Ocw Chapter 10
Ocw Chapter 10
Ocw Chapter 10
Vapor/Liquid
Equilibrium:
fi = i y i P
For
vapor
mixture
l = x f
f
For liquid solution!
i
i i i
VLE criteria (to be shown/derived in chapter 11),
f l = f v
i
i yi P = i xi f i
so
where,
i fugacity coefficient species i in gas mixture
Raoults
Law
For
ideal
gas
vapor
mixture
in
equilibrium
with
ideal
liquid
solu6on
equation becomes
yi P = xi f i
i = 1
i =1
and also for pure species in equlibrium and ideal gas vapor,
f i = f i l = f i v = P = Pi sat
we get,
yi P = xi Pi sat
Raoult's Law
(10.1)
i yi P = i xi f i
yi P = i xi Pi sat
(10.5)
K-value (Ki)
yi
Ki =
xi
(10.10)
yi P = xi Pi sat
Pi sat
Ki =
P
If Modified Raoults Law is valid,
(10.11)
yi P = xi i Pi sat
i Pi sat
Ki =
P
(10.12)
K-value
Using
DePriester
Chart
For light hydrocarbon mixture (commonly found in industry),
Ki is essentially function of T and P only.
Ki are tabulated in a chart called the DePriester chart.
Deriva6on
Overall mole balance
T = L +V
Component mole balance,
Tzi = Lxi + Vyi
(A)
zi
1 + V (K i 1)
yi
Substitute xi =
into (A),
Ki
yi
zi = (1 V )
+ yiV
Ki
zi K i
yi =
1 + V (K i 1)
zi K i = (1 V ) yi + yiVK i
(10.16)
Also,
xi yi = 0
zi
zi K i
1+ V (K 1) 1+ V (K 1) = 0
i
i
zi zi K i
1+ V (K 1) = 0
i
Bubblepoint
Calcula6on
At bubble point (practically all liquid) L=1, V=0 and z i = xi
zi zi K i
1+ V (K 1) = 0 becomes,
i
(xi xi K i ) = 0
xi = xi K i
xi K i
=1
(10.13)
Bubblepoint criteria
so,
P = xi Pi sat
(10.2)
i Pi sat
xi K i = xi P = 1
see example 10.3
so,
P = xi i Pi sat
(10.6)
Dewpoint
Calcula6on
At dewpoint (practically all vapor): L=0, V=1 and z i = yi
zi zi K i
1+ V (K 1) = 0
i
becomes,
yi yi K i
K =0
i
yi
K yi = 0
i
yi
=1
(10.14)
Dewpoint criteria
P=
1
yi
(10.3),
Pi sat
1
yi
i Pi sat
(10.7),
Relative Volatility!
ik =
yi
yk
xi
xk
Ki
=
Kk
1
at azeotrope ik = = 1
1
ik>1
ik<1
12 =
P1sat
P2sat
P1sat
sat
2
12 =
1 P1sat
2 P2sat
P
P
1 P1sat
2 P2sat
Example 10.1
o
Plot
Px1y1
at
T=75 C
Mixture: Acetonitrile(1)/Nitromethane(2)
Antoine Eqn,
2945.47
ln P / kPa = 14.2724
T / oC + 224.00
2972.64
sat
ln P2 / kPa = 14.2043
T / oC + 209.00
calculate at 75oC,
sat
1
P1sat = 83.21kPa
P2sat = 41.98kPa
xi K i
= 1 (10.13) .
(10.2)
Eqn A
x1 P1sat
also, y1 =
P
Eqn B
So,
Calculate P for a set of x1 (Eqn A) and then calculate y1 (Eqn B)
Calculate
Given or Set
T (oC)!
x1!
P=Pb(kPa)! y1!
75!
0!
sat
P
41.98! 2
0!
75!
0.2!
50.23!
0.3313!
75!
0.4!
58.47!
0.5692!
75!
