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CHAPTER 1: VAPOR
LIQUID EQUILIBRIUM
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
𝑀 ≡ 𝑥𝑖 𝑀𝑖
𝑖
4
5
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
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:
■ 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).
ANTOINE’S EQUATION:
CORRELATION OF VAPOR PRESSURE DATA
Bi
ln Pi sat
( kPa ) = Ai −
T ( K ) + Ci
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
x1 P1sat
y1 =
P
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
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
P-xy digram
DEW P calculation
y1 P
x1 =
P1sat
Describe the state
of points a, b, b’, c,
c’ & d
23
P-xy digram
BUBL P calculation
P-xy digram
DEW P calculation
24
T-xy digram 25
T/K
0.2280 0.3614 357.15
0.1424 0.2401 359.15 350
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
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
T (K ) =
B2
− C2
A2 − ln P2 (kPa )
sat
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
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
α P1 sat P2 sat
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.