TKM 406

Termodinamika Teknik Kimia II

Teknik Kimia UNTAN
 Sylabus:
Multicomponent Thermodynamics

• Phase Equilibria (80%)

• Chemical Equilibria (20%)
 Textbooks & References
• Smith, Introduction 2 Chemical Engineering
Thermodynamics

• Daubert, Chemical Engineering

Thermodynamics
Phase Equilbria:

Raoult’s Law
 Nomenclature
• Closed System
• xi : mol fraction in liquid phase
• yi : mol fraction in gas phase

• i = 1,2,3,…
• Sorted by
vapor pressure
from the higher one

• Vapor pressure: tendency of

certain liquid to vaporize
• The higher the temperature, the
higher the vapor pressure
 Vapor
Pressure
Model
Antoine

P [=] torr
t [=] oC
 Antoine Vapor Pressure Model

P [=] torr
t [=] oC
 Antoine Vapor Pressure Model

P [=] torr
t [=] oC
What will be needed in the near future:

Hand Calculator

Computer Programs
• Microsoft Excel
• MathCAD
 Phase Equilibria Problem

Relation among T,
P, xi & yi at
equilibrium
condition
 Experimental Approach
Mixture:
Methyl-ethyl-ketone (1) / Toluene (2)
Temperature:
50oC

Plot the P-x-y diagram

 Typical Diagram

P-x-y diagram t-x-y diagram

 Experimental Approach - Drawback
For the same binary mixture:
Methyl-ethyl-ketone (1) / Toluene(2)

What if we need the equilibrium data at 40oC?

You’ve got to make experiment at that temperature!
What if we need the equilibrium data at 60oC?
You’ve got to make experiment at that temperature!
What if we need the equilibrium data at 50oC?
You already have one!

Even for a simple binary mixture we must carry out many

experiment in order to gather data
 Experimental Approach - Drawback
What about other binary mixture:
Chloroform (1) / Dioxane (2)
You’ve got to perform other experiments!
Diethyl ketone (1) / n-hexane (2)
You’ve got to perform other experiments!
Acetonitrile (1) / Nitromethane (2)
You’ve got to perform other experiments!

How many experiment should be carried out to obtain binary

mixture vapor – liquid equilibria
from a combination of 8 components? Waw!
 Experimental Approach - Drawback

What about ternary mixture such as:

Benzene (1) / Toluene (2) / Ethylbenzene (3) ?
You’ve certainly got to perform other experiments!

What about multicomponents mixture such as:

Ethane (1) / Propane (2) / Isobutane (3) /
Isopentane (4) ?
You know the answer!

How many experiment should be carried out to obtain

mixtures vapor – liquid equilibria
from a combination of 100 components? Waw!
 Fundamental Question

Do we really have to do these experiments?

100 years ago the answer is Yes!
Not now!

That’s why we take this course, folks!

 Thermodynamics Approach:
Criteria for System in Equilibria
T   T   ....  T 
P   P   ....  P 
  
 i   i  ....   i i

The chemical potential of i-th

component is defined as:

  ( nG ) 
i   
 n i  T ,P,n j
 Criteria for Vapor - Liquid Equilibria
Tg  T
g 
P P
i g  i  i

The chemical potential of i-th

component is defined as:

  ( nG ) 
i   
 n i  T ,P,n j
 Raoult’s Law
  ( nG ) 
The chemical potential of i: i   
 n i  T , P,n j

For ideal gases:  i ig  G i ig  R  T  ln( y i )

For ideal solution:  i id  G i   R  T  ln(x i )


Neglecting effect of pressure on , we
G i obtain:

sat
Raoult’s law y i  P  x i  Pi
 Construction of Phase Diagram
Using Raoult’s Law: Binary Mixture
y i  P  x i  Pi sat
Physical Interpretation of Phase Diagram: Pxy
Physical Interpretation of Phase Diagram: txy
 Berdasarkan Diagram,
Tentukan dan Tunjukkan:
a. Titik didih normal asetonitril
b. Fasa campuran dengan fraksi mol asetonitril = 0,22 pada
tekanan 70 kPa dan suhu 95oC
c. Bila campuran ekimolar bersuhu kamar 25oC dipanaskan
perlahan-lahan hingga mendidih, tentukan komposisi
uap yang mula-mula terbentuk
d. Pada temperatur berapa seluruh cairan pada (c) teruapkan
?
e. Uap yang diperoleh pada (c) dikondensasikan. Cairan ini
kemudian dibiarkan setimbang dengan uapnya pada
tekanan 70 kPa. Gambarkan proses ini dalam diagram
dan tentukan komposisi uap baru yang terbentuk.
Raoult’s Law: Binary Mixture
Raoult’s Law: Binary Mixture
 Type of Phase Equilibria Calculations

Given T & P, find the equilibrium composition xi, yi

BUBL P calculation:
Given T & liquid composition xi,
Find the bubble point Pb & vapor composition

DEW P calculation:
Given T & vapor composition yi,
Find the dew point Pd & vapor composition
 Type of Phase Equilibria Calculations
BUBL t calculation:
Given P & liquid composition xi,
Find the bubble point tb & vapor composition

DEW t calculation:
Given P & vapor composition yi,
Find the dew point Pd & vapor composition

FLASH calculation:
Given P, T & overall composition,
Find the fraction of system which is liquid (L) & vapor (V) and
their respective compositions xi & yi
Raoult’s Law; Binary Mixture
 Type of Phase Equilibria Calculations

a. Given T= 100oC & P = 1 atm, find the equilibrium

composition xi, yi

b. BUBL P calculation:
Given T = 100oC & liquid composition x1 = 25%
Find the bubble point Pb & vapor composition

c. DEW P calculation:
Given T = 100oC & vapor composition y1 = 25%,
Find the dew point Pd & dew composition
 Type of Phase Equilibria Calculations
d. BUBL t calculation:
Given P = 1 atm & liquid composition x1= 25%
Find the bubble point tb & vapor composition

e. DEW t calculation:
Given P = 1 atm & vapor composition y1,= 25%
Find the dew point td & dew composition

f. FLASH calculation:
Given P = 1 atm, T = 115oC & overall composition, z1=25%
Find the fraction of system which is liquid (L) & vapor (V) and
their respective compositions xi & yi
Do we always have to prepare phase
diagram to make calculation?

No, we don’t have to

We can just perform the calculations

Raoult’s Law: Binary mixture
Raoult’s Law: Binary mixture
 Extention to ternary mixture

We can’t even prepare the diagram!

But we still able to make the calculations

Raoult’s Law: Ternary Mixture
Raoult’s Law: Ternary Mixture
Raoult’s Law: Ternary Mixture
Raoult’s Law: Ternary Mixture