Phase Equilibrium for Vapor Liquid System

Dr. Afaf Ghais Abadi

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y Vapor of A B C

A B C liquid x

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Nature and definition of equilibrium:
Equilibrium is static condition in which no changes in macroscopic
properties of a system with time. This implies a balance of all
potentials that may cause change.
Definition of vapor liquid equilibrium:

The state at which the rate of transfer from gas to liquid equals to the
rate of transfer from liquid to gas.
Measure of composition
* Concept of equilibrium is justified when it leads to results of
satisfactory accuracy.

Mass fraction. ..

Mole fraction ……….

Molar concentration ………

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Where:
xi = mole/mass fraction according to definition of
component i.
ni ,mi = moles and mass of component i respectively .
molar concentration of component i.
vi= solution or mixture total mass or moles respectively.
total solution or mixture molar volume .

The expression xi is restricted to liquid phase , for vapor phase is

used yi .

Firstly we define Gibbs law:

For any system the number of conditions which should be specified

so as to define the system completely is the degree of freedom .

Ø= number of component – number of phases +2

Ø= c-p+2
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Equilibrium relationship:
1- Raoult’s Law :
Pi  xi Pi 0
this law only applicable for ideal solutions.
Systems of low to moderate pressure, chemically similar
species.
2- Dalton’s law:
Pi  y i PT
Pi 0
x i Pi 0  y i PT yi  xi y i  K i xi
PT
3- Henry’s law :
Pi  Hxi
Species of low concentration, low to moderate
pressure.
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H= Henry’s law constant (solubility)
* the constant is obtained from tables.

4- Antoine Equation :
Calculation of ( poi )
B
log Pi 0  A 
C T

There are two structures of Antoine equation depending on

the Obtained A,B,C constants.

5-vapour pressure:
The pressure at which the
component vaporize.
PT  PB0
xA  0
PA  PB0
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 6- Relative avolatility:
Ki
 ij 
Kj
•Reference component Less Volatile Component (LVC)
•The higher αij easier separation by distillation:
αij > 1 easy separation
αij ≈ 1 difficult separation
αij < 1 impossible separation

Pi 0 yi x j
 ij  0 
Pj xiyj (1)

yi  (1  y j )and xi  (1  x j ) (2)

From (1) and (2) :

• x y
y x
1  x(  1)   y (1   )
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• It is a function of pressure and composition or
temperature and composition
K-value is the measure of the tendency of component
I to vapourize

K  valueof  i
 ij 
K  valueof  j

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Ki=mole fraction of comp. I in vapor Phase mole
fraction of comp. j in liquid phase
mole fraction of component I in liqui

The K-value
can be found
using ChemCad

Figure :De Priester chart — AT-values for hydrocarbons,

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low temperature
Liquid-Vapor Binary Systems

Liquid
+
Vapor

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 Lever Rule, nl/nv
When the point
xtot
corresponding to xtot is
closer to the liquid curve,
the amount of the liquid is Liquid
expected to predominate as +
compared to that in the Vapor
vapor phase.

When the point

corresponding to xtot is
closer to the vapor curve,
the amount of the vapor is
expected to predominate as
compared to that in the liquid
phase.

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 Lever Rule
xtot
nl y1  xtot

nv xtot  x1 Liquid
+
Vapor
bxtot

axtot

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 Temperature-Composition Phase Diagram

 The T-x (isobaric) phase diagram Vapor

is represented by a double curve compositions
or a lens, above which the vapor
phase exists and below which the
liquid phase exists, unlike the case
in the P-x phase diagram.
 The lowest part of the lens Boiling
point of
corresponds to the pure liquid liquid
with the highest vapor pressure
“the one that vaporizes more
easily”.
 The opposite is true for the
highest part end of the diagram.

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 Liquid-Vapor Equilibrium Deviating from
Raoult’s Law

When Raoult’s law holds,

then:
Ptot = PA + PB Liquid +
Vapor

The total vapor pressure

value will be somewhere
between the vapor
pressures of the pure
components.
P*B < Ptot < P*A

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 Liquid-Vapor Equilibrium Deviating from
Raoult’s Law

When we have positive

deviation from Raoult’s law,
Ptot could be in some parts
greater than both P*A and
P*B .
As a result, a maximum in
the pressure-composition
curve is observed.

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 Liquid-Vapor Equilibrium Deviating from
Raoult’s Law

When we have negative

deviation from Raoult’s law,
Ptot could be in some parts
less than P*A and P*B .
As a result, a minimum in
the pressure-composition
curve is observed.

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Examples of Azeotropes

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 Boiling point curves at constant
temperature& pressure
Example:
A mixture of A(heptane) with B(octane) which
may be to form ideal solution:
1. Plot x-y diagram
2. Plot T-x,y diagram
3. At 1100 c, plot P- x,y.

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 Boiling point curves at constant
temperature& pressure
• Solution: using equilibrium relationships for
binary systems

T {C} PA0 mmHg PB0 mmHg XA YA

98.4 760 333 1 1
105 940 417 0.655832 0.81116
110 1050 484 0.487633 0.673703
115 1200 561 0.311424 0.491722
120 1350 650 0.157143 0.279135
125.6 1540 760 0 0
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 • 1- Plot x-y diagram
1.2

1
X-Y diagram
1 0.8
0.9
0.8
0.7
0.6 0.6
Series1
0.5
Y

0.4
0.3 0.4
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.2
X

0
0 0.2 0.4 0.6 0.8 1 1.2

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 2- Plot T-x,y diagram
140

120
T-X,Y diagram
130 100
125
120
80
115
T©

110 Series1
105 60 Series3
100
95
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
40
x,y

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Series1 Series3

0
0 0.2 0.4 0.6 0.8 1 1.2

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3- At 1100 c, plot P- x,y.
pA0 =1050 mmHg , pB0 = 484 mmHg

XA PT YA
0 484 0
0.2 597.2 0.351641
0.4 710.4 0.591216
0.6 823.6 0.764934
0.8 936.8 0.89667
1 1050 1

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 1200

P-x,y diagram 1000

800

600

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x,y 400

Series1 Series3
200

Series1

Series3 0
0 0.2 0.4 0.6 0.8 1 1.2

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Thanks

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