XXX

CHAPTER 10
Vapor/Liquid Equilibrium
(VLE): Part 1
Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Topic Outcomes
Week Topic Topic Outcomes
12-13 Physical Equilibria It is expected that students are able to:
• Introduction to equilibrium systems • Describe the behaviour of VLE and how

• The equilibrium criteria and stability to simplify the VLE problem.
• The phase rule – Duhem’s theorem
• Introduction to vapor/liquid Equilibria (VLE) • Derive and simplify equations of VLE.
• VLE Behaviour and models
• VLE for low to moderate pressure system • Apply simplified VLE equations to obtain
o Raoult’s Law -Ideal gas and ideal solution data for P-XY, T-XY and X-Y diagrams.
(simple model)
o Modified Raoult’s Law • Apply Raoult’s law and Henry’s law to
o Henry’s Law solve simple thermodynamic problems.
• VLE for high pressure system
o VLE from equation of state. • Carry out bubble and Dewpoint
o K-Value correlation calculations for a given mixture
• Flash calculation.
• The Gamma/Phi Formulation of VLE • Carry out flash calculation in order to
determine the vapor/liquid fraction as
well as the mixture composition of each
phase at specified conditions using
available K-Values etc.

Scope of Lecture
Liquid Phase Properties from VLE data
Qualitative Behaviour
Simple Model for VLE
K-values Using DePriester Chart
Flash Calculations

Liquid Phase Properties
from VLE data

Phase Equilibrium
Application
• Distillation, absorption, and extraction bring phases of
different composition into contact.
Both the extent of change and the rate of transfer depend

on the departure of the system from equilibrium
For quantitative treatment of mass transfer the equilibrium

T, P and phase compositions must be known.

The Nature of Equilibrium
Equilibrium: a static condition in which no changes occur

in the macroscopic properties of a system with time.
An isolated system consisting of liquid and vapor phases in

intimate contact eventually reaches a final state wherein no
tendency exists for change to occur within the system
→ Fixed temperature, pressure and phase composition

Measure of Composition
Mass or mole fraction :
Mass species i Mole species i
mi mi ni n i
xi   or xi  
m m  n n
Total mass Total moles
xi
Molar concentration: Ci 
V
Molar volume

Measure of Composition (Cont.)
For flow processes convenience suggest its expression as a ratio of

rates:
Molar flow rate

n i
Ci 
q
Volumetric flow rate
Molar mass of a mixture or solution: mole-fraction-weighted sum of

the molar masses of all species present:
M   x iMi
i

Phase Rule vs. Duhem’s Theorem
The no. of variables that The no. of variables that The no. of independent
is independently fixed in = characterize the intensive – equations connecting the
a system at equilibrium state of the system variables
Phase rule: F  2  N 1π   π  1N  2  π  N
Duhem’s rule: F  2  N 1π   π  N 1N  N  2
• For any closed system form initially from given masses of

prescribed chemical species, the equilibrium state is completely
determined when any 2 independent variables are fixed.

Qualitative Behavior

PTxy Diagram for VLE
There are several diagram to describe the behavior for a mixture
in the equilibrium phase.
Binary mixture for species 1 and 2
RKAC1: vapor pressure vs. T

curve for species 1
UBHC2: vapor pressure vs. T

curve for species 2
C1 & C2 = critical point for species

1&2
Species 1 is more volatile

PTxy diagram for VLE
PTxy Diagram for VLE (Cont.)
Under surface is saturated-

vapor (P, T, y1 surface)
Below that is gas phase
Top surface is saturated-liquid

(P, T, x1 surface)
Above that is liquid phase

PTxy Diagram for VLE (Cont.)
F: Liquid solution
L: Bubblepoint
P
W: Dewpoint
G: Gas mixture
LV: Tie line
AEDBLA gives Pxy

phase diagram at const. T
Next
slide
KJIHLK gives Txy phase
diagram at const. P

Pxy Diagram for 3 T &Txy Diagram for 3 P
Saturated vapor (dew line)
Saturated liquid (bubble line)

Tie line
Most chemical processes

operate at this P, T range
Note: Species 1 has higher vapor pressure or lower boiling point
than species 2.
P-T Diagram
PT diagram for several compositions. Portion of a PT diagram in the critical region.

