SOLUTION THERMODYNAMICS:

APPLICATION
LIQUID PHASE PROPERTIES FROM VLE DATA
MODELS FOR THE EXCESS GIBBS ENERGY
 LIQUID PHASE PROPERTIES FROM
VLE DATA

The figure shows coexistence of a vapor mixture and liquid solution in

vapor/liquid equilibrium. T and P are uniform throughout the vessel and
can be measured with appropriate instruments.Vapor and liquid
samples may be withdrawn for analysis and this provides experimental
values for mole fractions in the vapor {yi} and mole fractions in the
liquid {xi}.

2
Fugacity
For species i in the vapor mixture, eq. (11.52) is written as
f

i i (11.52)
fi v yiiv P
yi P

The criterion of vapor/liquid equilibrium, as given by eq. (11.48), is

that f il f i v . Therefore,

fil yiiv P
VLE measurements are made at low pressure (P 1 bar) that the
vapor phase may be assumed an ideal gas. In this case iv 1 .
Therefore,

f il
fi v yi P

The fugacity of species i (in both the liquid and vapor phase) is
equal to the partial pressure of species i in the vapor phase.

3
 Fugacity increases from zero at infinite dilution (xi = yi 0) to Pisat
for pure species i. This is illustrated by the data of Table 12.1 for
methyl ethyl ketone(1)/toluene(2) at 50oC (323.15K). The first
three columns list a set of experimental P-x1-y1 data and columns 4
and 5 show f1 y1 P and f2 y2 P

yi P
i
xi Pisat
Eqn. (12.1)

4
 5

The fugacities are plotted in Fig.

12.2 as solid lines. The straight
dashed lines represent the
Lewis/Randall rule expressing the
composition dependence of the
constituent fugacities in an ideal
solution,

fiid xi fi
This figure illustrates the general fi id xi fi
nature of relationships
f and f vs. x for a binary liquid
1 2 1
solution at constant T.

5
 6

The equilibrium pressure P varies

with compositions but has
negligible influence on the liquid
phase values of f1 and f2 .
Therefore, a plot at constant T
and P is as shown in Fig. 12.3 for
species i (i = 1, 2) in a binary
solution at constant T and P.

6
 7

Activity coefficient
The lower dashed line in Fig. 12.3 represent the Lewis/Randall rule, which
characterize ideal solution behavior.
Activity coefficient as defined by eq. (11.90) provide the actual behavior
(non-ideal) from the idealize one:
f f
i i
i
x i f i f i id

The activity coefficient of a species in solution is the ratio of its actual

fugacity to the value given by Lewis/Randall rule at the same T, P and
composition. To obtain experimental values, both fi and fiid
are defined as follow:
yi P yP (12.1)
i i sat (i 1, 2,....N)
xi fi xi Pi

This is restatement of eq. (10.5), modified Raoults law, and allow

calculation of activity coefficient from VLE data as shown in the last two
columns of Table 12.1.
7
 The solid lines in Fig. 12.2 and 12.3, representing experimental values
of fi , become tangent to the Lewis/Randall rule lines at xi = 1.
In the other limit, xi 0, fi becomes zero. The ratio fi xi is
indeterminate in this limit, and application of lHopital rule yields

f df
lim i i i (12.2)
xi 0 x
i dxi xi 0
Eq. (12.2) defines Henrys constant, Hi as the limiting slope of the

fi vs xi curve at xi = 0.
As shown by Fig. 12.3, this is the slope of a line drawn tangent to the
curve at xi = 0.The equation of this tangent line expresses Henrys
law:
f x (12.3)
i i i

Henrys law as given by eq. (10.4) follows immediately from this

equation when fi yi P , i.e. when fi has its ideal gas value.
yi P xi Hi 10.4 8
 9

Henrys law is related to the Lewis/Randal rule through the

Gibbs/Duhem equation.
Writing eq. (11.14) for a binary solution and replacing M i by Gi i

x1d1 x2d2 0 const T , P x d M

i
i i 0 (11.14)

Differentiate eq. (11.46) at constant T and P yields:

i i T RT ln f i (11.46)

di RTd ln
fi
Therefore,
x1 d ln
f1 x2 d ln
f2 0 const T , P
Divide by dx1 becomes

d ln
f1 d ln
f2
x1 x2 0 const T,P (12.4)
dx1 dx1
This is the special form of the Gibbs/Duhem equation.

9
 Substitute dx1 by dx2 in the second term produces

d ln f1 d ln
f2 df1 dx1 d f2 dx2
x1 x2 or
dx1 dx2 f x f x
1 1 2 2

In the limit as x1 1 and x2 0,

d f1 dx1 d f2 dx2
lim lim
x1 1 f x x2 0 f x
1 1 2 2

Because f1 f1 when x1 = 1, this may be rewritten as

1 df1

d f2 dx2
x2 0

f1 dx1
x1 1
lim f2 x2
x 0
2

According to eq. (12.2), the numerator and denominator on the right
side of this equation are equal.
f df
lim i i (12.2)
x i 0 x dxi
i xi 0 10
 Therefore the exact expression of Lewis/Randall rule applied to
real solutions is:
df
1 f1 (12.5)
dx1
x1 1

It also implies that eq. (11.83) provides approximately correct

values of fi when xi 1: fi fiid xi fi

Henrys law applies to a species as it approaches infinite

dilution in a binary solution, and the Gibbs/Duhem equation
insures validity of the Lewis/Randall rule for the other species
as it approaches purity.

