Baxter, Warren P. (1926) The interionic attraction theory of ionized solutes. Testing the theory of alcohol solvents and by solubility experiments at higher temperature. Master's thesis, California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-11112004-144145
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Recently there have become available accurate electromotive-force data for concentration cells in which alcohols are used as solvents, and from which the activity coefficients of certain largely ionized solutes in alcoholic solutions can be calculated. This makes it possible to test the inter-ionic attraction theory developed by Milner and by Debye and Hückel, from the new view-point of the effect of the variation of the dielectric constant of the medium. It is the purpose of this article to show to what extent this aspect of the theory is confirmed by the existing data.
In the first article of this series, in which a critical review of the theory was given by A. A. Noyes, the following expression for the activity co-efficient or activation of an ion was derived: [...]. In this expression [...] denotes the activation of any ion of A of valence [...] (taken algebraically), R the gas constant, K the dielectric constant of the solution, and A a product of universal constants whose value is [...] c.g.s. units when the concentration c is expressed in moles per cc. The quantity [...] following the summation sign is to be summed for all the kinds of ions in the solution. Owing to certain simplifying assumptions made in its derivation this form of the equation may be expected to be reasonably accurate only when applied to dilute solutions, certainly not more concentrated than 0.55 N.
Experimental testings of this equation were presented in the early part of 1924 by means of the data then available for fairly dilute aqueous solutions. These tests showed that the equation holds true, at any rate as a first approximation, not only with respect to the predicted functional relations to valence and concentration, but also as to the numerical value of the coefficient A. Unusually accurate freezing-point determinations in highly dilute aqueous solutions have since been published by Randall and Vanselow, which have made possible the testing of the equation at lower concentrations, where it may be expected to be more nearly exact; and correspondingly, their data do in fact show an even closer conformity with the theory than those earlier available. Thus Scatchard has recently shown that this is true of their data with hydrochloric acid; and it can be readily shown that the statement applies also to their results with the other two substances, thallous chloride and lead nitrite.
|Item Type:||Thesis (Master's thesis)|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||1 January 1926|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||11 Nov 2004|
|Last Modified:||26 Dec 2012 03:09|
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