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SEM 1 (2012/2013)
VAPOR LIQUID
EQUILIBRUIM
Dr. Hayder Kh. Q. Ali
hayderali@unimap.edu.my
1
pressures,
and
that
allow
phase compositions
calculation
for
systems
of
in
Phase equilibrium
Application
Distillation, absorption, and extraction bring
phases of different composition into contact.
Duhems rule:
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.
Two ? When phase rule F = 1, at least one of the two
variables must be extensive, and when F = 0, both must
6
be extensive.
10
11
12
13
14
15
16
Fig 10.8
17
Fig 10.9
18
Raoults law:
the vapor phase is an ideal gas (apply for low to
moderate pressure)
the liquid phase is an ideal solution (apply when
the species that are chemically similar)
yi P xi Pi sat
(i 1, 2, ..., N )
where xi is a liquid-phase mole fraction, yi is a vaporphase mole fraction, and Pi sat is the vapor pressure
of pure species i at the temperature of the system. The
product yi P on the left side of Eq. is known as the partial
pressure of species i
19
20
yi P xi Pi
sat
(i 1, 2, ..., N )
P xi Pi sat
(i 1, 2, ..., N )
1
yi / Pi sat
(i 1, 2, ..., N )
Binary system
22
23
ln P
2945.47
2972.64
sat
/ kPa 14.2724
ln P2 / kPa 14.2043
t / C 224.00
t / C 209.00
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.
(a) BUBL P
e.g. x1 = 0.6
P 66.72
x1 P1sat (0.6)(83.21)
y1
0.7483
P
66.72
At 75C, a liquid mixture of 60 mol-% (1) and 40 mol-% (2) is in equilibrium with a vapor
containing 74.83 mol-% (1) at pressure of 66.72 kPa.
Fig. 10.11
24
25
Fig. 10.11
Select t
P1sat
P2sat
2945.47
2972.64
sat
ln
P
/
kPa
14
.
2043
2
t / C 224.00
t / C 209.00
P P2sat
x1 sat
P1 P2sat
t vs. x1
y1
26
sat
1 1
xP
P
t vs. y1
Fig. 10.12
(i 1, 2, 3, ...N )
1
P
yi / i Pi sat
i
27
28
For the system methanol (1)/methyl acetate (2), the following equations provide a reasonable
correlation for the activity coefficients:
3643.31
T ( K ) 33.424
2665.54
T ( K ) 53.424
Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25
(b): P and {xi} for T = 318.15 K and y1 = 0.60
(c): T and {yi} for P = 101.33 kPa and x1 = 0.85
(d): T and {xi} for P = 101.33 kPa and y1 = 0.40
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
(a) for T = 318.15, and x1 = 0.25
P1sat 44.51 P2sat 65.64 1 1.864 2 1.072
yi P xi i Pi sat
y1 0.282 y2 0.718
29
1
P
yi / i Pi sat
1 1 2 1
x1
Converges at: P 62.89 kPa 1 1.0378
y1 P
1 P1sat
x2 1 x1
2 2.0935 x1 0.8169
3643.31
T ( K ) 33.424
1 ... 2 ...
P xi i Pi sat
i
P1sat ...
Converges at:
T 331.20 K
1 1.0236 2 2.1182
y1 30
0.670
y2 0.330
1 1 2 1
ln Pi sat / kPa Ai
3643.31
T ( K ) 33.424
P1sat ...
Bi
T ( K ) Ci
P2sat ...
P xi i Pi sat
i
x1 ...
x2 ...
1 ... 2 ...
P1sat ...
Converges at:
T 326.70 K
1 1.3629 2 1.2523
P2sat ...
x1 31
0.4602 x2 0.5398
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
y1
Define the relative volatility:
Azeotrope
12
x1 0
12
y2
y1 x1 y2 x2
yi P xi i Pi sat
x1
x2
1 P1sat
12
2 P2sat
12 1
2.052 12
sat
P2
P1sat
0.224
x1 1
sat
P2 exp( 2.771 0.00523T )
1 P1sat
12
1
sat
2 P2
1az P2sat
sat 1.4747
az
2
P1
ln
1
(2.771 0.00523T )( x2 x1 ) (2.771 0.00523T )(1 2 x1 )
2
x 0.325 y
az
1
az
1
1az 1.657
32
P az
yi
xi
The Raoults
Pi sat
law:K i P
i Pi sat
Ki
law:
P
34
Fig 10.13
35
Fig 10.14
36
For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at 50F,
determine: (a) the dewpoint pressure, (b) the bubblepoint pressure. The K-values are given by
Fig. 10.13.
(a) at its dewpoint, only an insignificant amount of liquid is present:
Species
Methane
Ethane
Propane
yi
0.10
0.20
0.70
P = 100 (psia)
Ki
yi /Ki
20.0
0.005
3.25
0.062
0.92
0.761
(yi /Ki) = 0.828
P = 150 (psia)
Ki
yi /Ki
13.2
0.008
2.25
0.089
0.65
1.077
(yi /Ki) = 1.174
P = 126 (psia)
Ki
yi /Ki
16.0
0.006
2.65
0.075
0.762
0.919
(yi /Ki) = 1.000
Species
Methane
Ethane
Propane
xi
0.10
0.20
0.70
P = 380 (psia)
Ki
x i Ki
5.60
0.560
1.11
0.222
0.335
0.235
(xi Ki) = 1.017
P = 400 (psia)
Ki
xi Ki
5.25
0.525
1.07
0.214
0.32
0.224
(xi Ki) = 0.963
P = 385 (psia)
Ki
x i Ki
5.49
0.549
1.10
0.220
0.33
0.231
(xi Ki) = 1.000
37
Flash calculations
A liquid at a pressure equal to or greater than its
bubblepoint pressure flashes or partially
evaporates when the pressure is reduced,
producing a two-phase system of vapor and liquid
in equilibrium.
Consider a system containing one mole of
nonreacting chemical species:
L V 1
The moles of vapor
The moles of liquid
zi xi L yiV
zi xi (1 V ) yiV
yi
zi K i
1 V ( K i 1)
zi K i
1 V ( K 1) 1
i
The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80C and 110 kPa has the overall
composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoults law is appropriate to this
system, determine L, V, {xi}, and {yi}. The vapor pressures of the pure species are given.
Do a BUBL P calculation, with {zi} = {xi} :
Pdew
1
101.52 kPa
sat
sat
sat
y1 / P1 y2 / P2 y3 / P3
L 1 V 0.2636 mol
Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,
Pi sat
Ki
P
zi K i
1 V ( K 1) 1
i
yi
x1 0.2859
x2 0.3810
x3 0.3331
Ki
yi
xi
V 0.7364 mol
zi K i
1 V ( K i 1)
y1 0.5087
y2 0.3389
39
y3 0.1524