CHAPTER 1

VAPOR LIQUID
EQUILIBRIUM PART 2

 The nature of equilibrium

 The phase rule: Duhem’s Theorem
 VLE: Qualitative behavior
 Simple models for vapor-liquid equilibrium
 VLE by modified Raoult’s law
 VLE from K-value correlations
Henry’s Law
 Raoult’s law cannot be applied to a species whose critical
temperature is less than the equilibrium temperature of the
system.
 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 states that the partial pressure of the species in

the vapor phase is directly proportional to its liquid-phase
mole fraction

yi P = xi Η i where Η i is Henry' s constant Eq. (10.4)

Values of Hi come from experiment, and Table 10.1 lists values

at 25oC (298.15K) for a few gases dissolved in water.

2
Example of situation

If we have a container containing water and

nitrogen at room temperature, Raoult’s law can
apply to the water (which is below its critical
temperature) but not to the nitrogen (which has
a critical temperature of 126.2K).

Troom = 303.15K
Tc H2O = 648.15K
Tc N2 = 126.2K

3
Example 1
 If a system of air in contact with liquid water is presumed at
equilibrium, then the air is saturated with water.

 The mole fraction of water vapor in the air found from

Raoult’s law with the assumption that no air dissolves in the
liquid phase.

 Liquid water regarded is pure and Raoult’s law for the

water(species 2):
y2 P = P2sat

 At 25°C (298.15K) and atmospheric pressure,

P2sat 3.166 P2sat from steam
y2 = = = 0.0132 tables (pg. 716)
P 101.33
4
 To calculate the mole fraction of air dissolved in the water,
Raoult’s law cannot be applied because critical temperature of
air much lower than 25°C (298.15K).

 Henry’s law applied to the air (species 1):

y1 = 1 − 0.0312 = 0.9688
Hi from Table
y1 P (0.9688)(101.33)
x1 = = = 1.35 ×10 −5 10.1 (pg. 357)
Η1 72950
 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).

5
 Example 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 10°C (283.15K). Henry’s
constant for CO2 in water at 10°C (283.15K) is about 990 bar.

 Lets assumed mole fraction of CO2 in the liquid is x1 = 0.01,

 very dilute CO2 in liquid phase

 Henry’s law for species 1 and Raoult’s law for species 2:

y1 P = x1 Η1 y2 P = x2 P2sat
 These equations sum to give:
P = x1 Η1 + x2 P2sat

6
 With H1 = 990 bar and P2sat = 0.01227 bar (from steam table),
P = x1 Η1 + x2 P2sat
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar

 For species 2 using Raoult’s law:

x2 P2sat (0.99)(0.01227)
y2 = = = 0.0012
P 9.912
 So,

 the vapor phase is nearly pure CO2 as assumed.

y1 = 1 − y2 = 1 − 0.0012 = 0.9988

7
 VLE by Modified Raoult’s Law
 Apply for vapor phase is an ideal gas but the liquid
is not an ideal solution.

 Modified version of Raoult’s Law that can be stated

as
yi P = xiγ i Pi
sat
(i = 1,2 ,...,N ) Eq. (10.5)

where γi is activity coefficient

 Activity coefficients are functions of temperature

and liquid-phase composition, and ultimately are
based on experiment.

8
Bubblepoint calculations (xi given)
N N

∑ y P =∑xγ P
i =1
i
i =1
i i i
sat
(i = 1,2 ,...,N )
N N N
P ∑ yi = ∑ xiγ i Pi sat
∑y i =1
i =1 i =1 i =1

N
P = ∑ xiγ i Pi sat Eq. (10.6)

i =1

9
Dewpoint calculations (yi given)
yi P
= xi (i = 1,2 ,...,N )
γ i Pi sat

N N
yi P
∑
i =1 γ i Pi
sat
= ∑ xi = 1
i =1
N
yi
P∑ =1
i =1 γ i Pi
sat

1
P= N
yi
∑
Eq. (10.7)

i =1 γ i Pi
sat

10
Example 1
For the system methanol(1)/methyl acetate(2), the following equations
provide a reasonable correlation for the activity coefficients:
ln γ1 = Ax22 ln γ2 = Ax12 where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:
3643.31
ln P1sat = 16.59158 −
T − 33.424
2665.54
ln P2sat = 14.25326 −
T − 53.424
where T is in Kelvin 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
11
Solution (a) P and {yi}, for t/T = 45oC/318.15K and x1 = 0.25
BUBL P calculations
1) Calculate P1sat and P2sat using Antoine equations
At 318.15K, P1sat = 44.51kPa and P2sat = 65.64kPa
2) Calculate activity coefficients (γ) from the given equations:
A = 2.771 – 0.00523T = 2.771 – 0.00523(318.15) = 1.107
γ1 = exp(Ax22) = exp[(1.107)(0.75)2] = 1.864
γ2 = exp(Ax12) = exp[(1.107)(0.25)2] = 1.072
3) Calculate pressure, P:
N
P = ∑ xiγ i Pi sat
i =1

P = (0.25)(1.864)(44.51) + (0.750)(1.072)(65.64)
P = 73.50kPa
4) Calculate value of yi using Modified Raoult’s Law expression:
yi = ( xiγ i Pi sat ) / P
y1 = 0.282 y2 = 0.718
12
Solution (b) P and {xi}, for t/T = 45oC/318.15K and y1 = 0.60
DEW P calculations
1) Calculate P1sat and P2sat using Antoine equations
At 318.15K, P1sat = 44.51kPa and P2sat = 65.64kPa

2) Calculate the value of A from the given equations:

A = 2.771 – 0.00523T = 2.771 – 0.00523(318.15) = 1.107 (unchanged T)

3) Iteration procedure is required to find the liquid phase composition and

to calculate the activity coefficients.

