Skip to main content
Log in

The Effects of Sulphate and Tartrate Ions on the Molecular Organization of Water: Towards Understanding the Hofmeister Series (VI)

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Using the 1-propanol (1P) probing methodology we have developed earlier, we characterized the effects of sulphate and tartrate anions on the molecular organization of H2O. The results indicate that these two large anions belong to a new class of “hydrophobe-like hydration center”. That is, sulphate and tartrate ions act as “hydration centers” with the hydration number 14±3 for both, and leave the bulk H2O, away from hydration shells, unperturbed in the absence of the probing 1-propanol. As the mole fraction of the probe increases, however, the hydrogen bond probability of bulk H2O away from hydration shells appears to decrease smoothly, as occurs with “hydrophobes” in H2O. We plot the negative hydration number against the power to reduce the hydrogen bond probability of bulk H2O for the two large anions. We also plotted the characteristic indices for “hydrophiles” and “hydration centers” whose characteristics we determined in the same manner earlier. H2O defines the origin on this map. We found that a typical Hofmeister ranking for each anion matches reasonably well with that of the distance from the origin for each ion, in decreasing order starting from ions plotted in the north-west quadrant (representing the “hydrophobe-like” behavior) of the map and then in increasing order from the origin towards the south on the ordinate, the “hydrophile-like” behavior. These findings could be useful in understanding the Hofmeister series, pointing to the importance of the contribution made by the effect of each ion on H2O, in addition to helping understand direct ion-protein interactions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Koga, Y.: Solution Thermodynamics and Its Application to Aqueous Solutions: A Differential Approach. Elsevier, Amsterdam (2007), Chaps. VII and VIII

    Google Scholar 

  2. Koga, Y.: What some anions do to H2O: towards understanding the Hofmeister series. Netsu Sokutei 34, 3–13 (2007). ISSN 0386-2615. Available in a pdf form on request to author, koga@chem.ubc.ca

    CAS  Google Scholar 

  3. Koga, Y., Westh, P., Nishikawa, K., Subramanian, S.: Is a methyl group always hydrophobic? Hydrophilicity of trimethylamine-N-oxide, tetramethyl urea and tetramethylammonium ion. J. Phys. Chem. B 115, 2995–3002 (2011)

    Article  CAS  Google Scholar 

  4. Reference [1] but Chap. III

  5. Reference [1] but Chap. V

  6. Koga, Y.: Mixing schemes in aqueous solutions of nonelectrolytes: a thermodynamic approach. J. Phys. Chem. 100, 5172–5181 (1996)

    Article  CAS  Google Scholar 

  7. Koga, Y., Nishikawa, K., Westh, P.: “Icebergs” or no “icebergs” in aqueous alcohols? J. Phys. Chem. A 108, 3873–3877 (2004)

    Article  CAS  Google Scholar 

  8. Hu, J., Chiang, W.H., Westh, P., Chen, D.H.C., Haynes, C.A., Koga, Y.: Additive effect of 1-propanol and 2-propanol on molecular organization of H2O in the H2O-rich region: excess chemical potential, partial molar enthalpy and volume of 1-propanol in 1-propanol—2-propanol—H2O. Bull. Chem. Soc. Jpn. 74, 809–816 (2001)

    Article  CAS  Google Scholar 

  9. Miki, K., Westh, P., Koga, Y.: Hydrophobicity vs. hydrophilicity: effects of poly(ethyleneglycol) and tert-butanol on H2O as probed by 1-propanol. J. Phys. Chem. B 109, 19536–19541 (2005)

    Article  CAS  Google Scholar 

  10. Koga, Y.: Effect of ethylene glycol on molecular organization of H2O in comparison with methanol and glycerol: a calorimetric study. J. Solution Chem. 32, 803–818 (2003)

    Article  CAS  Google Scholar 

  11. Reference [1] but Chap. VI

  12. Koga, Y.: Mixing schemes in binary aqueous solutions of non-electrolytes. Netsu Sokutei 30, 54–65 (2003). ISSN 0386-2615. Available in a pdf file on request to the author, koga@chem.ubc.ca

    CAS  Google Scholar 

  13. Koga, Y.: Fluctuations in aqueous methanol, ethanol and 1-propanol: amplitude and wave length of fluctuations. Can. J. Chem. 77, 2039–2045 (1999)

