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Vapor-liquid equilibrium
(VLE)
yA + yB = 1
xA + xB = 1
yA xA
Tliq, Pliq
xA , xB
At equilibrium:
Tvap = Tliq
Pvap = Pliq
22+2=2
e can specify only 2 intensive variables (all others are fixed, by VLE)
Specify P and T
2 graphs in one:
T vs. xA
T vs. yA
superheated vapor
2-phase
region
TA
A subcooled liquid
feed of composition
zA, heated to
temperature TA, will
separate
spontaneously into
2 phases,
Figure 2-3 Temperature-composition diagram
for of
xA and
From Separation Process Engineering, Third Edition by Phillipcomposition
C. Wankat
ethanol-water
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All
reserved.
yrights
A
zA
subcooled liquid
yA
xA
dew point
boiling
range
bubble point
xE,initial
yE,initial
Useful definitions
Boiling/bubble point Tbp: temperature at which the
average liquid molecule has just enough kinetic energy
to escape from the surface of the liquid into the gas
phase
Recall that kinetic energy follows a Boltzmann distribution, so
molecules with higher than average kinetic energy can still
escape from the surface at T < Tbp, by evaporation
rearrange:V zA xA
isotherm
L MV
V
LM
E
VL
e
lin
cr.
n
i
T
K = yE/xE
y=
For a binary
system at
constant P, if
one
composition (xA
or yA) is
VLE:
chosen, all
K = yA/xA
others are
fixed:
mole balance:
xA + xB = 1
yA + yB = 1
volatility = K = K(T,
P, zi)
K(T)
azeotrope: K =
1.0
how can we
break an
azeotrope?
P0
P*
Tbp
K = 1.0
K<1
DePriester Chart
temperature
total
pressure
K>1
T*
(D. B. Dadyburjor, Chem. Eng. Prog.,85, April 1978; copyright 1978, AIChE; reproduced by permission of the American Institute of Chemical
Engineers)
Raoults Law
0
P
x
P
(T )
ideal liquid:
A
A A
non-ideal liquid:
PA A xAPA0 (T )
activity coefficient
Daltons Law
ideal gas:
non-ideal gas:
yA
PA
PTOTAL
yA
PA
APTOTAL
fugacity coefficient
yA
PA0 (T )
PA0 (T )
KA
xA APTOTAL PTOTAL
Trial-and-error method
Given the composition of a subcooled liquid and P TOTAL,
find Tbp and (yi)bp
VLE:
yi K i xi
mole balance:
1.0
Algorithm:
1. Pick a temperature T and find
the corresponding Ki(T) values
for each component
2. Calculate the yi value for each
Ki(T)
3. Check to see if yi = 1
4. If not, pick a new temperature,
repeat
To achieve rapid
convergence:
T ziTi (K i 1)
Initial guess:
i
(weighted average of boiling points of pure
components)
Next guess:
pick a reference
component (A)
K A (Tnext )
K A (Tprev )
(y )
i prev
Trial-and-error method
Given the composition of a superheated vapor and P TOTAL,
find Tdp and (xi)dp
VLE:
mole
xi
yi
Ki
Algorithm:
K A (Tnext )
(x )
i prev
Relative volatility
yA
KA
K A (T )
xA
volatility
yA
relative volatility
AB
KA
xA
K B yB
xB
strong function of
temperature
not a strong
function of
temperature; often
assumed
independent
AB xA
yA
1 ( AB 1)xA
sum:
Ki
xi
i
K ref K ref
yi i xi K ref
y 1.0 x K
i
K ref
ref
i xi
i
Algorithm:
given a solution composition (xi values), find relative volatilities (i values), then
1. guess Tinitial
2. calculate Kref
3. find T = T corresponding to K
XP
K
1.2
X
0.43
K P 2.8
K P (Tbp )
HP
K H 0.45
0.16
KP
2.8
1
1
2.0
i xi 0.3(1) 0.3(0.43) 0.4(0.16)
i
yi i xi K ref
Tbp = 58 C
yP 0.3(1)(2.0) 0.60
yX 0.3(0.43)(2.0) 0.26
yH 0.4(0.16)(2.0) 0.14
Check:
1.0