화학공학소재연구정보센터
Fluid Phase Equilibria, Vol.93, 75-99, 1994
Modeling of Solid-Phases in Thermodynamic Calculations via Translation of a Cubic Equation of State at the Triple Point
A simple methodology is demonstrated by which a cubic equation of state (EOS) can be modified to allow calculation of equilibria involving solid phases as well as thermodynamic properties of the solid phase itself. Volume translation of the EOS at the triple point is performed using experimental values of solid density. Temperature-dependent parameters of the translated equation (TEOS) are then regressed to vapour pressure data at temperatures below the triple point if data are available. A generalized procedure for calculation of temperature-dependent parameters in the translated equation is also described (for instances where data are unavailable) which requires the heat of sublimation at the triple point and the isobaric heat capacity of the solid. The translated equation can then be utilized to describe solid phases at temperature above the triple point temperature by extrapolation, with the result that the entire pressure-temperature space for a pure component can be accurately reproduced. The methodology is successfully applied to the Trebble-Bishnoi-Salim EOS and is used to calculate both pure component phase behaviour and binary solid-liquid and solid-vapour equilibria. Criteria are also discussed to ensure that the translated equation does not violate thermodynamic consistency.