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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

y1 P

y2 P

1

; 2

sat

sat

x1 P1

x2 P2

G / RT x1 ln 1 x2 ln 2

E

E

G

A21 x1 A12 x2

x1 x2 RT

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

2

2

2

1

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

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

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

2

1

[P

exp

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

sat

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

sat 2

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

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