ITK-234

Termodinamika Teknik Kimia II

(2 SKS)

Dicky Dermawan
2d@itenas.ac.id

Sylabus:
Multicomponent Thermodynamics
(80%)
Phase Equilibria
Chemical Equilibria (20%)

Textbooks & References

Smith, Introduction 2 Chemical
Engineering Thermodynamics

Daubert, Chemical Engineering

Thermodynamics

Score & Grade

20 4 all homework & quiz
25 4 1st midterm exam
25 4 2nd midterm exam
30 4 final term examination
A

4 74.5 ++
B 4 59.5 ++
C 4 49.5 ++
D 4 39.5 ++

Phase Equilbria:
Raoults 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 40 oC?

Youve got to make experiment at that temperature!

What if we need the equilibrium data at 60 oC?

Youve got to make experiment at that temperatu
What if we need the equilibrium data at 50 oC?

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)

Youve got to perform other experiments!

Diethyl ketone (1) / n-hexane (2)
Youve got to perform other experiments!
Acetonitrile (1) / Nitromethane (2)
Youve 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) ?
Youve 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!

Thats why we take this course, folks!

Thermodynamics Approach:
Criteria for System in Equilibria
T T .... T
P P .... P

i i .... i

The chemical potential of ith 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

The chemical potential of ith component is defined as:

(nG )
i

n i T,P,n j

Raoults 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

Gi
Raoults law

y i P x i Pi

sat

, we obtain:

Construction of Phase Diagram

sat
y

P
i
i i
Using Raoults Law: Binary Mixture

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 95 oC
c. Bila campuran ekimolar bersuhu kamar 25 oC
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.

Raoults Law: Binary Mixture

Raoults 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

Raoults 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 x 1= 25%

Find the bubble point tb & vapor composition

e. DEW t calculation:
Given P = 1 atm & vapor composition y 1,= 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 x i & yi

Do we always have to prepare

phase diagram to make
calculation?
No, we dont have to
We can just perform the
calculations

Raoults Law: Binary mixture

Raoults Law: Binary mixture

Extention to ternary mixture

We cant even prepare the diagram!

But we still able to make the
calculations

Raoults Law: Ternary

Mixture

Raoults Law: Ternary

Mixture

Raoults Law: Ternary

Mixture

Raoults Law: Ternary

Mixture