Pxy Diagram at Constant T
THF(1)/CCl4(2) at 30˚C CHCl3(1)/THF(2) at 30˚C
250
200
180 200
P-x1
P-x1
160
P-y1 150 P-y1
Dashed lines: Px relation Azeotrope
for Raoult’s law 140
P/Torr
Furan(1)/CCl3(2) at 30˚C EtOH(1)/toluene(2) at 65˚C

800 Azeotrope
450
P-x1
600 P-x1
400 300
P-y1
200 P-y1
Similar shape to previous
figure (left) 150
0 0.5 1.0 0 0.5 1.0
Note: THF, tetrahydrofuran; CCl4, carbon tetrachloride; CCl3, chloroform x1, y1
Txy Diagrams for Const. P (1 atm)
THF(1)/CCl4(2) CHCl3(1)/THF(2)
t-y1
75 70
This diagram is of practical t-y1
interest as most VLE Azeotrope
applications occur at const P 70 t-x1 65 t-x1
(e.g. in distillation column)
65 60
t/C
Furan(1)/CCl3(2) EtOH(1)/toluene(2)
110
t-y1
75 100
t-y1
Azeotrope
50 90
t-x1
t-x1
Similar shape to previous 80
figure (right) 25
0 0.5 1.0 0 0.5 1.0
x1, y1
Azeotrope
x1 = y1 x2 = y2
Liquid gas
Azeotrope =
composition composition

Simple Model for VLE

VLE (Chapter 11)
Consider a multicomponent system in VLE, the fugacity of species i

for each phase
For vapor mixture fî v  îv y iP
For liquid solution fî l   i x i f i
VLE criteria
fî v  fî l îv y iP   i x i f i

Raoult’s Law
For,
1. The vapor phase is ideal gas → î  1

→ Apply for low to moderate P
y iP  x i fi
2. The liquid phase is an ideal solution→  i  1
→ Apply when the species that are chemically similar
For pure species in equilibrium and ideal gas vapor
fi  fi l  fi v  P  Pisat
Vapor-phase mole fraction Liquid-phase mole fraction
y iP  x iPisat Vapor pressure of pure species i

at the T of the system

VLE from Modified Raoult’s Law
For ideal-gas mixture in equilibrium with non-ideal liquid solution
=1
î y i P   i x i Pisat
y i P   i x i Pisat i  1, 2, 3, N
 i  f T, x i 
P    i x i Pisat
i
1
P
 i i i
y / 
i
P sat

VLE
VLE from
FROM K-Value Correlation
K-VALUE CORRELATION
A convenient measure of the tendency of a given chemical species to
partition itself preferentially between liquid and vapor phases is the
equilibrium ratio Ki, defined as:
y 1
i
i
K x i i 1 For bubblepoint
yi i
Ki 
xi  y /K i i 1 For dewpoint
 xi  1
i
i
If Raoult’s law is valid,
y iP  x P sat Pisat
i i Ki 
P
If Modified Raoult’s law is valid,
yi P   i x i P sat  iPisat
i Ki 
P
K-values Using DePriester
(Dadyburjor) Chart

Low-T Range
For light hydrocarbon mixture,
→Ki is essentially function of T

& P.
→The value could be simply

tabulated as in DePriester
chart.
Read value of K-value at given T

&P
→E.g. 1000 kPa and 0 C for

CH4

High-T Range

Example 1 (K-Value Correlations, Example 10.4)
For a mixture of 10 % methane , 20 % ethane and 70 % propane at 50

˚F , determine :
a) The dewpoint pressure
b) The bubblepoint pressure
The K- values are given by Fig .10.13

Tutorial 1
Assuming the validity of the De Priester (Dadyburjor) charts, make the

following VLE calculations for the methane(1)/ ethylene(2)/ ethane(3)
system:
a) BULB P, given x1 = 0.10, x2 = 0.50 and T = –51 C
b) DEW P, given y1 = 0.50, y2 = 0.25 and T = –51 C
c) BULB T, given x1 = 0.12, x2 = 0.40 and P = 17.24 bar
d) DEW T, given y1 = 0.50, y2 = 0.25 and P = 17.24 bar

CHAPTER 10
Vapor/Liquid Equilibrium
(VLE): Part 2
Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

Dewpoint & Bubblepoint
Calculation

Bubl P
To calculate the P when the 1st bubble appear as a result of

decrease in P at constant T. Also calculate the bubble’s composition
{yi}.
To calculate the P when the last bubble disappear as a result of

increase in P at constant T. Also calculate the bubble’s composition
{yi} of this bubble.

