Chapter 10 VLE - Updated

Chemical Engineering Thermodynamics II (CEB 2023) September 2019
Vapor/Liquid Equilibrium:
Introduction
Chapter 10
CLO2 : Identify, formulate, research literature and analyse

complex chemical engineering problems reaching substantiated
conclusions using principles of mathematics, natural sciences
and engineering sciences.
m.moniruzzaman@utp.edu.my
Learning Outcome
2
Equilibrium
3
Equilibrium
 Thermal equilibrium: If the temperature is the same
throughout the entire system.
 Mechanical equilibrium: If there is no change in

pressure at any point of the system with time.
 Phase equilibrium: If a system involves two phases and

when the mass of each phase reaches an equilibrium
level and stays there.
 Chemical equilibrium: If the chemical composition of a

system does not change with time, that is, no chemical
reactions occur.
A system is not in thermodynamic equilibrium unless
all the above equilibrium conditions are satisfied.
4
Vapor Liquid Equilibrium (VLE)

 The state of coexistence of liquid and vapor phases.
 All equilibrium states of a binary system can be
represented in P-T-composition diagram. (PTxy
diagram)
6
7
8
9
10
12
11
13
Simple Models for VLE
14
Raoult’s Law
15
Raoult’s Law: Applications
16
Bubbles Point Calculations
17
VLE for Ideal Mixtures

Class Example 1: Find the vapor composition above a liquid
mixture of 50 mol% benzene(1) and hexane(2) at 25 ºC if it is
assumed that both the liquid and vapor form ideal solutions.
The vapor pressure of benzene and hexane at 25 ºC are 93.9
and 149.2 mmHg respectively.
Using BUBL P, Calculate for y1 and y2.
According to Raoult’s law,
y1 P = x1P1sat =0.5 x 93.9 y2 P= x2 P2sat = 0.5 x 149.2
P = y1 P + y2 P = x1 P1sat + x2 P2sat = 121.5 mmHg
The composition in vapor could then be calculated
y1 = 0.386; y2 = 0.614
18
Book 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:
𝑠𝑎𝑡 /𝑘𝑃𝑎
2945.47
ln 𝑃1 = 14.2724 −
𝑇 − 49.15
𝑠𝑎𝑡 /𝑘𝑃𝑎
2972.64
ln 𝑃2 = 14.2043 −
𝑇 − 64.15
(a) Prepare a graph showing P vs x1 and P vs y1 for a

temperature of 75 ºC (348.15K)
(a) Prepare a graph showing T vs x1 and T vs y1 for a

pressure of 70kPa.
19
Example 10.1: Solution

Given, Acetronitrile (1) and nitromethane (2)
(a) At t= 75 ºC, P1sat = 83.21 kPa and P2sat = 41.98 kPa
x1 x2 P = x1P1sat +x2P2sat y1 = x1P1sat /P

0.0 1.0 41.98 0.0
0.2 0.8 50.23 0.3313
0.4 0.6 58.47 0.5692
0.6 0.4 66.72 0.7483
0.8 0.2 74.96 0.8880
1.0 0.0 83.21 1.00
20
Example 10.1: Solution (Cont’d)
21
Book Example 10.1 (Cont’d)

(b) At given P= 70 kPa, we cannot solve it explicitly
The temperature range is bounded by the saturation

temperatures t1sat and t2sat at P=70 kPa
Guess t between , t1sat and , t2sat , calculate P1sat and P2sat

from antoine equation, then calculate x1 and y1 from
the following equations:
𝑃 − 𝑃2𝑠𝑎𝑡
𝑥1 = 𝑠𝑎𝑡
𝑃1 − 𝑃2𝑠𝑎𝑡
𝑥1 𝑃1𝑠𝑎𝑡
𝑦1 =
𝑃
22
At P= 70 kPa, t1sat = 69.84 ºC/342.99 K and

t2sat = 89.58 ºC/362.73 (From Antoine equation)
T (K) P1 sat P2 sat x1 x2 y1 = x1P1sat /P

Guess (kPa) (kPa)
362.73 131.54 70 0.0 1.0 0.0

359.15 0.1424 0.2401
355.15 0.3184 0.4742
351.15 0.5156 0.6759
347.15 0.7378 0.8484
342.99 70 34.24 1.0 0.0 1.00
24
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Class Example 2
Assuming the Raoults law to be valid, prepare a P-x-y diagram
for a temperature 90 ºC for benzene (1)/ ethylbenzene (2).Vapor
pressures for the pure species of benzene and ethylbenzene
are given as P1sat = 135.5367 kPa and P2sat = 24.24732 kPa,
respectively.
To be solved in the class
26
Class Example 2: Solution (Cont’d)
29
Self-assessment assignment: 1
Develop a T-x,y diagram for a system containing n-pentane(1)
and n-heptane(2) at pressure 101.3 kPa. Given the Antoine eqn.
for saturation vapor pressure for the 2 components as below;
Component 1 : ln P10 (kPa)= 13.818 – 2477.07 / (T (K) + 233.21)
Component 2 : ln P20 (kPa)= 13.8587 – 2911.32 / (T (K)+ 216.64)
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Henry’s Law
 In the case that chemical constituents in the liquid phase is
very small or dilute, Raoult’s law can not be applied.
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Henry’s Law: Example 10.2

