Vapor Pressure and Heat of Vaporization of Molecules That Associate in the Gas Phase

Abstract

© 2018 American Chemical Society. A model of the temperature dependence of the vapor pressure and the heat of vaporization of liquids whose vapors contain associates is presented for two cases: dimers and linear associates in the gas phase. The results are analytic generalizations of the Clausius-Clapeyron equation, valid with accuracy of 0.1%-1%, as demonstrated with 11 liquids: formic and acetic acids, methanol, ethanol, n-propanol, n-butanol, water, benzene, toluene, heptane, and isooctane. The model involves only readily available handbook parameters: the room-temperature heat of vaporization, vapor pressure, heat capacities, second virial coefficient, and heat of dissociation of the dimers in the gas phase.