Dew P
To calculate the P when the 1st dew ( a drop of liquid) appear as a

result of increase in P at constant T. Also calculate the bubble’s
composition {xi} of this dew.
To calculate the P when the last dew disappear as a result of

decrease in P at constant T. Also calculate the composition {xi} of this
dew.

Pxy Diagram
100
t = 75 C
Subcooled liquid BULB P

P1sat
Saturated liquid
P/kPa
P-x1
P-y1
v+l
Saturated vapor
P2sat
DEW P
Superheated vapor
20
0 x1, y1 1

Bubl T
To calculate the T when the 1st bubble appear as a result of increase

in T at constant P. Also calculate the composition {yi} of this bubble.
To calculate the T when the last bubble disappear as a result of

decrease in T at constant P. Also calculate the bubble’s composition
{yi} of this bubble.

Dew T
To calculate the T when the 1st dew ( a drop of liquid) appear as a

result of decrease in T at constant P. Also calculate the bubble’s
composition {xi} of this dew.
To calculate the T when the last dew disappear as a result of

increase in T at constant P. Also calculate the composition {xi} of this
dew.

txy Diagram
90
Superheated DEW T
vapor
t2sat Saturated vapor
t-y1
t/C t-x1
v+l
Saturated liquid
Subcooled
liquid t1sat
BULB T
65
0 x1, y1 1

Derivation
Overall mole balance

V
T L V
L
Component mole balance
Tz i  Lx i  Vy i
Let T = 1 mol, so V and L are mole fractions,
z i  Lx i  Vy i
z i  1 V x i  Vy i
Note: zi, overall composition Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Derivation
z i  1 V x i  Vy i
Substitute
yi  K ix i
z iK i
yi 
1  V K i  1
z i  1 V x i  K i x i V
 x i 1 V  VK i   x i 1 V K i  1
Also,
zi
xi 
1  V K i  1
x  y i i 0
y i Substitute
xi  z i  1 V x i  Vy i zi z iK i
Ki  1 V K  1 1 V K  1  0

i i
yi
z i  1 V   y i V
Ki z i  z iK i
 1 V K  1  0
i
z iK i  1 V yi  K iyi V
Bubblepoint Calculation
At bubblepoint (practically all If Raoult’s Law valid

liquid) L = 1, V = 0 and zi =xi
Pisat
 x iK i   x i P  1
z i  z iK i
 1 V K  1  0 P   x iPisat
i
Binary system
 x i  x iK i   0 
P  P2sat  P1sat  P2sat x 1 
If Modified Raoult’s Law valid
x  x K
i i i
 iPisat
x K  x
i i i
P
1
x K i i 1 Bubblepoint criteria P   x i iPisat

Dewpoint Calculation
At dewpoint (practically all If Raoult’s Law valid

vapor) L = 0, V = 1 and zi =yi
yi yi
 K  P sat / P  1

z i  z iK i i i
 1 V K  1  0
i 1
P
 yi/Pisat
y i  y iK i
 K 0 If Modified Raoult’s Law valid
i
yi yi
yi
 K   yi  0  K   P sat / P  1

i i i
i
yi 1
 K 1 Dewpoint criteria P
 y i/ iPisat
i

Summary: Bubblepoint & dewpoint
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
y iP  x P
i i
sat P   x iPisat 
P  P2sat  P1sat  P2sat x 1 
y i 1
i
P   x i iPisat
i Binary system
Bubblepoint calculation
Equation applied in bubble point calculations, where the vapor-

pressure composition is unknown.
Plot of P vs x1 at const. T is a straight line connecting P2sat at x1 = 0

with P1sat at x1 = 1.
Summary (Cont.)
1
y iP  x P sat
i  1, 2,N P
i i
 y i/Pisat
x
i
i 1 i
1
P
 i ii
y / P sat
An equation applied in Dewpoint calculations, where liquid-

phase composition are not known.

