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Vle Part 1 PDF
Vle Part 1 PDF
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.
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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
xi n ni
V n q
5
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.
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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.
9
Fig. 10.4 shows the enlarged nose section of a single P-T loop.
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12
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14
15
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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:
yiP = xiPisat
(10.1)
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(i = 1,2, ..., N)
(10.2)
Pi sat
(10.3)
20
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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:
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
ln P2 sat
21
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):
sat
0.7483
x1
y1
41.98
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
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)
Bi
Ci
Ai ln P
1
59.74kPa
0.6 83.21 0.4 41.98
Select T1sat < T < T2sat to calculate P1sat and P2sat for these temperature by
using Antoine equation, and evaluate x1 by equation:
y P 0.6 59.74
x1 1sat
0.4308
P1
83.21
x1
P P2 sat
P1 sat P2 sat
x1 = 0.5156
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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
365
T2sat=362.73K
Superheated vapor
360
P
x1 x2
Bubble point
345
Subcooled liquid
P2 sat
Dew point
355
T/K
x1
0.8596
26
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 .
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
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.
2945.47
49.15
14.2724 ln P1 sat
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