VAPOR LIQUID

EQUILIBRIUM
THE NATURE OF EQUILIBRIUM
THE PHASE RULE: DUHEMS THEOREM
VLE: QUALITATIVE BEHAVIOR
SIMPLE MODELS FOR VAPOR LIQUID EQUILIBRUM: RAOULTS
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.
mi m&i ni n&i
xi 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 n
rate,
n&i
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; DUHEMS
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
Duhems 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 5
 Phase Rule for Intensive Variables
For a 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
 The Phase Rule & Duhems
Theorem
Duhems theorem
It is another rule, similar to the phase rule, but less celebrated. It
applies to closed systems at equilibrium for which the extensive
state as well as intensive state of the system is fixed. The state of
such a system is said to be completely determined, and is
characterized not only by the 2 + (N-1) intensive phase-rule
variables but also by the extensive variables represented by the
masses (or mole numbers) of the phases.
 The Phase Rule & Duhems
Theorem
Thus the total number of variables is:
2 + (N-1) + = 2 + N
For a closed system formed from specified
amount of the chemical species present, a
material-balance equation can be written for
each of the N chemical species.
 The Phase Rule & Duhems
Theorem
These in addition to the (N-1) phase-
equilibrium equations represent a number of
independent equations equal to:
(-1) N + N = N
The difference between the number of
variables and the number of equations is
therefore:
2 + N - N = 2
 The Phase Rule & Duhems Theorem

On the basis of this result, Duhems 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
800
all VLE
intensive
for Purevariables.
Components

600
Pressure: kPa

400

200

0
270 320 370 420
Temperature: K
Acetonitrile Nitromethane
CHEE 311
Correlation of Vapour Pressure
Data
P , or the vapour pressure of component i, is commonly represented
sat
i
by Antoine Equation (Appendix B, Table B.2, SVNA 7 th ed.):

B
ln Pisat A
TC

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.

22
 SIMPLE MODELS FOR
VAPOR/LIQUID EQUILIBRIUM
VLE calculation provides information on temperatures,
pressures, and compositions of phases in equilibrium.
Two simplest models, Raoults law and Henrys law
are used to predict the behavior of systems in vapor
liquid equilibrium.

Raoults 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
Raoults
yiP = law
xiPisatas:
(i = 1,2, ..., N) (10.1)

where xi = mole fraction of liquid phase

yi = mole fraction of vapor phase 23
 Dewpoint and Bubblepoint
Calculations with Raoults
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

24
Application of Raoults 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, 1this yields
P
y i Pi sat
(10.3)
i

This equation applied in dewpoint calculations, where the

liquid phase compositions are unknown.
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26
27
28
 Antoines 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)

29
 Example 10.1
Binary system acetonitrile(1)/nitromethane(2) conforms
closely to Raoults 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

30
Solution:
(a) Prepare P-x1-y1 diagram ( T is given (348.15K), x1 and y1
in the range 01)
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

sat
(10.1):
x1 P1
y1 0.7483
P

*At 75oC (384.15 K) a liquid mixture of 60 mole %

acetonitrile and 40 mole % nitromethane is in 31
Similar calculation of P and y1 at various x1 (01).
The results of calculations:

x1 y1 P
0 0 41.98
0.1 0.1805 46.10 P1sat=83.21
0.2 0.3313 50.23
Subcooled liquid
0.3 0.4593 54.35
Bubble point
0.4 0.5692 58.47
0.5 0.6647 62.60
0.748
Dew point
0.6 3 66.72
0.7 0.8222 70.84
0.8 0.8880 74.96 Superheated vapor
P2sat=41.98
0.9 0.9469 79.09
1 1 83.21

At 75oC and x1 = 0.45,

P = ?, y1 = ? BUBL P
At 75oC and y1 = 0.6,
Either can be read from the graph or calculate
P = ?, x1 = ? DEW P
32
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

33
(b) Prepare T-x1-y1 diagram ( P is given (70 kPa), x1 and y1 in
the range 01)
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 x 1 by
equation: P P2 sat
x1 sat From eqn. (10.2)
P1 P2 sat

For example take T = 78oC (351.15K),

P1sat = 91.76 kPa P2sat = 46.84 kPa x1 = 0.5156
Calculate y1 by equation (10.1),
x1 P1 sat 0.5156 91.76
y1 0.6759
P 70
34
Similar calculation of x1 and y1 for T1sat < T < T2sat.
The results of calculations:
x1 y1 T (K)
1.0000 1.0000 342.99
0.8596 0.9247 345.15
0.7378 0.8484 347.15 T2sat=362.73K
Superheated vapor
0.6233 0.7656 349.15
0.5156 0.6759 351.15
0.4142 0.5789 353.15
Dew point
0.3184 0.4742 355.15
0.2280 0.3614 357.15
0.1424 0.2401 359.15
0.0613 0.1098 361.15
Bubble point
0.0000 0.0000 362.73
Subcooled liquid
T1sat=342.99K

At x11 = 0.6 and P = 70 kPa,

T = ?, y1 = ? BUBL T
At y11 = 0.6 and P = 70 kPa,
T = ?, x1 = ? DEW T
35
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:
Use Antoine eqn.
T = x1T1sat + x2T2sat
or select T1sat < T < T2sat as initial T.
2. Calculate P1sat and P2satsat at initial T.
3. Calculate . P1 P2 sat

4. With the P value of , calculate P2sat .

sat current
P2 From eqn. (10.2)
xx
1 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).

Use T
(a) subtract ln P2sat from ln P1sat as given by Antoine equations.
2945.47 2972.64 from
ln 0.0681
T 49.15 T 64.15 step 5
or
(b) calculate P1sat and P2sat at T, then find new value of . 36
Initial T = 350.89 K
P1sat = 90.99 kPa, P2sat = 46.40 kPa
P2sat T
Calculate new 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
P1sat P2sat P2sat T
Calculate new 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 (76.42 oC). From Antoine equation, P1sat =

87.17 kPa and by eq (10.1), y1 = 0.7472

37
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:
Use Antoine eqn.
T = y1T1sat + y2T2sat
or select T1sat < T < T2sat as initial T.
2. Calculate P1sat and P2sat at initial T.
3. Calculate . P1 sat P2 sat

4. With the current value of , calculate P1sat .

P1 = P y 1 +y 2
sat

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 Use T
2945.47 2972.64 from
ln 0.0681
equations.
T 49.15 T 64.15 step 5

or 38
Initial T = 350.89 K
P1sat = 90.99 kPa, P2sat = 46.40 kPa
Calculate new P1sat
by using Iteration (kPa) T (K)
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 Iteratio P1sat P2sat P1sat T

n (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

39
 40

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

40
PREPARED BY:
MDM. LIM YING PEI
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
yingpei@salam.uitm.edu.my
03-55448018