CHAPTER 2

SIMPLE MODEL FOR VLE

{1 RAOULT’S LAW
}
Two-component System

Vapor Thermodynamic
(T, P, y1)
variables:
T, P, x1, y1
Liquid (4 variables)
T, P, x1
Degrees of freedom:
F=N–+2=2

Number of equations = 4 – 2 = 2
1V = 1L
2V = 2L
The two major assumptions :
• The vapor phase is an ideal gas  only for low
to moderate pressures  iV  yi P.
• The liquid phase is an ideal solution  only
when the species that comprise the system are
chemically similar  iL  xi Pisat.
Quantitative expression to Raoult's law is

y i P  x i Pi sat (i = 1, 2, …, N) (2.1)
Cases for a binary system:
1. y1 and T are fixed  dew P
2. y1 and P are fixed  dew T
3. x1 and T are fixed  bubble P
4. x1 and P are fixed  bubble T
5. T and P are fixed  flash calc.
6. x1 and y1 are fixed  boiling point calc.
 Dew Pressure Calculation

The dew pressure is the pressure at

which a gas mixture will start to
condense at a given temperature.

Given T and yi  Calculate P and xi

 yi P
xi  sat (2.2)
Pi
yi
 xi  1   sat P
i i Pi

1
P  (2.3)
yi
 sat
i Pi
Algorithm
1. Input: T, yi
2. Calculate: Pisat (Antoine eq.)
3. Calculate P (eq. 2.3)
4. Calculate xi (eq. 2.2)
Example 2.1
Calculate P and xi of acrylonitrile (1)/nitro-
methane (2) mixture having y1 = 0.6 at
75C. The mixture conforms closely to
Raoult’s law. Pisat for the pure species are
given by :
sat 2945 .47
ln P1  14.2724 
T  49.15 T is in K
2972 .64 P is in kPa
sat
ln P2  14.2043 
T  64.15
 Solution (Selasa, 27-8-2019)

ln P1sat  4.421 P1sat  83.207 kPa

ln P2sat  3.737 P2sat  41.983 kPa

1 1
P    59.742 kPa
yi 0.6 0.4
 sat 
i Pi 83.207 41.983
y1P 0.659.742 
x1  sat   0.431 x2  0.569
P1 83.207
 Dew Temperature Calculation
The dew temperature is the temperature
at which a gas mixture will start to
condense at a given pressure.

Given P and yi  Calculate T and xi

 yi P
xi  sat
Pi
yi
 xi  1   sat P
i i Pi

sat B
ln Pi  A
T C
Algorithm
1. Input: P, yi
2. Assume T
3. Calculate: Pisat (Antoine eq.)
4. Calculate xi (eq. 2.2)
5. Calculate xi
6. If xi  1, go to step 2
Example 2.2
Calculate T and xi of acrylonitrile (1)/nitro-
methane (2) mixture having y1 = 0.6 at 70
kPa. The mixture conforms closely to Raoult’s
law. Pisat for the pure species are given by the
Antoine equation as in Example 2.1.
P = 70 kPa
P = 70 kPa = P1sat P = 70 kPa = P2sat
T=? T=? T=?

y1 = 0,6 y1 = 1 y1 = 0

x1 = ? x1 = 1 x1 = 0
 2945 .47
ln P1sat  14.2724 
T  49.15

2945.47
ln70  14.2724 
T  49.15

T = 343K
 sat 2972 .64
ln P2  14.2043 
T  64.15

2972.64
ln70  14.2043 
T  64.15

T = 362.7K
Solution
Iteration 1
T = 350 K  P1sat = 88.403 kPa
P2sat = 44.925 kPa
y1P 0.670
x1  sat   0.4751
P1 88.403
 xi  1.0984
y2P 0.470
i
x2  sat   0.6233
P2 44.925
 2945 .47
ln P1sat  14.2724 
T  49.15

sat Bi sat Bi
ln Pi  Ai  Ti  sat
 Ci
T  Ci Ai  ln Pi

T1sat = 343.99 K
T2sat = 362.73 K
 T P1sat P2sat x1 x2 x1 + x2

350.00 88.403 44.925 0.4751 0.6233 1.0984

355.00 103.748 53.719 0.4048 0.5212 0.9261
352.73 96.539 49.570 0.4351 0.5649 1.0000

T = 352.73 K
x1 = 0.4351
x2 = 0.5649
 Bubble Pressure Calculation
The bubble pressure is the pressure at
which a liquid mixture will start to form
bubble at a given temperature.

Given T and xi  Calculate P and yi

 sat
y i P  xi Pi

sat
 yi P   xi Pi
i i

P  y i  P   xi Pi sat (2.4)
i i

xi Pi sat
yi  (2.5)
P
Algorithm
1. Input: T, xi
2. Calculate: Pisat (Antoine eq.)
3. Calculate P (eq. 2.4)
4. Calculate yi (eq. 2.5)
Example 2.3
Calculate P and yi of acrylonitrile (1)/nitrome-
thane (2) mixture having x1 = 0.4 at 350K.
The mixture conforms closely to Raoult’s law.
Pisat for the pure species are given by the
Antoine equation as in Example 2.1.
Solution

T = 350 K  P1sat = 88.403 kPa

P2sat = 44.925 kPa

P   xi Pi sat  0.488.403  0.644.925

i

= 62.32 kPa
 xi Pi sat
yi 
P
x1P1sat 0.488.403
y1    0.5674
P 62.32

y2 
xP 2 2
sat

0.6 44.925
 0.4326
P 62.32
Bubble Temperature Calculation
The bubble temperature is the
temperature at which a liquid mixture
will start to form bubble at a given
pressure.

