CHE553 (CHEMICAL ENGINEERING

THERMODYNAMICS)

CHAPTER 1: VAPOR
LIQUID EQUILIBRIUM

EDITED BY: MEOR MUHAMMAD HAFIZ SHAH BUDDIN

 2

OVERVIEW
■ Vapor liquid equilibrium (VLE) is a state where vapor and liquid
phase are in equilibrium with each other.
■ Many processes in chemical engineering do not only involve a single
phase but a stream containing both gas and liquid. It is very
important to recognize and be able to calculate the temperature,
pressure and composition of each phase at equilibrium.
■ VLE information is useful in separation processes, e.g. distillation,
evaporation, liquid-liquid extraction, adsorption, etc.
CONTENT - PART 1
THE NATURE OF EQUILIBRIUM

THE PHASE RULE: DUHEM’S THEOREM

VLE: QUALITATIVE BEHAVIOR

SIMPLE MODELS FOR VAPOR LIQUID EQUILIBRUM:

RAOULT’S LAW

COURSE LEARNING OUTCOME

■ Identify and apply the concept of equilibrium
■ Calculate dew point and bubble point pressure or
temperature, vapor and liquid compositions at equilibrium
3
 MEASURES OF COMPOSITION
■ Mass or mole fraction is defined as the ratio of mass or number of moles of
a particular chemical species in a mixture or solution to the total mass or
number of moles of mixture or solution.
𝑚𝑖 𝑛𝑖
𝑥𝑖 ≡ 𝑥𝑖 ≡
𝑚 𝑛
■ Molar concentration is defined as the ratio of mole fraction of a particular
chemical species in a mixture or solution to molar volume of the mixture or
solution.
𝑥𝑖
𝐶𝑖 ≡
𝑉
or multiplying and dividing by molar flow rate,
𝑛𝑖
𝐶𝑖 ≡
𝑞
The molar mass of a mixture or solution is the mole fraction-weighted sum of the
molar masses of all species.

𝑀 ≡ ෍ 𝑥𝑖 𝑀𝑖
𝑖
4
 5

THE NATURE OF EQUILIBRIUM

■ Equilibrium is a condition where no changes occur in the
properties of a system with time.
■ The temperature, pressure and phase compositions reach final
values which thereafter remain fixed.
 6

THE PHASE RULE; DUHEM’S THEOREM

■ Phase rule:
F = 2 − + N
F = no. of variables that may be independently fixed in a system at
equilibrium (degree of freedom).
 = no. of phases
N = no. of chemical species
■ Duhem’s theorem:

For any closed system, the equilibrium state is completely

determined when any two independent variables are fixed.

■ The two independent variables subject to specification may in

general be either intensive or extensive. However, the number of
independent intensive variables is given by the phase rule.
■ Thus, when F = 1, at least one of the two variables must be
extensive, and when F = 0, both must be extensive.
Single Component System
■For a two phase (=2) system of a single component (N=1):
■ F = 2-  + N
■ F = 2- 2 + 1 = 1
■Therefore, for the single component system, specifying either T
or P fixes all intensive variables.

800
VLE for Pure Components

Pressure: kPa
600

400

200

0
270 320 370 420
Temperature: K
Acetonitrile Nitromethane

7
Two components system
■(General Case)
■For a two phase (=2), binary system (N=2):
■ F = 2- 2 + 2 = 2
■Therefore, for the binary case, two intensive variables must be
specified to fix the state of the system.

