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Dr.T.

M 1
Concept of Equilibrium
The separation process considered are
based on the equilibrium stage concept
i.e. the streams leaving a stage are in
equilibrium
What do we meant by Equilibrium?
Dr.T.M 2
The objective is:

To understand the concept of equilibrium

Able to estimate the concentration in vapour and liquid
phases
Chapter : 2
Dr.T.M 3
Vapour-Liquid Equilibrium
Consider a vapor and liquid that are in contact
with each other as shown:
vapor condensing + liquid vaporizing
P
liquid
, T
liquid

P
vapour
, T
vapour

A
B
A B
Dr.T.M 4
Not at equilibrium liquid + vapor at different T, P, mole
fractions
At equilibrium
1. T, P and fractions of the two phases cease to change
2. Rate of each species condensing is equal to the rate at
which it evaporates
3. No further changes in T, P, or compositions
Dr.T.M 5
Phase Rule and Equilibrium
F = C - P + 2
degrees
of freedom

number
of components

number
Of phases
Degrees of freedom is the number of intensive variables that must
be specified to define the equilibrium state of a system.
Dr.T.M 6
Intensive variables: P, T, or mole
fraction which do not depend on the total
amount of material present
Extensive variables: number of moles,
flow rate, volume, which depend on the
amount of material present
Dr.T.M 7
Example: O2 Water system
F = 2 - 2 + 2 = 2
2 degrees of freedom
Phase rule refers to intensive variables such as
T
P
Mass or mole fraction
density, specific volume
If the pressure and temperature are set, all the degrees of freedom are used and at
equilibrium all compositions are determined from experiment
Dr.T.M 8
Vapour-Liquid Equilibrium
100
o
C
T
bp
1 atm
One Component Example:Water
2 variables: T and P
V&L
T
P
Dr.T.M 9
Two Components Example: A and B
- 3 variables: T, P and composition
Boiling Point Diagram @Txy diagram at P= 1 atm
L
V
T
bp
of A
V&L
T
bp
of B
mole fraction A
T
dew

T
bp

bubble point when heating
a subcooled liquid, the
temperature at which the first
bubble forms
dew point when cooling a
superheated vapour, the
temperature at which the first
drop of dew forms
Dr.T.M 10
x
tie line
y
T
Two Components A and B
x = mole fraction of more
volatile component in
liquid phase
y = mole fraction of more
volatile component in
vapour phase
Dr.T.M 11
Vapour-Liquid Equilibrium
Raoults law: p
i
= x
i
P*
i
Ideal Solutions Obey Raoults Law
Consider an ideal solution in equilibrium with an ideal gas to
predict the Txy diagram. Assume we are at some temperature
for which both phases co-exist at equilibrium
Let P = total pressure
P*
i
= vapour pressure of pure I
x
i
, y
i
= mole fractions in liq or vap at equil
p
i
y
i
P = partial pressure of component i

Partial Pressure = Vap.Pressure X Conc.

Dr.T.M 12
Ideal Binary Mixtures
Now, we consider to a system with only 2 components, which we
will call A and B.
The mole fractions must sum to one for each phase, so we can
express the mole fraction of B in terms of that for A:
x
B
= 1 x
A
and y
B
= 1 - y
A

Applying Raoults law to each component:
p
A
= x
A
P*
A
= y
A
P

(1)



p
B
= (1-x
A
)

P*
B
= (1 y
A
)

P

(2)

Dr.T.M 13
Adding the partial pressures from (1) and (2), we obtain the total
pressure:
P = p
A
+ p
B
= x
A
P*
A
+ (1-x
A
)

P*
B

Solving for the mole fraction x
A
:
(3)

From (1): y
A
= x
A
P*
A
/ P (4)
If you specify a T and P, the vapour pressure can be determined
and calculate the compositions which will be at equilibrium from
(3) and (4). Thus, you can construct a complete phase diagram
using only vapour pressure data for the pure components.
* *
*
B A
B T
A
P P
P P
X

=
Dr.T.M 14
T-x-y Diagram
Dr.T.M 15
Vapour-Liquid Equilibrium
Txy diagram
xy diagram
(used in distillation
calculations)
tie line
x y
T
x
y
Dr.T.M 16
Relative Volatility
Relative volatility is a measure of the differences in volatility
between 2 components. It indicates how easy or difficult a
particular separation will be. The relative volatility of component i
with respect to component j is shown with the relationship
between x and y :
o
ij
K
i
/ K
j

Where Ks are called the distribution coefficient which in turn
are defined as:
K
i
y
i
/ x
i
|
|
.
|

\
|
|
|
.
|

\
|
=
j
j
i
i
ij
x
y
x
y
o
i.e.,

Dr.T.M 17
The normal boiling points of the pure, n-heptane and n-octane
are 98.4
o
C and 125.6
o
C, respectively. The vapor pressure
data are given below. Estimate the mole fraction of n-heptane
in both liquid and vapor phase.
Example - 1


Temp VP mm Hg
0
C n- heptane Octane

98.4 760 333
105 940 417
110 1050 484
115 1200 561
120 1350 650
125.6 1540 760


Dr.T.M 18
T (
o
C) heptane octane x y
98.4 760 333 1.000 1.000
105 940 417 0.656 0.811
110 1050 484 0.488 0.674
115 1200 561 0.311 0.492
120 1350 650 0.157 0.279
125.6 1540 760 0.000 0.000
Mole Fraction n-heptane
at 1 atm
Vapour Pressure (mmHg)
Vapour Pressure and Equilibrium-Mole-Fraction Data for
heptane-octane system
Dr.T.M 19
98
100
102
104
106
108
110
112
114
116
118
120
122
124
126
0.000 0.200 0.400 0.600 0.800 1.000
mole fraction of heptane
T
e
m
p
e
r
a
t
u
r
e

(
d
e
g

C
)