0.6!
66.72!
0.7483!
75!
0.8!
74.96!
0.8880!
1!
sat
P
83.21! 1
1!
75!
x1 P1sat
y1 =
P
Point b
(i.e. what is the dew P for gas mixture at 75oC and 60% acetonitrile)
yi
K =1 (10.14),
i
Pd =
1
0.6
0.4
+
83.21 41.98
x1 =
(10.3)
Pi sat
= 59.74kPa
1
yi
y1 Pd
P1sat
0.6(59.74)
=
= 0.43
83.21
2945.47
T / C=
224.00
14.2724 ln P / kPa
2972.64
sat o
T2 / C =
209.00
14.2043 ln P / kPa
sat
1
so at 70kPa,
T1sat = 69.84o C
T2sat = 89.58o C
xi K i
= 1 (10.13)
sat
(10.2)
P P2sat
P P
sat
1
sat
2
Eqn C
sat
1 1
xP
y1 =
P
x1 =
P P2sat
x1 P1sat
y1 =
P
P1sat P2sat
P (kPa)!
T=Tb(oC)! x1!
70!
sat
T
69.84! 1 1 (x2=0)! 1 (y2=0)!
70!
74!
0.7378!
0.8484!
70!
78!
0.5156!
0.6759!
70!
82!
0.3184!
0.4742!
70!
86!
0.1424!
0.2401!
70!
sat
T
89.58! 2 0 (x2=1)! 0 (y2=1)!
y1!
xi K i
= 1 (10.13),
sat
Pksat
Pi sat
Pk
Pk
sat
sat
x
P
=
P
x
k i
sat i i
(10.2)
sat
=
P
x
k i ik
sat
Pb = Pksat xi ik
where ik =
Pb
P =
xi ik
sat
k
Pi
sat
sat
k
(A)
Also,
ln ik = ln
Pi sat
Pksat
Bi
=lnPi -lnP = Ai
T + Ci
sat
sat
k
Bk
- Ak + T + C
k
T = xiTi sat
Bi
Bk
ln ik = Ai
- Ak +
T
+
C
T
+
C
i
k
we get,
12 = 1.9611
22 = 1
P
P =
xi ik
sat
k
P
70
P =
=
=44.3977kPa
x112 + x2 22
0.6(1.9611)+0.4(1)
sat
2
T=
Bk
Ak ln P
sat
k
Ck
2972.64
T=
209 = 76.53o C
14.2043 ln 44.3977
T!
77.74!
76.53!
76.43!
12!
1.9611!
1.9703!
1.9717!
P2sat!
44.39!
44.24!
44.22!
T!
76.53!
76.43!
76.42!
Answer
(point b)
DEW
T
calcula6on
Calculate Td and x1, given y1 and P.
Example: Calculate Td and x1 for z1= y1 =0.6 and P=70kPa.
See page 356 for the solution (also by iteration) of DEW T
calculation.
Answer:
Td =79.58oC
x1=0.4351
Example
10.4
Calcula6on
of
dew
pressure
and
bubble
pressure
using
K-value
from
DePriester
chart.
Note:
Why
the
solu6on
is
by
trial
and
error?
Flash Calculation!
Flash
Calcula6on
An
important
applica6on
of
VLE!
Liquid at pressure equal or higher than Pb!
flashes or partially evaporates when the P is!
reduced, thus producing a vapor and liquid.!
Flash calculation is to determine !
V , L, {xi}, and {yi} at !
T and P by assuming VLE.!
{xi}, L!
{yi},V!
yi = 1,
(10.16)
so:
zi K i
1 + V (K 1) = 1
i
(10.17)
Examples
of
Flash
Calcula6on
Example
10.5:
Flash
calcula6on
for
system
where
Raoults
Law
valid
Example 10.6:!
Flash calculation using K-value from!
