Alternate Author Name(s)

Dr. Floyd L. Wilcox Sr., PhD '70

Document Type

Dissertation

Date of Award

1971

Keywords

Solution (Chemistry), Thermal properties, Activity coefficients

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Walter E. Kaskan

Second Advisor

Gilbert Janauer

Third Advisor

K. Keith Innes

Series

Science and Mathematics

Abstract

The variation of the logarithm of the activity coefficient of the four alcohols, ethylene glycol, methanol, ethanol, and l-propanol, on the addition of three salts, sodium chloride, sodium bromide, and sodium iodide, has been measured. The data were fit to an empirical equation of the form: (∂ log ɣ2/∂ m1)m2 = a + bm10.5 + cm1 + dm2 where a, b, c, and d are constants.

The parameter, d, was shown to be characteristic of the particular alcohol being studied but independent of the anion of the salt. This phenomenon was attributed to the interaction between the cation of the salt and the alcohol rather than between the anion and the alcohol.

The limiting interaction parameter, a, (usually termed the salting-out parameter) was shown to be characteristic of both the salt and the alcohol. The parameter, a, was shown to be composed of additive contributions arising from each of the functional groups that composed the alcohol molecule. The methyl and methylene groups were shown to give rise to salting-out while the hydroxyl group contributes to salting-in.

The scaled particle theory was applied to the twelve systems studied and the parameter, a, was calculated. The agreement with the experimental values was excellent indicating that the theory in its present form can be used for the alcohols as well as nonpolar nonelectrolytes.

Download

Share

COinS