11
When the second species is
methanol, acetone exhibits positive
deviations from ideality and with
chloroform it exhibits negative
deviations.
The fugacity of pure acetone, facetone
is the same regardless of the identity
of the second species.
Henrys constants are represented
by the slopes of the two dotted
lines.

12
 Excess Gibbs Energy
For a binary system,
GE
x1 ln 1 x2 ln 2 (12.6)
RT

Experimen Properties
tal data of liquid
phase

yi P
i
xi Pisat

13
 P-x1 data points all lie
above dash line (Raoults For i 1 and ln i 0
law) positive deviation.

Raoults law

Activity coefficient of a species in solution becomes unity as the species becomes

pure, each ln i (i=1,2) tends to zero as xi 1.
As xi 0, species i becomes infinitely dilute, ln i approaches a finite limit, namely
ln i.
14
 MODEL FOR THE EXCESS GIBBS
ENERGY
Model Equations
Margules ln 1 x22 A12 2 A21 A12 x1
GE (12.10a)
A21 x1 A12 x2 (12.9a)
x1 x2 RT
ln 2 x12 A21 2 A12 A21 x2
(12.10b)
Van Laar A' x
2

G E
A A ' ' ln 1 A 12 1 ' 12 1
'
(12.17a)
' 12 21' (12.16) A 21 x2
x1 x2 RT A 12 x1 A 21 x2
2
A' x (12.17b)
ln 2 A 21 1 '21 2
'

A 12 x1

Wilson 12 21
GE ln 1 ln x1 x2 12 x2 (12.19a)
x1 ln x1 x2 12 x2 ln x2 x1 21 x1 x2 12 x2 x1 21
RT
(12.18)
Vj aij 12 21
ij exp (i j) ln 2 ln x2 x1 21 x1 (12.19b)
Vi RT (12.24) x1 x2 12 x2 x1 21

NRTL
GE G21 21 G12 12 G21
2
G12 12
(12.20) ln 1 x22 21
x1 x2 RT x1 x2G21 x2 x1G12
x1 x2G21 x2 x1G12 2 (12.21a)

G12 exp( 12 ) G21 exp( 21 ) G12

2
G21 21
ln 2 x12 12 (12.21b)
12
b
12
b
21 21
2
x x1 12
G x1 x G
2 21 2


RT RT 15
16
 17

Margules Equation
Set of points in Fig. 12.5(b) provide linear From Fig. 12.5(b), the intercepts at
relation for GE/x1x2RT x1 = 0 and x1 =1 of the straight line
GE/x1x2RT gives the parameters A12
GE
A21 x1 A12 x2 (12.9a) and A21.
x1 x2 RT
A12 = 0.372
where A21 and A12 are constant.
Alternatively,
GE
A21 x1 A12 x2 x1 x2 (12.9b) A21 = 0.198
RT
From eqn. (12.10a) & (12.10b), the limiting
conditions of infinite dilution (at xi = 0)
ln 1 x22 A12 2 A21 A12 x1 (12.10a)

ln 2 x12 A21 2 A12 A21 x2 (12.10b)

ln 1 A12 at x1 0 and ln 2 A21 at x2 0

Fig. 12.5(b)
17
 Van Laar Equation
Linear relation for GE/x1x2RT
GE A'12 A'21
(12.16)
x1 x2 RT A'12 x1 A'21 x2

where A21 and A12 are constant.

Alternatively,
x1 x2 RT A'12 x1 A'21 x2 x1 x2

GE A'12 A'21 A'21 A'12
From eqn. (12.17a) & (12.17b), the limiting conditions of infinite dilution
(at xi = 0)
2 2
' A'12 x1 ' A'21 x2
ln 1 A 12 1 ' (12.17a) ln 2 A 21 1 ' (12.17b)
A 21 x2 A x
12 1

ln 1 A '12 at x1 0 and ln 2 A '21 at x2 0

Values of A12 and A21 are obtained from the intercept of plot GE/x1x2RT vs. x1
at x1 = 0 and x1=1. Or from plot of x1x2RT/GE vs. x1, intercept at x1=0 is 1/A12
and at x1=1 is 1/A21. 18
Wilson Equation
GE
x1 ln x1 x2 12 x2 ln x2 x1 21 (12.18)
RT
Vj aij
ij exp (i j) (12.24)
Vi RT

