Phase diagrams
Phase behavior of a pure component
H2O 2
Phase behavior of a pure component
3
Phase behavior of a pure component
Critical isotherm
T = 304.19 K
4
p-T diagram of a pure
component [1, 2]
For water like substances if we increase
pressure, the solid melts to liquid. So, for
water, ice melts to liquid water and is
helpful for skating.
5
Phase behavior of a mixture of
components
For mixture of
components
6
pv diagram of mixture of components
7
p-T diagram of a mixture
of components
Cricondenbar
Cricondentherm
8
T-x-y diagram of a near ideal binary mixture
9
p-x-y diagram of a near ideal binary mixture
10
T-x, p-x, and x-y diagrams of various types
11
p-x-y diagrams of various binary mixtures
RT
dGig = VigdP (constant T) V
ig
dGig = RT dlnP
G R T ln P T
i
ig
i
(11.27)
G R T ln f T
i i i
(11.30)
f
G G R T ln ig i (11.31)
i i
P
G R T ln
i
R
f
i (11.32)
P
i
f i P , GiR 0 and 1 i
The fugacity coefficient is a measure of non-ideality.
f=P
Three possible sources to find the fugacity
- Equation of state
- Generalized correlations
Problem:
Determine the fugacity and the fugacity coefficient for saturated steam at 1 atm.
Fugacity coefficient of a pure gas and mixture using EOS
Fugacity coefficient of a pure gas and mixture using EOS
Fugacity coefficient of a gas mixture using EOS
Evaluation of f and i through cubic equations of state (e.g.
vdw, RK, SRK, or PR eqns.)
G R
Z 1 ln Z q I (6.36b)
RT
Then ln Z 1 ln Z
i i
q I i i
(11.36)
P T
where r
q r
T r
T r
1
Z
I ln (for )
Z
I (For = , vdw eqn.only)
Z
For vapor phase
Z
Z 1 q
Z Z
Lee/Kesler
ln ln ln 0 1
(11.63)
( ) ( ) 0 1
(11.64)
T r
or
P
exp B B r 0 1
T r
0.422 0.172
B 0.083
0
and B 1 0.139
T r 1 .6 T r 4 .2
Vapor/liquid equilibrium for pure species
The fugacity of pure species i, as a saturated vapor, may be written as:
G iv R T ln f i v i T (11.37a)
G il R T ln f i l i T (11.37b)
By difference,
f iv
G i G i R T ln l
v l
fi
i
l
therefore:
f f f
i
v
i
l
i
sat
(11.38)
Where f i s at indicates the value for either saturated vapor or saturated liquid.
Since coexisting phases of saturated liquid and saturated vapor are in equilibrium
For a pure species coexisting liquid and vapor phases are in equilibrium
f sat
sat i
(11.39)
i
P i
sat
whence
i
v
i
l
i
sat
(11.40)
V i l P Pi s at
f i i Pi
s at s at
exp
RT
The exponential is known as a Poynting factor.
Example
2 ,142.66
ln P kPa 13.7578
sat
T K 34.3
bar is LIQUID
V l
P P sat
V Z 89.376 cm mol
1 Tr 0.2 8 5 7
V sat
c c
3 1
V P P
l sat
89.376 10 10 4.32 10
6 5
exp i i
exp 1.02
RT 8.314 313
P sat
exp r
B B
0 1
T r
0.422 0.172
B 0.083
0
0.606 and B 0.139
1
0.484
T 1 .6
r
Tr
4 .2
0.101
sat
exp 0.606 0.19 0.484 0.9086
0.736
i
V P P l sat
f P exp sat sat i i
0.9086 ( 4.32 ) (1.02 ) 4.002 bar
i
RT i i
Example
Calculate the fugacity and GR of 1,3-butadiene at 313 K and
10 bar using RK EOS and compare with correlation.
2 ,142.66
ln P kPa 13.7578
sat
T K 34.3
Fugacity and Fugacity Coefficient of a Mixture
From virial EOS
Written for a gas mixture it is exactly the same as for a pure species
BP
Z 1
RT
For gases at low or moderate pressure
B y y B
i j i j ij
B11 y22 12
P
For binary ln 1 11.63a
RT
B22 y12 12
P 11.63b
ln 2
RT
Equations (11.63) are readily extended for application to multicomponent
gas mixture; the general equation is:
P 1
y y 2
ln k
B
kk
i j ik ij
RT 2 i j
Where the dummy indices i and j run over all species, and
2B B B
ik ik ii kk
2B B B
ij ij ii jj
with 0
ii
, 0
kk
. etc., and
ki ik
, etc.
