Negative Wien Effects

Bailey, F. E.; Spinnler, Joseph F.; Patterson, Andrew D.

doi:10.1021/ja01468a048

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“…In each, there is considerable improvement in the match between experiment and theory at the high fields, but an actual deterioration in the agreement at the low fields, near the origin. Here, the theoretical curves plunge below the experimental and actually become negative, a result not to be expected in these systems, although experimental negative Wien effects have been observed with some uranyl ion solutions (8). This is the result of the approximation made in order to use Eq.…”

Section: Discussionmentioning

confidence: 72%

The Wien Effect and lonic Association

Patterson¹,

Freitag²

1961

J. Electrochem. Soc.

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High field conductance is sensitively dependent on ion association, so that if one has available theoretical means to compute high field conductances, experimental measurements can be used to determine association constants. The authors have programmed for machine computation the Onsager-Kim strong electrolyte theory of the Wien effect, combined with the Onsager weak electrolyte theory in such a way as to account for the high field conductances of associated electrolytes. The computation is a considerable improvement over previous ones, being both more precise and much faster. Graphs are presented of a number of computed results, compared with experimental measurements, illustrating the way in which theory and measurement can be combined to obtain information about ion association. The majority of these calculations have not been attempted previously.Experimental measurements of the high field conductance quotient (Wien effect) have been found useful for studying ionic association in solutions ranging from those which one would characterize as involving strong electrolytes, through the middle ground where ionic association significantly alters the behavior of what would otherwise be regarded as strong electrolytes, to those of electrolytes which are sufficiently associated to be classified as weak. It is convenient to compare the experimental Wien effect measurements with computed theoretical results and to use the theory to derive estimates of ionic association in the solutions. Until recently, application of this approach has been hindered by the lack of a theory of the Wien effect for nonsymmetrical valence-type strong electrolytes and by the complexity and tediousness of the calculations required. The first of these impediments has been removed by the appearance of the Onsager-Kim theory (1) for the high field conductance of nonsymmetrical strong electrolytes. The authors have now programmed this theory for machine computation on the IBM 650 computer, have included in this program a correction for association utilizing the Onsager theory for weak electrolytes, and have also incorporated into the program a computation of the mean activity coefficient of the electrolyte under examination, at zero field, by the method developed by Poirier (2) based on the Mayer cluster theory of imperfect gases. The present authors have used this program to refine considerably an earlier calculation of Bailey and Patterson (3) and to show a number of possible ways to study ionic association, the results of these computations being presented in the sections which follow.

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Section: Discussionmentioning

confidence: 72%