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ION–SOLVENT INTERACTIONS 179

2. P. Debye and W. McAuley, “Theory of Salting Out,” Z. Phys. Chem. 26: 22 (1925).
3. J. O’M. Bockris, J. Bowler-Reed, and J. A. Kitchener, “The Salting In Effect,” Trans.
Faraday Soc. 47: 184 (1951).
4. R. McDevilt and F. Long, “Salting Out,” Chem. Rev. 51: 119 (1952).

Reviews
1. B. E. Conway, Ionic Hydration in Chemistry and Biology, pp. 444–465, Elsevier, New
York (1981).
2. G. A. Krestov, Thermodynamics of Solvation, Ellis Harwood, New York (1991).

Papers
1. W. Lang and R. Zander, Ind. Eng. Chem. Fundam. 25: 775 (1986).
2. J. Butz, P. H. Karpinski, J. Mydiarz, and J. Nyvil, Ind. Eng. Chem. Prod. Res. Dev. 25:
657 (1986).
3. D. C. Leggett, T. F. Jenkins, and P. H. Miyeres, J. Anal. Chem. 62: 1355 (1990).
4. G. Mina-Makarius and K. L. Pinder, Can. J. Chem. Eng. 69: 308 (1991).

2.21. DIELECTRIC BREAKDOWN OF WATER

2.21.1. Phenomenology

Experiment shows that the magnitude of the electric field between two plates
depends on the medium contained between them. The quantity dielectric constant is
used as a measure of the effect of the medium in reducing the field that exists if nothing
is there. Water has a particularly large dielectric constant (ca. 78 at 25 °C). This
means that if the field between two plates separated by a vacuum amounts to
the field would be reduced to if water were used to fill the space between
the plates.
Dielectric constants depend little upon the strength of the applied field until
extremely high fields are reached—fields greater than . However, at some
critical field strength, a complex phenomenon occurs (Figs. 2.70 and 2.71). It is called
dielectric breakdown. It can be described in a general way by saying that a dielectric
liquid subjected to a sufficiently high electric field suddenly ceases to behave in the
customary field-reducing manner. At the same time, a number of characteristic
phenomena (e.g., light emission) occur.
44
What are the phenomena characteristic of dielectric breakdown? The first six in
importance are:

44
The phenomenon occurs for solids, liquids, and gases. Because this chapter is concerned with ionic
solutions, the material here is limited to liquids and dilute solutions.