New developments in differential ebulliometry: Experimental and theoretical

Abstract

A new ebulliometer has been developed in which superheat is discharged from the vapour–liquid mixture issuing from the Cottrell pump before it impinges on an otherwise vacuum-insulated temperature sensor. The convoluted chamber through which the mixture passes should also assist the attainment of phase equilibrium in binary mixtures. Measurements for several solvents showed unusually broad plateau regions with slopes much smaller than those reported by other researchers. Vapour pressures for several solvents were in close agreement with literature values. For the measurement of limiting activity coefficients, a new experimentally very simple procedure was developed for finding the difficult-to-determine evaporation ratio, ϕ, based on the steady-state macroscopic energy balance. Results are presented for two pure solvents, viz. ethylacetate and cyclohexane. Exact equations, based on material balances and equilibrium relationships involving ϕ then permit calculation of limiting activity coefficients. Measured temperature-composition data are presented for the ethylacetate (1)–toluene (2) and hexane (1)–ethylacetate (2) systems and the ebulliometer characterization procedure is illustrated for three binary systems. Exact differential equations for the temperature and pressure derivatives with respect to composition, and incorporating the full Gibbs-Duhem equation, are derived. These can be used to find the very useful temperature–pressure derivative (∂ T/∂ p) x 1 at any composition and also form the basis for a new thermodynamic consistency test.