Journal of Solution Chemistry

, Volume 48, Issue 10, pp 1378–1392 | Cite as

Thermodynamic and Spectroscopic (UV–Vis, FT IR) Studies of Solutions of CoCl2 (or NiCl2) in Diethylsulfoxide

  • Shiraz A. MarkarianEmail author
  • Heghine H. Ghazoyan
  • Hasmik R. Sargsyan
  • Gohar A. Shahinyan


Densitometry, UV–Vis and FT IR spectroscopy were used to study the complex formation of cobalt(II) chloride and nickel(II) chloride with diethylsulfoxide (DESO). The apparent molar volumes and partial molar volumes were determined for solvated ions in DESO. The complex formation of nickel(II) and cobalt(II) ions with DESO molecules via oxygen atom of SO group was revealed from the SO stretching band in the FT IR spectra. UV–Vis spectra show the coexistence of two types of complexes with DESO in solution. The results show that solvating ability of DESO is stronger than that of dimethylsulfoxide.


Diethylsulfoxide Dimethylsulfoxide Ions solvation Densitometry UV–Vis FT IR spectra 



The research is supported by the Science Committee of Republic of Armenia.

Supplementary material

10953_2019_924_MOESM1_ESM.docx (45 kb)
Supplementary material 1 (DOCX 45 kb)