Relative Volatility
ik > 1, species i is relatively more volatile

y i /xi K
αik   i ik < 1, species k is relatively more volatile
y k /xk K k
At azeotrope ik = 1/1=1
If Raoult’s Law valid
P1sat /P P1sat
αik  sat  sat Note: for higher vapor pressure
means more volatile 12 > 1
P2 /P P2
If Modified Raoult’s Law valid
 1P1sat /P  1P1sat
αik  
 2P2 /P  2P2sat
sat

Example 2 (Example 10.1)
Binary system acetonitrile(1)/nitromethane(2) conforms closely to

Raoult’s law. Vapor pressures for the pure species are given by the
following Antoine equations:
2,945.47
lnP1sat kPa  14.2724 
t  C  224.00
2,972.64
lnP2sat kPa  14.2043 
t  C  209.00
a) Prepare a graph showing P vs. x1 and P vs. y1 for a temp. of 75 C.
b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

Solution 2
Plot Px1y1 at T = 75 C
Mixture: Acetonitrile(1)/Nitromethane(2)
Antoine equation,
2,945.47 2,972.64
lnP1sat kPa  14.2724  lnP2sat kPa  14.2043 
t  C  224.00 t  C  209.00
Calculate at 75 C
P1sat  83.21kPa P2sat  41.98kPa
Note: Acetonitrile is more volatile

Solution 2 (Cont.)
Calculate P and y1, given a set of x1 and T = 75 C
→ BULB P calculation x K i i 1
Let us assume Raoult’s Law is valid, P  Pb  x P i i

sat
P  x 1P1sat  x 2P2sat  x 1P1sat  1 x 1 P2sat
 
P  P1sat  P2sat x 1  P2sat A (A linear line, y = mx + c)
Also,
x 1P1sat
y1  B
P
So, calculate P for a set of x1 (Eqn. A) and then calculate y1 (Eqn. B)

Solution 2 (Plot Pxy Diagram)
100
t = 75 C
Given or set
P1sat = 83.21
Liq. solution/
T C x1 P = Pb(kPa) y1 subcooled liquid a
80
75 0 41.98 P2sat 0
Sat. liq. solution/
75 0.2 50.23 0.3313 bubblepoint (Pb is BUBL P) b
b’
75 0.4 58.47 0.5692
P/kPa
59.74 kPa c’
60 c Sat. vap.
75 0.6 66.72 0.7483 Point b
P-x1 solution/
75 0.8 74.96 0.8880
P-y1 d dewpoint (Pd
75 1 83.21P1sat 1 is DEW P)
40 P2sat = 41.98
x 1P1sat
y1 
P Gas mix./ superheated
 
vap. mix.
P  Pb  P1sat  P2sat x 1  P2sat
20
0 0.2 0.4 0.6 0.8 1.0
x1,y1
Calculate
Solution 2 (Cont.)
E.g. Calculate Pd and x1, given y1 = 0.6 & T = 75 C

→ i.e What is the dew P for gas mixture at 75 C & 60% acetonitrile
This POINT c (previous Px1y1 diagram)
yi
Dew P calculation (Note: z1 = y1)  K 1
i
If Raoult’s Law valid
1 1
Pd    59.74kPa Compare with values
 y i/Pi sat
0.6

0.4 from Pxy diagram
83.21 41.98
y 1Pd 0.6 59.74 
Then calculate x1 using x 1    0.43
P1 sat
83.21
Solution 2: Dew P
We could also plot Pxy diagram using Dew pressure

calculation
Set yi, calculate Pd and xi
DIY
Plot Pxy using Pdxiyi

Solution 2 (Cont.)
Plot Tx1y1 at P = 70kPa
Mixture: Acetonitrile(1)/Nitromethane(2)
Antoine equation,
2,945.47 2,972.64
T1sat / C   224.00 T2sat / C   209.00
14.2724  lnP1sat kPa 14.2043  lnP2sat kPa
So at 70 kPa
T1sat  69.84  C T2sat  89.58  C
As expected Acetonitrile(1) is more volatile

Solution 2 (Cont.)
x K i i 1
If Raoult’s Law valid, P  Pb   ii

x P sat
P  x 1P1sat  x 2P2sat  x 1P1sat  1 x 1 P2sat
P  P2sat
x 1  sat C
P1  P2sat
Since we use BUBL point calculation, T = Tb
Choose T between T1sat and T2sat, the using Antoine equation

calculate P1sat and P2sat at the chosen T and then calculate by Eqn. C
x 1P1sat
Then calculate y1 using, y 1 
P
Solution 2 (Plot Txy Diagram)
t2sat = 89.58 P= 70 kPa
90
Given or set
Gas mix./ superheated
t-y1
P (kPa) T = Tb C x1 y1 85
vap. mix.
d Sat. vap.
70 69.84 T1sat 1(x1 = 0) 1(y2 = 0) t-x1 solution/
70 74 0.7378 0.8484 dewpoint (Td
c
70 78 0.5156 0.6759 80 is DEW T)
c’
t/C
70 82 0.3184 0.4742
b’
70 86 0.1424 0.2401 Sat. liq. solution/ b
75 bubblepoint (Tb
70 89.58 T2sat 0(x2 = 1) 0(y2 = 1) is BUBL T)
a
Liq. solution/
70
subcooled liquid
P  P2sat x 1P1sat t1sat = 69.84
x 1  sat y1 
P1  P2sat P 65
0 0.2 0.4 0.6 0.8 1.0
x1,y1
Solution 2 (Cont.)
E.g. Calculate Tb and y1, given x1 = 0.6 & P = 70kPa