12 21
ln 1 ln x1 x2 12 x2 (12.19a)
x
1 x
2 12 x 2 x
1 21

12 21
ln 2 ln x2 x1 21 x1 (12.19b)
x
1 x
2 12 x2 x
1 21

The limiting conditions of infinite dilution (at xi = 0),

ln 1 ln 12 1 21 at x1 0 and ln 2 ln 21 1 12 at x2 0

19
NRTL Equation
GE G21 21 G12 12
(12.20)
x1 x2 RT x1 x2G21 x2 x1G12

G12 exp( 12 ) G21 exp( 21 )

b12 b21
12 21
RT RT

G
2
G12 12
ln 1 x2 21
2 21 (12.21a)
x1 x2G21

x2 x1G12
2

G12
2
G21 21
ln 2 x1 12
2
(12.21b)
x2 x1G12

x1 x2G21
2

The limiting conditions of infinite dilution (at xi = 0),

ln 1 21 12 exp( 12 ) and ln 2 12 21 exp( 21 )

20
 21
All models provide eqns. for ln 1 and ln 2. This allow construction of a
correlation of the original P-x1-y1 data set (experimental values). Eq.
(12.1) is rearranged to give

y1 P x1 1 P1sat and y2 P x2 2 P2sat

Addition gives
P x1 1 P1sat x2 2 P2sat (12.11)

From eqn. (12.1), therefore

yi P yP
i i sat (12.1)
xi fi xi Pi

x1 1 P1sat x1 1 P1sat
y1 (12.12)
P x1 1 P1sat x2 2 P2sat
Values of 1 and 2 from all models with their parameters are
combined with experimental values of P1sat and P2sat to calculate
P and y1 by eqs. (12.11) and (12.12) at various x1.
Then, P-x1-y1 diagram can be plotted to compare the experimental data
and calculated values.
21 21
 experimental
calculated

Comparison of
experimental and
calculated data by
Margules eqn. These
clearly provide an
adequate
correlation of the
experimental data
Fig. 12.5(a) points.

22
Thermodynamic Consistency
The Gibbs Duhem eqn imposes a constraint on activity coefficients
that may not be satisfied by a set of experimental values derived
from P-x1-y1 data.
d ln 1 d ln 2
x1 x2 0 const T,P (12.7)
dx1 dx1
The Gibbs Duhem eqn is implicit in eq. (11.96), and activity
coefficients derived from this equation necessarily obey the Gibbs
Duhem eqn.

nG E RT
ln i

ni (11.96)
P ,T ,n j

These derived activity coefficients cannot possibly be consistent

with the experimental values unless the experimental values also
satisfy the Gibbs Duhem eqn.
23
 If the experimental data are inconsistent with the Gibbs Duhem eqn,
they are necessarily incorrect as the result of systematic error in the
data.
Therefore simple test is develop for the consistency with respect to
the Gibbs Duhem eqn of a P-x1-y1 data set.
Application of the test for consistency is represented by Eq. (12.13)
which requires calculation of the residuals
1 d ln 1* d ln 2*
ln x1 x2 (12.13)
2 dx1 dx1
Asterisk * denote the experimental values
The right side of this equation is exactly the quantity that eq. (12.7),
the Gibbs/Duhem equation, requires to be zero for consistent data.
d ln 1 d ln 2
x1 x2 0 const T,P (12.7)
dx1 dx1
The residual on the left therefore provides a direct measure of
deviation from the Gibbs/Duhem equation.
The extent to which a data set departs from consistency is measured
by the degree to which these residuals fail to scatter about zero.
24
 Experimental
values
calculated from
eqn. (12.1) &
(12.6)

yi P yP
i i sat (i 1, 2,....N) (12.1)
xi fi xi Pi
GE
x1 ln 1 x2 ln 2 (12.6)
RT 25
 P-x1-y1 data and experimental values,
ln 1*, ln 2* and (GE/x1x2RT )* are
shown as points on Figs. 12.7(a) and
12.7(b) .
The data points of Fig. 12.7(b) for
(GE/x1x2RT )* show scatter. The
straight line drawn is represented by
GE
0.70x1 1.35 x2
x1 x2 RT
This is eq. (12.9a) with A21 = 0.70
and A12 = 1.35.
Values of ln 1, ln 2 at the given
values of x1, derived from this eqn,
experimental are calculated by eqs. (12.10) and
calculated derived values of P and y1 at the
Barkers method same values of x1 come from eqs.
(12.11) and (12.12).
This results are plotted as the solid
ln 1 x22 A12 2 A21 A12 x1
lines of Fig. 12.7(a) and 12.7(b). They
(12.10a)
clearly do not represent a good
ln 2 x12 A21 2 A12 A21 x2 (12.10b) correlation of the data.

P x1 1 P1sat x2 2 P2sat (12.11) x1 1 P1sat

y1 (12.12)
x1 1 P1sat x2 2 P2sat
26
Application of test for consistency
represented by Eq. 12.13 requires
calculation of the residuals
G E RT and ln 1 2
which plotted vs. x1 in Fig. 12.8.

The residuals G E RT
distribute themselves about zero,
as required by the test, but the
residual ln 1 2 , do not,
which show the data fail to satisfy
the Gibbs/Duhem eqn.

27
REFERENCE
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005.
Introduction to Chemical Engineering Thermodynamics.
Seventh Edition. Mc Graw-Hill.

28
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303