CHAPTER 2:

VAPOR/LIQUID EQUILIBRIUM
VLE BY MODIFIED RAOULTS LAW
LEARNING OUTCOMES
At the end of the lecture, you should be able to apply
modified Raoults law by performing VLE calculations.
2
VLE BY MODIFIED RAOULTS LAW
Raoult's law can be modified by multiplying the right side of the equation
by an activity coefficient, . This equation accounts for non-ideal
solutions, or non-idealities in the liquid phase.
This equation is a much more realistic representation of vapor-liquid
equilibrium behavior when dealing with low pressures.
Modified Raoults law:


where
i
is activity coefficient
Activity coefficients are functions of temperature and liquid-phase
composition, and ultimately are based on experiment.
For present purposes, the necessary values are assumed known.

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( ) ( )
= =1,2,..., 10.5
sat
i i i i
y P x P i N
Because
i
y
i
= 1, eq. (10.5) may be summed over all species to yield



Because
i
x
i
= 1, eq. (10.5) may be summed over all species to yield

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( )
=

10.6
sat
i i i
i
P x P
( )

1
10.7
/
sat
i i i
i
P
y P
5
Example 10.3
For the system methanol(1)/methyl acetate(2), the following equations
provide a reasonable correlation for the activity coefficients:
ln
1
= Ax
2
2
ln
2
= Ax
1
2
where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:
= =

1 2
3643.31 2665.54
ln 16.59158 ln 14.25326
33.424 53.424
sat sat
P P
T T
where T is in kelvins and the vapor pressures are in kPa. Assuming the
validity of eq. (10.5), calculate
(a) P and {y
i
}, for t/T = 45
o
C/318.15K and x
1
= 0.25
(b) P and {x
i
}, for t/T = 45
o
C/318.15K and y
1
= 0.60
(c) T and {y
i
}, for P = 101.33 kPa and x
1
= 0.85
(d) T and {x
i
}, for P = 101.33 kPa and y
1
= 0.40
(e) The azeotropic pressure, and the azeotropic composition, for t/T =
45
o
C/318.15K

6
Solution:
(a) BUBL P calculation
1. Calculate P
1
sat
and P
2
sat
using Antoine equation for T = 318.15K



P
1
sat
= 44.51 kPa P
2
sat
= 65.64 kPa
2. Calculate activity coefficients from the given equation
ln
1
= Ax
2
2
ln
2
= Ax
1
2
where A = 2.771 - 0.00523T
A = 1.107
1
= 1.864
2
= 1.072
3. Calculate P by eq. (10.6)



P = 73.50 kPa
4. Calculate y
i
by eq. (10.5)


y
1
= 0.282 y
2
= 0.718
= =

1 2
3643.31 2665.54
ln 16.59158 ln 14.25326
33.424 53.424
sat sat
P P
T T
1 1 1 2 2 2
sat sat sat
i i i
i
P x P x P x P = = +

sat
i i i i
y x P P =
7
(b) DEW P calculation
Values of P
1
sat
, P
2
sat
and A are unchanged from part (a).
Iteration procedure is required to find the liquid phase composition
and to calculate the activity coefficients.
Initial values for
1
and
2
= 1.0.
The required steps, with the current value of
1
and
2
, are:
1. Calculate P by eq. (10.7), written



2. Calculate x
1
by eq. (10.5)



3. Evaluate activity coefficients;
ln
1
= Ax
2
2
ln
2
= Ax
1
2

4. Return to the first step.
Iterate to convergence on a value for P, x
i
and
i .

1
1 2 1
1 1
and x 1
sat
y P
x x
P
= =

=
+
1 1 1 2 2 2
1
/ /
sat sat
P
y P y P
8
Iteration P x1 x2 1 2
1 51.1034 0.6886 0.3114 1.1133 1.6903
2 63.6626 0.7705 0.2295 1.0600 1.9294
3 63.0141 0.8010 0.1990 1.0448 2.0345
4 62.9267 0.8115 0.1885 1.0401 2.0732
5 62.9163 0.8151 0.1849 1.0386 2.0865
6 62.9152 0.8163 0.1837 1.0381 2.0909
7 62.9150 0.8166 0.1834 1.0379 2.0924
8 62.9150 0.8168 0.1832 1.0379 2.0929
9 62.9150 0.8168 0.1832 1.0378 2.0931
10 62.9150 0.8168 0.1832 1.0378 2.0931
Initial 1 = 2 = 1,

Final values:
P = 62.915 kPa x
1
= 0.8168
1
= 1.0378
2
= 2.0931
(c) BUBL T calculation
Calculate T
1
sat
and T
2
sat
using Antoine equation for P = 101.33 kPa



T
1
sat
= 337.71 K T
2
sat
= 330.08 K
A mole fraction weighted average of these values then provides an initial T:
T = x
1
T
1
sat
+ x
2
T
2
sat
= 336.57 K
An iterative procedure consists of the steps:
1. For the current value of T calculate values for A,
1
,
2
, P
1
sat
, P
2
sat
, and o =
P
1
sat
/P
2
sat

2. Find a new value for P
1
sat
from eq. (10.6) written:



3. Find a new value for T from the Antoine equation for species 1


4. Return to the initial step

9
o
=
+
1
1 1 2 2
sat
P
P
x x
1
1
1 1
ln
sat
B
T C
A P
=

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

Iterate to convergence on a value for T.

Initial T = x
1
T
1
sat
+ x
2
T
2
sat
= 336.57 K











Final values:
T = 331.194 K or 58.044
o
C
P
1
sat
= 77.9966 kPa P
2
sat
= 105.3247 kPa
A = 1.0389
1
= 1.0236
2
= 2.1182
Calculate vapor phase mole fractions by eq. (10.5)


y
1
= 0.67 y
2
= 0.33
10
1 1 1
1 2 1
1
sat
x P
y y y
P

= =
Iteration A 1 2 P1sat P2sat o P1sat new Tnew
1 1.0108 1.0230 2.0757 96.8550 126.3286 0.7667 79.4337 331.6390
2 1.0365 1.0236 2.1147 79.4337 106.9537 0.7427 78.1175 331.2317
3 1.0387 1.0236 2.1179 78.1175 105.4619 0.7407 78.0068 331.1972
4 1.0388 1.0236 2.1182 78.0068 105.3363 0.7406 77.9974 331.1943
5 1.0389 1.0236 2.1182 77.9974 105.3257 0.7405 77.9966 331.1940
6 1.0389 1.0236 2.1182 77.9966 105.3248 0.7405 77.9966 331.1940
7 1.0389 1.0236 2.1182 77.9966 105.3247 0.7405 77.9966 331.1940
8 1.0389 1.0236 2.1182 77.9966 105.3247 0.7405 77.9966 331.1940
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(d) DEW T calculation
From part (c),
P = 101.33 kPa T
1
sat
= 337.71 K T
2
sat
= 330.08 K
Initial value of T:
T = (0.4)(337.71) + (0.6)(330.08) = 333.13 K or t = 59.98
o
C
Because the liquid phase composition is unknown, the activity coefficients
are initialized as
1
=
2
= 1.
Iterative procedure:
1. Evaluate A, P
1
sat
, P
2
sat
, and o = P
1
sat
/P
2
sat
for the current value of T
2. Calculate x
1
by eq. (10.5)



3. Calculate
1
and
2
from the correlating equation
4. Find a new value for P
1
sat
from eq. (10.7) written:



5. Find a new value of T from Antoine equation for species 1



6. Return to the initial step
o

| |
= +
|
\ .
1 2
1
1 2
sat
y y
P P
1
1 2 1
1 1
and x 1
sat
y P
x x
P
= =
1
1
1 1
ln
sat
B
T C
A P
=

Iterate to convergence on the value of T.

Initial T = x
1
T
1
sat
+ x
2
T
2
sat
= 333.13 K,
1
=
2
= 1.












Final values:
T = 326.69 K or t = 53.54
o
C
P
1
sat
= 64.64 kPa P
2
sat
= 89.92 kPa
A = 1.0624
1
= 1.3632
2
= 1.2520
x
1
= 0.4600 x
2
= 0.5400
12
Iteration
A P1sat P2sat o x1 x2 1 new 2 new
P1sat
new
Tnew
1 1.0287 84.41 112.55 0.7499 0.4802 0.5198 1.3204 1.2677 66.66 327.42
2 1.0586 66.66 92.29 0.7223 0.4605 0.5395 1.3609 1.2516 64.87 326.78
3 1.0620 64.87 90.19 0.7192 0.4591 0.5409 1.3643 1.2509 64.67 326.70
4 1.0624 64.67 89.95 0.7189 0.4594 0.5406 1.3641 1.2513 64.64 326.69
5 1.0624 64.64 89.93 0.7188 0.4597 0.5403 1.3637 1.2517 64.64 326.69
6 1.0624 64.64 89.92 0.7188 0.4598 0.5402 1.3634 1.2519 64.64 326.69
7 1.0624 64.64 89.92 0.7188 0.4599 0.5401 1.3633 1.2520 64.64 326.69
8 1.0624 64.64 89.92 0.7188 0.4600 0.5400 1.3632 1.2520 64.64 326.69
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(e) First determine whether or not an azeotrope exists at the given temperature.
This calculation is facilitated by the definition of a quantity called the relative
volatility:




At an azeotrope y
1
= x
1
, y
2
= x
2
, and o
12
= 1. By eq. (10.5),



Therefore,



( )
o
1 1
12
2 2
10.8
y x
y x

=
sat
i i i
i
y P
x P
( )

=
1 1
12
2 2
10.9
sat
sat
P
P
14
The correlating equations for activity coefficients:
ln
1
= Ax
2
2
ln
2
= Ax
1
2

when x
1
= 0, ln
2
= Ax
1
2
= A(0) = 0
2
= exp(0) = 1
x
2
= 1, ln
1
= Ax
2
2
= A(1) = A
1
= exp(A)
and
when x
1
= 1, ln
2
= Ax
1
2
= A(1) = A
2
= exp(A)
x
2
= 0, ln
1
= Ax
2
2
= A(0) = 0
1
= exp(0) = 1

Therefore in these limits,



For T = 318.15 K or 45
o
C, from part (a)
P
1
sat
= 44.51 kPa P
2
sat
= 65.64 kPa A = 1.107

The limiting values of o
12
are therefore
(o
12
)
x1=0
= 2.052 (o
12
)
x1=1
= 0.224

Because the value at one limit is greater than 1, whereas the value at the other
limit is less than 1, an azeotrope does exist, because o
12
is a continuous function
of x
1
and must pass through the value of 1.0 at some intermediate composition.
( )
( )
( )
( )
o o
= =
= =
1
1
12 12
1 0 1 1
2 2
exp
and
exp
sat
sat
sat sat
x x
P A
P
P P A
15
For the azeotrope, o
12
= 1, and eq. (10.9) becomes



The difference between the correlating equations for ln
1
and ln
2
provides the
general relation:



Thus the azeotropic occurs at the value of x
1
for which this equation is satisfied when
the activity coefficient ratio has its azeotrope value of 1.4747 (from eq. (A)).



When ln
1
/
2
= 0.388, substitute into eq. (B), gives x
1
az
= 0.325. For this value
of x
1
,
ln
1
az
= Ax
2
2

1
az
= exp[(1.107)(1-0.325)
2
] = 1.657

With x
1
az
= y
1
az
, eq. (10.5) becomes
P
az
=
1
az
P
1
sat
= (1.657)(44.51) = 73.76 kPa
x
1
az
= y
1
az
= 0.325

= =
1
2
ln ln1.4747 0.388
( )

= = =
1 2
2 1
65.64
1.4747
44.51
az sat
az sat
P
A
P
( )( ) ( ) ( ) ( ) ( )
2 2
1
2 1 2 1 2 1 2 1 1 1 1
2
ln 1 1 2 Ax Ax A x x x x A x x A x x A x B

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

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