Thermodynamics plays a key role in understanding, modeling, and designing reactive separation processes. The basic concepts of thermodynamic modeling of simultaneous chemical and phase equilibrium are summarized here with emphasis on the different options provided by classical thermodynamics. Several types of

RD process models are compared with each other and with experimental data on the background of the model complexity and the amount of information needed to parameterize the models.

Reliable models of reactive separation processes have to be based on a sound knowledge of the properties of the reacting fluid. Thermodynamics provides both the experimental methods and models to study and describe these properties. Different aspects of their use in RD process design are discussed, namely the question of sensitivity to inaccurate input data, predictions of properties of multicom-ponent mixtures from binary data, benefits of thermodynamically consistent models, and consequences of inconsistent models. These topics are addressed using examples from different esterifications and intrinsically chemically reactive systems. The examples given throughout the paper show the prime importance of reliable experimental data for the development of predictive process models of RDs. Therefore, also a brief survey on experimental techniques for studies of reactive phase equilibria is included.

Applying thermodynamics to RD processes is a fascinating subject, which covers all aspects, from experimental laboratory studies over modeling and simulation up to the industrial application of these complex processes.

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