Given P and xi  Calculate T and yi

Algorithm
1. Input: P, xi
2. Assume T
3. Calculate: Pisat (Antoine eq.)
4. Calculate yi (eq. 2.5)
5. Calculate yi
6. If yi  1, assume new T and go to
step 2
Example 2.4
Calculate T and yi of acrylonitrile (1)/nitrome-
thane (2) mixture having x1 = 0.4 at 70 kPa.
The mixture conforms closely to Raoult’s law.
Pisat for the pure species are given by the
Antoine equation as in Example 2.1.
Solution
Iteration 1
T = 350 K  P1sat = 88.403 kPa
P2sat = 44.925 kPa

y1 
x1P1sat

0.488.403 
 0.5052
P 70
x2P2sat 0.6 44.925 
y2    0.3851
P 70
y1 + y2 = 0.8903
 T P1sat P2sat y1 y2 y1 + y2

350.00 88.403 44.925 0.5052 0.3851 0.8902

355.00 103.748 53.719 0.5928 0.4605 1.0533

353.44 98.750 50.839 0.5643 0.4357 1.0000

T = 353.44 K
y1 = 0.5643 y2 = 0.4357
VLE Composition Calculation

At fixed value of pressure and

temperature, a binary mixture has
certain composition both in liquid and
vapor phases.
 sat
y i P  xi Pi
Algorithm
1. Input: P, T
2. Calculate: Pisat (Antoine eq.)
3. Assume x1  x2 = 1 – x1
xi Pi sat
4. Calculate yi (eq. 2.5) yi 
P
5. Calculate yi
6. If yi  1, go to step 3
Example 2.5
Calculate xi and yi of acrylonitrile (1)/nitro-
methane (2) mixture at 350 K and 70 kPa.
The mixture conforms closely to Raoult’s
law. Pisat for the pure species are given by
the Antoine equation as in Example 2.1.
Solution
T = 350 K  P1sat = 88.403 kPa
P2sat = 44.925 kPa
Iteration 1: x1 = 0.5

y1 
x1P1sat

0.588.403 
 0.6315
P 70
x2P2sat 0.544.925 
y2    0.3209
P 70
y1 + y2 = 0.9523
 x1 x2 y1 y2 y1 + y2
0.5000 0.5000 0.6315 0.3209 0.9523
0.6000 0.4000 0.7577 0.2567 1.0145
0.5767 0.4233 0.7283 0.2717 1.0000

x1 = 0.5767 x2 = 0.4233
y1 = 0.7283 y2 = 0.2717
 Boiling Point Calculation

At fixed compositions of both in liquid

and vapor phases, the mixture has a
certain value of temperature and
pressure (boiling point).
Algorithm 1
P 
yi
1. Input: x1, y1  sat
i Pi
2. Assume: T
3. Calculate: Pisat (Antoine eq.)
4. Calculate P (eq. 2.3)
yi P
5. Calculate x1 (eq. 2.2) xi  sat
Pi
6. If x1,calc  x1,data, go to step 2
Example 2.6
Calculate T and P of acrylonitrile (1)/nitrome-
thane (2) mixture having liquid composition
x1 = 0.4571 and vapor composition y1 = 0.6.
The mixture conforms closely to Raoult’s law.
Pisat for the pure species are given by the
Antoine equation as in Example 2.1.
Solution
T = 350 K  P1sat = 88.403 kPa
P2sat = 44.925 kPa
1 1
P    63.73
yi 0.6 0.4
 sat 
i Pi 88.403 44.925
y1P 0.6 63.73
x1  sat   0.4325
P1 88.403
 T P1sat P2sat P x1
350.00 88.40 44.93 63.73 0.4326
360.00 121.13 63.85 89.14 0.4415
379.80 213.64 119.91 162.76 0.4571

T = 379.8 K
P = 162.76 kPa
{2 HENRY’S LAW
}
Raoult’s law:
y i P  x i Pi sat

What if one component is at supercritical state

(T > Tc)?

Raoult’s law is not appropriate for any species at

T > Tc.
 Pc

Psat

Tc T2
T1
Raoult’s law:
sat sat
xwater Pwater Pwater
ywater  
P P
because xwater  1

For oxygen in water:

yO P
xO  sat  ??
2
2
PO2
At a constant temperature, the amount of
a given gas dissolved in a given type and
volume of liquid is directly proportional to
the partial pressure of that gas in
equilibrium with that liquid.

The proportionality factor is called the

Henry’s law constant.
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 (2.6)
Henry’s law only applies when the gas and its
solution are essentially ideal, i.e.
• Pressure is low enough that the vapor phase may
be assumed an ideal gas.
• Concentration of gas in solution is low
• Partial pressure above solution is low
• Solute does not interact strongly with the solvent
Example 2.7
Assuming that carbonated water contains
only CO2 and H2O, determine the composition
of the vapor phase in a sealed can of “soda”
and the pressure exerted on the can at 10C
where the composition of CO2 in the liquid
phase is 0.01. Henry’s volatility constant for
CO2 in water at 10C is about 990 bar.
Solution

For CO2 : y1 P = x1 H1
For H2O : y2 P = x2 P2sat
(y1 +y2) P = x1 H1 + x2 P2sat

From Steam Table, at 10C:

P2sat = 1.227 kPa = 0.01227 bar
P = x1 H1 + x2 P2sat
= (0.01) (990) + (0.99) (0.01227)
= 9.912 bar

y2 
xP
2 2
sat

0.990.01227 
 0.0012
P 9.912
y1  1  y2  1  0.0012  0.9988
THANK YOU