VAPOR LIQUID

EQUILIBRIUM

 SIMPLE MODELS FOR VAPOR LIQUID EQUILIBRIUM:

HENRY’S LAW
 VLE BY MODIFIED RAOULT’S LAW
 HENRY’S LAW
 Application of Raoult’s law to species i requires a value of Pisat at
the temperature of application.
 Raoult’s law cannot be applied to a species whose critical
temperature is less than the temperature of application.
 For example air (1)/water (2) system at 25oC (298.15 K) and
atmospheric pressure.
◦ Tcr (Air) = -140.65oC, Tcr (H2O) = 373.95oC
◦ Tcr (H2O) > T  Raoult’s law can be applied to species 2
◦ Tcr (Air) < T  Raoult’s law can’t be applied to species 1
*Henry’s law can be applied to species 1
 Henry’s law is applied for:
◦ Very low pressure that the vapor phase may be assumed an ideal
gas
◦ Very dilute solute in the liquid phase

Henry's Law is only useful when applied to solutes, and the solvent
component of the solution will follow Raoult's Law.
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Henry’s law states that the partial pressure of the species in the
vapor phase is directly proportional to its liquid-phase mole
fraction.

yi P  xi Hi 10.4
where Hi is Henry’s constant.Values of Hi come from experiment,
and Table 10.1 lists values at 25oC (298.15K) for a few gases
dissolved in water.

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 For the case air (1)/water (2) system in equilibrium, the air is
saturated with water.
 Raoult’s law is applied for water (species 2) with the assumption
that no air dissolves in the liquid phase. Thus, the liquid water is
regarded as pure.

y2 P  x2 P2 sat
P2sat for water at
y2 
x2 P2 sat

1  3.166kPa   0.0312 25oC from steam
P 101.33kPa tables (pg. 716)

 Henry’s law is applied for air (species 1),

y1  1  0.0312  0.9688
y1 P (0.9688)(101.33) Hi from Table 10.1
x1    1.35  105
Η1 72950 (pg. 357)

 This result justifies the assumption made in application of Raoult’s

law to the water  no air dissolved in the liquid phase (very small
mole fraction of air).
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 Example 10.2
Assuming that carbonated water contains only CO2(1) and H2O(2),
determine the compositions of the vapor and liquid phases in a
sealed can of “soda” and the pressure exerted on the can at 10oC
(283.15K). Henry’s constant for CO2 in water at 10oC (283.15K) is
about 990 bar.

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Solution:
F = 2, only T is given. Need to specify the mole fraction to solve
the problem. CO2 is very dilute in H2O. Assume x1 = 0.01.
Henry’s law is applied to species 1 and Raoult’s law is applied to
species 2 :
y1P = x1H1 y2P = x2P2sat
Sum the two equations give
P = x1H1 + x2P2sat
With H1 = 990 bar, x1 = 0.01 and P2sat = 0.01227 bar (Table F.1 at
10oC or 283.15 K),
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar
Then by Raoult’s law, eq. (10.1) written for species 2:
x2 P2 sat  0.99  0.01227 
y2    0.0012
P 9.912
y1 = 1 - y2 = 1 - 0.0012 = 0.9988, and the vapor phase is nearly
pure CO2 as assumed.

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 7

VLE BY MODIFIED RAOULT’S LAW

 Raoult's law can be modified by multiplying the right side of the
equation by an activity coefficient, γ. This equation accounts for
non-ideal solutions, or non-idealities in the liquid phase.
 Modified Raoult’s law:

yi P  xi i Pi sat  i  1,2,..., N  10.5 

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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 Bubblepoint and dewpoint calculation by modifed Raoult’s law:
Because iyi = 1, eq. (10.5) may be summed over all species to yield

P   xi i Pi sat 10.6

i

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

1
P 10.7 
 i i i
y /
i
P sat

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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 = Ax22 ln 2 = Ax12 where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:

3643.31 2665.54
ln P1 sat  16.59158  ln P2 sat  14.25326 
T  33.424 T  53.424

where T is in kelvins and the vapor pressures are in kPa. Assuming the
validity of eq. (10.5), calculate
(a) P and {yi}, for t/T = 45oC/318.15K and x1 = 0.25
(b) P and {xi}, for t/T = 45oC/318.15K and y1 = 0.60
(c) T and {yi}, for P = 101.33 kPa and x1 = 0.85
(d) T and {xi}, for P = 101.33 kPa and y1 = 0.40
(e) The azeotropic pressure, and the azeotropic composition, for t/T =
45oC/318.15K
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Solution:
(a) BUBL P calculation
1. Calculate P1sat and P2sat using Antoine equation for T = 318.15K
3643.31 2665.54
ln P1 sat  16.59158  ln P2 sat  14.25326 
T  33.424 T  53.424
P1sat = 44.51 kPa P2sat = 65.64 kPa
2. Calculate activity coefficients from the given equation
ln 1 = Ax22 ln 2 = Ax12 where A = 2.771 - 0.00523T
A = 1.107 1 = 1.864 2 = 1.072
3. Calculate P by eq. (10.6)
P   xi i Pi sat  x1 1 P1sat  x2 2 P2sat
i
P = 73.50 kPa
4. Calculate yi by eq. (10.5)
yi  xi i Pi sat P
y1 = 0.282 y2 = 0.718

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(b) DEW P calculation
Values of P1sat, P2sat 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 Raoult’s 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
1
P
y1 /  1 P1 sat  y2 /  2 P2 sat
2. Calculate x1 by eq. (10.5)
y1 P
x1  and x 2  1  x1
 1 P1 sat

3. Evaluate activity coefficients;

ln 1 = Ax22 ln 2 = Ax12
4. Return to the first step.
Iterate to convergence on a value for P.