4) Lets take initial values of activity coefficients, γ1 = γ2 = 1

5) Calculate pressure, P using Eq. (10.7):

1
P=
y1 y2
+
γ 1 P1sat γ 2 P2sat

13
6) Calculate x1 using modified Raoult’s Law equations
y1 P
x1 = x2 = 1 − x1
γ 1 P1sat
7) Evaluate activity coefficient; return to the first step.

8) Iteration to convergence on a value for P.

P = 62.89kPa x1 = 0.8168 x2 = 0.1832

γ1 = 1.0379 γ2 = 2.0929

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Solution (c) T and {yi}, for P = 101.33 kPa and x1 = 0.85
BUBL T calculations
1) Calculate T1sat and T2sat using Antoine equations
Bi
Ti sat = − Ci
Ai − ln P
At P = 101.33kPa, T1sat = 337.71K and T2sat = 330.08K

2) A mole fraction weighted average of these values then provides an initial T:

T = (0.85)(337.71) + (0.15)(330.08) = 336.57K

3) Iteration procedure is required as follows step:

i. For the current values of T, calculate values for A, γ1, γ2 and
α =P1sat/P2sat
ii. Find a new value for P1sat from Eq. (10.6) written:
P
P sat
=
x1γ 1 + ( x2γ 2 ) / α
1

iii. Find a new value for T from the Antoine equation for species 1
iv. Return to the initial step. 15
4) Iteration to convergence on a value for T yields final values:

T = 331.20K (58.05°C) P1sat = 77.98kPa P2sat = 105.35kPa

A = 1.0388 γ1 = 1.0236 γ2 = 2.1182

5) Calculate vapor phase mole fraction using modified Raoult’s

Law equations,
x1γ 1 P1sat
y1 = = 0.670 y2 = 1 − y1 = 0.330
P

16
Solution (d) T and {xi}, for P = 101.33 kPa and y1 = 0.40
DEW T calculations
1) Calculate T1sat and T2sat using Antoine equations
Bi
Ti sat = − Ci
Ai − ln P
At P = 101.33kPa, T1sat = 337.71K and T2sat = 330.08K

2) A mole fraction weighted average of these values then provides an initial T:

T = (0.40)(337.71) + (0.60)(330.08) = 333.13K

3) Lets take initial values of activity coefficients, γ1 = γ2 = 1

4) Iteration procedure is required as follows step:

i. For the current values of T, calculate values for A, P1sat, P2sat and
α =P1sat/P2sat
ii. Calculate x1 using modified Raoult’s Law equations,
yP
x1 = 1 sat x2 = 1 − x1
γ 1 P1
17
 iii. Calculate values of γ1 and γ2 from the correlating equations.

iv. Find a new values for P1sat from Eq. (10.7) written:
 y1 y2 
P sat
= P + α 
 γ1 γ 2 
1

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

vi. Return to initial step and iterate with current value of γ1 and γ2 until
convergence value of T.

5) Iteration to convergence on a value for T.

T = 326.70K (53.55°C) P1sat = 64.64kPa P2sat = 89.95kPa
A = 1.0624 γ1 = 1.3633 γ2 = 1.2520
x1 = 0.4599 x2 = 0.5401

18
Solution (e) The azeotropic pressure, and the azeotropic composition,
for t/T = 45oC/318.15K
1) 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
α= Eq. (10.8)
y 2 x2
At azeotrope, y1 = x1, y2 = x2 and α12 = 1. By Eq. (10.5),
yi γ i Pi sat
=
Therefore:
xi P

γ 1 P1sat
α12 = Eq. (10.9)
γ 2 P2sat

19
 The correlating equations for activity coefficients show that
when x1 = 0, γ2 = 1 and γ1 = exp(A);
when x1 = 1, γ1 = 1 and γ2 = exp(A).
Therefore in these limits,
P1sat exp( A) P1sat
(α12 ) x1 =0 = sat
and (α12 ) x1 =1 = sat
P2 P2 exp( A)
 For T = 318.15 K or 45oC, calculate
P1sat = 44.51 kPa P2sat = 65.64 kPa A = 1.107

 The limiting values of α12 are therefore,

P1sat exp( A) (44.51) exp(1.107)
(α12 ) x1 =0 = sat
= = 2.052
P2 65.64
P1sat 44.51
(α12 ) x1 =1 = sat = = 0.224
P2 exp( A) (65.64) exp(1.107)

20
 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 α12 is a continuous function of x1 and must pass through
the value of 1.0 at some intermediate composition.

2) For the azeotrope, α12 = 1, Eq. (10.9) becomes

γ 1 P1sat
α12 =1=
γ 2 P2sat
γ 1az P2sat 65.64
= sat = = 1.4747
γ2 az
P1 44.51
3) The differences between the correlating equations for ln γ1 and ln
γ2 provides general relation:
γ
ln 1 = Ax22 − Ax12 = A( x2 − x1 )( x2 + x1 ) = A( x2 − x1 ) = A(1 − 2 x1 ) Eq. D
γ2
21
4) 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, when γ
ln 1
= ln 1.4747 = 0.388
γ2
5) Substitute to Eq. D to calculate value of x1az.
γ1
ln = ln 1.4747 = 0.388
γ2
0.388 = (1.107)(1 − 2 x1az )
x1az = 0.325
6) For this value of x1az, calculate value of γ1az
γ1az = exp [Ax22] = [(1.107)(1 – 0.325)2] = 1.657

7) With x1az = y1az, Eq. (10.5) becomes

Paz = γ1azP1sat = (1.657)(44.51) = 73.76 kPa
x1az = y1az = 0.325
22