures were recorded in the range of 0 < x < 1 DMSO mole fraction in the spectral region of 400–6000 cm−1. The combination and libration bands of water and the S = O band of DMSO were used to monitor changes in the system. The combination and libration bands of water were analyzed in terms of different degrees of connectivity of water molecules. Two types of complexes differing by their water–DMSO ratio and the nature of water participating in their formation were found in the mixture. Complex I involves large water clusters stabilized by DMSO molecules and gradually diminishing in their size with increasing DMSO content. Water molecules separated from the bulk water interact with DMSO to form complex II. The water clusters were shown to exist in the mixture up to 90 mol% DMSO. The inertness of the inner molecules of the water cluster is the reason of the begining of DMSO accumulation at the notable water excess.

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References

  1. Safford, G.J., Schaffer, P.C., Leung, P.S., Doebbler, G.F., Brady, G.W., Lyden, E.F.X.: Neutron inelastic scattering and X–ray studies of aqueous solutions of dimethylsulphoxide and dimethylsulphone. J. Chem. Phys. 50, 2140–2159 (1969)

    Article  CAS  Google Scholar 

  2. Fox, M.F., Whittingham, K.P.: Component interactions in aqueous dimethyl sulphoxide. J. Chem. Soc. Faraday Trans. 71, 1407–1412 (1975)

    Article  CAS  Google Scholar 

  3. Tokuhiro, T., Menafra, L., Szmant, H.H.: Contribution of relaxation and chemical shift results to the elucidation of the structure of the water–DMSO liquid system. J. Chem. Phys. 61, 2275–2282 (1974)

    Article  CAS  Google Scholar 

  4. Packer, K.J., Tomlinson, D.: Nuclear spin relaxation and self-diffusion in the binary system, dimethylsulphoxide (DMSO) +  water. J. Chem. Soc. Faraday Trans. 67, 1302–1314 (1971)

    Article  CAS  Google Scholar 

  5. Gordalla, B.C., Zeidler, M.D.: Molecular dynamics in the system water–dimethylsulphoxide. Mol. Phys. 59, 817–828 (1986)

    Article  CAS  Google Scholar 

  6. Kaatze, U., Pottel, R., Schafer, M.: Dielectric spectrum of dymethyl sulfoxide/water mixtures as a function of composition. J. Phys. Chem. 93, 5623–5627 (1989)

    Article  CAS  Google Scholar 

  7. Luzar, A., Chandler, D.: Structure and hydrogen bond dynamics of water–dimethylsulfoxide computer simulations. J. Chem. Phys. 98, 8160–8174 (1993)

    Article  CAS  Google Scholar 

  8. Cowie, J.M.G., Toporowski, P.M.: Association in the binary liquid system dimethyl sulphoxide–water. Can. J. Chem. 39, 2240–2243 (1961)

    Article  CAS  Google Scholar 

  9. Bowen, D.E., Priesand, M.A., Eastman, M.P.: Ultrasound propagation in binary mixtures of dimethylsulfoxide and water. J. Phys. Chem. 78, 2611–2615 (1974)

    Article  CAS  Google Scholar 

  10. Madigosky, W.M., Warfield, R.W.: Ultrasonic measurements and liquid structure of DMSO–water mixture. J. Chem. Phys. 78, 1912–1916 (1983)

    Article  CAS  Google Scholar 

  11. Kinart, C.M., Kinart, W.J.: Dimethylsulfoxide–water binary mixtures and their assumed internal structures. Pol. J. Chem. 60, 879–899 (1986)

    CAS  Google Scholar 

  12. Glasel, J.A.: Deutron magnetic relaxation studies on the solution properties of some denaturing agents and surfactants. J. Am. Chem. Soc. 92, 372–375 (1970)

    Article  CAS  Google Scholar 

  13. Burneau, A.: Near infrared spectroscopic study of the structure of the water in proton acceptor solvents. J. Mol. Liq. 46, 99–127 (1990)

    Article  CAS  Google Scholar 

  14. Higashigaki, Y., Christense, D.H., Wang, C.H.: Studies of the reorientational motion and intermolecular interaction of dimethylsulphoxide in water by depolarized Rayleigh scattering. J. Phys. Chem. 85, 2531–2535 (1981)

