Chemical Engineering

Thermodynamics

VAPOR/LIQUID EQUILIBRIUM
 Measures of composition

Measures
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
10.3 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 sat
i
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 P2sat 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  P2sat  P1sat  P2sat x1 ( A)

At 750C, the saturated pressure is given by Antoine
equation;

P 1
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 P 1
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  P2sat 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 P1sat
P2sat  ( B) Where;   sat
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;

x1 P1sat 0.687.17 
y1    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 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


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
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 1 P1sat  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  1P1sat  y2  2 P2sat

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 ,

P sat , P sat   P1 P2
sat sat
1 2

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
Pi sat
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,
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 dew - Composition of

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 when
Feed, F P is reduced, producing 2-
phase system of V & L in
L 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 pressure Find BUBL P with zi  xi ; Pbubble

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