  1. 1.
    Markarian, S.A., Gabrielyan, L.S.: Dielectric relaxation study of diethylsulfoxide/water mixtures. Phys. Chem. Liq. 47(3), 311–321 (2007)CrossRefGoogle Scholar
  2. 2.
    Markarian, S.A., Zatikyan, A.L., Grigoryan, V.V., Grigoryan, G.S.: Vapor pressures of pure diethyl sulfoxide from (298.15 to 318.15) K and vapor–liquid equilibria of binary mixtures of diethyl sulfoxide with water. J. Chem. Eng. Data 50(1), 23–25 (2005)CrossRefGoogle Scholar
  3. 3.
    Markarian, S.A., Terzyan, A.M.: Surface tension and refractive index of dialkylsulfoxide + water mixtures at several temperatures. J. Chem. Eng. Data 52(5), 1704–1709 (2007)CrossRefGoogle Scholar
  4. 4.
    Markarian, S.A., Asatryan, A.M., Zatikyan, A.L.: Volumetric properties of aqueous solutions of diethylsulfoxide at temperatures from 298.15 K to 343.15 K. J. Chem. Thermodyn. 37, 768–777 (2005)CrossRefGoogle Scholar
  5. 5.
    Markarian, S.A., Asatryan, A.M., Grigoryan, K.R., Sargsyan, H.R.: Effect of diethylsulfoxide on the thermal denaturation of DNA. Biopolymers 82, 1–5 (2006)CrossRefGoogle Scholar
  6. 6.
    Torreggiani, A., Di Foggia, M., Manco, I., De Maio, A., Markarian, S.A., Bonora, S.: Effect of sulfoxides on the thermal denaturation of hen lysozyme: a calorimetric and Raman study. J. Mol. Struct. 891, 115–122 (2008)CrossRefGoogle Scholar
  7. 7.
    Markarian, S.A., Poladyan, A.A., Kirakosyan, G.R., Trchounian, A.A., Bagramyan, K.A.: Effect of diethylsulphoxide on growth, survival and ion exchange of Escherichia coli. Lett. Appl. Microbiol. 34, 417–421 (2002)CrossRefGoogle Scholar
  8. 8.
    Chaban, V.V.: Force field development and simulations of senior dialkyl sulfoxides. Phys. Chem. Chem. Phys. 18, 10507–10515 (2016)CrossRefGoogle Scholar
  9. 9.
    Chaban, V.V.: Binary mixtures of novel sulfoxides and water: intermolecular structure, dynamic properties, thermodynamics, and cluster analysis. Phys. Chem. Chem. Phys. 20, 23754–23761 (2018)CrossRefGoogle Scholar
  10. 10.
    Libus, W., Pilarczyk, M., Szuchnicka, T.: Ionization equilibria of copper chloride in dimethyl sulfoxide. Electrochim. Acta 25, 1033–1039 (1980)CrossRefGoogle Scholar
  11. 11.
    Libus, W., Chachulski, B., Grzybkowski, W., Pilarczyk, M., Puchalska, D.: Mobilities of complex forming cations in non-aqueous donor solvents. J. Solution Chem. 10(9), 631–648 (1981)CrossRefGoogle Scholar
  12. 12.
    Inada, Y., Hayashi, H., Sugimoto, K., Funahashi, S.: Solvation structures of manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II) and gallium(III) ions in methanol, ethanol, dimethyl sulfoxide, and trimethyl phosphate as studied by EXAFS and electronic spectroscopies. J. Phys. Chem. A 103, 1401–1406 (1999)CrossRefGoogle Scholar
  13. 13.
    Bobicz, D., Grzybkowski, W.: Apparent molar volumes of divalent transition metal cations in dimethyl sulfoxide solutions. J. Solution Chem. 27(9), 817–826 (1998)CrossRefGoogle Scholar
  14. 14.
    Calligaris, M.: Structure and bonding in metal sulfoxide complexes. Coordin. Chem. Rev. 248, 351–375 (2004)CrossRefGoogle Scholar
  15. 15.
    Bobicz, D., Grzybkowski, W., Lewandowski, A.: Apparent molar volume of divalent transition metal chlorides and perchlorates in dimethylsulfoxide solutions. J. Mol. Liq. 105(1), 93–104 (2003)CrossRefGoogle Scholar
  16. 16.
    Warminska, D., Krakowiak, J., Grzybkowski, W.: Apparent molar volumes of divalent transition metal bromides in dimethyl sulfoxide solutions. J. Mol. Liq. 116, 61–65 (2005)CrossRefGoogle Scholar
  17. 17.
    Warminska, D., Wawer, J., Grzybkowski, W.: Thermodynamic properties of inorganic salts in nonaqueous solvents. VI. Apparent molar volumes, expansibilities, and compressibilities of divalent transition metal ions in methanol and dimethylsulfoxide. J. Chem. Eng. Data 55, 2116–2122 (2010)CrossRefGoogle Scholar
  18. 18.
    Warminska, D., Koziel, H., Grzybkowski, W.: Volumetric properties of zinc(II) chloride in N, N-dimethylacetamide and dimethylsulfoxide. J. Mol. Liq. 177, 252–256 (2013)CrossRefGoogle Scholar
  19. 19.
    Marcus, Y.: On the molar volumes and viscosities of electrolytes. J. Solution Chem. 35, 1271–1286 (2006)CrossRefGoogle Scholar
  20. 20.
    Suzuki, H., Ishiguro, S.-I., Ohtaki, H.: Formation of chloro complexes of manganese(II), cobalt(II), nickel(II) and zinc(II) in dimethyl sulphoxide. J. Chem. Soc. Faraday Trans. 86(12), 2179–2185 (1990)CrossRefGoogle Scholar
  21. 21.
    Magnell, K.R., Reynolds, W.L.: Complexes of cobalt(II) with chloride and thiocyanate ions in dimethyl sulfoxide. Inorg. Chim. Acta 6, 571–574 (1972)CrossRefGoogle Scholar
  22. 22.