    Article  CAS  Google Scholar 

  15. Kelm, H., Klosowski, J., Steger, E.: The association in the mixtures of dimethylsulphoxide and water as studied by Raman spectroscopy. J. Mol. Struct. 28, 1–4 (1975)

    Article  CAS  Google Scholar 

  16. Gordalla, B.C., Zeidler, M.D.: NMR proton relaxation and chemical exchange in the system [H162O/H172O-2H6] dimethylsulphoxide. Mol. Phys. 74, 975–984 (1991)

    Article  CAS  Google Scholar 

  17. Baker, E.S., Jonas, J.: Transport and relaxation properties of dimethylsulfoxide–water mixtures at high pressure. J. Phys. Chem. 89, 1730–1735 (1985)

    Article  CAS  Google Scholar 

  18. Feder, W., Dreizler, H., Rudolph, H.D., Typke, V.: rs-Struktur von dimethylsulfoxid im vergleih zur r0-Struktur. Z. Naturforsch. 24A, 266–278 (1969)

    Google Scholar 

  19. Verstakov, E.S., Yastremskii, P.S., Kessler, Y.M., Goncharov, V.V., Kokovin, V.V.: Dielectric and structural properties of aqueous solutions of dimethylformamide and dimethylsulfoxide. Zh. Strukt. Khim. 21, 91–95 (1980)

    CAS  Google Scholar 

  20. Koga, Y., Kasahara, Y., Yoshino, K., Nishikawa, K.: Mixing scheme for aqueous dimethyl sulfoxide: Support by X-ray diffraction data. J. Solution Chem. 30, 885–893 (2001)

    Article  CAS  Google Scholar 

  21. Lyashchenko, A.K., Novskova, T.A., Gaiduk, V.I.: Concentration dependence of dielectric spectra and molecular kinetic properties in aqueous nonelectrolyte. J. Mol. Liq. 94, 1–16 (2001)

    Article  CAS  Google Scholar 

  22. Shashkov, S.N., Kiselev, M.A., Tioutionnikov, S.N., Kiselev, A.M., Lesieur, P.: The study of DMSO/water and DPPC/DMSO/water system by means of the X-ray, neutron small-angle scattering, calorimetry and IR spectroscopy. Physica B 271, 184–191 (1999)

    Article  CAS  Google Scholar 

  23. Zhukovskii, A.P., Rovnov, N.V., Petrov, L.N., Sorvin, S.V., Vuks, E.M.: Investigation of the structure of aqueous solution of dimethyl sulfoxide by IR spectroscopy. Zh. Strukt. Khim. 33, 100–104 (1992)

    CAS  Google Scholar 

  24. Catalan, J., Diaz, C., Garcia-Blanco, F.: Characterization of binary solvent mixtures of DMSO with water and other cosolvents. J. Org. Chem. 66, 5846–5852 (2001)

    Article  CAS  Google Scholar 

  25. Vaisman, I.I., Berkowitz, M.L.: Local structural order and molecular associations in water–DMSO mixtures. Molecular dynamics study. J. Am. Chem. Soc. 114, 7889–7896 (1992)

    Article  CAS  Google Scholar 

  26. Mizuno, K., Imafuji, S., Ochi, T., Ohta, T., Maeda, S.: Hydration of the CH groups in dimethylsulfoxide probed by NMR and IR. J. Phys. Chem. B 104, 11001–11005 (2000)

    Article  CAS  Google Scholar 

  27. Rallo, F., Rodante, F., Silvestroni, P.: Calorimetric determination of partial molar enthalpies of solution of water and dimethylsulphoxide in their mixtures. Thermochim. Acta 1, 311–316 (1970)

    Article  CAS  Google Scholar 

  28. Werblan, L., Lesinski, J.: Structure and selected properties of water–dimethylsulphoxide mixtures. Pol. J. Chem. 52, 1211–1219 (1978)

    CAS  Google Scholar 

  29. Soper, A.K., Luzar, A.: A neutron diffraction study of dymethyl sulphoxide–water mixtures. J. Chem. Phys. 97, 1320–1329 (1992)

    Article  CAS  Google Scholar 

  30. Medvedev, N.N., Naberukhin, Y.I.: Structural studies of the simple liquids and amorphous substances by the methods of statistic geometry. Zh. Strukt. Khim. 28, 117–132 (1987)

