Excess Gibbs Energy Models

Purpose of this lecture: To introduce some popular empirical models (Margules, van Laar) that can be used for activity coefficients in binary mixtures Highlights • Margules and van Laar equations (Lecture 18) are simple correlations to obtain activity coefficients. • They are derived by assuming GE/RT x1 x2 follows a polynomial • They only work for binary mixtures

Reading assignment: Sections 12.1 and 12.2

CHEE 311

Lecture 17


Uniquac Some fundamental basis Parameters are temperature dependent. These correlations: reduce vast quantities of experimental data into a few empirical parameters. and the models usually cannot be extended beyond binary systems. Unisym. Margules. van Laar No fundamental basis but easy to use Parameters apply to a given temperature. Local composition models Wilson.Excess Gibbs Energy Models Practicing engineers usually get information about activity coefficients from correlations obtained by making assumptions about excess Gibbs Energy. provide information an equation format that can be used in thermodynamic simulation packages (Provision. CHEE 311 Lecture 17 2 . NRTL. and multicomponent behaviour can be predicted from binary data. Aspen) Simple empirical correlations Symmetric.

and to learn how to use these models to calculate activity coefficients.Excess Gibbs Energy Models Our objectives are to learn how to fit Excess Gibbs Energy models to experimental data. ⎛ y 1P ⎞ ln γ 1 = ln⎜ ⎜ x P sat ⎟ ⎟ ⎝ 1 1 ⎠ ⎛ y 2P ⎞ ln γ 2 = ln⎜ ⎜ x P sat ⎟ ⎟ ⎝ 2 2 ⎠ GE / RT = x 1 ln γ 1 + x 2 ln γ 2 CHEE 311 Lecture 17 3 .

but a more accurate equation is the Margules correlation: GE = A 21x1 + A12 x 2 (12.9a) RTx1x 2 Note that as x1 goes to zero. GE RTx 1x 2 Also.Margules’ Equations While the simplest Redlich/Kister-type correlation is the Symmetric Equation. E = A 12 x1 →0 G ∞ = ln γ1 lim x1→0 RTx1x 2 so that ∞ A12 = ln γ1 and similarly A 21 = ln γ ∞ 2 4 CHEE 311 Lecture 17 .

A knowledge of A12 and A21 at the given T is all we require to calculate activity coefficients for a given solution composition.Margules’ Equations If you have Margules parameters. CHEE 311 Lecture 17 5 . the activity coefficients can be derived from the excess Gibbs energy expression: GE = A 21x1 + A12 x 2 (12.9a) RTx1x 2 to yield: ln γ1 = x 2 [ A 12 + 2( A 21 − A 12 )x1] 2 2 ln γ 2 = x1 [ A 21 + 2( A12 − A 21 )x 2 ] (12.10ab) These empirical equations are widely used to describe binary solutions.

The activity coefficients can be calculated from the Margules model . x1) are given in Figure 1. CHEE 311 Lecture 17 6 P-x-y data for the mixture n-pentane (1)/acetone (2) . Using information provided below.Reduced experimental P-x-y data for this mixture (GE/RTx1x2 vs. determine whether or not separation of the mixture can be accomplished under these operating conditions.DewP = 45 kPa (at T= 24 oC) . you can assume here that all fugacity coefficients and Poynting factors are equal to one.Example 1 You desire to separate an equimolar binary mixture of n-pentane (1) and acetone (2) by feeding it into a flash drum that operates at T=24 oC and P=50 kPa.0 kPa .P1sat(24 oC )=65. P2sat(24 oC )=31. . .0 kPa.Due to low pressures involved.

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