Journal of Solution Chemistry

, Volume 24, Issue 4, pp 343–355 | Cite as

Pressure effect on proton jumps in dioxane-water mixtures at 25°C

  • Yuichiro Tada
  • Masakatsu Ueno
  • Kiyoshi Shimizu
Article
Received:
Revised:

Abstract

The limiting molar conductances Λo of hydrochloric acid and potassium chloride in 2.5, 5, 10, and 15 mol% 1,4-dioxane-water mixtures were determined at 25°C as a function of pressure up to 196.1 MPa from the conductances measured in the dilute concentration range. The value of Λo(HCl) was two to three times larger than that of Λo(KCl) in each solvent mixture as well as in pure water. The excess proton conductance, as estimated by the equation [λ E o =Λo(HCl)−Λo(KCl)], increased with pressure in each solvent mixture, although the value of λ E o itself decreased rapidly with an increase in the dioxane content. The rate of increase in λ E o with pressure was not so large in dioxane-water mixtures as in pure water, and became smaller with an increase in the dioxane content in contrast to the cases of ethanol-water and t-butyl alcohol (TBA)-water mixtures. These results are discussed in terms of the difference between a dioxane and an ethanol or a TBA molecule in ability to stabilize the hydrogen-bonded networks of water in the water-rich region.

Key Words

Proton jump hydrogen-bonded networks excess proton conductance 1,4-dioxane-water mixtures pressure effect 
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. Nakahara and J. Osugi,Rev. Phys. Chem. Jpn. 47, 1 (1977).Google Scholar
  2. 2.
    M. Ueno, M. Nakahara, and J. Osugi,J. Solution Chem. 8, 881 (1979).Google Scholar
  3. 3.
    Y. Tada, M. Ueno, N. Tsuchihashi, and K. Shimizu,J. Solution Chem. 21, 971 (1992).Google Scholar
  4. 4.
    Y. Tada, M. Ueno, N. Tsuchihashi, and K. Shimizu,J. Solution Chem. 22, 1135 (1993).Google Scholar
  5. 5.
    Y. Tada, M. Ueno, N. Tsuchihashi, and K. Shimizu,J. Solution Chem. 23, 973 (1994).Google Scholar
  6. 6.
    B. E. Conway, J. O'M. Bockris, and H. Linton,J. Chem. Phys. 24, 834 (1956).Google Scholar
  7. 7.
    M. Ueno, K. Ito, N. Tsuchihashi, and K. Shimizu,Bull. Chem. Soc. Jpn. 59, 1175 (1986).Google Scholar
  8. 8.
    M. Ueno, K. Matsukawa, N. Tsuchihashi, and K. Shimizu,Bull. Chem. Soc. Jpn. 64, 931 (1991).Google Scholar
  9. 9.
    K. Nakanishi,Bull. Chem. Soc. Jpn. 33, 793 (1960).Google Scholar
  10. 10.
    R. L. Kay, G. P. Cunningham, and D. F. Evans, inHydrogen-Bonded Solvent System, A. Covington and P. Jones, eds.), (Taylor and Francis, London, 1968) p. 249.Google Scholar
  11. 11.
    T. L. Broadwater and R. L. Kay,J. Phys. Chem. 74, 3802 (1970).Google Scholar
  12. 12.
    R. L. Kay and T. L. Broadwater,Electrochimica Acta,16, 667 (1971).Google Scholar
  13. 13.
    M. Ueno, A. Yoneda, N. Tsuchihashi, and K. Shimizu,J. Chem. Phys. 86, 4678 (1987).Google Scholar
  14. 14.
    M. Sakurai,J. Chem. Eng. Data,37, 492 (1992).Google Scholar
  15. 15.
    P. J. Pearce and W. Strauss,Aust. J. Chem. 21, 1213 (1968).Google Scholar
  16. 16.
    The density data for dioxane-water mixtures at high pressures were calculated by using the densities at 1 atm reported in Ref. 14 and the compression factors ΔV/V in Ref. 15.Google Scholar
  17. 17.
    M. Ueno, N. Tsuchihahsi, and K. Shimizu,Sci. Eng. Rev. Doshisha Univ. 29, 1 (1988).Google Scholar
  18. 18.
    M. Ueno, N. Tsuchihahsi, and K. Shimizu,Bull. Chem. Soc. Jpn. 58, 2929 (1985).Google Scholar
  19. 19.
    R. L. Kay,J. Am. Chem. Soc. 82, 2099 (1960).Google Scholar
  20. 20.
    R. M. Fuoss and F. Accascina,Electrolytic Conductance (Interscience, New York, 1959) Chap. 15.Google Scholar
  21. 21.
    P. C. Carmen,J. Phys. Chem. 74, 1653 (1970).Google Scholar
  22. 22.
    T. Erdey-Grúz and S. Lengyel, inModern Aspect of Electrochemistry, Vol. 12, J. O'M. Bockris and B. E. Conway, eds., (Butterworths, London, 1977) Chap. 1.Google Scholar
  23. 23.
    Y. Lee and J. Jonas,J. Chem. Phys. 59, 4845 (1973).Google Scholar
  24. 24.
    S. K. Grag and C. P. Smyth,J. Chem. Phys. 43, 2959 (1965).Google Scholar
  25. 25.
    D. E. Buck,U. S. Govt. Res. Develop. Rept. 40, 59 (1965).Google Scholar
  26. 26.
    G. A. Gaballa and G. W. Neilson,Mol. Phys. 50, 97 (1983).Google Scholar
  27. 27.
    Y. Tanaka, private communication.Google Scholar
  28. 28.
    M. Sakurai,Bull. Chem. Soc. Jpn. 60, 1 (1987).Google Scholar

Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • Yuichiro Tada
    • 1
  • Masakatsu Ueno
    • 1
  • Kiyoshi Shimizu
    • 1
  1. 1.Department of Molecular Science and Technology, Faculty of EngineeringDoshisha UniversityKyotoJapan

Personalised recommendations