    CAS  Google Scholar 

  31. Lai, J.T.W., Lau, F.W., Robb, D., Westh, P., Nielsen, G., Trandum, C., Hvidt, A., Koga, Y.: Excess partial molar enthalpies, entropies, Gibbs energies, and volumes in aqueous dimethylsulfoxide. J. Solution Chem. 24, 89–102 (1995)

    Article  CAS  Google Scholar 

  32. Scherer, J.R., Go, K.M., Kint, S.: Raman spectra of water in dimethyl sulfoxide. J. Phys. Chem. 77, 2108–2117 (1973)

    Article  CAS  Google Scholar 

  33. Meade, M., Waghorne, E.W., Symons, M.C.R.: Spectroscopic study of the solvation of dimethyl sulfoxide in aqueous acetonitrile and acetone solvent systems. J. Chem. Soc. Faraday Trans. 92, 4395–4399 (1996)

    Article  CAS  Google Scholar 

  34. Fornes, V., Chaussidon, J.: An interpretation of the evolution with temperature of the ν2 + ν3 combination band in water. J. Chem. Phys. 68, 4667–4671 (1978)

    Article  CAS  Google Scholar 

  35. Choppin, G.R., Downey, J.R.: Near-infrared studies of the structure of water. IV. Water in relatively nonpolar solvents. J. Chem. Phys. 56, 5899–5904 (1972)

    Article  CAS  Google Scholar 

  36. Inoue, A., Kojima, K., Taniguchi, Y., Suzuki, K.: Near-infrared spectra of water and aqueous electrolyte solutions at high pressures. J. Solution Chem. 13, 811–823 (1994)

    Article  Google Scholar 

  37. Buijs, K., Choppin, G.R.: Near-infrared studies of the structure of the water I. Pure water. J. Chem. Phys. 39, 2035–2041 (1963)

    Article  CAS  Google Scholar 

  38. Thomas, M.R., Scheraga, H.A., Schrier, E.E.: A near–infrared study of hydrogen bonding in water and deuterium oxide. J. Phys. Chem. 69, 3722–3726 (1965)

    Article  CAS  Google Scholar 

  39. Robertson, C.W., Curnutte, B., Williams, D.: The infra-red spectrum of water. Mol. Phys. 26, 183–191 (1973)

    Article  CAS  Google Scholar 

  40. Saitow, K., Kobayashi, K., Nishikawa, K.: How are hydrogen bonds perturbed in aqueous NaClO4 solutions depending on the concentration?: A near-infrared study of water. J. Solution Chem. 33, 689–698 (2004)

    Article  CAS  Google Scholar 

  41. Svishchev, I.M., Kusalik, P.G.: Rotational dynamics in liquid water: a simulation study of libration motions. J. Chem. Soc. Faraday Trans. 90, 1405–1409 (1994)

    Article  CAS  Google Scholar 

  42. Figueroa, R.H., Roig, E., Szmant, H.H.: Infrared study on the self-association of dymethyl sulfoxide. Spectrochim. Acta 22, 587–592 (1966)

    Article  CAS  Google Scholar 

  43. Luzar, A., Soper, A.K., Chandler, D.: Combined neutron diffraction and computer simulation study of liquid dimethyl sulphoxide. J. Chem. Phys. 99, 6836–6847 (1993)

    Article  CAS  Google Scholar 

  44. Sedlák, M.: Large-scale supramolecular structure in solutions of low molar mass compounds and mixtures of liquids: II. Kinetics of the formation and long-time stability. J. Phys. Chem. B 110, 4339–4345 (2006)

    Article  Google Scholar 

  45. Frank, H.S., Wen, W.Y.: Ion–solvent interaction. Structural aspects of ion–solvent interaction in aqueous solutions: a suggested picture of water structure. Discuss. Faraday Soc. 24, 133–140 (1957)

    Article  Google Scholar 

  46. Singh, U.C., Kollman, P.A.: A water dimmer potential based on based on ab initio calculations using Morokuma component analysis. J. Chem. Phys. 83, 4033–4040 (1985)

    Article  CAS  Google Scholar 

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  1. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova street, 119991, Moscow, Russian Federation

    Z. S. Klemenkova & E. G. Kononova

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  1. Z. S. Klemenkova
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  2. E. G. Kononova
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Klemenkova, Z.S., Kononova, E.G. Elucidation of the Water–DMSO Mixing Process Based on an IR Study. J Solution Chem 44, 280–292 (2015). https://doi.org/10.1007/s10953-015-0300-x

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