Part I. The Distribution of Cyclohexene Between Carbon Tetrachloride and Aqueous Solutions of Acids and Salts. Part II. The Solubility of Some Nonpolar Organic Liquids in Water in Aqueous Solutions of Strong Acids, Alkali Salts, and Silver Nitrate. The Coordination of Silver Ion with Benzene. Part III. A Proposed Enium Nomenclature for Ionic Complexes Involving Carbon-Carbon Multiple Bonds

Citation

Koenig, Nathan Hart (1950) Part I. The Distribution of Cyclohexene Between Carbon Tetrachloride and Aqueous Solutions of Acids and Salts. Part II. The Solubility of Some Nonpolar Organic Liquids in Water in Aqueous Solutions of Strong Acids, Alkali Salts, and Silver Nitrate. The Coordination of Silver Ion with Benzene. Part III. A Proposed Enium Nomenclature for Ionic Complexes Involving Carbon-Carbon Multiple Bonds. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/evmw-7s52. https://resolver.caltech.edu/CaltechTHESIS:06162025-172908063

Abstract

It has been shown that cyclohexene distributed at 25° between carbon tetrachloride and dilute aqueous solutions is less soluble in aqueous solutions of alkali salts, hydrochloric acid, and sulfuric acid than in water, but is more soluble in aqueous solutions of perchloric acid and nitric acid. Analysis of the data relative to general salting effects indicates that if aqueous proton-olefin complexes exist, they are present only in very low concentration.

A new procedure, stripping analysis, has been employed to determine the solubility of benzene at 100° and 25°, and of carbon tetrachloride and cyclohexane at 25° in water and in aqueous solutions of strong acids, alkali salts, and silver nitrate. Each of the organic liquids is somewhat more soluble in 3 M perchloric acid than in water, and benzene is much more soluble in 1 M silver nitrate than in water. Qualitative data on the change of solubility, with temperature have been obtained by the cloudiness method. The combined solubility data, together with related data for cyclohexene, are discussed in terms of the salting and complexing factors involved.

Equilibrium constants and heats of complex formation have been calculated for the coordination of silver ion with benzene.

The nature of ionic complexes involving carbon-carbon multiple bonds is discussed, and an enium nomenclature is proposed for such complexes because of their distinctive character. The terms "enium" and "onium" are compared.

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