    Article  CAS  Google Scholar 

  14. To, E.C.H., Hu, J., Haynes, C.A., Koga, Y.: Interactions in 1-propanol—urea—H2O: chemical potentials, partial molar enthalpies and entropies at 25 °C. J. Phys. Chem. B 102, 10958–10965 (1998)

    Article  CAS  Google Scholar 

  15. Parsons, M.T., Westh, P., Davies, J.V., Trandum, Ch., To, E.C.H, Chiang, W.M., Yee, E.G.M., Koga, Y.: A thermodynamic study of 1-propanol—glycerol—H2O: effect of glycerol on molecular organization of H2O. J. Solution Chem. 30, 1007–1028 (2001)

    Article  CAS  Google Scholar 

  16. To, E.C.H., Davies, J.V., Tucker, M., Westh, P., Trandum, Ch., Suh, K.S.H., Koga, Y.: Excess chemical potentials, excess partial molar enthalpies, entropies, volumes and isobaric thermal expansivities of aqueous glycerols at 25 °C. J. Solution Chem. 28, 1137–1157 (1999)

    Article  CAS  Google Scholar 

  17. Koga, Y., Tamura, K.: Fluctuations in water, aqueous t-butanol and 2-butoxyethanol: amplitude and wavelength of fluctuations. Netsu Sokutei 27, 195–204 (2000). ISSN 0386-2615. Available in a pdf file on request to the author, koga@chem.ubc.ca

    CAS  Google Scholar 

  18. Koga, Y., Miyazaki, Y., Nagano, Y., Inaba, A.: Mixing schemes in a urea—H2O system: a differential approach in solution thermodynamics. J. Phys. Chem. B 112, 11341–11346 (2008)

    Article  CAS  Google Scholar 

  19. Koga, Y., Nishikawa, K., Westh, P.: Relative hydrophobicity/hydrophilicity of fructose, glucose, sucrose and trehalose as probed by 1-propanol: a differential approach in solution thermodynamics. J. Phys. Chem. B 111, 13943–13948 (2007)

    Article  CAS  Google Scholar 

  20. Westh, P., Kato, H., Nishikawa, K., Koga, Y.: Towards understanding the Hofmeister series. III: The effects of Na-halides on the molecular organization of H2O as probed by 1-propanol. J. Phys. Chem. A 110, 2072–2078 (2006)

    Article  CAS  Google Scholar 

  21. Matuso, H., To, E.C.H., Wong, D.C.Y., Sawamura, S., Taniguchi, Y., Koga, Y.: Excess partial molar enthalpy of 1-propanol in 1-propanol—NaCl—H2O at 25 °C: the effect of NaCl on molecular organization of H2O. J. Phys. Chem. B 103, 2981–2983 (1999)

    Article  Google Scholar 

  22. Koga, Y., Katayanagi, H., Davies, J.V., Kato, H., Nishikawa, K.: The effects of chloride salts of some cations on the molecular organization of H2O: towards understanding the Hofmeister series (II). Bull. Chem. Soc. Jpn. 79, 1347–1354 (2006)

    Article  CAS  Google Scholar 

  23. Bakker, H.J.: Structural dynamics of aqueous salt solutions. Chem. Rev. 108, 1456–1473 (2008)

    Article  CAS  Google Scholar 

  24. Heisler, I.A., Mazur, K., Meech, S.R.: Low frequency modes of alkali halide solutions: an ultrafast optical Kerr effect study. J. Phys. Chem. B 115, 1863–1973 (2011)

    Article  CAS  Google Scholar 

  25. Heisler, I.A., Meech, S.R.: Low frequency modes of aqueous alkali halide solutions: glimpsing the hydrogen bonding vibration. Science 327, 857–860 (2010)

    Article  CAS  Google Scholar 

  26. Waluyo, I., Huang, C., Nordlund, D., Bergmann, U., Weiss, T.M., Petersson, L.G.M., Nilsson, A.: The structure of water in the hydration shell of cations from X-ray, Raman and small angle X-ray scattering measurements. J. Chem. Phys. 134, 064513 (2010)

    Article  Google Scholar 

  27. Cappa, C.D., Smith, J.D., Wilson, K.R., Messer, B.M., Gilles, M.K., Cohen, R.C., Saykally, R.J.: Effects of alkali halide salts on the hydrogen bond network of liquid water. J. Phys. Chem. B 109, 7046–7052 (2005)

    Article  CAS  Google Scholar 

  28. Lin, Y.S., Auer, B.M., Skinner, J.L.: Water structure, dynamics and vibrational spectroscopy in sodium bromide solutions. J. Chem. Phys. 131, 144511-1–144511-13 (2009)

