Advertisement

Journal of Solution Chemistry

, Volume 37, Issue 8, pp 1037–1049 | Cite as

New Physico-Chemical Properties of Extremely Diluted Solutions. Electromotive Force Measurements of Galvanic Cells Sensible to the Activity of NaCl at 25 °C

  • L. Ciavatta
  • V. EliaEmail author
  • E. Napoli
  • M. Niccoli
Article

Abstract

The mean ionic activity coefficients for sodium chloride in the NaCl+H2O binary system have been experimentally determined at 298.15 K, from electromotive force measurements of the cell:
$$(-)\,\mathrm{Pt}|\mathrm{Ag}|\mathrm{AgCl}|\mathrm{NaCl}(\mathrm{m}_{2})\|\mathrm{NaCl}(\mathrm{m}_{1})|\mathrm{AgCl}|\mathrm{Ag}|\mathrm{Pt}\,(+)$$
The electrolyte molality, m, ranged from 0.01 to 3 mol⋅kg−1. The measurements of electromotive force were carried out on solutions containing pure water as solvent, or a mix of water and “extremely diluted solutions” (EDS), obtained using the iterative procedure of successive dilutions and succussions of Homeopathic Medicine, at the same concentration of sodium chloride. The measurements of the mean activity coefficient of sodium chloride, on the solutions containing the EDS, showed evidence of some relevant differences compared to those with just water as solvent. In the performed experiments, the differences in electromotive force between the two systems must be attributed substantially to a difference in the activity of the solute between the two solvents.

The analysis of the activity coefficients was interpreted by considering the different kinds of interactions that can take place in the mixed system, due to the presence of molecular aggregates of water molecules, i.e., dissipative structures.

