Thermochemical Investigationsn of Hydrogen-Bonded Solutions. Part 7. Extension of Mobile Order Theory to Inert Solutes Dissolved in Binary Alcohol + Ether and Other Interactive Cosolvent Mixtures

Abstract For the thermodynamics of Mobile Order and Disorder a molecule B in a liquid does not occupy a given place in a quasi-lattice, but rather occupies a mobile domain whose volume is equal to the total volume V of the liquid divided by the number NB molecules of the same kind, i.e., Dom B= V/NB. the center of this domain perpetually moves. Highest mobile disorder is achieved whenever groups visit all part of their domain without preference. Hydrogen-bonded contacts lead to deviations with respect to this “random” visiting. These principles enable new equations to be derived for the entropy of mixing, and for the effect of H-bonds on the chemical potential of dissolved substances. From this point-of-view, addition and insertion H-bonds are essentially different. in the present study general equations are deduced for predicting the solubilities of inert solutes in various noncomplexing and complexing binary solvent mixtures. Nonspecific solute-solvent interactions are eliminated from the final derived ...