    Griffiths, T.R., Phillips, N.J.: The nickel(II)-bromide system in dimethyl sulphoxide: a detailed study of the influences of temperature and mole ratio. J. Chem. Soc. Dalton Trans. 2, 325–330 (1989)CrossRefGoogle Scholar
  23. 23.
    Chiboub-Fellah, A., Meullemeestre, J., Spies, C., Vierling, F., Khan, M.A.: Octahedral and tetrahedral conguration changes of nickel(II) chloro complexes from spectrophotometric studies in aprotic solvents. Transit. Metal Chem. 24(2), 135–140 (1999)CrossRefGoogle Scholar
  24. 24.
    Libuś, W., Pilarczyk, M., Pastewski, R., Szuchnicka, T.: Ionization equilibria of cobalt (II) chloride in dimethyl sulphoxide. Electrochim. Acta 27(5), 573–580 (1982)CrossRefGoogle Scholar
  25. 25.
    Gorbunov, A.O., Tsyrulnikov, N.A., Tikhomirova, A.A., Bogachev, N.A., Skripkin, M.Y., Nikolskii, A.B., Pestova, O.N.: Solubility of d-element salts in organic and aqueous–organic solvents: II. Effect of halocomplex formation on solubility of cobalt bromide and chloride and nickel chloride. Russ. J. Gen. Chem. 86(4), 771–777 (2016)CrossRefGoogle Scholar
  26. 26.
    Meek, D.W., Straub, D.K., Drago, R.S.: Transition metal ion complexes of dimethyl sulfoxide. J. Am. Chem. Soc. 82(23), 6013–6016 (1960)CrossRefGoogle Scholar
  27. 27.
    Moniz, W., Poranski, C., Venezky, D.: Dimethyl sulfoxide complexes of chromium (III), manganese (II), iron (III), nickel (II), and copper (II) nitrates and magnesium and nickel (II) perchlorates. Part 1—preparation and nuclear magnetic resonance and infrared studies. Defense Technical Information Center (1967)Google Scholar
  28. 28.
    Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry, 2nd edn. VCH, New York (1988)Google Scholar
  29. 29.
    Fawcett, W.R., Kloss, A.A.: Solvent-induced frequency shifts in the infrared spectrum of dimethyl sulfoxide in organic solvents. J. Phys. Chem. 100, 2019–2024 (1996)CrossRefGoogle Scholar
  30. 30.
    Fawcett, W.R., Kloss, A.A.: Attenuated total reflection Fourier-transform IR spectroscopic study of dimethyl sulfoxide self-association in acetonitrile solutions. J. Chem. Soc. Faraday Trans. 92(18), 3333–3337 (1996)CrossRefGoogle Scholar
  31. 31.
    Markarian, S.A., Gabrielian, L.S., Bonora, S., Fagnano, C.: Vibrational spectra of diethylsulfoxide. Spectrochim. Acta A 59, 575–588 (2003)CrossRefGoogle Scholar
  32. 32.
    Markarian, S.A., Zatikyan, A.L., Bonora, S., Fagnano, C.: Raman and FT IR ATR study of diethylsulfoxide/water mixtures. J. Mol. Struct. 655, 285–292 (2003)CrossRefGoogle Scholar
  33. 33.
    Markarian, S.A., Gabrielian, L.S., Zatikyan, A.L., Bonora, S., Trinchero, A.: FT-IR and Raman study of lithium salts solutions in diethylsulfoxide. Vib. Spectrosc. 39, 220–228 (2005)CrossRefGoogle Scholar
  34. 34.
    Markarian S.A., Tadevosyan N.: Method of purification of diethyl sulfoxide. Patent of Republic of Armenia, No. 20010041 (2002)Google Scholar
  35. 35.
    Setua, P., Seth, D., Sarkar, N.: To probe the structure of methanol and aerosol OT (AOT) in AOT reverse micelles by FTIR measurements. Phys. Chem. Chem. Phys. 11, 8913–8922 (2009)CrossRefGoogle Scholar
  36. 36.
    Antonov, L., Nedeltcheva, D.: Resolution of overlapping UV-vis absorption bands and quantitative analysis. Chem. Soc. Rev. 29, 217–227 (2000)CrossRefGoogle Scholar
  37. 37.
    Harned, H., Owen, B.: The Physical Chemistry of Electrolytic Solutions. Reinhold Pub Corp., New York (1963)Google Scholar
  38. 38.
    Marcus, Y.: Electrostriction, ion solvation, and solvent release on ion pairing. J. Phys. Chem. B 109, 18541–18549 (2005)CrossRefGoogle Scholar
  39. 39.
    Padova, J.: Ion-solvent interaction. II. Partial molar volume and electrostriction: a thermodynamic approach. J. Chem. Phys. 39(6), 1552–1557 (1963)CrossRefGoogle Scholar
  40. 40.
    Martens, W.N., Frost, R.L., Kristol, J., Kloprogge, J.T.: Raman spectroscopy of dimethyl sulphoxide and deuterated dimethyl sulphoxide at 298 and 77 K. J. Raman Spectrosc. 33(2), 84–91 (2002)CrossRefGoogle Scholar
  41. 41.
    Markaryan, ShA: 1H NMR of paramagnetic cobalt(II) and nickel(II) complexes of dialkylsulfoxides in aqueous solution. J. Struct. Chem. 29, 715–720 (1989)CrossRefGoogle Scholar
  42. 42.
    Sandstrom, M., Persson, I., Ahrland, S.: On the coordination around mercury (II), cadmium (II) and zinc (II) in dimethyl sulfoxide and aqueous solutions. An X-ray diffraction, Raman and infrared investigation. Acta Chem. Scand. 32, 607–625 (1978)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Shiraz A. Markarian
    • 1
    Email author
  • Heghine H. Ghazoyan
    • 1
  • Hasmik R. Sargsyan
    • 1
  • Gohar A. Shahinyan
    • 1
  1. 1.Department of ChemistryYerevan State UniversityYerevanArmenia

Personalised recommendations