Chemical Engineering

Thermodynamics

Chapter 4
VAPOR/LIQUID EQUILIBRIUM
• 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
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
Measure
of
composition

Molar mass for

Mass or Molar
a mixture or
mole fraction concentration
solution

xi 
mi m i
 Ci 
xi M   xi M i
m m V i
 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)
yi P  xi Pi sat
 i  1,2,..., N 
Where;
xi : L  phase mole fraction
yi : V  phase mole fraction
Pi sat : Vapor pressure of pure species i
P : Total pressure
 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
PP 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
y P sat P
i 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 P
1
sat
kPa  14.2724  0
t C  244.00
2,972.64
ln P
2
sat
kPa  14.2043  0
t C  209.00
a)Prepare a graph showing P vs. x1 and P vs.
y1 at temperature 750C
b)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.

PP 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  41.98 0.6 

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 i
sat
  Ci
Ai  ln P
 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;

P P sat
P2
sat
 ( B ) Where;   1sat
x1  x2 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;

1. For pressure low

It is so low that it can be assume as ideal
gas
2. For species present as a very dilute
solution in liquid phase
 Henry’s Law

yi P  xi H i  i  1,2,..., N 
Where;
xi : L  phase mole fraction
yi : V  phase mole fraction
H i : Henry's constant
P : Total pressure
 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 P 2 2
sat

P  x1 H1  x P 2 2
sat

With H1=990 bar & P2sat = 0.01227 bar (from

steam tables at 100C)

P   0.01 990   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 go 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

yi P  xi i Pi sat
 i  1,2,..., N 
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
 yi  i Pi
i
sat

(See Example 10.3)

BUBL P
DEW P
 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 & x 2  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
P exp A
12  x 0  1
sat If one limit is >1 &
1
P2 the other limit is
<1; azeotrope
sat exists.
P
12  x1 1  sat 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 Pisat
Ki 
P
 For binary systems to solve for
bubble point calculation;

y i i 1

Hence,
Kx
i 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
DePriester
chart
-Low T
range
K-value
from
DePriester
chart
-High T
range
When given a mixture of composition at certain
T or P;
Bubble point Dew point

- Insignificant L -System is almost

condensed
-The given mole -The given mole
fraction is yi fraction is xi

- Need to satisfy - Need to satisfy

equation 10.14 equation 10.13

- Composition of - Composition of
dew is xi=yi/Ki 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,

zi K i
yi   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