→ i.e What is the dew P for gas mixture at 75 C & 60% acetonitrile
This POINT b (previous Tx1y1 diagram)
Bubble T calculation (Note: z1 = x1) x K i i 1
The solution is not straightforward as T is unknown. Let’s see how to

solve mathematically

Solution 2 (Cont.)
For Raoult’s Law, Pb  x P i i

sat
Pksat P sat
Pb  sat
Pk
x P
i i
sat
 Pksat  x i isat  Pksat  x iαik
Pk
Where k is a component
that arbitrarily chosen
Pb
Pksat  A
 x iαik
Also,
Pisat  Bi   Bk 
lnαik  ln sat  lnPi  lnPk   A i 
sat sat
 
   Ak 
 
Pk  T  Ci   T  Ck 

Solution 2 (Iteration)
1. Start with an initial guess of T as follows
T   x iTisat T  0.669.84   0.489.58   77.74  C
2. Arbitrarily pick a component
E.g. Nitromethane so, k = 2
3. Calculate ik
(Note: Number of ik is equal to total number of component)
 Bi   Bk  α12  1.9611
lnαik   A i     A k  
 T  Ci   T  Ck  α22  1

Solution 2 (Iteration)
Pb
4. Calculate Pk sat using Eqn. A Pksat 
 x iαik
Pb 70
P2sat    44.3977kPa
x 1α12  x 2 α22 0.6 1.9611  0.4 1
5. Calculate a new value of T using the Antoine equation
2,972.64
T2sat / C   209.00  76.53  C
14.2043  lnP2 kPa
sat
6. Stop if this T equal or close to earlier value of T, else use this value
as a new guess. Repeat steps 3, 4 & 5 until converge

Solution 2 (Cont.)
t2sat = 89.58 P= 70 kPa

90
T ik P1sat P2sat T
t-y1
77.74 1.9611 87.49 44.39 76.53 85
d
t-x1
76.53 1.9703 87.20 44.24 76.43 c
80
Answer c’
t/C
76.43 1.9717 87.17 44.22 76.42 point b
b b’
75
7. Finally, calculate yi using Raoult’s law a
(use the Antoine equation for Pisat)
70
y i  0.7472
t1sat = 69.84
65
0 0.2 0.4 0.6 0.8 1.0

Solution 2: Dew T
t2sat = 89.58 P= 70 kPa

90
Calculate Td and x1, given y1 and P
t-y1
85
d
t-x1
E.g. Calculate Td and x1 for z1 = y1 = 0.6 c
and P = 70kPa. See text book (page 80
c’
t/C
356) for the solution (also iteration) of
Dew T calculation. b b’
75
a
Answer: Td = 79.58 C, x1 = 0.4351
70
t1sat = 69.84
65
0 0.2 0.4 0.6 0.8 1.0
x1,y1

Tutorial 2
Assuming Raoult’s law to be valid, prepare p-x-y

diagram for the temperature of 90C (363.15 K) and a t-
x-y diagram for a pressure of 90 kPa fo Benzene(1)/
ethylbenzene(2)

Example 3 (Modified Raoult’s Law, Example 10.3)
For the system methanol(1 )/methyl acetate(2), the following equations provide
a reasonable correlation for the activity coefficients:
ln γ1 = Ax22 ln γ2 = Ax12 where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:
3,643.31 2,665.54
lnP1sat  16.59158  lnP2sat  14.25326 
T  33.424 T  53.424
where T is in kelvins and the vapor pressures are in kPa.
Assuming the validity of Modified Raoult’s Law, calculate:
(a) P and {yi}, for T = 318.l5 K and x1 = 0.25.

(b) P and {xi}, for T = 318.l5 K and y1 = 0.60.
(c) T and {yi} , for P = 101.33 kPa and x1 = 0.85.
(d) T and {xi}, for P = 101.33 kPa and y1 = 0.40.
(e) The azeotropic pressure, and the azeotropic composition, for T = 318.15 K.