DePriester Chart!
y2 P = x2 P2sat
The dew is 100% H2O, so x2=1!
so
P2sat = y2 P
Example
Dewpoint
T
of
Combus6on
Products
For
stoichiometric
combus6on
of
methane,
calculate
dew
point
T
of
the
combus6on
products.
CH4
+
2O2
+
2(79/21)N2
------>
CO2
+2H2O
+
2(79/21)N2
Mole
frac6on
of
H2O
is
2/(1+2+2(79/21))
=
0.19
P2sat = y2 P
P2sat =0.19(101.325kPa)=19.25kPa
Henrys Law!
i yi P = i xi f i
yi P = xi i f i = xi i P sat
i
let H i = i f i = i Pi sat
i is Henrys constant (in bar) for dissolved gas (i).!
so
!
yiP = xii
!
!Henrys
!!
Law!
yiP = xii
So at dilute solution,
yi = (i/P) xi
For constant system pressure P,
yi = (Constant)xi
If we plot yi vs xi , we get a straight line
through the origin.
So Henrys constant for dissolved gas (i) can
be easily determined from experiment.
y1 P (1 / (1 + 2 + 7.52))(1.013bar)
x1 =
=
=3.4622x10-5 0
1
1670bar
As expected, only small amount of CO2 present !
in liquid water.!
See also example 10.2!
fi = i xi f i = xi i
If
the
gas
is
ideal
solu6on
(Lewis/Randall
is
valid),
fi id = i yi P
i yi P = xi i
x1
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
G1 is gamma1
G1
3.03
2.72
2.45
2.23
2.03
1.86
1.72
1.60
1.49
1.40
1.32
1.25
1.19
1.15
1.10
1.07
1.05
1.03
1.01
1.00
1.00
G2
1.00
1.00
1.01
1.03
1.05
1.07
1.10
1.15
1.19
1.25
1.32
1.40
1.49
1.60
1.72
1.86
2.03
2.23
2.45
2.72
3.03
P
65.64
68.57
70.64
72.06
72.97
73.50
73.73
73.73
73.54
73.17
72.63
71.92
70.99
69.81
68.29
66.36
63.88
60.70
56.60
51.31
44.51
y1
0.00
0.09
0.15
0.21
0.25
0.28
0.31
0.34
0.36
0.38
0.40
0.43
0.45
0.47
0.50
0.54
0.58
0.64
0.72
0.83
1.00
T=318.15
Series1
Series2
80.00
75.00
70.00
KPa
65.00
60.00
55.00
50.00
45.00
40.00
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
x1, Y1
T=318.15
Series1
Series2
80.00
75.00
70.00
KPa
65.00
60.00
55.00
50.00
45.00
40.00
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
x1, Y1
T=318.15
Series1
Series2
80.00
75.00
70.00
KPa
65.00
60.00
55.00
50.00
45.00
40.00
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
x1, Y1
T=318.15
1.00
0.90
0.80
0.70
y1
0.60
0.50
Series1
12<1
0.40
12>1
0.30
0.20
0.10
0.00
0
0.2
0.4
0.6
0.8
x1
Pd<P<Pb
T=318.15
Series1
Series2
80.00
75.00
70.00
KPa
65.00
60.00
55.00
50.00
45.00
40.00
0
0.1
0.2
0.3
0.4
0.5
x1, Y1
0.6
0.7
0.8
0.9
(a)
P=68.29
x1 = 0.8
P=63.88
x1 = 0.75
P=66.36
x1 = 0.76
P=65.91......good enough
(10.17)
0.431
0.754
+
=1
1 0.281V 1 + 0.885V
Guess,
V=0.50
V=0.55
V=0.70
V=0.75
V=0.73
1.024
1.017
1.002
0.999
1.000
So V=0.73
=1
L=1-V=0.27
zi K i
yi =
1 + V (K i 1)
y1 = ..........
y2 = ..........
yi
xi =
Ki
x1 = .........
x2 = .........
(10.16)