Skip to main content
SpringerLink
Log in

Pressure and isotope effects on the proton jump of the hydroxide ion at 25°C

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

Abstract

The limiting molar conductances Λ0 of potassium deuteroxide KOD in D2O and potassium hydroxide KOH in H2O were determined at 25°C as a function of pressure to disclose the difference in the proton-jump mechanism between an OH− (OD−) and a H3O+ (D3O+) ion. The excess conductance of the OD− ion in D2O λ OE (OD -), as estimated by the equation

$$\lambda _E^O (OD^ - ) = \Lambda ^O (KOD/D_2 O) - \Lambda ^O (KCl/D_2 O)$$

increases a little with pressure as well as the excess conductance of the OH− ion in H2O

$$\lambda _E^O (OH^ - ) = \Lambda ^O (KOH/H_2 O) - \Lambda ^O (KCl/H_2 O)$$

However, their rates of increase with pressure are much smaller than those of the excess deuteron and proton conductances, λ OE (D +) and λ OE (H +). With respect to the isotope effect on the excess conductance, λ OE (OH -)/λ OE (D +) decreases with presure as in the case of λ OE (H +)/λ OE (D +), but the value of λ OE (OH -)/λ OE (OD -) itself is much larger than that of λ OE (H +)/λ OE (D +) at each pressure. These results are ascribed to the difference in the pre-rotation of water molecules, which is brought about by the difference in the intial orientation of the rotating water molecule adjacent to the OH− (OD−) or the H3O+ (D3O+) ion.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. L. S. Darken and H. F. Meier,J. Am. Chem. Soc. 64, 621 (1942).

    Article  CAS  Google Scholar 

  2. S. D. Hamann,Physico-Chemical Effects of Pressure, (Butterworths, London, 1957) Chap. 7; S. D. Hamann and W. Strauss,Trans. Faraday Soc. 51, 1684 (1955).

    Google Scholar 

  3. R. A. Horne, B. R. Myers, and G. R. Frysinger,J. Chem. Phys. 39, 2666 (1963).

    Article  CAS  Google Scholar 

  4. K. N. Marsh and R. H. Stokes,Aust. J. chem. 17, 740 (1964).

    Article  CAS  Google Scholar 

  5. D. A. Lown and H. R. Thirsk,Trans. Faraday Soc. 67, 132 (1971).

    Article  CAS  Google Scholar 

  6. E. Conway, J. O'M. Bockris, and H. Linton,J. Chem. Phys. 24, 834 (1956).

    Article  CAS  Google Scholar 

  7. Y. Tada, M. Ueno, N. Tsuchihashi, and K. Shimizu,J. Solution Chem. 21, 971 (1992).

    Article  CAS  Google Scholar 

  8. M. Ueno, Y. Sakata, N. Tsuchihashi, and K. Shimizu,Bull. Chem. Soc. Jpn. 59, 3723 (1986).

    Article  CAS  Google Scholar 

  9. G. S. Kell,J. Chem. Eng. Data 12, 66 (1967).

    Article  CAS  Google Scholar 

  10. C. T. Chen and F. J. Millero,J. Chem. Phys. 75, 3553 (1981).

    Article  CAS  Google Scholar 

  11. G. S. Kell,J. Chem. Eng. Data 20, 97 (1975).

    Article  CAS  Google Scholar 

  12. C. T. Chen, R. A. Fine, and F. J. Millero,J. Chem. Phys. 66, 2142 (1977).

    Article  CAS  Google Scholar 

  13. F. J. Millero, R. Dexter, and E. Hoff,J. Chem. Eng. Data 16, 85 (1971).

    Article  CAS  Google Scholar 

  14. A. Harlow, Ph. D. Thesis, London University, (1969).

  15. L. Korson, W. Drost-Hansen, and F. J. Millero,J. Phys. Chem. 73, 34 (1969).

    Article  CAS  Google Scholar 

  16. J. B. Cappi, Ph. D. Thesis, London University, (1964); K. E. Bett and

  17. K. R. Srinivasan and R. L. Kay,J. Chem. Phys. 60, 3645 (1974).

    Article  CAS  Google Scholar 

  18. M. Ueno, N. Tsuchihashi, and K. Shimizu,Bull. Chem. Soc. Jpn. 58, 2929 (1985).

    Article  CAS  Google Scholar 

  19. R. L. Kay,J. Am. Chem. Soc. 82, 2099 (1960).

    Article  CAS  Google Scholar 

  20. R. M. Fuoss and F. Accascina,Electrolytic Conductance, (Interscience, New York, 1959), Chap. 15.

    Google Scholar 

  21. P. C. Carmen,J. Phys. Chem. 74, 1653 (1970).

    Article  Google Scholar 

  22. R. A. Robinson and R. H. Stokes,Electrolyte Solutions, 2nd edn. revised, (Butter-Worths, London, 1970), Appendix 6.1.

    Google Scholar 

  23. M. Nakahara, M. Zenke, M. Ueno, and K. Shimizu,J. Chem. Phys. 83, 280 (1985).

    Article  CAS  Google Scholar 

  24. G. A. Gaballa and G. W. Neilson,Mol. Phys. 50, 97 (1983).

    Article  CAS  Google Scholar 

  25. F. H. Stillinger and A. Rahman,J. Chem. Phys. 61, 4973 (1974).

    Article  CAS  Google Scholar 

  26. E. Whalley,J. Chem. Phys. 63, 5205 (1975).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Faculty of Engineering, Doshisha University, Kamigyo-ku, 602, Kyoto, Japan

    Yuichiro Tada, Masakatsu Ueno, Noriaki Tsuchihashi & Kiyoshi Shimizu

Authors
  1. Yuichiro Tada
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Masakatsu Ueno
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Noriaki Tsuchihashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kiyoshi Shimizu
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Tada, Y., Ueno, M., Tsuchihashi, N. et al. Pressure and isotope effects on the proton jump of the hydroxide ion at 25°C. J Solution Chem 22, 1135–1149 (1993). https://doi.org/10.1007/BF00651695

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00651695

Key words

Search

Navigation