Solution 3
(a) For T = 318.15 K and x1 = 0.25
P1sat  44.51kPa P2sat  65.64kPa  1  1.864  2  1.072
P   x i iPisat  0.25 1.864 44.51  0.75 1.072 65.64   73.50
y iP   x i iPisat y1  0.282 y 2  0.718

Solution 3 (Cont.)
(b) For T = 318.15 K and y1 = 0.60
P1sat  44.51kPa P2sat  65.64kPa
1
An iterative process is applied, with  1  1  2  1 P
 y i/ iPisat
y 1P
x1 
 1P1sat
x 2  1 x 1
Converges at: P  62.89kPa x 1  0.8169  1  1.0378  2  2.0935

Solution 3 (Cont.)
(c) For P = 101.33 kPa and x1 = 0.85
T1sat  337.71 T2sat  330.08
An iterative process is applied, with T  0.85 T1sat  0.15 T2sat  336.57
3,643.31 1   2 
T  33.424
16.59158  lnP1sat
P   x i iPisat
P1sat   P1sat  P
x 1 1  x 2 2 /α12
Converges at: T  331.20K y1  0.670 y 2  0.330
 1  1.0236  2  2.1182
Solution 3 (Cont.)
(d) For P = 101.33 kPa and y1 = 0.40
T1sat  337.71 T2sat  330.08
An iterative process is applied, with T  0.40 T1sat  0.60 T2sat  333.13
1  1  2 1
Bi
lnPisat /kPa  A i 
T K   C i
P1sat   P2sat  
3,643.31 y 1P
lnP sat
 16.59158  x1  ; x 2  1 x 1
1
T  33.424 γ1P1sat
x1   x 2  
y y 
P1sat  P  1  2 α12 
1    2    1  2 
y1 y
P2sat   2
P1sat   P2sat    1α12  2 α22
Converges at: T  327.70K x 1  0.4602 x 2  0.5398  1  1.3629  2  1.2523
Solution 3 (Cont.)
(e) Paz & xaz =yaz, for T = 318.15 K.
y /x y iP   x i iPisat
αik  i i  1P1sat
Define the relative volatility αik 
y k /xk  2P2sat
Azeotrope y1  x 1 y 2  x 2 αik  1
P sat
exp 2.771  0.00523T  P sat
α12 γx 1exp
0  1
 2.052 α12 γx 111  sat 2
 0.224
1
γ 2 1
A 
P2sat >1
1
γ 2  exp  A  P1 exp 2.771  0.00523T  <1
Since 12 is a continuous function of x1: from 2.052 to 0.224, 12 = 1 at

some point, there exists the azeotrope
 1P1sat  1 P2sat
αik  1   1.4747
 2P2sat  2 P1sat
ln 1  2.771 0.00523T x 22 1

ln  2.771  0.00523T x 2  x 1   2.771  0.00523T 1 2x 1 
2
ln 2  2.771  0.00523T x 12
γ1az  1.657
x 1az  y1az  0.325
P az   1az P1sat  73.76kPa
Special Case of Dew T Calculation
Dewpoint T of mixture of water vapor and non-condensable gases
Solution is straightforward by the application of Raoult’s Law to the

condensable component H2O (here identified as component 2)
The system contains a dew (liquid water) in VLE with mixture of water
vapor and non-condensable gases (such as N2, CO2, O2 etc)
The dew is 100% H2O, so x2 = 1
y 2P  x 2P2sat P2sat  y 2P

Example: Dew T of Combustion Products
For stoichiometric combustion of CH4, calculate dewpoint T of the

combustion products
CH 4  2O2  279/21N2  CO 2  2H2O  279/21N2
Mole fraction of H2O is 2/(1+2+2(79/21)) = 0.19
P2sat  y 2P
P2sat  0.19 101.325kPa   19.25kPa
From steam table, Td = T2sat = 59.5 C
Or Antoine equation

Tutorial 3
For the system ethyl ethanoate(1)/n-heptane(2) at 70C (343.17)
ln γ1 = 0.95x22 ln γ2 = 0.95x12
P1sat = 79.80 kPa P2sat = 40.50 kPa
Assuming the validity of Modified Raoult’s Law,

a) Make a BUBL P calculation for T = 343.15, x1 = 0.05
b) Make a DEW P calculation for T = 343.15, y1 = 0.05
c) What is the azeotrope composition and pressure at T = 343.15