Keywords

EDS Activity coefficients Emf measurements Dissipative structure 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Mishima, O., Stanley, H.E.: Decompression-induced melting of ice IV and the liquid–liquid transition in water. Nature 392, 164–168 (1998) CrossRefGoogle Scholar
  2. 2.
    Malescio, G., Franzese, G., Skibinsky, A., Buldyrev, V., Sergey, V., Stanley, H.E.: Liquid-liquid phase transition for an attractive isotropic potential with wide repulsive range. Phys. Rev. E 71, 061504/1–061504/8 (2005) CrossRefGoogle Scholar
  3. 3.
    Bakker, H.J., Kropman, M.F., Omta, A.W.: Effect of ions on the structure and dynamics of liquid water. J. Phys. Condens. Matter 17, 3215–3224 (2005) CrossRefGoogle Scholar
  4. 4.
    Robinson, G.W., Cho, C.H., Gellene, G.I.: Refractive index mysteries of water. J. Phys. Chem. B 104, 7179–7182 (2000) CrossRefGoogle Scholar
  5. 5.
    Woutersen, S., Bakker, H.J.: Resonant intermolecular transfer of vibrational energy in liquid water. Nature 402, 507–509 (1999) CrossRefGoogle Scholar
  6. 6.
    Lobyshev, V.I., Shikhlinskaya, R.E., Ryzhikov, B.D.: Experimental evidence for intrinsic luminescence of water. J. Mol. Liq. 82, 73–81 (1999) CrossRefGoogle Scholar
  7. 7.
    Lobyshev, V.I., Solovey, A.B., Bulienkov, N.A.: Computer construction of modular structures of water. J. Mol. Liq. 106, 277–297 (2003) CrossRefGoogle Scholar
  8. 8.
    Elia, V., Niccoli, M.: Thermodynamics of extremely diluted aqueous solutions. Ann. N.Y. Acad. Sci. 879, 241–248 (1999) CrossRefGoogle Scholar
  9. 9.
    Elia, V., Niccoli, M.: New Physico-chemical properties of water induced by mechanical treatments. J. Therm. Anal. Calorim. 61, 527–537 (2000) CrossRefGoogle Scholar
  10. 10.
    Elia, V., Niccoli, M.: New physico-chemical properties of extremely diluted solutions. J. Therm. Anal. Calorim. 75, 815–836 (2004) CrossRefGoogle Scholar
  11. 11.
    Elia, V., Napoli, E., Niccoli, M., Nonatelli, L., Ramaglia, A., Ventimiglia, E.: New physico-chemical properties of extremely diluted aqueous solutions. A calorimetric and conductivity study at 25 °C. J. Therm. Anal. Calorim. 78, 331–342 (2004) CrossRefGoogle Scholar
  12. 12.
    Elia, V., Marchese, M., Montanino, M., Napoli, E., Niccoli, M., Nonatelli, L., Ramaglia, A.: Hydrohysteretic phenomenon of “extremely diluted solutions” induced by mechanical treatments. A calorimetric and conductometric study at 25 °C. J. Solution Chem. 34, 947–960 (2005) CrossRefGoogle Scholar
  13. 13.
    Elia, V., Elia, L., Cacace, P., Napoli, E., Niccoli, M., Savarese, F.: “Extremely Diluted Solutions” as multi-variables systems: a study of calorimetric and conductometric behaviour as a function of the time parameter. J. Therm. Anal. Calorim. 84, 317–323 (2006) CrossRefGoogle Scholar
  14. 14.
    Elia, V., Elia, L., Napoli, E., Niccoli, M.: Conductometric and calorimetric studies of serially diluted and agitated solutions: the dependence of intensive parameters on volume. Int. J. Ecodynamics 1, 1–12 (2006) CrossRefGoogle Scholar
  15. 15.
    Elia, V., Elia, L., Marchese, M., Montanino, M., Napoli, E., Niccoli, M., Nonatelli, L., Savarese, F.: Interaction of “extremely diluted solutions” with aqueous solutions of hydrochloric acid and sodium hydroxide. A calorimetric study at 298 K. J. Mol. Liq. 130, 15–20 (2007) CrossRefGoogle Scholar
  16. 16.
    Elia, V., Elia, L., Montanino, M., Napoli, E., Niccoli, M., Nonatelli, L.: Conductometric studies of the serially diluted and agitated solutions on an anomalous effect that depends on the dilution process. J. Mol. Liq. 135, 158–165 (2007) CrossRefGoogle Scholar
  17. 17.
    Elia, V., Napoli, E., Niccoli, M., Marchettini, N., Tiezzi, E.: Physico-chemical properties of extremely diluted aqueous solutions in relation to ageing. J. Solution Chem. 37, 85–96 (2007) CrossRefGoogle Scholar
  18. 18.
    Belon, P., Elia, V., Elia, L., Montanino, M., Napoli, E., Niccoli, M.: Conductometric and calorimetric studies of the serially diluted and agitated solutions. On the combined anomalous effect of time and volume parameters. J. Therm. Anal. Calorim. (2007, in press) Google Scholar
  19. 19.
    Elia, V., Elia, L., Napoli, E., Niccoli, E.: On the stability of extremely diluted aqueous solutions at high ionic strength. A calorimetric study at 298 K. J. Therm. Anal. Calorim. (2007, in press) Google Scholar
  20. 20.
    Elia, V., Elia, L., Marchettini, N., Napoli, E., Niccoli, M., Tiezzi, E.: Conductometric behaviour of extremely diluted solutions in relation to ageing. J. Therm. Anal. Calorim. (2007, in press) Google Scholar
  21. 21.
    Rey, L.: Thermoluminescence of ultra-high dilutions of lithium chloride and sodium chloride. Physica A 323, 67–74 (2003) CrossRefGoogle Scholar
  22. 22.
    Samal, S., Geckeler, K.E.: Unexpected solute aggregation in water on dilution. Chem. Commun. 2224–2225 (2001) Google Scholar
  23. 23.
    Lo, S.Y.: Anomalous state of ice. Mod. Phys. Lett. B 10, 909–919 (1996) CrossRefGoogle Scholar
  24. 24.
    Lo, S.Y., Lo, A., Chong, L.W., Tianzhang, L., Hua, L.H., Geng, X.: Physical properties of water with I E structure. Mod. Phys. Lett. B 10, 921–930 (1996) CrossRefGoogle Scholar
  25. 25.
    Hahnemann, S.: Organon of Medicine, VI edn., RED Edizioni (1985) Google Scholar
  26. 26.
    Galleguillos-Castro, H.R., Hernández-Luis, F., Fernández-Mérida, L., Esteso, M.A.: Thermodynamic study of the NaCl+Na2SO4+H2O system by Emf measurements at four temperatures. J. Solution Chem. 28, 791–807 (1999) CrossRefGoogle Scholar
  27. 27.
    Hamer, W.J., Wu, Y.-C.: Osmotic coefficients and mean activity coefficients of univalent electrolytes in water at 25 C. J. Phys Chem. Ref. Data 1, 1047–1099 (1972) CrossRefGoogle Scholar
  28. 28.
    Inoue, Y., Liu, Y., Tong, L., Shen, B., Jin, D.: Calorimetric titration of inclusion complexation with modified beta-cyclodextrins. Enthalpy-entropy compensation in host-guest complexation: from ionophore to cyclodextrin and cyclophane. J. Am. Chem. Soc. 115, 10637–10644 (1993) CrossRefGoogle Scholar
  29. 29.
    Nicolis, G.: Physics of far-equilibrium systems and self-organization. In: Davies, P. (ed.) The New Physics. Cambridge University Press, New York (1989) Google Scholar
  30. 30.
    Prigogine, I.: Time, Structure and Fluctuations. Nobel Lecture, 8 December 1977 Google Scholar
  31. 31.
    Magnani, A., Marchettini, N., Ristori, S., Rossi, C., Rossi, F., Rustici, M., Spalla, O., Tiezzi, E.: Chemical waves and pattern formation in the 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/water lamellar system. J. Am. Chem. Soc. 126, 11406–11407 (2004) CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  1. 1.Department of ChemistryUniversity “Federico II” of NaplesNaplesItaly

Personalised recommendations