VAPOR LIQUID

EQUILIBRIUM Part 1

1. The nature of equilibrium

2. The phase rule: Duhem’s Theorem
3. VLE: Qualitative behavior
4. Simple models for vapor-liquid equilibrium
5. VLE by modified Raoult’s law
6. VLE from K-value correlations
Course learning outcomes
The student should be able to:

1. Derive and simplify equations of VLE.

2. Apply simplified VLE equations to obtain data for P-xyY, T-xy
and x-y diagrams.
3. Apply Raoult’s law and Henry’s law to solve simple
thermodynamic problems.
4. Carry out bubble and dew point calculations for a given
mixture
5. Carry out flash calculation in order to determine the
vapor/liquid fraction as well as the mixture composition of
each phase at specified conditions using available K-values.
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.

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 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
4
 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

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 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.
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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

600
Pressure: kPa

400

200

0
270 320 370 420
Temperature: K
Acetonitrile Nitromethane
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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 / kPa  14.2043 
P2sat
T / C  209
 These functions are the only component properties needed to
characterize ideal VLE behaviour

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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.

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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

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11
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
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 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.

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 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 ℃

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 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 ℃
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 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 ℃
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 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 ℃
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 Simple Models For VLE

This Figure shows four types of systems:

Ideal, Real, Maximum and Minimum azeotropes
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 VLE QUALITATIVE BEHAVIOR

 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.

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 Consider a system comprising of two chemical species
(N=2), the phase rule becomes
F = 2-  + N = 2-  + 2 =4 - 
 Because there must at least one phase ( = 1),
 maximum number of phase rule variables = 3
 P, T and one mole (or mass) fraction.

 All equilibrium states of the system can be represented in

three-dimensional (3D) P-T-composition space.

 Within this space, the states of pairs of phases coexisting at

equilibrium (F = 4 - 2 = 2) define surfaces.

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3D diagram: surfaces for VLE

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 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

The vapor phase is an ideal gas

 It means can apply only for low to moderate pressures.
The liquid phase is an ideal solution
 It have approximate validity when the species that
comprise the system are chemically similar

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 Mathematical expression reflecting the two
assumptions above is expressed quantitatively in
Raoult’s law as:

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

where
xi is the mole fraction of liquid phase
yi is the mole fraction of vapor phase
Pisat is the vapor pressure of pure species i at the temperature of
the system

(10.1)

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 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

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Application of Raoult’s law:
Because iyi = 1, eq. (10.1) may be summed over all species to yield
P   xi Pi sat
i (10.2)
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.

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28
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 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)

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

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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. 32
 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.
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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

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(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)
P1 = 91.76 kPa
sat P2 = 46.84 kPa
sat x1 = 0.5156
Calculate y1 by equation (10.1),

x1 P1 sat  0.5156  91.76 

y1    0.6759
P 70
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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
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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 P2 sat
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.
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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, P1sat = 87.17 kPa and by
eq (10.1), y1 = 0.7472

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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 P2 sat
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.
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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

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 41

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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PREPARED BY:
DR LIM YING PEI
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
yingpei@salam.uitm.edu.my
03-55448018

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