Flash Calculations

An Important Application of VLE
A liquid at a pressure equal to or greater than its Bubblepoint

pressure (Pb) “flashes” or partially evaporates when the pressure is
reduced, producing a 2-phase system of vapor and liquid in equilibrium.
Flash calculation is to determine V, L, {xi} and {yi} at T and P by

assuming VLE.
T P
{yi} V
{xi} L

Equations
Consider a system containing one mole of reacting chemical species,
L  V 1 z i  x iL  yiV z i  x i 1 V   y i V
Moles of vapor Vapor mole fraction z iK i

yi 
Moles of liquid Liquid mole fraction 1  V K i  1
Mole fractions of
z iK i
overall composition
 1 V K  1  1
i
Solution is by trial and error → guess V until the summation term

equal to 1
Need to know whether the system is actually 2-phase. In general,
If Pd< P < Pb → 2-phase or If Tb< T < Td → 2-phase

Flash calculation for system where Raoult’s Law valid
The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80˚C and 110

kPa has the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20.
Assuming that Raoults law is appropriate to this system, determine L, V,
{x1}, and {y1}. The vapor pressures of the pure species at 80˚C are:
P1sat = 195.75 P2sat = 97.84 P3sat= 50.32 kPa

Solution 4
Do the BUBL P calculation, with {zi} = {xi}
Pbubl  x 1P1sat  x 2P2sat  x 3P3sat  0.45 195.75   0.35 97.84   0.20 50.32   132.40kPa
Do the DEW P calculation, with {zi} = {yi}

1
Pdew   101.52kPa
y 1/P1sat  y 2 /P2sat  y 3 /P3sat
Since Pdew < P = 110 kPa < Pbubl, the system in in 2-phase region
L  1 V  0.2636 mol
K 1  1.7795
Pi
sat Substitute z iK i Trial & error
Ki 
P
K 2  0.8895  1 V K  1  1 V  0.7364 mol
i
K 3  0.4575 z iK i
yi 
1  V K i  1
x 1  0.2859
yi y1  0.5087
Ki 
xi
x 2  0.3810 y 2  0.3389
x 3  0.3331 y 3  0.1524
Flash calculation using K-value from DePriester Chart
For the system described in Example 1, what fraction of the system is

vapor when the pressure is 200(psia) and what are the compositions of the
equilibrium vapor and liquid phases?
Solution 5:
Since Pdew = 126 (psia) < P = 200 (psia) < Pbubl = 385 (psia), the
system in in 2-phase region
With K-values from Fig. 10.13 → find by trial that value of V
z iK i
 1 V K  1  1
i

Solution 5
yi for yi for yi for xi = yi / Ki

Species Zi Ki
V = 0.35 V = 0.25 V = 0.273 for V = 0.273
Methane 0.10 10.0 0.241 0.308 0.289 0.029
Ethane 0.20 1.76 0.278 0.296 0.292 0.166
Propane 0.70 0.52 0.438 0.414 0.419 0.805
Σyi=0.957 Σyi=1.018 Σyi=1.000 Σxi=1.000
z iK i
Satisfied when V = 0.273  1 V K  1  1
i

Tutorial 5
An equimolar mixture n-butane and n-hexane at pressure P is

brought to a temperature of 95C, where it exists as a vapor/liquid
mixture in equilibrium. If the mole fraction of n-hexane in the
liquid phase is 0.75,
1. What is pressure P (in bar),
2. What is the mole fraction of the system that is liquid, and
3. What is the composition of the vapor phase?

Henry’s Law

Introduction
VLE relation that is valid for ideal-gas mixture in equilibrium with dilute
solution, where we want to know the composition of dissolve gas i
in the dilute solution.
E.g.
• CO2 and H2O system
• Air and H2O system
1
îy iP   i x i f i y iP  x i i fi  x i iPisat
Let Hi   i fi   iPisat y i P  xi Hi
Henry’s constant (in bar) for dissolved gas (i)

Henry’s Costant
So, at dilute solution

yi  Hi / P x i Henry’s constant for gases dissolved
in H2O at 25 ˚C
Gas H / bar Gas H / bar
For constant system pressure P,
C2H2 1,350 He 126,600
yi  constantx i Air 72,950 H2 71,600
CO2 1,670 H2S 55,200
If we Plot yi vs. xi CO 54,600 CH4 41,850
C2H6 30,600 N2 87,650
Straight line from the origin C2H4 11,550 O2 44,380
Henry’s constant for dissolved gas (i) can be easily determined from
experiment

