Abstract
The conductance of tetrabutylammonium tetraphenylboride, picrate, perchlorate, and nitrate has been measured at 25°C in mixtures ofi-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dicholorobenzene, 1,2-dichloroethane, andn-pentanol covering the range of dielectric constants 10≤D≤20. In these mixtures of polar solvents, both association constants and ionic mobilities depend on ion-solvent interaction energies and on free volume in a manner that is specific for each system. This failure of the primitive model (rigid charged spheres in a continuum) is shown to be the consequence of short-range spatial and energetic interactions between ions and adjacent solvent molecules.
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References
A. D'Aprano and R. M. Fuoss,J. Solution Chem. 3, 45 (1974).
C. J. James and R. M. Fuoss,J. Solution Chem. 4, 91 (1975).
A. D'Aprano,J. Phys. Chem. 78, 652 (1974).
J. E. Lind, Jr., J. J. Zwolenik, and R. M. Fuoss,J. Am. Chem. Soc. 81, 1557 (1959).
R. M. Fuoss,J. Am. Chem. Soc. 57, 488 (1935).
A. D'Aprano and R. M. Fuoss,J. Phys. Chem. 67, 1704, 1871 (1963).
R. M. Fuoss,J. Am. Chem. Soc. 80, 5059 (1958).
N. Bjerrum,Kgl. Danske Videnskab. Selskab 7, No. 6 (1926).
R. M. Fuoss,Trans. Faraday Soc. 30, 967 (1934).
H. Sadek and R. M. Fuoss,J. Am. Chem. Soc. 76, 5905 (1954).
D. F. Evans, C. Zawoyski, and R. L. Kay,J. Phys. Chem. 69, 3878 (1965).
R. L. Kay, C. Zawoyski, and D. F. Evans,J. Phys. Chem. 69, 4208 (1965).
F. Accascina, E. L. Swarts, P. L. Mercier, and C. A. Kraus,Proc. Nat. Acad. Sci. U.S. 39, 917 (1953).
J. F. Skinner and R. M. Fuoss,J. Phys. Chem. 68, 2998 (1964).
R. Zwanzig,J. Chem. Phys. 52, 3625 (1970).
S. Glasstone, K. J. Laidler, and H. Eyring,The Theory of Rate Processes (McGraw-Hill, New York, 1941), pp. 480–484, 516–521, 552–555.
P. Hemmes,J. Phys. Chem. 78, 907 (1974).
D. S. Berns and R. M. Fuoss,J. Am. Chem. Soc. 82, 5585 (1960).
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D'Aprano, A., Fuoss, R.M. Conductance in isodielectric mixtures. III.i-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dichlorobenzene, 1,2-dichloroethane, andn-pentanol. J Solution Chem 4, 175–189 (1975). https://doi.org/10.1007/BF00649157
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DOI: https://doi.org/10.1007/BF00649157
Key words
- Conductance
- tetrabutylammonium tetraphenylboride
- tetrabutylammonium picrate
- tetrabutylammonium perchlorate
- tetrabutylammonium nitrate
- i-butyronitrile-chlorobenzene mixtures
- i-butyronitrile-o-dichlorobenzene mixtures
- i-butyronitrile-p-dichlorobenzene mixtures
- i-butyronitrile-1,2-dichloroethane mixtures
- i-butyronitrile-n-pentanol mixtures
- isodielectric mixtures