Example
Determine the fugacity coefficients as given (11.63a) and (11.63b) for
nitrogen and methane in a N2(1)/CH4(2) mixture at 200K and 30 bar if
the mixture contains 40 mol-%N2. experimental virial-coefficient data
are as follows: B11 = -35.2 B22 = -105.0 B12 = -59.8 cm3 mol-1
By definition,
Whence, 1
= 0.9511 and 2
= 0.8324
Note that the second virial coefficient of the mixture as given by eqn.
Z ci Z cj
Z cij
2
3
1 1
V V 3 3
ci cj
Vcij
2
ln 2
P
RT
B22 y12 12
25
(8,314) (323.15)
2
1,860 0.5 25 0.0172
Whence, 1
= 0.987 and 2
= 0.983
Problem: Nitrogen gas is pressurized from 1 atm to 60 atm at constant temperature
100 oC. The fugacity of nitrogen can be determined by using equation as follows:
P
ln Z 1
dP
0
P
Calculate fugacity coefficient and fugacity of nitrogen from 1 atm to 60 atm by using
above equation. Also, plot fugacities obtained as function of pressure.
P (atm) Z Z-1
0 1 0
14 0.95 -0.05
22 0.92 -0.08
30 0.89 -0.11
44 0.84 -0.16
58 0.79 -0.21
68 0.76 -0.24
A directly proportional relation can be used as a reasonable approximation where
R2 = 0.9993. The linear relation is,
Z-1 = -0.0036 P
From given equation
P P
ln 0.0036P
dP
0.0036 dP 0.0036P
0
P 0
exp( 0.0036P)
P (atm) f (atm)
1 0.9964 0.9964
10 0.9646 9.6464
20 0.9305 18.610
30 0.8976 26.928
40 0.8658 34.635
50 0.8352 41.763
60 0.8057 48.344
Problem:
Determine the fugacity and fugacity coefficients for nitrogen and methane in a
N2(1)/CH4(2) mixture at 200K and 30 bar if the mixture contains 40 mol-%N2.
12
Vapor Liquid Equilibrium (VLE)
Problem:
Problem:
Problem:
A binary vapor mixture contains 48% ethanol in water at 70 oC. Determine the
pressure at which this vapor develops the first drop of liquid. What is the liquid
composition? The marguels parameters are as follows:
A = 3590 J/mol and B = -1180 J/mol
Margules Equation
= +
= +
1 = 0.4741
2 =
0.9746
Wilson Equation
GE
x1 ln( x1 x 2 12 ) x 2 ln( x 2 x1 21 ) (10.64)
RT
V2 12 11 V2 a12
12 exp( ) exp( )
V1 RT V1 RT
V1 12 22 V1 a21
21 exp( ) exp( )
V2 RT V2 RT
Wilson Equation
12 21
ln 1 ln( x1 12 x 2 ) x 2 ( )
x1 12 x 2 x 2 21 x1
12 21
ln 2 ln( x 2 21 x1 ) x1 ( )
x1 12 x 2 x 2 21 x1
NRTL (Non-Random Two-Liquid Equation)
GE 21 G21 12 G12
x1 x 2 ( )
RT x1 x 2 G21 x 2 x1 G12
G21 12 G12
ln 1 x 2 ( 21 (
2
)
2
)
x1 x 2 G21 ( x 2 x1 G12 ) 2
G12 21 G21
ln 2 x1 (12 (
2
)
2
)
x 2 x1 G12 ( x1 x 2 G21 ) 2
Example
V2 a12 V1 a21
12 exp( ) 0.147 21 exp( ) 0.403
V1 RT V2 RT
12 21
ln 1 ln( x1 12 x 2 ) x 2 ( )
x1 12 x 2 x 2 21 x1
ln 1 0.8208 1 2.27
12 21
ln 2 ln( x 2 21 x1 ) x1 ( )
x1 12 x 2 x 2 21 x1
ln 2 0.223 2 1.25
NRTL Equation
b12 b21
12 1.06 21 1.87
RT RT
G21 12 G12
ln 1 x 2 ( 21 (
2
)
2
)
x1 x 2 G21 ( x 2 x1 G12 ) 2
ln 1 0.772 1 2.164
NRTL Equation
G12 21 G21
ln 2 x1 (12 (
2
)
2
)
x 2 x1 G12 ( x1 x 2 G21 ) 2
ln 2 0.234 2 1.263