8
 9

VLE: QUALITATIVE BEHAVIOR

■ Vapor/liquid equilibrium (VLE) is
the state of coexistence of liquid
and vapor phases.
■ For a system of two chemical
species (N=2), the phase rule
becomes F=4-.
■ Because there must be at least
one phase (=1), the max number
of phase rule variables which must
be specified to fix the intensive
state of the system is three,
namely P, T and one mole/mass
fraction.
■ All equilibrium states of the
system can therefore be
represented in 3D P-T-composition
space as shown in Fig. 10.1.
■ This fig. contains the equilibrium
states of saturated vapor and
saturated liquid for species 1 and
2 of a binary system.
• Line AEDBLA in Fig. 10.1 can be represented by Fig 10.2(a) P-x1-y1 diagram at Ta.
• The horizontal lines are tie lines connecting the compositions of phase in equilibrium.
• The temperatures Tb and Td lie between the two pure species critical temperature identified
by C1 and C2 in Fig. 10.1.
• Line KJIHLK in Fig. 10.1 can be represented by Fig. 10.2(b) T-x1-y1 diagram at Pa.
• Pressure Pb lies between the critical pressures of the two pure species at points C1 and C2
in Fig. 10.1.
• Pressure Pd is above the critical pressures of both pure species, therefore the T-x1-y1
diagram appears as an island.
• Vertical plane and perpendicular to the composition axis, passes through points SLMN
and Q is shown as Fig. 10.3 PT diagram.
• Each interior loop represents the P-T behavior of saturated liquid and of saturated vapor
for a mixture of fixed composition. Different loops are for different compositions.
Figure 10.8 shows P-x-y
diagrams at constant T for
four systems (much lower
temperature and pressure).
Figure 10.9 shows t-x-y behavior
for four systems at low pressure
– 1 atm).

Azeotrope?
Figure 10.10: The y1-x1 diagrams at constant P for four systems.
The point at which a curve crosses the diagonal line of the diagram represents an
azeotrope, for such a point x1 = y1 (for (b) and (d)).
 SIMPLE MODELS FOR 15

VAPOR/LIQUID EQUILIBRIUM
■ VLE calculation provides information on temperatures, pressures, and
compositions of phases in equilibrium.
■ Two simplest models, Raoult’s law and Henry’s law are used to predict the
behavior of systems in vapor liquid equilibrium.

RAOULT’S LAW
■ Assumption
– Vapor phase is an ideal gas (apply for low to moderate pressure)
– Liquid phase is an ideal solution (apply for species that are chemically
similar)
■ Mathematical expression reflecting the two assumptions above is expressed
quantitatively in Raoult’s law as:

yiP = xiPisat (i = 1,2, ..., N) (10.1)

where xi = mole fraction of liquid phase

yi = mole fraction of vapor phase
Pisat = vapor pressure of pure species i at the temperature of the system
 16

DEWPOINT AND BUBBLEPOINT

CALCULATIONS

■ Bubble point is the point at which the first drop of a liquid mixture
begins to evaporate (the first bubble of vapor appears).
■ Dew point is the point at which the first drop of a gas mixture begins to
condense (the last drops of liquid disappear).

BUBL P : Calculate {yi} and P, given {xi} and T

DEW P : Calculate {xi} and P, given {yi} and T
BUBL T : Calculate {yi} and T, given {xi} and P
DEW T : Calculate {xi} and T, given {yi} and P
 17

Application of Raoult’s law:

Because iyi = 1, eq. (10.1) may be summed over all species to yield
P =  xi Pi sat (10.2)
i

This equation applied in bubblepoint calculations, where the vapor phase

compositions are unknown.
For a binary system with x2 = 1-x1,
( )
P = P2 sat + P1sat − P2sat x1
A plot of P vs. x1 at constant temperature is a straight line connecting P2sat at x1 =
0 with P1sat at x1 = 1.
Equation (10.1) may also be solved for xi and summed over all species. With ixi =
1, this yields
1
P= (10.3)
 yi Pi sat
i

This equation applied in dewpoint calculations, where the liquid phase

compositions are unknown.
 18

ANTOINE’S EQUATION:
CORRELATION OF VAPOR PRESSURE DATA

Antoine’s equation is used to calculate Pisat :

Bi
ln Pi sat
( kPa ) = Ai −
T ( K ) + Ci

*Refer Table B.2 for values of Antoine parameters (A, B and C)

