Journal of Solution Chemistry

, Volume 3, Issue 7, pp 515–522 | Cite as

Effects of substituted ligands on the mobility of complexed anions

  • Dominique J. Pirson
  • Pierre L. Huyskens
Article

Abstract

From conductance and viscosities measurements on Pr4NCl, Et4NBr, and AgNO3 in acetonitrile and Et3NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10−4 ohm-cm−5 mole-cP−1.

Key words

Acetonitrile conductivity ligands molar volume of ions nitrobenzene solvation Stokes' law viscosity Walden's rule 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    P. Walden,Z. Phys. Chem. 55, 207 (1906).Google Scholar
  2. 2.
    P. Walden and J. Birr,Z. Phys. Chem. A160, 327 (1932).Google Scholar
  3. 3.
    R. M. Fuoss and L. Onsager,Proc. Nat. Acad. Sci. U.S. 41, 274, 1010 (1955);J. Phys. Chem.,61, 668 (1957).Google Scholar
  4. 4.
    R. M. Fuoss and F. Accascina,Electrolytic Conductance (Interscience Publishers, New York, 1959).Google Scholar
  5. 5.
    D. F. Evans, G. Zawoyski, and R. L. Kay,J. Phys. Chem. 69, 3878 (1965).Google Scholar
  6. 6.
    J. F. Coetzee,Progr. Phys. Org. Chem. 4, 45 (1967); see also: C. H. Springer, J. F. Coetzee, and R. L. Kay,J. Phys. Chem. 73, 472 (1969).Google Scholar
  7. 7.
    C. R. Witschonke and C. A. Kraus,J. Am. Chem. Soc. 69, 2472 (1947).Google Scholar
  8. 8.
    P. Walden and E. J. Birr,Z. Phys. Chem. A163, 281 (1933).Google Scholar
  9. 9.
    D. J. Pirson and P. L. Huyskens,J. Solution Chem. 3, 503 (1974).Google Scholar
  10. 10.
    R. L. Kay and D. F. Evans,J. Phys. Chem. 70, 2325 (1966).Google Scholar

Copyright information

© Plenum Publishing Corporation 1974

Authors and Affiliations

  • Dominique J. Pirson
    • 1
  • Pierre L. Huyskens
    • 1
  1. 1.Department of ChemistryUniversity of Louvain (K.U.L.)HeverleeBelgium

Personalised recommendations