CHE553 Chemical Engineering Thermodynamics

2/29/2016

OVERVIEW
Vapor liquid equilibrium 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.

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.

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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.
n n
m m
xi i i
xi i i
n n
m m
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.
Ci

The molar mass of a mixture or solution is the mole fractionweighted sum of the molar masses of all species.
M xi M i
i

xi
V

or multiplying and dividing by molar flow rate, n

Ci

xi n ni

V n q
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THE PHASE RULE; DUHEMS THEOREM

VLE: QUALITATIVE BEHAVIOR

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 extensive.
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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.

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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.
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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.
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Fig. 10.4 shows the enlarged nose section of a single P-T loop.

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13

Figure 10.8 shows

P-x-y diagrams at
constant T for four
systems (much
lower temperature
and pressure).

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Figure 10.9 shows

t-x-y behavior for
four systems at low
pressure 1 atm).

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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, Raoults law and Henrys law are used to predict the
behavior of systems in vapor liquid equilibrium.

Raoults 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 Raoults law as:

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)).

yiP = xiPisat

(10.1)

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Dewpoint and Bubblepoint Calculations with

Raoults Law

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Application of Raoults law:

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

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
DEW P
BUBL T
DEW T

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

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

(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

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

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

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
P

Pi sat

(10.3)

This equation applied in dewpoint calculations, where the liquid phase

compositions are unknown.
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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:

Antoines equation is used to calculate Pisat :

ln Pi sat kPa Ai

Bi
T K Ci

2945.47
T 49.15
2972.64
14.2043
T 64.15

ln P1 sat 14.2724

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

ln P2 sat

(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

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Solution:
(a) Prepare P-x1-y1 diagram ( T is given 75oC (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
and
P2sat = 41.98 kPa
Calculate P from equation (10.2):

Similar calculation of P and y1 at various x1 (01).

The results of calculations:

P P2 sat P1sat P2sat x1

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

Calculate y1 from equation (10.1):
xP
y1 1 1
P

sat

0.7483

*At 75oC (348.15 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.

x1

y1

41.98

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

100

0.1

0.1805

46.10

0.2

0.3313

50.23

90

0.3

0.4593

54.35

80

0.4

0.5692

58.47

70

0.5

0.6647

62.60

0.6

0.7483

66.72

0.7

0.8222

70.84

P1sat=83.21
Subcooled liquid

P/kPa

22

Bubble point

60

Dew point

50

0.8

0.8880

74.96

40

0.9

0.9469

79.09

30

83.21

20
0

23

At 75oC and x1 = 0.45,

P = ?, y1 = ? BUBL P
At 75oC and y1 = 0.6,
P = ?, x1 = ? DEW P

Superheated vapor

P2sat=41.98
0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

x1, y1
x1

y1

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(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

DEW P calculation
Calculate P from equation (10.3)
P

Ti sat

1
y1 P1 sat y2 P2

sat

For P = 70kPa,
T1sat = 342.99 K (69.84oC)

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

P

Bi
Ci
Ai ln P

1
59.74kPa
0.6 83.21 0.4 41.98

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:

Calculate x1 by equation (10.1),

y P 0.6 59.74
x1 1sat
0.4308
P1
83.21

x1

P P2 sat
P1 sat P2 sat

From eqn. (10.2)

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

P1sat = 91.76 kPa
P2sat = 46.84 kPa

x1 = 0.5156

Calculate y1 by equation (10.1),

y1

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y1

T (K)

1.0000

342.99

0.9247

345.15

0.7378

0.8484

347.15

0.6233

0.7656

349.15

0.5156

0.6759

351.15

0.4142

0.5789

353.15

0.3184

0.4742

355.15

0.2280

0.3614

357.15

0.1424

0.2401

359.15

0.0613

0.1098

361.15

0.0000

0.0000

362.73

T-xy diagram for acetonitrile(1)/nitromethane(2) at 70 kPa

365

T2sat=362.73K
Superheated vapor

360

P
x1 x2

From eqn. (10.2)

5. Calculate T from Antoine equation for species 2:

350

Bubble point
345

Subcooled liquid

At x1 = 0.6 and P = 70 kPa,

T = ?, y1 = ? BUBL T
At y1 = 0.6 and P = 70 kPa,
T = ?, x1 = ? DEW T

P2 sat

Dew point

355
T/K

x1
0.8596

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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
Use Antoine eqn.
or select T1sat < T < T2sat as initial T.
2. Calculate P1sat and P2sat at initial T.
3. Calculate .
P1sat P2sat
4. With the current value of , calculate P2sat .

Similar calculation of x1 and y1 for T1sat < T < T2sat.

The results of calculations:
1.0000

x1 P1 sat 0.5156 91.76

0.6759
P
70

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

y1

x1

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2972.64
64.15
14.2043 ln P2 sat

6. If TT(previous iteration), find a new value of (step 3).

(a) subtract ln P2sat from ln P1sat as given by Antoine equations.
2945.47 2972.64
ln 0.0681

T 49.15 T 64.15
or
(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.

Use T
from
step 5
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REFERENCE

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
Use Antoine eqn.
or select T1sat < T < T2sat as initial T.
2. Calculate P1sat and P2sat at initial T.
3. Calculate .
P1sat P2sat
4. With the current value of , calculate P1sat .
P1 sat = P y 1 +y 2

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

From eqn. (10.3)

5. Calculate T from Antoine equation for species 1:

T

2945.47
49.15
14.2724 ln P1 sat

6. If TT(previous iteration), find a new value of (step 3).

(a) subtract ln P2sat from ln P1sat as given by Antoine equations.
2945.47 2972.64
ln 0.0681

T 49.15 T 64.15
or
(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.

Use T
from
step 5
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PREPARED BY:
NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303