CHEE 311 Lecture 18 1

van Laar Correlation

Another two-parameter excess Gibbs energy model was developed
from an expansion of (RTx
1
x
2
)/G
E
instead of G
E
/RTx
1
x
2
. The end
results are:
(12.16)
for the excess Gibbs energy and:
(12.17a)
(12.17b)
for the activity coefficients.
Note that: as x
1
0, ln
1

A
12

and as x
2
0, ln
2

A
21

2
/
21 1
/
12
/
21
/
12
2 1
x A x A
A A
x RTx
G
E
+

2
2
/
21
1
/
12
/
12 1
x A
x A
1 A ln

,
_

+
2
1
/
12
2
/
21
/
21 2
x A
x A
1 A ln

,
_

+
CHEE 311 Lecture 18 2
Example 2 (Problem 5, Practice Problem Set #4)
P5. Vapour liquid data for the system 1,4 dioxane(1)/ethylbenzene(2) at 85
o
C
are provided below. From these data obtain estimates of the van Laar coefficients
(estimates based on smoothly drawn curves on the enclosed graph paper are
sufficient). Estimate values of P-x
1
-y
1
for x
1
=0.5 based on these parameter values.
Table 2: VLE data for the system 1,4 dioxane/ethylbenzene at 85
o
C
P (kPa)
x
1
y
1
20.2 0 0
23.4 0.065 0.15
35.2 0.29 0.55
41.6 0.44 0.7
52.4 0.78 0.91
57.8 1 1
CHEE 311 Lecture 18 3
Local Composition Models
Unfortunately, the previous approach cannot be extended to
systems of 3 or more components. For these cases, local
composition models are used to represent multi-component
systems.

Wilsons Theory

Non-Random-Two-Liquid Theory (NRTL)

Universal Quasichemical Theory (Uniquac)

While more complex, these models have two advantages:

the model parameters are temperature dependent

the activity coefficients of species in multi-component liquids

can be calculated using information from binary data.
A,B,C A,B A,C B,C
tertiary mixture binary binary binary
CHEE 311 Lecture 18 4
Wilsons Equations for Binary Solution Activity
A versatile and reasonably accurate model of excess Gibbs Energy
was developed by Wilson in 1964. For a binary system, G
E
is
provided by:
(12.18)
where
(12.24)
V
i
is the molar volume at T of the pure component i.
a
ij
is determined from experimental data.
The notation varies greatly between publications. This includes,
a
12
= (
12
-
11
), a
21
= (
12
-
22
) that you will encounter in
Holmes, M.J. and M.V. Winkle (1970) Ind. Eng. Chem. 62,
21-21.
) x x ln( x ) x x ln( x
RT
G
21 1 2 2 12 2 1 1
E
+ +
1
]
1

1
]
1

RT
a
exp
V
V
RT
a
exp
V
V
21
2
1
21
12
1
2
12
CHEE 311 Lecture 18 5
Wilsons Equations for Binary Solution Activity
Activity coefficients are derived from the excess Gibbs energy
using the definition of a partial molar property:
When applied to equation 11.16, we obtain:
(12.19a)
(12.19b)

,
_

+ +
21 1 2
21
12 2 1
12
2 12 2 1 1
x x x x
x ) x x ln( ln

,
_

+
21 1 2
21
12 2 1
12
1 21 1 2 2
x x x x
x ) x x ln( ln
j
n , P , T
i
E
E
i
i
n
nG
G ln RT

CHEE 311 Lecture 18 6
Wilsons Equations for Multi-Component Mixtures
The strength of Wilsons approach resides in its ability to describe
multi-component (3+) mixtures using binary data.

