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.

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 Scope of Lecture

Liquid Phase Properties from VLE data

Qualitative Behaviour

Simple Model for VLE

K-values Using DePriester Chart

Flash Calculations

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Liquid Phase Properties
from VLE data

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 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.

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 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

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 Measure of Composition

Mass or mole fraction :

Mass species i Mole species i

mi mi ni n

xi   or xi   i
m m  n n 
Total mass Total moles

xi
Molar concentration: Ci 
V
Molar volume

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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   xiMi
i

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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.

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Qualitative Behavior

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 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
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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

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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

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 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.
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 P-T Diagram

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

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 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 , y 1
Azeotrope

x1 = y1 x2 = y2

Liquid gas
Azeotrope =
composition composition

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Simple Model for VLE

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 VLE (Chapter 11)

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

for each phase

For vapor mixture fˆi v  ˆiv yiP

For liquid solution fˆi l   i xi f i

VLE criteria

fˆi v  fˆi l ˆiv yiP   i xi f i

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 Raoult’s Law
For,

1. The vapor phase is ideal gas → ˆi  1

→ Apply for low to moderate P
yiP  xi f i
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  f i l  fi v  P  Pisat

Vapor-phase mole fraction Liquid-phase mole fraction

yiP  xiPisat Vapor pressure of pure species i

at the T of the system

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VLE from Modified Raoult’s Law

For ideal-gas mixture in equilibrium with non-ideal liquid solution

=1
ˆi yi P   i xi Pisat

yi P   i xi Pisat  i  1, 2, 3,N

 i  f  T, xi 

P    i xi Pisat
i

1
P
 i i i
y /
i
 P sat

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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  1
i i For bubblepoint
yi i
Ki 
xi  y /K i i 1 For dewpoint
 xi  1
i
i

If Raoult’s law is valid,

yiP  x P sat Pisat

i i Ki 
P

If Modified Raoult’s law is valid,

yi P   i xi P sat  iPisat
i Ki 
P
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K-values Using DePriester
(Dadyburjor) Chart

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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

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High-T Range

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Example 1 (K-Value Correlations, Example 10.4)

For a mixture of 10 % methane , 20 % ethane and 70 % propane at

50˚F (10C), determine :

a) The dewpoint pressure

b) The bubblepoint pressure

The K- values are given by Fig .10.13

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 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

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 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

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Dewpoint & Bubblepoint
Calculation

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 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.

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 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.

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 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

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 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.

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 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.

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 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

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 Derivation

Overall mole balance

V
T LV
L
Component mole balance
Tzi  Lxi  Vyi

Let T = 1 mol, so V and L are mole fractions,

zi  Lxi  Vyi

zi  1 V  xi  Vyi

Note: zi, overall composition Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Derivation
Substitute
yi  K ixi zi  1 V  xi  Vyi ziK i
yi 
1 V K i  1
zi  1 V  xi  K ixiV
 xi 1 V  VK i   xi 1 V K i  1 
Also,
zi
xi 
1 V K i  1
x y  0
i i

yi Substitute
xi  zi  1 V  xi  Vyi zi ziK i
Ki  1 V K  1 1 V K  1  0

i i

yi
zi  1 V   yiV
Ki zi  ziK i
 1 V K  1  0
i
ziK i  1 V  yi  K iyiV
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 Bubblepoint Calculation

At bubblepoint (practically all If Raoult’s Law valid

liquid) L = 1, V = 0 and zi =xi
Pisat
 xiK i   xi P  1
zi  ziK i
 1 V K  1  0 P   xiPisat
i

Binary system

  xi  xiK i   0 
P  P2sat  P1sat  P2sat x1 
If Modified Raoult’s Law valid
 x   xK
i i i
 iPisat
 xiK i   xi P  1
 xK i i 1 Bubblepoint criteria P   xi iPisat

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 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

zi  ziK i
 1 V K  1  0
i i

i 1
P
 yi/Pisat
yi  yiK 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
 yi/ iPisat
i

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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

yiP  x P
i i
sat P   xiPisat 
P  P2sat  P1sat  P2sat x1 
y 1
i
i

Binary system
i P   xi iPisat
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.
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 Summary (Cont.)

1
yiP  x P sat
 i  1, 2,N P
i i
 yi/Pisat
x 1
i
i i

1
P
 yi/ iPisat

An equation applied in Dewpoint calculations, where liquid-

phase composition are not known.

