| Summary: | In modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the use of the Gibbs-Helmholtz equation.
In this connection excess molar enthalpies for several binary and ternary mixtures involving ethers and hydrocarbons have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. Values of the excess molar enthalpies were measured by means of a modified flow microcalorimeter (LKB 10700-1) and the systems show endothermic behavior.
The Redlich-Kister equation has been used to correlate experimental excess molar enthalpy data of binary mixtures. Smooth representations of the excess molar enthalpy values of ternary mixtures are accomplished by means of the Tsao-Smith equation with an added ternary contribution term and are used to construct excess enthalpy contours on Roozeboom diagrams. The values of the standard deviations indicate good agreement between experimental results and those calculated from the smoothing equations.
The experimental excess enthalpy data are also correlated and predicted by means of solution theories (Flory theory and Liebermann-Fried model) for binary and ternary mixtures, respectively. These solution theories correlate the binary heats of mixing data with reasonable accuracy. The prediction of ternary excess molar enthalpy by means of the solution theories are also presented on Roozeboom diagrams. The predictions of ternary excess enthalpy data by means of these theories are reasonably reliable.
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