VLE by Modified Raoult’s Law
31
Book Example 10.3
To be solved in the class 32

A binary liquid mixture containing 40.5 mol% ethanol (1) and the rest
methylcyclohexane (2) exerts an equilibrium pressure of 152.4 mm at
35oC. The vapor phase contains 54.7 mol% ethanol.
The Antoine equations for ethanol (1) and methylcyclohexane (2) are given below:
 
ln P1
sat  1652.05 
 8.2130  
T  231.480 
   6.8230  T1270
ln P2
sat .763 
 221.416 
 
where, P sat and T are in mmHg and oC, respectively.
Calculate the activity coefficients of ethanol (1) and

methylcyclohexane (2) in the binary mixture.
33
VLE from K-value correlations
35
K-value correlations
36
Book Example 10.4
(b) Bubble point pressure

P = 26.2 bar P = 27.6 bar P = 26.54 bar
Species xi Ki Kixi Ki Kixi Ki Kixi
Methane 0.1 5.6 0.56 5.25 0.525 5.49 0.549
Ethane 0.2 1.11 0.222 1.07 0.214 1.1 0.22
Propane 0.7 0.335 0.235 0.32 0.224 0.33 0.231
Σ (Kixi) = 1.017 Σ (Kixi) = 0.963 Σ (Kixi) = 1.000
Book Example 10.4
Flash Calculations
Flash Calculations: example 10.5

Check list
 Vapor liquid equilibrium (VLE)
 Raoult’s/modified Raoult’s Laws
 Pxy and Txy diagram
 Determination of T, P and phase compositions

for systems in VLE
 Henry’s Law
 K-value correlations
 Flash calculation
Example of Previous Year Question

Example of Previous Year Question (Cont’d)
TEST 2
Date: November 7, 2019 (Thursday)
Time: 8:00 pm 9: 00 pm
Syllabus: TBA
Venue: Pocket C6 (For G1&2)
Pocket C7 (For G3&4)

Chapter 10 VLE - Updated

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Chemical Engineering Thermodynamics II (CEB 2023) September 2019

CLO2 : Identify, formulate, research literature and analyse

 Mechanical equilibrium: If there is no change in

 Phase equilibrium: If a system involves two phases and

 Chemical equilibrium: If the chemical composition of a

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Vapor Liquid Equilibrium (VLE)

Simple Models for VLE

Raoult’s Law: Applications

Bubbles Point Calculations

VLE for Ideal Mixtures

P = y1 P + y2 P = x1 P1sat + x2 P2sat = 121.5 mmHg

The composition in vapor could then be calculated

Book Example 10.1 : Binary system acetonitrile (1)/

(a) Prepare a graph showing P vs x1 and P vs y1 for a

(a) Prepare a graph showing T vs x1 and T vs y1 for a

Example 10.1: Solution

(a) At t= 75 ºC, P1sat = 83.21 kPa and P2sat = 41.98 kPa

x1 x2 P = x1P1sat +x2P2sat y1 = x1P1sat /P

Example 10.1: Solution (Cont’d)

Book Example 10.1 (Cont’d)

The temperature range is bounded by the saturation

Guess t between , t1sat and , t2sat , calculate P1sat and P2sat

Book Example 10.1 (Cont’d)

At P= 70 kPa, t1sat = 69.84 ºC/342.99 K and

T (K) P1 sat P2 sat x1 x2 y1 = x1P1sat /P

362.73 131.54 70 0.0 1.0 0.0

Book Example 10.1 (Cont’d)

Class Example 2: Solution (Cont’d)

Henry’s Law: Example 10.2

VLE by Modified Raoult’s Law

Book Example 10.3

To be solved in the class 32

Calculate the activity coefficients of ethanol (1) and

VLE from K-value correlations

Book Example 10.4

(b) Bubble point pressure

Flash Calculations: example 10.5

 Vapor liquid equilibrium (VLE)

 Raoult’s/modified Raoult’s Laws

 Pxy and Txy diagram

 Determination of T, P and phase compositions

Example of Previous Year Question

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