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 Relative Volatility

ik > 1, species i is relatively more volatile

yi/xi K i
αik   ik < 1, species k is relatively more volatile
yk /xk K k
At azeotrope ik = 1/1=1

If Raoult’s Law valid

P1sat/P P1sat Note: for higher vapor pressure

αik  sat  sat means more volatile 12 > 1
P2 /P P2

If Modified Raoult’s Law valid

 1P1sat/P  1P1sat
αik  
 2P2 /P  2P2sat
sat

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 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.

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 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

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 Solution 2 (Cont.)

Calculate P and y1, given a set of x1 and T = 75 C

→ BULB P calculation  xK i i 1

Let us assume Raoult’s Law is valid, P  Pb   xP i i

sat

P  x1P1sat  x2P2sat  x1P1sat  1 x1P2sat

 
P  P1sat  P2sat x1  P2sat A (A linear line, y = mx + c)

Also,
x1P1sat
y1  B
P
So, calculate P for a set of x1 (Eqn. A) and then calculate y1 (Eqn. B)

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 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
x1P1sat
y1 
P Gas mix./ superheated
vap. mix.
 
P  Pb  P1sat  P2sat x1  P2sat
20
0 0.2 0.4 0.6 0.8 1.0
x1,y1
Calculate
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 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 Compare with values

Pd    59.74kPa
 yi/Pisat
0.6

0.4 from Pxy diagram
83.21 41.98
y1Pd 0.6 59.74
Then calculate x1 using x1  sat
  0.43
P1 83.21
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 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

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 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 T2
sat 
/ 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

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 Solution 2 (Cont.)
 xK i i 1

If Raoult’s Law valid, P  Pb   ii

x P sat

P  x1P1sat  x2P2sat  x1P1sat  1 x1P2sat

P  P2sat
x1  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

x1P1sat
Then calculate y1 using, y1 
P
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 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 vap. mix.
85
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 P sat t1sat = 69.84
x1  sat y  1 1
P1  P2sat 1 P 65
0 0.2 0.4 0.6 0.8 1.0
Calculate Psat1 & Psat2 for each temp. x1,y1
(74, 78, 82, 86) to calculate x1 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 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)  xK i i 1

The solution is not straightforward as T is unknown. Let’s see how to

solve mathematically

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 Solution 2 (Cont.)

For Raoult’s Law, Pb   xPi i

sat

Pksat P sat
Pb  sat  xiPisat  Pksat xi isat  Pksat xiαik Where k is a component
Pk Pk that arbitrarily chosen

Pb
Pksat  A
 xiαik
Also,

Pisat  Bi   Bk 

lnαik  ln sat  lnPi  lnPk   A i 
sat sat

 
  Ak  
Pk  T  Ci   T  Ck 

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 Solution 2 (Iteration)

1. Start with an initial guess of T as follows

T   xiTisat 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

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 Solution 2 (Iteration)

Pb
4. Calculate Pk sat
using Eqn. A Pksat 
 xiαik
Pb 70
P2sat    44.3977kPa
x1α12  x2α22 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

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 Solution 2 (Cont.)

t2sat = 89.58 P= 70 kPa

90

T ik P1sat P2sat T

t-y1
85
77.74 1.9611 87.49 44.39 76.53 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

t1sat = 69.84
yi  0.7472
65
0 0.2 0.4 0.6 0.8 1.0

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 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
80
and P = 70kPa. See text book (page c’

t/C
356) for the solution (also iteration) of
b b’
Dew T calculation.
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
x 1,y1

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 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)

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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.

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 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   xi iPisat   0.251.864 44.51   0.751.072 65.64  73.50

yiP   xi iPisat y1  0.282 y2  0.718

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 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
 yi/ iPisat
ln γ1 = Ax22 ln γ2 = Ax12
where A = 2.771 – 0.00523T

y1P
x1 
 1P1sat
x2  1 x1

Converges at: P  62.89kPa x1  0.8169  1  1.0378  2  2.0935

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 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

ln γ1 = Ax22
3,643.31 ln γ2 = Ax12
T1sat   33.424 1   2 
16.59158 lnP1sat
P   xi iPisat