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Example 10.1
Binary system acetonitrile(1)/nitromethane(2) conforms closely to Raoult’s law.
Vapor pressures for the pure species are given by the following Antoine
equations:
2945.47
ln P1 sat = 14.2724 −
T − 49.15
2972.64
ln P2 sat = 14.2043 −
T − 64.15
(a) Prepare a graph showing P vs x1 and P vs y1 for a temperature of
348.15K
(b) Prepare a graph showing T vs x1 and T vs y1 for a pressure of 70kPa
 20

P-xy digram
BUBL P calculation
Solution:
(a) Prepare P-x1-y1 diagram (given T = 348.15 K, x1 and y1 in the range 0→1)
Calculate P1sat and P2sat from Antoine equations at 348.15K
■ Calculate P from equation (10.2) at any x1

( )
P = P2 sat + P1sat − P2sat x1

■ Calculate y1 from equation (10.1):

x1 P1sat
y1 =
P

■ Repeat the calculation of P and y1 at various x1 (x1 = 0→1)

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The results of calculations: P-xy digram

x1 y1 P P-xy diagram for acetonitrile(1)/nitrom ethane(2) at 75oC

0 0 41.98
100
0.1 0.1805 46.10 P1sat=83.21
90
0.2 0.3313 50.23 P1sat=83.21
Subcooled liquid
0.3 0.4593 54.35 80
Bubble point
Subcooled liquid
0.4 0.5692 58.47 70

0.5 0.6647 62.60

P/kPa
60
0.6 0.7483 66.72 Dew point
50
0.7 0.8222 70.84
40
0.8 0.8880 74.96
Superheated vapor
0.9 0.9469 79.09 30 P2sat=41.98
Superheated vapor
1 1 83.21 20 P2sat=41.98
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1, y1

At 348.15 K and x1 = 0.35, x1 y1

P = ?, y1 = ?
At 348.15 K and y1 = 0.6, At 75°C, a liquid mixture of 60 mol-% acetonitrile
P = ?, x1 = ? and 40 mol-% nitromethane is in equilibrium with
a vapor containing 74.83 mol-% acetonitrile at a
pressure of 66.72 kPa
 22

P-xy digram
DEW P calculation

(given y1 = 0.6 and T = 348.15K)

 Calculate P from equation (10.3)
1
P= sat
y1 P1 sat
+ y2 P2

 Calculate x1 by equation (10.1),

y1 P
x1 =
P1sat
Describe the state
of points a, b, b’, c,
c’ & d

23
P-xy digram
BUBL P calculation

Find 𝑃1𝑠𝑎𝑡 &

Find P Calculate 𝑦𝑖
𝑃2𝑠𝑎𝑡 using from Raoults’
Antoine’s

P-xy digram
DEW P calculation

Find P from Raoults’ Calculate 𝑥𝑖

assuming σ 𝑥𝑖 = 1
from Raoults’

24
T-xy digram 25

(b) Prepare T-x1-y1 diagram (given P = 70 kPa, x1 and y1 in the range

0→1)
 Calculate T1sat and T2sat at the given pressure by using Antoine
equation
Ti sat
(K ) = Bi
− Ci
Ai − ln P(kPa )
 Select T1sat < T < T2sat to calculate P1sat and P2sat for these
temperature by using Antoine equation
Bi
ln Pi sat ( kPa ) = Ai −
T ( K ) + Ci
 Evaluate x1 by equation:

P − P2 sat From eqn. (10.2)

x1 = sat
P1 − P2 sat

 Calculate y1 by equation (10.1)

x1 P1sat
y1 =
P
T-xy digram 26

Repeat similar calculation of x1 and y1 for T1sat < T < T2sat.

