Chapter 2

Thermodynamics of Separation Operations

§2.0 INSTRUCTIONAL OBJECTIVES

After completing this chapter, you should be able to:
Make energy, entropy, and availability balances around a separation process.
Explain phase equilibria in terms of Gibbs free energy, chemical potential, fugacity, fugacity coefficient, activity,
and activity coefficient.
Understand the usefulness of equilibrium ratios (K-values and partition coefficients) for liquid and vapor phases.
Derive K-value expressions in terms of fugacity coefficients and activity coefficients.
Explain how computer programs use equations of state (e.g., Soave–Redlich–Kwong or Peng–Robinson) to com-
pute thermodynamic properties of vapor and liquid mixtures, including K-values.
Explain how computer programs use liquid-phase activity-coefficient correlations (e.g., Wilson, NRTL,
UNIQUAC, or UNIFAC) to compute thermodynamic properties, including K-values.
For a given weak acid or base (including amino acids), calculate pH, pKa, degree of ionization, pI, and net charge.
Identify a buffer suited to maintain activity of a biological species at a target pH and evaluate effects of tempera-
ture, ionic strength, solvent and static charge on pH, and effects of pH on solubility.
Determine effects of electrolyte composition on electrostatic double-layer dimensions, energies of attraction, criti-
cal flocculation concentration, and structural stability of biocolloids.
Characterize forces that govern ligand–receptor–binding interactions and evaluate dissociation constants from free
energy changes or from batch solution or continuous sorption data.

T hermodynamic properties play a major role in separation
operations with respect to energy requirements, phase equili-
bria, biological activity, and equipment sizing. This chapter
develops equations for energy balances, for entropy and
availability balances, and for determining densities and com-
positions for phases at equilibrium. The equations contain
thermodynamic properties, including specific volume,
enthalpy, entropy, availability, fugacities, and activities, all
as functions of temperature, pressure, and composition. Both
ideal and nonideal mixtures are discussed. Equations to de-
termine ionization state, solubility, and interaction forces of
biomolecular species are introduced. However, this chapter is
not a substitute for any of the excellent textbooks on
thermodynamics.
Experimental thermodynamic property data should be
used, when available, to design and analyze the operation of
separation equipment. When not available, properties can of-
ten be estimated with reasonable accuracy. Many of these
estimation methods are discussed in this chapter. The most
comprehensive source of thermodynamic properties for pure
compounds and nonelectrolyte and electrolyte mixtures—
including excess volume, excess enthalpy, activity coeffi-
cients at infinite dilution, azeotropes, and vapor–liquid,
liquid–liquid, and solid–liquid equilibrium—is the computer-
ized Dortmund Data Bank (DDB) (www.ddbst.com), initi-
ated by Gmehling and Onken in 1973. It is updated annually
and is widely used by industry and academic institutions. In
2009, the DDB contained more than 3.9 million data points
for 32,000 components from more than 64,000 references.
Besides openly available data from journals, DDB contains a
large percentage of data from non-English sources, chemical
industry, and MS and PhD theses.
§2.1 ENERGY, ENTROPY, AND
AVAILABILITY BALANCES
Industrial separation operations utilize large quantities of
energy in the form of heat and/or shaft work. Distillation sep-
arations account for about 3% of the total U.S. energy con-
sumption (Mix et al. [1]). The distillation of crude oil into its
fractions is very energy-intensive, requiring about 40% of the
total energy used in crude-oil refining. Thus, it is important to
know the energy consumption in a separation process, and to
what degree energy requirements can be reduced.
Consider the continuous, steady-state, flow system for the
separation process in Figure 2.1. One or more feed streams
flowing into the system are separated into two or more

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