P1sat   P1sat  P
x1 1  x2 2/α12
Converges at: T  331.20K y1  0.670 y2  0.330
P
P2sat 
 1  1.0236  2  2.1182 x1 1α12  x2 2

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 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
3,643.31 lnPisat/kPa  A i 
T1sat   33.424 T K   C i
16.59158 lnP1
sat
P1sat   P2sat  
y1P
x1  ; x2  1 x1
γ1P1sat
x1   x2  
y y 
P1sat  P  1  2 α12 
ln γ1 = Ax22 1   2   1  2 
ln γ2 = Ax12 y1 y
P2sat   2
P1sat   P2sat    1α12  2α22
Converges at: T  327.70K x1  0.4602 x2  0.5398  1  1.3629  2  1.2523
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 Solution 3 (Cont.)
(e) Paz & xaz =yaz, for T = 318.15 K.

y /x yiP   xi iPisat

Define the relative volatility αik  i i  1P1sat
αik 
yk /xk  2P2sat
Azeotrope y1  x1 y2  x2 αik  1

P1satexp 2.771 0.00523T P sat

α12 γx1exp
0   2.052 α12 γx111  sat 2
 0.224
1
γ2 1
 A sat
P2 >1 γ
1
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

 x22 1
ln   2.771 0.00523T
 x2  x1   2.771 0.00523T1 2x1
2
ln 2   2.771 0.00523T
 x12
γ1az  1.657
x1az  y1az  0.325
P az   1azP1sat  73.76kPa
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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

y2P  x2P2sat P2sat  y2P

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Example: Dew T of Combustion Products

For stoichiometric combustion of CH4, calculate dewpoint T of the

combustion products

CH4  2O2  2 79/21

N2  CO2  2H2O  2 79/21N2

Mole fraction of H2O is 2/(1+2+2(79/21)) = 0.19

P2sat  y2P

P2sat   0.19101.325kPa  19.25kPa

From steam table, Td = T2sat = 59.5 C

Or Antoine equation

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 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

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Flash Calculations

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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

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 Equations
Consider a system containing one mole of reacting chemical species,

L V 1 zi  xiL  yiV zi  xi 1 V   yiV

Moles of vapor Vapor mole fraction ziK i

yi 
Moles of liquid Liquid mole fraction 1 V K i  1

Mole fractions of
ziK 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

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 Example 4 (Example 10.5)

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

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 Solution 4
Do the BUBL P calculation, with {zi} = {xi}

Pbubl  x1P1sat  x2P2sat  x3P3sat   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
y1/P1sat  y2/P2sat  y3/P3sat

Since Pdew < P = 110 kPa < Pbubl, the system in in 2-phase region
L  1 V  0.2636mol
K 1  1.7795
P sat Substitute ziK i Trial & error
Ki  i
P
K 2  0.8895  1 V K  1  1 V  0.7364mol
i
K 3  0.4575 ziK i
yi 
1 V K i  1

x1  0.2859
yi y1  0.5087
Ki 
xi
x2  0.3810 y2  0.3389
x3  0.3331 y3  0.1524
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 Example 5 (Example 10.6)

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

ziK i
 1 V K  1  1
i

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 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

ziK i
Satisfied when V = 0.273  1 V K  1  1
i

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 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?

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Henry’s Law

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 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
ˆiyiP   i xi f i yiP  xi i f i  xi iPisat

Let Hi   i f i   iPisat yi P  xi Hi

Henry’s constant (in bar) for dissolved gas (i)

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 Henry’s Costant

So, at dilute solution

yi   Hi / P  xi 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
 xi 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

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 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 CO 2

(component 1) in the dew (liquid)?

We could solve this using Henry’s Law for dissolved gases (CO2)

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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.

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 Henry’s Law (Ideal Solution)

If the fugacity of i in liquid phase is given by Henry’s law

fˆi   i xi f i  xi Hi

If the ideal gas is ideal solution (Lewis/Randall is valid)

fˆi  i xi Pi

So, we get the following version of Henry’s Law if gas mixture is ideal
solution

i xi Pi  xi Hi

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 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.

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 Solution 6
Henry’s law for species 1: y1 P  x1 H1

Raoult’s law for species 2: y2P  x2P2

sat

P  x1H1  x2P2sat
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 x1  0.0100

x2P2sat
y2 
P
y2  0.0012
y1  0.9988 Justified the assumption
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 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

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 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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