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

Excess Gibbs Energy Models

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

Excess Gibbs Energy Models

Our objectives are to learn how to fit Excess Gibbs Energy models to experimental data, and to learn how to use these models to calculate activity coefficients.

y 1P ln 1 = ln x P sat 1 1 y 2P ln 2 = ln x P sat 2 2

GE / RT = x 1 ln 1 + x 2 ln 2

CHEE 311

Lecture 17

Margules Equations
While the simplest Redlich/Kister-type correlation is the Symmetric Equation, 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,
E

= A 12
x1 0

G = ln 1 lim x10 RTx1x 2

so that
A12 = ln 1

and similarly

A 21 = ln 2
4

CHEE 311

Lecture 17

Margules Equations
If you have Margules parameters, 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 1 = x 2 [ A 12 + 2( A 21 A 12 )x1] 2
2 ln 2 = x1 [ A 21 + 2( A12 A 21 )x 2 ]

(12.10ab)

These empirical equations are widely used to describe binary solutions. A knowledge of A12 and A21 at the given T is all we require to calculate activity coefficients for a given solution composition.

CHEE 311

Lecture 17

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. Using information provided below, determine whether or not separation of the mixture can be accomplished under these operating conditions. - DewP = 45 kPa (at T= 24 oC) - P1sat(24 oC )=65.0 kPa; P2sat(24 oC )=31.0 kPa - Reduced experimental P-x-y data for this mixture (GE/RTx1x2 vs. x1) are given in Figure 1. - The activity coefficients can be calculated from the Margules model - Due to low pressures involved, you can assume here that all fugacity coefficients and Poynting factors are equal to one.

CHEE 311

Lecture 17

6 P-x-y data for the mixture n-pentane (1)/acetone (2)