Chemical Engineering
Thermodynamics
Chapter 8
VAPOR/LIQUID EQUILIBRIUM
Sumber: Http://[Link]/.../CHAPTER%204%20VAPORLIQU..
• So far we have only dealt with pure
substances and constant composition
mixtures.
• We will move a step further where
the desired outcome is the
composition change.
• In system such as distillation &
absorption, if the system is not in
equilibrium, the mass transfer
between system will alter their
composition.
Chapter Outline (Smith)
10.1 Nature of Equilibrium
– Definition
– Measures of composition
10.2 The Phase Rule
– Duhem’s Theorem
10.3 VLE : Qualitative behavior
10.4 Simple Models for VLE
- Raoult’s Law
-Dewpoint & Bubblepoint Calculations with
Raoult’s Law
- Henry’s Law
10.1 THE NATURE OF EQUILIBRIUM
Equilibrium : A static condition in
which no changes occur in the
macroscopic properties of a system
with time.
The T, P,
composition
reaches final
value which
will remain
fixed:
equilibrium
Measures of composition
Measures
of
composition
Molar mass for
Mass or Molar
a mixture or
mole fraction concentration
solution
10.2 PHASE RULE & DUHEM’S
THEORY
Equilibrium states are determined by;
–Phase Rule
–Duhem’s Theory
The Phase Rule
Number of variables that may be
independently fixed in a system at
equilibrium =
Difference between total number of variables
that characterize the intensive state of the
system and number of independent
equation
F = 2-π+N
Where : F – degrees of freedom
π – No of phase
N – No of species
Duhem’s Theory
For any closed system formed
initially from given masses of
prescribed chemical species,
the equilibrium state is
completely
determined when any two (2)
independent variables are fixed
10.3 VLE: QUALITATIVE BEHAVIOR
VLE: State of
coexistence of
L & V phases
Fig. 10.1 – Shows the P-T-
composition surfaces of
equilibrium states of
saturated V & saturated
L of a binary system
• Under surface- sat. V states (P-T-y1)
• Upper surface- sat. L states (P-T-x1)
• Liquid at F, reduces pressure at
constant T & composition along FG,
the first bubble appear at L – bubble
point
• As pressure reduces, more & more L
vaporizes until completed at W; point
where last drop of L (dew) disappear
– dew point
10.4 SIMPLE MODELS FOR VLE
Simple Models
For VLE :
Find T, P, composition
Raoult’s Law Henry’s Law
Raoult’s Law
Assumptions;
• V phase is an ideal gas
– Applicable for low to moderate pressure
• L phase is an ideal solution
– Valid only if the species are chemically
similar (size, same chemical nature e.g.
isomers such as ortho-, meta- & para-
xylene)
Where;
Dewpoint & Bubblepoint
Calculations with Raoult’s Law
FIND GIVEN
BUBL P: Calculate {yi} and P, given {xi} and T
DEW P: Calculate {xi} and P, given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P
For binary systems to solve for
bubblepoint calculation (T is
given);
y i i 1
P xi Pi
i
sat
PP 2
sat
P 1
sat
P
2
sat
x
1
x1 P1 sat
y1
P
Raoult’s law equation can be solved
for xi to solve for dewpoint
calculation (T is given)
i xi 1
P
1 1
i i sat P
y
i
P
y1 / P1 y2 / P2
sat sat
y1 P
x1 sat
P1
Example 10.1
Binary system acetonitrile(1)/nitromethane(2)
conforms closely to Raoult’s law. Vapor
pressure for the pure species are given by
the following Antoine equations:
2,945.47
ln Psat
kPa 14.2724 0
t C 244.00
1
2,972.64
ln Psat
kPa 14.2043 0
t C 209.00
2
• Prepare a graph showing P vs. x1 and P vs.
y1 at temperature 750C
• Prepare a graph showing t vs. x1 and t vs.
y1 for a pressure of 70 kPa
a) BUBL P calculations are required. Since this
is a binary system, Eq. 10.2 may be used.
PP 2
sat
P 1
sat
P
2
sat
x1 ( A)
At 750C, the saturated pressure is given by
Antoine equation;
P1
sat
83.21 P 2
sat
41.98
Substitute both values in (A) to find P;
P 41.98 83.21 41.980.6
P 66.72kPa
The corresponding value of y1 is found from
Eq. 10.1.
yi P xi Pi sat
x1 P1sat 0.6 83.21
y1 0.7483
P 66.72
x1 y1 P/kPa x1 y1 P/kPa
0.0 0.0000 41.98 0.6 0.7483 66.72
0.2 0.3313 50.23 0.8 0.8880 74.96
0.4 0.5692 58.47 1.0 1.0000 83.21
At point c, the vapor composition is y1=0.6,
but the composition of liquid at c’ and the
pressure must read from graph or
calculated. This is DEW P, by Eq. 10.3;
1
P
y1 P1
sat
y2 P2sat
For y1=0.6 and t=750C
1
P 59.74kPa
0.6 83.21 0.4 41.98
And by Eq. 10.1,
y1 P 0.6 59.74
x1 sat 0.4308
P1 83.21
This is the liquid-phase composition at point c’
b) When P is fixed, the T varies along T1sat
and T2sat, with x1 & y1. T1sat & T2sat are
calculated from Antoine equation;
Bi
t sat
Ci
Ai ln P
i
For P=70kPa, T1sat=69.840C, T2sat=89.580C.