Experimental data of the mixture of interest (ie. acetone,

ethanol, benzene) is not required

We only need data (or parameters) for acetone-ethanol,

acetone-benzene and ethanol-benzene mixtures
The excess Gibbs energy for multicomponent mixtures is written:
(12.22)
and the activity coefficients become:
(12.23)
where
ij
= 1 for i=j. Summations are over all species.
) ln(


i j
ij j i
E
x x
RT
G

k
j
kj j
ki k
i
ij j i
x
x
x ln 1 ln
CHEE 311 Lecture 18 7
Wilsons Equations for 3-Component Mixtures
For three component systems, activity coefficients can be
calculated from the following relationship:
Model coefficients are defined as (
ij
= 1 for i=j):
3 32 2 31 1
i 3 3
23 3 2 21 1
i 2 2
13 3 12 2 1
i 1 1
3 i 3 2 i 2 1 i 1 i
x x x
x
x x x
x
x x x
x
) x x x ln( 1 ln
+ +

+ +

+ +

+ +
1
]
1

RT
a
exp
V
V
ij
i
j
ij
CHEE 311 Lecture 18 8
Comparison of Liquid Solution Models

Activity coefficients of 2-methyl-
2-butene + n-methylpyrollidone.
Comparison of experimental
values with those obtained from
several equations whose
parameters are found from the
infinite-dilution activity
coefficients.
(1) Experimental data.
(2) Margules equation.
(3) van Laar equation.
(4) Scatchard-Hamer equation.
(5) Wilson equation.
CHEE 311 Lecture 18 9
Non-Ideal VLE to Moderate Pressures: Overview SVNA 14.1
We now have the tools required to describe and calculate vapour-
liquid equilibrium conditions for even the most non-ideal systems.
1. Equilibrium Criteria:

In terms of chemical potential

In terms of mixture fugacity

2. Fugacity of a component in a non-ideal gas mixture:
3. Fugacity of a component in a non-ideal liquid mixture:
l
i
v
i

l
i
v
i
f

P ) y ,..., y , y , P , T (

y ) y ,..., y , y , P , T ( f

n 2 1
v
i i n 2 1
v
i

1
]
1

RT
) P P ( V
exp P ) x ,..., x , x , P , T ( x
f ) x ,..., x , x , P , T ( x ) x ,..., x , x , P , T ( f

sat
i i
sat
i
sat
i n 2 1 i i
l
i n 2 1 i i n 2 1
l
i
CHEE 311 Lecture 18 10
, Formulation of VLE Problems
To this point, Raoults Law was only description we had for VLE
behaviour:
We know that calculations based on Raoults Law do not predict
actual phase behaviour due to over-simplifying assumptions.
Accurate treatment of non-ideal phase equilibrium requires the use
of mixture fugacities. At equilibrium, the fugacity of each
component is the same in all phases. Therefore,
or,
determines the VLE behaviour of non-ideal systems where Raoults
Law fails.
sat
i i i
P x P y
1
]
1

RT
) P P ( V
exp P x P

y
f

sat
i i
sat
i
sat
i i i
v
i i
l
i
v
i
CHEE 311 Lecture 18 11
Non-Ideal VLE to Moderate Pressures
A simpler expression for non-ideal VLE is created upon defining a
lumped parameter, .
The final expression becomes,
(i = 1,2,3,,N) 14.1
To perform VLE calculations we therefore require vapour pressure
data (P
i
sat
), vapour mixture and pure component fugacity
correlations (
i
) and liquid phase activity coefficients (
i
).
sat
i i i i i
P x P y
sat
i
v
i
sat
i
l
i
sat
i
v
i
i

RT
) P P ( V
exp

1
]
1

CHEE 311 Lecture 18 12
Non-Ideal VLE to Moderate Pressures
Sources of Data:
1. Vapour pressure: Antoines Equation (or similar correlations)
14.3
2. Vapour Fugacity Coefficients: Viral EOS (or others)
14.6
3. Liquid Activity Coefficients

Binary Systems - Margules,van Laar, Wilson, NRTL,

Uniquac

Ternary (or higher) Systems - Wilson, NRTL, Uniquac

i
i
i
sat
i
C T
B
A P ln
+

1
1
1
]
1

+

RT
) 2 ( y y P 5 . 0 ) P P ( B
exp
jk
j k
ji k j
sat
i ii
i