On permittivity and density of the systems {triglyme + (dimethyl or diethyl carbonate)} and formulation of Δ ε in terms of volume or mole fraction

Abstract

Relative permittivity and density on mixing from T = (288.15 to 328.15) K and atmospheric pressure have been measured over the whole composition range for {CH 3O(CH 2CH 2O) m CH 3 polyoxyethyleneglycol dimethyl ether with m = 3 (also called 2,5,8,11, tetraoxadodecane or triglyme) + (dimethyl or diethyl carbonate)}. For these systems, the deviation of permittivity, Δ ε, changes sign depending on whether it is defined on the basis of mole fractions or volume fractions. Arguments are put forward that support the choice of the definition in terms of mole fraction. The density and excess molar volumes as a function of temperature and mole fraction were fitted to a polynomial equation. The temperature dependence of derived quantities, such as the isobaric thermal expansion coefficient, α , ∂ V m E ∂ T P , x and ∂ H m E ∂ P T , x were computed, due to their importance in the study of specific molecular interactions. The excess molar volumes were analyzed using the Prigogine–Flory–Patterson (PFP) theory of solution thermodynamics. Different traditional mixing rules were applied to predict the permittivity of the mixtures.