Select T between these two temperatures and
calculate P1sat & P2sat for the two
temperatures.
Evaluate x1 by Eq. (A). For example;
P P2sat 70 46.84
x1 sat x1 0.5156
P1 P2 sat
91.76 46.84
Get y1 from Eq. 10.1
x1 P1sat 0.5156 91.76
y1 0.6759
P 70
Summary;
x1 y1 P/kPa
0.0000 0.0000 89.58
(t2sat)
0.1424 0.2401 86
0.3184 0.4742 82
0.5156 0.6759 78
0.7378 0.8484 74
1.0000 1.0000 69.84
(t1sat)
For x1=0.6 & P=70kPa, T is determined by BUBL
T calculation, which requires iteration. Eq. 10.2
is rewritten;
sat
P P
P sat
( B) Where; 1sat
x1 x2
2
P2
Subtracting lnP2sat from lnP1sat as given by
Antoine equations yields;
2,945.47 2,972.64
ln 0.0681 (C )
t 224.00 t 209.00
Initial value for α is from arbitrary intermediate t
With α, calculate
P2sat by Eq. (B)
Calculate T from Antoine
eq. for species 2
Find new α by Eq. (C)
Return to initial step and iterate
until converge for final value of T
The result is t=76.420C. From Antoine eq.,
P1sat=87.17kPa and by (10.1), the
composition at b’ is;
y1
xP
1 1
sat
0.6 87.17
0.7472
P 70
Vapor composition at point c is y=0.6. P is known
(p=70kPa), a DEW T calculation is possible.
The steps are the same as BUBL T, but it is based
on P1sat, rather than P2sat.
The result is t=79.580C. From Antoine eq.,
P1sat=96.53kPa and by (10.1), the
composition at c’ is;
y1 P 0.6 70
x1 sat 0.4351
P1 96.53
This shows that the temperature rises from
76.420C to 79.580C during vaporization step
from point b to c. Continued heating simply
superheats the vapor to point d.
Henry’s Law
Assumptions;
• For pressure low
It is so low that it can be assume as ideal
gas
• For species present as a very dilute
solution in liquid phase
Henry’s Law
Where;
Example 10.2
Assuming that carbonated water contains only
CO2(1) and H2O(2), determine the
compositions of the V & L phases in a sealed
can of ‘soda’ & the P exerted on the can at
100C. Henry’s constant for CO2 in water at
100C is about 990 bar and x1=0.01.
Henry’s law for species 1 & Raoult’s law for
species 2 are written;
y1 P x1 H1 y2 P x P2 2
sat
P x1 H1 x P 2 2
sat
With H1=990 bar & P2sat = 0.01227 bar (from
steam tables at 100C)
P 0.01990 0.99 0.01227
P 9.912 bar
Then by Raoult’s law, Eq. 10.1 written for species
2;
x2 P2sat 0.99 0.01227
y2 0.0012
P 9.912
Whence y1=1-y2=0.9988, and the vapor phase
is nearly pure CO2, as expected.
Review
• What is bubble point?
• What is dew point?
• We have previously went through the
2 simplest models for solving VLE
problems
– Raoult’s Law
– Henry’s Law
Chapter Outline
10.5 VLE by modified Raoult’s law
10.6 VLE from K-value correlations
- Flash calculation
VLE
Modified
Raoult’s Law Henry’s Law K-Values
Raoult’s Law
10.5 VLE BY MODIFIED RAOULT’S
LAW
The 2nd assumption of Raoult’s Law is
abandoned, taking into account the deviation
from solution ideality in L phase.
Thus, activity coefficient is introduced in
Raoult’s Law
Activity coefficients are function of T & liquid
phase composition, x
Since;
y i i 1
P xi i Pi sat
For bubble point
i
i xi 1
1 For dew point
P
y i
i i Pi sat
(See Example 10.3)
BUBL P
BUBL P CALCULATION
Find Pi sat
Find i
Find P from equation 10.6
P x1 1P1sat x2 2 P2sat
Find yi from equation 10.5
yi xi i Pi sat P
DEW P CALCULATION
DEW P
Find Pi sat
Find 1 & 2 . Initial guess its=1
Find P using equation 10.7
1
P
y1 1 P1 y2 2 P2sat
sat
Find xi using equation 10.5
xi yi P i Pi sat
Evaluate from the given
equation
Converge?