    Google Scholar 

  29. Smith, J.D., Saykally, R.L., Geisler, P.L.: The effects of dissolved halide anions on hydrogen bonding in liquid water. J. Am. Chem. Soc. 129, 13847–13856 (2007)

    Article  CAS  Google Scholar 

  30. Koga, Y., Westh, P., Davies, J.V., Miki, K., Nishikawa, K., Katayanagi, H.: Towards understanding the Hofmeister series (I): the effects of Na-salts of some anions on the molecular organization of H2O. J. Phys. Chem. A 108, 8533–8541 (2004)

    Article  CAS  Google Scholar 

  31. White, J.A., Schwegler, E., Galli, G., Gygi, F.: The solvation of Na+ in H2O: first principles simulation. J. Chem. Phys. 113, 4668–4673 (2000)

    Article  CAS  Google Scholar 

  32. Varma, S., Rempe, S.B.: Coordination numbers of alkali metal ions in aqueous solutions. Biophys. Chem. 124, 192–199 (2006)

    Article  CAS  Google Scholar 

  33. Ansell, S., Barnes, S., Mason, P.E., Neilson, G.W., Ramos, S.: X-ray and neutron scattering studies of the hydration structure of alkali ions in concentrated aqueous solutions. Biophys. Chem. 124, 171–179 (2006)

    Article  CAS  Google Scholar 

  34. Hofmeister, F.: Zur Lehre von der Wirkung der Salze. Arch. Exp. Pathol. Pharmakol. XXIV, 2437 (1887). Translation in: Kunz, W., Henle, J., Ninham, B.W.: About science of the effect of salts. Curr. Opin. Colloid Interface Sci. 9, 19–37 (2004)

    Google Scholar 

  35. Marshall, A.G.: Biophysical Chemistry: Principles, Techniques and Applications. Wiley, New York (1978). 62 pp.

    Google Scholar 

  36. Collins, K.D., Washabaugh, M.W.: The Hofmeister effect and the behaviour of water at interfaces. Q. Rev. Biophys. 18, 323–422 (1985)

    Article  CAS  Google Scholar 

  37. Creighton, T.E.: Proteins: Structure and Molecular Properties. 2nd edn. Freeman, New York (1993). 156 pp.

    Google Scholar 

  38. Lopez-Leon, T., Joder-Rayes, A.B., Bastos-Gonzalez, D., Ortega-Vinnesa, J.L.: Hofmeister effects in the stability and electrophoretic mobility of polyethylene latex particles. J. Phys. Chem. B 107, 5696–5708 (2003)

    Article  CAS  Google Scholar 

  39. Balasubramanian, G., Murad, S., Kapiyoor, R., Puri, I.K.: Structure of aqueous MgSO4 solution: dilute to concentrated. Chem. Phys. Lett. 508, 38–42 (2011)

    Article  CAS  Google Scholar 

  40. Kato, H., Miki, K., Mukai, T., Nishikawa, K., Koga, Y.: Hydrophobicity/hydrophilicity of 1-butyl-2,3-dimethyl and 1-ethyl-3-methylimidazolium ions: towards characterization of room temperature ionic liquid cations. J. Phys. Chem. B 113, 14754–14760 (2009)

    Article  CAS  Google Scholar 

  41. Kato, H., Nishikawa, K., Koga, Y.: Relative hydrophobicity/hydrophilicity of some ionic liquid anions: A differential approach in solution thermodynamics. J. Phys. Chem. B 112, 2655–2660 (2008)

    Article  CAS  Google Scholar 

  42. Westh, P., Rasmussen, E.L., Koga, Y.: Intermolecular interactions in ternary glycerol—sample—H2O: towards understanding the Hofmeister series (V). J. Solution Chem. 40, 93–105 (2011)

    Article  CAS  Google Scholar 

Download references

Acknowledgement

This work was supported by Ministry of Education, Science, Culture and Sports of Japan. Contribution # 19 from Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yoshikata Koga.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Cite this article

Koga, Y., Kondo, T., Miyazaki, Y. et al. The Effects of Sulphate and Tartrate Ions on the Molecular Organization of Water: Towards Understanding the Hofmeister Series (VI). J Solution Chem 41, 1388–1400 (2012). https://doi.org/10.1007/s10953-012-9880-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-012-9880-x

Keywords

Navigation