Example: Henry’s Law
Previous example of dewpoint for combustion product (slide 66),

we assume the liquid is all H2O (x2 = 1).
What if we want to know the mole fraction of dissolved CO2

(component 1) in the dew (liquid)?
We could solve this using Henry’s Law for dissolved gases (CO2)

Example: Henry’s Law (Cont.)
Apply Henry’s Law for component 1.
Use H1 data from Table 10.1 (Note: this actually valid at 25 C)
x1 
y1 P

1/1 2  7.52 1.013bar 
H1 1670bar
x1  3.4622 10 5  0
As expected, only small amount of CO2 present in liquid water.

Henry’s Law (Ideal Solution)
If the fugacity of i in liquid phase is given by Henry’s law
fî   i x i f i  xi Hi
If the ideal gas is ideal solution (Lewis/Randall is valid)
fî  i x i Pi
So, we get the following version of Henry’s Law if gas mixture is ideal
solution
i x i Pi  x i Hi

Example 6 (Henry’s Law, 10.2)
Assuming that carbonated water contains only CO2

and H2O, determine the compositions of the vapor
and liquid phases in a sealed can of “soda” and the
pressure exerted on the can at 10˚C.
*Henry’s constant for CO2 in water at 10˚C is about

990 bar.

Solution 6
Henry’s law for species 1: y1 P  x1 H1
Raoult’s law for species 2: y 2P  x 2P2

sat
P  x1 H1  x 2P2sat
Assuming x1 = 0.01 Steam tables
P  0.01990  0.99 0.01227   9.912
at 10C
P
x1  Assuming y1  1.0
H1
Justified the assumption x 1  0.0100
x 2P2sat
y2 
P
y 2  0.0012
y1  0.9988 Justified the assumption
Tutorial 4
A concentrated binary solution containing mostly species

2 (but x2 ≠ 1) is in equilibrium with vapor phase
containing both species 1 and 2. The pressure of this
two-phase system is 1 bar; the temperature 25 C .
Determine from the following data good estimates of
x1 and y1.
H = 200 bar P2sat = 0.10 bar

Homework
10.1, 10.26, 10.30, 10.36, 10.41

Chapter 10 : 10.21, 10.9, 10.11, 10.25, 10.27, 10.28,
10.29, 10.31, 10.32, 10.33, 10.34
Dateline : Xxx 00, 0000 (Xxx)

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What are the main topics covered in vapor-liquid equilibrium?

What are the main topics covered in vapor-liquid equilibrium?

What models are used to describe VLE behavior?

What models are used to describe VLE behavior?

CHAPTER 10

Mohd Asmadi Bin Mohammed Yussuf

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

• Introduction to equilibrium systems • Describe the behaviour of VLE and how

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Liquid Phase Properties from VLE data

Simple Model for VLE

K-values Using DePriester Chart

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Both the extent of change and the rate of transfer depend

For quantitative treatment of mass transfer the equilibrium

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Equilibrium: a static condition in which no changes occur

An isolated system consisting of liquid and vapor phases in

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Mass or mole fraction :

Mass species i Mole species i

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

For flow processes convenience suggest its expression as a ratio of

Molar flow rate

Molar mass of a mixture or solution: mole-fraction-weighted sum of

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Phase rule: F  2  N 1π   π  1N  2  π  N

Duhem’s rule: F  2  N 1π   π  N 1N  N  2

• For any closed system form initially from given masses of

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Binary mixture for species 1 and 2

RKAC1: vapor pressure vs. T

UBHC2: vapor pressure vs. T

C1 & C2 = critical point for species

Species 1 is more volatile

Under surface is saturated-

Below that is gas phase

Top surface is saturated-liquid

Above that is liquid phase

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

LV: Tie line

AEDBLA gives Pxy

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Saturated vapor (dew line)

Saturated liquid (bubble line)

Most chemical processes

PT diagram for several compositions. Portion of a PT diagram in the critical region.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Furan(1)/CCl3(2) at 30˚C EtOH(1)/toluene(2) at 65˚C

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Consider a multicomponent system in VLE, the fugacity of species i

For vapor mixture fˆi v  ˆiv y iP

For liquid solution fˆi l   i x i f i

fî v  fî l îv y iP   i x i f i

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia