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CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013

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VAPOR LIQUID EQUILIBRIUM
SIMPLE MODELS FOR VAPOR LIQUID
EQUILIBRIUM: HENRYS LAW
VLE BY MODIFIED RAOULTS LAW

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Henrys law states that the partial pressure of the species in the vapor
phase is directly proportional to its liquid-phase mole fraction.

where H
i
is Henrys constant.Values of H
i
come from experiment.
Application of Raoults law and Henrys law:
Liquid mixtures that form an ideal solution at low pressure
Use Raoults law for all species
Liquid mixtures that do not form an ideal solution and at low pressure
Use Raoults law for solvent
Use Henrys law for solute
Gases that dissolve in a liquid mixture (e.g. air in water)
Use Henrys law for the dissolved gaseous species



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( ) = 10.4
i i i
y P x H
Table 10.1 lists Henrys constant values at 25
o
C (298.15K) for a few gases
dissolved in water.
Henrys constant is also an indicator for solubility of a gas in the solvent.
The greater the Henrys constant, the lower is the solubility.

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Least soluble
in water
Very soluble
in water
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013
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Assuming that carbonated water contains only CO
2
(1) and H
2
O(2),
determine the compositions of the vapor and liquid phases in a sealed can
of soda and the pressure exerted on the can at 10
o
C (283.15K). Henrys
constant for CO
2
in water at 10
o
C (283.15K) is about 990 bar.

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Solution:
Given Henrys constant for CO
2
in water = 990 bar (i.e CO
2
dissolved in
water)
Henrys law is applied to species 1 and Raoults law is applied to species 2 :
y
1
P = x
1
H
1
y
2
P = x
2
P
2
sat

F = 2-2+2 = 2, only T is given. Need to specify the mole fraction to solve
the problem. Assume the vapor phase is nearly pure CO
2
(y
1
~1) and the
liquid phase is nearly pure H
2
O (x
2
~1). Take x
1
= 0.01.
Sum the two equations give
P = x
1
H
1
+ x
2
P
2
sat
With H
1
= 990 bar, x
1
= 0.01 and P
2
sat
= 0.01227 bar (Table F.1 at 10
o
C or
283.15 K),
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar
Then by Raoults law, eq. (10.1) written for species 2:


y
1
= 1 - y
2
= 1 - 0.0012 = 0.9988, and the vapor phase is nearly pure CO
2

as assumed.

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( )( )
= = =
2 2
2
0.99 0.01227
0.0012
9.912
sat
x P
y
P
In real life, most solutions are non ideal i.e they do not obey Raoults law.
Non ideal solution deviate from Raoults law.
The non ideality exhibit by these solutions due to dissimilarity in the sizes
of molecules, shapes of the molecules, and inter-molecular interactions
between molecules.
Modified Raoults law accounts for non-ideal solutions, or non-idealities in the
liquid phase:


where
i
is activity coefficient.
There are a number of correlations that can be used to predict the value
of activity coefficient e.g. Margules,Van Laar, Non-Random Two Liquid
(NRTL), Wilson, etc.

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( ) ( ) = =1, 2,..., 10.5
sat
i i i i
y P x P i N
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The simplest correlation to predict activity coefficient for binary mixture
is as follow:
ln
1
= Ax
2
2
ln
2
= Ax
1
2

where A is a function of temperature only or simply a constant.
This correlation can only be used in some liquid mixtures which exhibit
small deviation from ideal solution.
Bubblepoint and dewpoint calculation by modifed Raoults law:
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
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013
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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

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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 =
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(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 are provided by Raoults law, for which
1
=
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.


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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
=
+
12
Iteration 1 2 P x1 x2
1 1 1 51.09 0.689 0.311
2 1.113 1.691 63.64 0.771 0.229
3 1.060 1.930 62.99 0.801 0.199
4 1.045 2.035 62.91 0.812 0.188
5 1.040 2.074 62.90 0.815 0.185
6 1.039 2.087 62.89 0.816 0.184
7 1.038 2.091 62.89 0.817 0.183
8 1.038 2.093 62.89
Initial
1
=
2
= 1,

Final values:
P = 62.89 kPa x
1
= 0.817
1
= 1.038
2
= 2.093
Iteration P x1 x2 1 2
1 51.09 0.689 0.311 1.113 1.691
2 63.64 0.771 0.229 1.060 1.930
3 62.99 0.801 0.199 1.045 2.035
4 62.91 0.812 0.188 1.040 2.074
5 62.90 0.815 0.185 1.039 2.087
6 62.89 0.816 0.184 1.038 2.091
7 62.89 0.817 0.183 1.038 2.093
8 62.89 0.817 0.183 1.038 2.093
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013
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(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
Iterate to convergence on a value for T.

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

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

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







Final values:
T = 331.20 K or 58.05
o
C
P
1
sat
= 77.99 kPa P
2
sat
= 105.35 kPa
A = 1.0388
1
= 1.0236
2
= 2.1182

Calculate vapor phase mole fractions by eq. (10.5)


y
1
= 0.67 y
2
= 0.33
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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 2.0756 96.85 126.36 0.7664 79.43 331.65
2 1.0365 1.0236 2.1146 79.43 106.98 0.7424 78.11 331.24
3 1.0386 1.0236 2.1179 78.11 105.49 0.7405 78.00 331.20
4 1.0388 1.0236 2.1181 78.00 105.36 0.7403 77.99 331.20
5 1.0388 1.0236 2.1182 77.99 105.35 0.7403 77.99 331.20
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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
Iterate to convergence on the value of T.
1 2
1
1 2
sat y y
P P o

| |
= +
|
\ .
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
=

Initial T = y
1
T
1
sat
+ y
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
= 64.63 kPa P
2
sat
= 89.94 kPa
A = 1.0624
1
= 1.3631
2
= 1.2521
x
1
= 0.4600 x
2
= 0.5400
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Iteration A P1sat P2sat o x1 x2 1 new 2 new
P1sat
new
Tnew
1 1.0287 84.39 112.57 0.7496 0.4803 0.5197 1.3203 1.2679 66.65 327.43
2 1.0586 66.65 92.30 0.7221 0.4606 0.5394 1.3606 1.2518 64.86 326.78
3 1.0620 64.86 90.21 0.7190 0.4593 0.5407 1.3641 1.2511 64.65 326.71
4 1.0624 64.65 89.97 0.7186 0.4596 0.5404 1.3638 1.2516 64.63 326.70
5 1.0624 64.63 89.94 0.7186 0.4599 0.5401 1.3634 1.2519 64.63 326.70
6 1.0624 64.63 89.94 0.7186 0.4600 0.5400 1.3631 1.2521 64.63 326.70
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013
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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,



( )
1 1
12
2 2
10.8
y x
y x
o
sat
i i i
i
y P
x P

=
( )
1 1
12
2 2
10.9
sat
sat
P
P

=
18
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, eqn. (10.9) becomes



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.
( )
( )
( )
( )
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
o o
= =
= =
19
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

= = + = = =
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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CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 14/3/2013
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PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303