VAPOR LIQUID

EQUILIBRIUM
 THE NATURE OF EQUILIBRIUM
 THE PHASE RULE: DUHEM’S THEOREM
 VLE: QUALITATIVE BEHAVIOR
 SIMPLE MODELS FOR VAPOR LIQUID EQUILIBRUM: RAOULT’S LAW
THE NATURE OF EQUILIBRIUM
 Equilibrium is a static condition in which no changes occur in the
macroscopic properties of a system with time.
 The temperature, pressure and phase compositions reach final
values which thereafter remain fixed.

2
 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.

m m ni ni
xi  i  i xi  
m m n 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, n
ni
Ci 
q 3
 The molar mass of a mixture or solution is the mole fraction-
weighted sum of the molar masses of all species.

M   xi M i
i

4
 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.
5
 Phase Rule for Intensive Variables
Fora system of  phases and N species, the degree of freedom is:
F=2-+N
# variables that must be specified to fix the intensive state of the
system at equilibrium

Phase Rule Variables:

The system is characterized by T, P and (N-1) mole fractions for each
phase
Requires knowledge of 2 + (N-1) variables
Phase Rule Equations:
At equilibrium i = i  = i  for all N species
These relations provide (-1)N equations

The difference is F = 2 + (N-1) - (-1)N

 = 2-  +N
Conditions :
 Applicable to non-reactive system (i.e
constituents which do not combine with
each other)
 Systems must be thermodynamic
equilibrium
 Every constituents must be present in
each phase

7
 The Phase Rule & Duhem’s Theorem
On the basis of this result, Duhem’s theorem is
stated as follows:
For any closed system formed initially from
given masses of prescribed chemical species,
the equilibrium state is completely determined
when any two independent variables are fixed.
Phase Rule in VLE: Single Component Systems
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
CHEE 311
Correlation of Vapour Pressure Data
Pisat, or
the vapour pressure of component i, is commonly represented
by Antoine Equation (Appendix B, Table B.2, SVNA 7th ed.):

B
ln Pisat  A 
TC

For acetonitrile (Component 1):

2945.47
ln P1sat / kPa  14.2724 
T / C  224
For nitromethane (Component 2):
2972.64
ln P2sat / kPa  14.2043 
T / C  209

These functions are the only component properties needed to

characterize ideal VLE behaviour
Phase Rule in VLE: Ideal Binary Mixtures
(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.
Phase Rule in VLE: Binary Systems (Pxy
diagrams)
Example: Acetonitrile (1) / Nitromethane (2) system

Acetonitrile(1) - Nitromethane(2) @ 75C

90

80
Pressure, kPa

70

60

50

40
0.0 0.2 0.4 x1,y1 0.6 0.8 1.0
y1 x1
Phase Rule in VLE: Binary Systems (Txy
diagrams)
Alternatively, we can specify a system pressure and examine the VLE behaviour
as a function of temperature and composition.

Acetonitrile(1) Nitromethane(2) @ 70kPa

90.0

85.0
Temp, deg C

80.0

75.0

70.0

65.0
0.00 0.20 0.40 0.60 0.80 1.00
x1,y1
y1 x1
 Simple Models For VLE
The preceding section describes what is
observed through experiment. When
thermodynamics is applied to vapor/liquid
equilibrium, the goal is to find by calculation
the temperatures, pressures, and compositions
of phases in equilibrium.
 Simple Models For VLE

Figure 10.8: P x y diagrams at constant T:

(a) tetrahydrofuran(1)/carbon tetrachloride(2) at 30 ℃
(b) chloroform(1)/tetrahydrofuran(2) at 30 ℃
 Simple Models For VLE

Figure 10.8: P x y diagrams at constant T:

(c) furan(1)/carbon tetrachloride(2) at 30 ℃
(d) ethanol(1)/toluene(2) at 65 ℃
 Simple Models For VLE

Figure 10.9: t x y diagrams at constant P (1 atm.):

(a) tetrahydrofuran(1)/carbon tetrachloride(2) at 30 ℃
(b) chloroform(1)/tetrahydrofuran(2) at 30 ℃
 Simple Models For VLE