The results of calculations:
x1 y1 T (K) T-xy diagram for acetonitrile(1)/nitromethane(2) at 70 kPa

1.0000 1.0000 342.99

0.8596 0.9247 345.15
365
0.7378 0.8484 347.15 T2sat=362.73K
Superheated vapor
0.6233 0.7656 349.15
360
0.5156 0.6759 351.15
0.4142 0.5789 353.15
Dew point
0.3184 0.4742 355.15 355

T/K
0.2280 0.3614 357.15
0.1424 0.2401 359.15 350

0.0613 0.1098 361.15

Bubble point
0.0000 0.0000 362.73 345

Subcooled liquid
T1sat=342.99K
340
At x1 = 0.6 and P = 70 kPa, 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
T = ?, y1 = ? x1, y1
At y1 = 0.6 and P = 70 kPa,
T = ?, x1 = ? y1 x1
Preparing T-xy digram

Find 𝑇1𝑠𝑎𝑡 & 𝑇2𝑠𝑎𝑡 using Antoine’s

Find 𝑃1𝑠𝑎𝑡 & 𝑃2𝑠𝑎𝑡 using T in between 𝑇1𝑠𝑎𝑡 &

𝑇2𝑠𝑎𝑡

Calculate 𝑥𝑖

Calculate 𝑦𝑖

27
T-xy digram 28

BUBL T calculation
BUBL T calculation (given x1 = 0.6 and P = 70kPa)
Iterate as follow:
1. Calculate initial T using mole fraction-weighted average of T1sat and T2sat:
T = x1T1sat + x2T2sat
2. Calculate P1sat and P2sat at initial T
3. Calculate    P sat P sat
1 2

4. With the current value of , calculate P2sat

P
P2 sat =
x1 + x2
5. Calculate T from Antoine equation for species 2:

T (K ) =
B2
− C2
A2 − ln P2 (kPa )
sat

6. If TT(previous iteration), repeat step 2-5 until T converge to a final value

OR
Find new value of  by subtracting ln P2sat from ln P1sat as given by Antoine Use T
equations and repeat step 4-5 until T converge to a final value from
step 5
 B1   B2 
ln  = ( A1 − A2 ) −   +  
 T + C1   T + C2 
T-xy digram 29

DEW T calculation
DEW T calculation (given y1 = 0.6 and P = 70kPa)
Iterate as follow:
1. Calculate initial T using mole fraction-weighted average of T1sat and T2sat:
T = y1T1sat + y2T2sat
2. Calculate P1sat and P2sat at initial T
3. Calculate .
  P1 sat P2 sat
4. With the current value of , calculate P1sat
From eqn. (10.3)
P1 sat = P ( y 1 +y 2 )
5. Calculate T from Antoine equation for species 1:

T (K ) =
B1
− C1
A1 − ln P1 (kPa )
sat

6. If TT(previous iteration), repeat step 2-5 until T converge to a final value

OR
Find new value of  by subtracting ln P2sat from ln P1sat as given by Antoine Use T
equations and repeat step 4-5 until T converge to a final value from
step 5
 B1   B2 
ln  = ( A1 − A2 ) −   +  
 T + C1  T + C 2 
 T-xy digram
BUBL T calculation

Initial T T = x1T1sat + x2T2sat

Find 𝑃1𝑠𝑎𝑡 & 𝑃2𝑠𝑎𝑡 using Antoine’s at initial T

α   P1 sat P2 sat

P
P2 sat =
𝑃2𝑠𝑎𝑡 using α x1 + x2

T (K ) =
B2
− C2
T from Antoines’ A2 − ln P2 (kPa )
sat

 B   B 
Find new α until converge ln  = ( A1 − A2 ) −  1  +  2 
 T + C1 30  T + C2 
 T-xy digram
DEW T calculation

Initial T T = y1T1sat + y2T2sat

Find 𝑃1𝑠𝑎𝑡 & 𝑃2𝑠𝑎𝑡 using Antoine’s at initial T

α   P1 sat P2 sat

𝑃1𝑠𝑎𝑡 using α P1 sat = P ( y 1 +y 2 )

T (K ) =
B1
T from Antoines’ − C1
A1 − ln P1 (kPa )
sat

 B   B 
Find new α until converge ln  = ( A1 − A2 ) −  1  +  2 
 T + C1  31  T + C2 
 32

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