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

Final values:
P = 62.89 kPa x1 = 0.817 1 = 1.038 2 = 2.093

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(c) BUBL T calculation
Calculate T1sat and T2sat using Antoine equation for P = 101.33 kPa

Bi
Ti sat
  Ci
Ai  ln P
T1sat = 337.71 K T2sat = 330.08 K
A mole fraction weighted average of these values then provides an initial T:
T = x1T1sat + x2T2sat = 336.57 K
An iterative procedure consists of the steps:
1. For the current value of T calculate values for A, 1, 2, P1sat, P2sat, and  =
P1sat/P2sat
2. Find a new value for P1sat from eq. (10.6) written:
P
P1 sat 
x1 1  x2 2 
3. Find a new value for T from the Antoine equation for species 1
B1
T  C1
A1  ln P1sat

4. Return to the initial step

Iterate to convergence on a value for T.
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 Initial T = x1T1sat + x2T2sat = 336.57 K
Iteration A 1 2 P1sat P2sat  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

Final values:
T = 331.20 K or 58.05oC
P1sat = 77.99 kPa P2sat = 105.35 kPa
A = 1.0388 1 = 1.0236 2 = 2.1182

Calculate vapor phase mole fractions by eq. (10.5)

x1 1 P1sat
y1  y2  1  y1
P
y1 = 0.67 y2 = 0.33 14
(d) DEW T calculation
From part (c), P = 101.33 kPa T1sat = 337.71 K T2sat = 330.08 K
Initial value of T:
T = (0.4)(337.71) + (0.6)(330.08) = 333.13 K or t = 59.98oC
Because the liquid phase composition is unknown, the activity coefficients
are initialized as 1 = 2 = 1.
Iterative procedure:
1. Evaluate A, P1sat, P2sat, and  = P1sat/P2sat for the current value of T
2. Calculate x1 by eq. (10.5)
y1 P
x1  and x 2  1  x1
 1 P1 sat
3. Calculate 1 and 2 from the correlating equation
4. Find a new value for P1sat from eq. (10.7) written:
y y 
P1 sat  P  1  2  
 1 2 
5. Find a new value of T from Antoine equation for species 1
B1
T  C1
A1  ln P1sat

6. Return to the initial step

Iterate to convergence on the value of T.
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 Initial T = y1T1sat + y2T2sat = 333.13 K, 1 = 2 = 1.

P1sat
Iteration A P1sat P2sat  x1 x2 1 new 2 new Tnew
new
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

Final values:
T = 326.69 K or t = 53.54oC
P1sat = 64.63 kPa P2sat = 89.94 kPa
A = 1.0624 1 = 1.3631 2 = 1.2521
x1 = 0.4600 x2 = 0.5400

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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:
y1 x1
12  10.8
y2 x2

At an azeotrope y1 = x1, y2 = x2, and 12 = 1. By eq. (10.5),

yi  i Pi sat

Therefore, xi P

 1 P1 sat
12  10.9
 2 P2 sat

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The correlating equations for activity coefficients:
ln 1 = Ax22 ln 2 = Ax12
when x1 = 0, ln 2 = Ax12 = A(0) = 0  2 = exp(0) = 1
x2 = 1, ln 1 = Ax22 = A(1) = A  1 = exp(A)
and
when x1 = 1, ln 2 = Ax12 = A(1) = A  2 = exp(A)
x2 = 0, ln 1 = Ax22 = A(0) = 0  1 = exp(0) = 1

Therefore in these limits, eqn. (10.9) becomes

P1 sat exp  A  P1 sat
12 x 10  and 12 x 11  sat
P2 sat P2 exp  A 
For T = 318.15 K or 45oC, from part (a)
P1sat = 44.51 kPa P2sat = 65.64 kPa A = 1.107

The limiting values of 12 are therefore

(12)x1=0 = 2.052 (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.

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 For the azeotrope, 12 = 1, and eq. (10.9) becomes
 1az P2 sat 65.64
   1.4747  A
 2az P1 sat 44.51
The difference between the correlating equations for ln 1 and ln 2 provides
the general relation:

ln 1  Ax22  Ax12  A  x2  x1  x2  x1   A  x2  x1   A 1  x1  x1   A 1  2x1  B
2

Thus the azeotropic occurs at the value of x1 for which this equation is
satisfied when the activity coefficient ratio has its azeotrope value of 1.4747
(from eq. (A)).
1
ln  ln1.4747  0.388
2

When ln 1/2 = 0.388, substitute into eq. (B), gives x1az = 0.325. For this value
of x1,
ln 1az = Ax22  1az = exp[(1.107)(1-0.325)2] = 1.657

With x1az = y1az, eq. (10.5) becomes

Paz = 1azP1sat = (1.657)(44.51) = 73.76 kPa
x1az = y1az = 0.325
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 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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