Association of the Butyl Alcohols and n-Decanol

Abstract
The dielectric constants at 0.1 MHz of n-, iso-, sec-, and t-butanol and n-decanol each at nine concentrations in the range 0.2–1.0 mole fraction in cyclohexane, p-dioxane, mesitylene, and p-xylene have been measured at 25 °C. Apparent dipole moments and Kirkwood correlation factors have been evaluated. Cyclohexane is regarded as an inert solvent in which alcohol self association alone is considered responsible for the anomalous electric polarization. The other three solvents have a disassociating effect which increases p-xylene ≤ mesitylene < p-dioxane. At the lowest concentrations the alcohols have larger apparent dipole moments in these solvents than in cyclohexane. The opposite tends to be the case for the more concentrated alcohol solutions. The results suggest that alcohol association is initially dominated by the formation of small, weakly polar multimers, and eventually larger highly polar multimers predominate.