NO
YES
It is the P dew.
Find liquid phase mole fraction
yP
x1 1 sat & x2 1 x1
1 P1
BUBL T CALCULATION
BUBL T Find Ti sat
Find initial T from mole-fraction weighted average
T x1T1sat x2T2sat
For current T, find A, 1 , 2 ,
P1 sat , P2sat P1sat P2sat
Find new value for P1sat from equation 10.6;
P
P1sat
x1 1 x2 2
Find new T from Antoine equation for species 1
B1
T C1
A1 ln P1sat
NO Converge?
YES
It is the T bubble.
Find Pi sat , A and 1 & 2
Find vapor phase mole fraction
y1 x1 1 P1sat P & y 2 1 y1
DEW T CALCULATION
DEW T Find Ti sat
Find initial T from mole-fraction weighted average
T y1T1sat y 2T2sat
For current T, find A, P1sat , P2sat
P1sat P2sat
Find x1 y1 P 1 P1sat & x2 1 x1
Calculate 1 & 2 from given correlation
Find new value for P1sat from equation 10.7;
y y
P1sat P 1 2
1 2
Find new T from Antoine equation for species 1
B1
T C1
A1 ln P1sat
NO Converge?
It is the T bubble.
Find Pi sat , A and 1 & 2
YES
Find vapor phase mole fraction
y1 x1 1 P1sat P & y 2 1 y1
AZEOTROPE
When x1=y1, the dew
point and bubble
point curves are
tangent to the same
horizontal line
A boiling L of this
composition produce
a vapor exactly the
same composition; L
does not change in
composition as it
evaporates
Relative volatility;
y1 x1
12 (10.8)
y 2 x2
sat
12 x 0 P1 exp A
sat If one limit is <1 &
1
P2 the other limit is
<1; azeotrope
sat exists.
12 x1 1 sat
P 1
P2 exp A
10.6 VLE FROM K-VALUE
CORRELATTIONS
The partition between liquid and vapor
phases of a chemical species is
equilibrium ratio, Ki.
yi
Ki
xi
This quantity is called K-value.
K-value for Raoult’s Law yi P xi Pi sat
sat
Pi
Ki
P
K-value for modified Raoult’s Law yi P xi i Pi sat
i Pi sat
Ki
P
For binary systems to solve for
bubble point calculation;
y i i 1
Hence,
Kxi i i 1
For binary systems to solve for
dew point calculation;
x i i 1
Hence, yi
i K 1
i
K-value
from
DePriest
er chart
-Low T
range
K-value
from
DePriest
er chart
-High T
range
When given a mixture of composition at certain
T or P;
Bubble point Dew point
- Insignificant L • System is
almost
• The given mole condensed
fraction is yi • The given mole
fraction is xi
• Need to satisfy
equation 10.14 • Need to satisfy
equation 10.13
- Composition of
dew is xi=yi/Ki - Composition of
buble is yi=Kixi
Flash Calculation
The most important application of VLE.
Originates from a fact that a liquid at a
pressure equal to or greater that its
bubble point pressure ‘flashes’ or
evaporates when the pressure is
reduced, producing a two-phase
system of vapor and liquid in
equilibrium.
FLASH CALCULATION
Vapor, V
Liquid at P < Pbubble
V partially evaporates
Feed, F when P is reduced,
producing 2-phase
L system of V & L in
equilibrium
Liquid, L
Find; T, P, z
In a system with one mole chemical
species with an overall composition by
set of mole fraction, zi.
Li would be the moles of liquid with mol
fraction xi and V be the moles of vapor
with the mol fraction of yi:
z
L V 1
zi xi L yiV i 1,2,.....N
From zi xi L yiV
Eliminate for L gives:
zi xi 1 V yiV i 1,2,.....N
yi yi
From K-value Ki xi
xi Ki
Hence solving for yi,
yi
zi K i
i 1,2,.....N
1 V K i 1
Because y i i 1
Hence, zi K i
yi 1 V K 1 1
i
(See Example 10.5 and 10.6)
Flowchart for FLASH CALCULATION
flash Find BUBL P with zi xi ; Pbubble
pressure
Find DEW P with zi yi ; Pdew
Is the given P
between NO
Pbubble & Pdew ?
No need for flash
calculation
YES
Using equation 10.11, find K i
Substitute K i in equation 10.17. By trial & error,
solve for V. Then L=1-V
Solve equation 10.16 for each component - yi
Solve equation 10.10 for each component - xi
The End