Figure 10.9: t x y diagrams at constant P (1 atm):

(c) furan(1)/carbon tetrachloride(2) at 30 ℃
(d) ethanol(1)/toluene(2) at 65 ℃
 Simple Models For VLE

This Figure shows four types of systems:

Ideal, real, Maximum and Minimum azeotropes
 VAPOR LIQUID EQUILIBRIUM
(VLE)
 Vapor-liquid equilibrium (VLE) is a condition where a liquid
and its vapor (gas phase) are in equilibrium with each other.
 Many processes in chemical engineering do not only involve a single
phase but a combination of two immiscible liquids, or a stream
containing both gas and liquid. It is very important to recognize and
be able to calculate when these phases are in equilibrium with each
other, and how much is in each phase.
 VLE information is useful in separation processes, e.g. distillation,
evaporation, liquid-liquid extraction, adsorption, etc.

20
 SIMPLE MODELS FOR
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
◦ Vapour phase is an ideal gas
◦ Liquid phase is an ideal solution
 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 21
 Dewpoint and Bubblepoint
Calculations with Raoult’s Law
 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

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

22
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
y
i
i Pi sat (10.3)

This equation applied in dewpoint calculations, where the liquid phase

compositions are unknown.

23
24
25
26
 Antoine’s equation is used to calculate P1sat and P2sat :

Bi
ln Pi sat  kPa   Ai 
T  K   Ci

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

27
 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
75oC (348.15K)
(b) Prepare a graph showing T vs x1 and T vs y1 for a pressure of
70kPa

28
Solution:
(a) Prepare P-x1-y1 diagram ( T is given (348.15K), x1 and y1 in the range
01)
BUBL P calculation
Calculate P1sat and P2sat from Antoine equations
At 348.15K,
P1sat = 83.21 kPa andP2sat = 41.98 kPa

Calculate P from equation (10.2):

 
P  P2 sat  P1sat  P2sat x1

E.g. At x1 = 0.6, P = 66.72 kPa

Calculate y1 from equation (10.1):

x1 P1 sat
y1   0.7483
P
*At 75oC (384.15 K) a liquid mixture of 60 mole % acetonitrile and 40
mole % nitromethane is in equilibrium with a vapor containing 74.83 mole
% acetonitrile at a pressure of 66.72 kPa. 29
 Similar calculation of P and y1 at various x1 (01).
The results of calculations:

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
0.2 0.3313 50.23 90
Subcooled liquid
0.3 0.4593 54.35 80
Bubble point
0.4 0.5692 58.47 70
0.5 0.6647 62.60

P/kPa
60
0.6 0.7483 66.72
50 Dew point
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
1 1 83.21 20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1, y1
At 75oC and x1 = 0.45,
P = ?, y1 = ?  BUBL P x1 y1

At 75oC and y1 = 0.6,

P = ?, x1 = ?  DEW P Either can be read from the graph or calculated.
30
DEW P calculation
Calculate P from equation (10.3)
1
P sat
y1 P1 sat  y2 P2

For y1 = 0.6 and T = 75oC (348.15K),

1
P  59.74kPa
0.6 83.21  0.4 41.98

Calculate x1 by equation (10.1),

y1 P  0.6  59.74 
x1  sat
  0.4308
P1 83.21

31
(b) Prepare T-x1-y1 diagram ( P is given (70 kPa), x1 and y1 in the range 01)
Calculate T1sat and T2sat at the given pressure by using Antoine equation
Bi
Ti sat   Ci
Ai  ln P
For P = 70kPa,
T1sat = 342.99 K (69.84oC) and T2sat = 362.73 K (89.58oC)

Select T1sat < T < T2sat to calculate P1sat and P2sat for these temperature by
using Antoine equation, and evaluate x1 by equation:

P  P2 sat
x1  sat
P1  P2 sat
For example take T = 78oC (351.15K), From eqn. (10.2)
sat
P1 = 91.76 kPa sat
P2 = 46.84 kPa x1 = 0.5156
Calculate y1 by equation (10.1),

x1 P1 sat  0.5156  91.76 

y1    0.6759
P 70
32
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
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

x1, y1

At x1 = 0.6 and P = 70 kPa,

T = ?, y1 = ?  BUBL T
y1 x1

At y1 = 0.6 and P = 70 kPa,

T = ?, x1 = ?  DEW T
33
BUBL T calculation
For x1 = 0.6 and P = 70kPa, T is determine by iteration.
Iterate as follow:
1. Calculate initial T using mole fraction-weighted average of T1sat and T2sat:
T = x1T1sat + x2T2sat
or select T1sat < T < T2sat as initial T. Use Antoine eqn.
2. Calculate P1sat and P2sat at initial T.
3. Calculate .
  P1 sat P2sat
4. With the current value of , calculate P2sat .
P
P2 sat 
x1  x2 From eqn. (10.2)
5. Calculate T from Antoine equation for species 2:
2972.64
T  64.15
14.2043  ln P2 sat

6. Find a new value of  (step 3).

(a) subtract ln P2sat from ln P1sat as given by Antoine equations.
2945.47 2972.64 Use T
ln   0.0681   from
or T  49.15 T  64.15
step 5
(b) calculate P1sat and P2sat at T, then find new value of .
7. Repeat step 4-5 and iterate to convergence for a final value of T.
34
Initial T = 350.89 K
P1sat = 90.99 kPa, P2sat = 46.40 kPa

Calculate new  P2sat T

Iteration 
(kPa) (K)
by using step 6(a)
1 1.961 44.40 349.68
2 1.970 44.24 349.58
3 1.971 44.23 349.57
4 1.971 44.23 349.57
OR

Calculate new  P1sat P2sat P2sat T

Iteration 
(kPa) (kPa) (kPa) (K)
by using step 6(b)
1 90.99 46.40 1.961 44.40 349.68
2 87.47 44.40 1.970 44.24 349.58
3 87.20 44.24 1.971 44.23 349.57
4 87.18 44.23 1.971 44.23 349.57
*The result is T = 349.57K (76.42oC). From Antoine equation, P 1sat = 87.17 kPa and by
eq (10.1), y1 = 0.7472

35
DEW T calculation
For y1 = 0.6 and P = 70kPa,T is determine by iteration .
Iterate as follow:
1. Calculate initial T using mole fraction-weighted average of T1sat and T2sat:
T = y1T1sat + y2T2sat
or select T1sat < T < T2sat as initial T. Use Antoine eqn.
2. Calculate P1sat and P2sat at initial T.
3. Calculate .
  P1 sat P2sat
4. With the current value of , calculate P1sat .
P1sat = P  y 1 +y 2  From eqn. (10.3)
5. Calculate T from Antoine equation for species 1:
2945.47
T  49.15
14.2724  ln P1 sat

6. Find a new value of  (step 3).

(a) subtract ln P2sat from ln P1sat as given by Antoine equations.
2945.47 2972.64 Use T
ln   0.0681   from
or T  49.15 T  64.15
step 5
(b) calculate P1sat and P2sat at T, then find new value of .
7. Repeat step 4-5 and iterate to convergence for a final value of T.
36
Initial T = 350.89 K
P1sat = 90.99 kPa, P2sat = 46.40 kPa
Calculate new  Iteration  P1sat (kPa) T (K)
by using step 6(a) 1 1.961 96.91 352.85
2 1.947 96.51 352.72
3 1.948 96.53 352.73
4 1.948 96.53 352.73

Calculate new  P1sat P2sat P1sat T

Iteration 
(kPa) (kPa) (kPa) (K)
by using step 6(b)
1 90.99 46.40 1.961 96.91 352.85
2 96.91 49.78 1.947 96.51 352.72
3 96.51 49.55 1.948 96.53 352.73
4 96.53 49.57 1.948 96.53 352.73

*The result is T = 352.73K (79.58oC) and P1sat = 96.53 kPa. From eq (10.1), x1 =
0.4351

37
 38

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

38