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Solution Thermodynamics:

Applications
Chapter 12-Part II

Find parameter values for the Margules equation that give the best fit of G E/RT to
the data, and prepare a P x y diagram that compares the experimental points with
curves determined from the correlation

1) Calculate EXPERIMENTAL values of activity coefficients 1 and 2 and GE

y1 P
y2 P
1
; 2
sat
sat
x1 P1
x2 P2
G / RT x1 ln 1 x2 ln 2
E

In the previous class we showed


E

G
A21 x1 A12 x2
x1 x2 RT
ln 1 x [ A12 2( A21 A12 ) x1 ]
2
2

ln 2 x [ A21 2( A12 A21 ) x2 ]


2
1

Now we have our analytical model


E

G
0.475 x1 0.683x2
x1 x2 RT
Lets calculate ln 1, ln 2, GE/x1x2RT, and:

calc

x1 1 P

calc

y1

sat
1

x P

sat
1 1 1
calc

x 2 2 P

sat
2

RMS= SQRT ( (Pi-Picalc)2/n = 0.398 kPa

Thermodynamic consistency
We need to check that the experimentally
obtained activity coefficients satisfy the
Gibbs-Duhem equation.
If the experimental data are inconsistent
with the G-D equation, they are not correct

Consistency test
*

G
*
*

x1 ln 1 x2 ln 2
RT
E

d (G / RT )

dx1
d (G E / RT )
1
ln
dx1
2
d (G E / RT )
1 d ln 1*
d ln 2*

ln x1
x2
dx1
2
dx1
dx1

Consistency test

d (G / RT )
1
d ln
d ln
ln x1
x2
dx1
2
dx1
dx1
E

1
d ln
d ln
0 ln x1
x2
2
dx1
dx1
1
ln 0
2
*
1

*
1

*
2

*
2

The experimental data is not thermodynamically consistent

An alternative consistency test:


Barkers method
Fit the model GE/RT to make the
calculated pressures the closest possible
to the experimental data.
For example, obtain A12 and A21 for the
Margules equation to minimize the
calculated pressures with respect to the
experimental values. (see dashed lines in
Figure 12.7)

example
Using Barkers method, find parameters
for the Margules eqn that provide the best
fit of GE/RT to the data, and prepare a Pxy
diagram that compares the experimental
points with curves determined form the
correlation.

solution
ln 1 x [ A12 2( A21 A12 ) x1 ]
2
2

ln 2 x [ A21 2( A12 A21 ) x2 ]


2
1

Minimize the sum of squares of the following function:

[P

exp

x1 1 ( A12 , A21 , x1 , x2 ) P1

sat

x2 2 ( A12 , A21 , x1 , x2 ) P2 ]

sat 2

Starting with A12=0.5, A21=1, get A12= 0.758, A21=0.435

Calculate the RMS for P


RMS= SQRT ( (Pi-Picalc)2/n = 0.167 kPa