THERMODYNAMICS OF

SEPARATION OPERATIONS

Thermodynamic properties and equations play a major role in separation

operations, particularly with respect to energy requirements, phase equilibria, and
sizing equipment.

Consider the continuous, steady-state, flow system for a general separation

process in the following figure. One or more feed streams flowing into the system
are separated into two or more product streams that flow out of the system.
n =molar flow rates.
zi = component mole
fractions.
T = temperature .
P = pressure.
h = molar enthalpies.
S= molar entropies.
b = molar availabilities.
ChE 334: Separation Processes

Dr Saad Al-Shahrani

THERMODYNAMICS OF
SEPARATION OPERATIONS

ENERGY, ENTROPY, AND AVAILABILITY BALANCES

Energy balance:

Entropy balance:

Availability balance:

where b = h T0s = availability function

ChE 334: Separation Processes

Dr Saad Al-Shahrani

THERMODYNAMICS OF
SEPARATION OPERATIONS

Minimum work of separation:

Second-law efficiency:

Where LW = T0Sirr = lost work

ChE 334: Separation Processes

Dr Saad Al-Shahrani

THERMODYNAMICS OF
SEPARATION OPERATIONS
The criterion of equilibrium is that all potentials for change are in

balance: there are no changes in the equilibrium state and no

tendency to leave that state
For three phases (vapor (V), Liquid (L), and solid (S), the

temperatures and pressures must be equal at equilibrium:

TV=TL=TS

thermal equilibrium

PV=PL=PS

mechanical equilibrium

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
Vapor-liquid equilibrium data can be measured by placing
a mixture of the two components in a vessel held at either
constant temperature or constant pressure
Equilibrium between the liquid and
vapor phases will be approached
slowly, but may be promoted by
agitating the vessel or by
circulating the vapor phase so that
it bubbles through the liquid.

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
After equilibrium, the pressure and temperature are
measured and samples are taken to determine the vapor
and liquid compositions.
There are several different types of plots for binary system:
1. Pxy diagram: x and y as functions of pressure at constant temperature.
2. Txy diagram: x and y as functions of temperature at constant pressure.
3. xy diagram: x versus y at constant pressure (temperature is a
parameter along the curve).

Since most applications require data at constant pressure, Txy and xy

diagrams are the most commonly used.
ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM

1. Pxy Diagrams

Pxy diagram for a binary mixture at

constant temperature. In this diagram,
compositions are given as mole fraction
of the light component
The upper curve gives the liquid
composition x versus pressure P. The
lower curve gives the vapor composition y
versus pressure.

PL
Pure light

Subcooled liquid
x
Pressure

Constant T

PH

se
ha
p
oTw

e
sr

n
gio

Superheated Vapor
Pure heavy

1.0
0
x, y
Composition (mole fraction light component

PH= vapor pressure of pure heavy component at the temperature at

which the data were collected (x=0).
PL= vapor pressure of pure light component at the temperature at which
the data were collected (x=1.0).
ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
The

liquid

and

Constant T

vapor

compositions x1 and y1 are

obtained

from

the

intersection of the phase

envelope

with

the

Subcooled liquid

P1
Pressure

P1

constant pressure line.

Superheated Vapor

x1

x, y

y1

Composition (mole fraction light

component

ChE 334: Separation Processes

Dr Saad Al-Shahrani

1.0

BINARY VAPOR-LIQUID
EQUILIBRIUM

For

composition

pressure

is

z.

If

the

increased

at

Constant T

PBP

PDP is called the dew point

pressure,

because

the

Pressure

liquid phase will begin to form.

Subcooled liquid

constant temperature to PDP a

Saturated liquid
line

Saturated vapor
line

P1
PDP

first

drops of liquid form as "dew."

The liquid droplets that form will

Superheated Vapor

be much leaner in the light

component. The composition of
the first drop of liquid formed at
PDP is xDP.
ChE 334: Separation Processes

xDP

x1

yz1

yBP

Composition (mole fraction light

component
Dr Saad Al-Shahrani

1.0

BINARY VAPOR-LIQUID
EQUILIBRIUM

As the pressure is increased further, more liquid forms. At a

pressure P1 there is almost as much liquid of composition x1 as
vapor of composition y1.

As the pressure is further increased, PBP is reached. Here the last

bit of the vapor phase exists as bubbles, so this pressure is known
as the bubble point pressure of the mixture with composition z at
the specified temperature.

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
Txy Diagrams
The boiling point temperature

in

the

diagram

is

the

Superheated Vapor

TDP

of the pure light component

TL at the pressure specified

y
x

Temperature

TH

Saturated vapor
line

T1
TBP

temperature at the point x =

y = 1. TH is the boiling

TL
Saturated liquid
line

Subcooled liquid

temperature of the heavy

component at the system
pressure.
ChE 334: Separation Processes

0 xDP

x1

yz1

yBP

1.0

Composition (mole fraction light component)

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
The mixture is all liquid until it reaches the bubble point
temperature TBP, where the first bubble of vapor forms
and has a composition yBp.
Increasing the temperature further to the dew point
temperature TDP yields a mixture that is all vapor. The last
drops of liquid have a composition xDP.

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
Effect of pressure on Txy diagram

TH at P2

If Txy diagrams for the same system at

different total pressures, then:

TL at P2

1. P2 > P1

x
TH at P1

2. The
vapor-liquid
equilibrium
temperatures are higher at P2 than
at P1
2.

T
y
x

The phase equilibrium lines at the

higher pressure are usually closer
together.

TL at P1

0
ChE 334: Separation Processes

x and y
Dr Saad Al-Shahrani

1.0

BINARY VAPOR-LIQUID
EQUILIBRIUM

y Diagrams

in

equilibrium with each other.

0.4

xA

ChE 334: Separation Processes

=1
yA

These
diagrams
can
be
generated from either constantP or constant-T data. However,
they are most commonly drawn
for constant pressure, since
most applications are essentially
isobaric.

phases

ve

li n
e4

vapor

i um
r
b
i li

r
cu

and

u
Eq

xA

liquid

relates the compositions of the

yA

xy diagram for a binary system,

Vapor composition y (mole fraction, light component)

xy diagram for binary system

0.2
Liquid composition x (mole fraction, light component)
Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
If the diagram is plotted for a constant pressure,

temperature is a parameter along the curve.

If the diagram is plotted for a constant temperature,

pressure is a parameter along the curve.

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
Example:
In a 2-component (binary) mixture, an equilibrium
condition can exist between the vapour and the liquid
phase. The Figure shows a typical equilibrium
condition attained under a certain pressure P and
temperature T. The 2 components that made up the
mixture distribute themselves unequally in both the
vapour and liquid phases.
The substance with the lower boiling point is known as the more volatile
component (MVC) and correspondingly the substance with the higher boiling
point is known as the less volatile component (LVC).
If we let A = MVC and B = LVC, we can use mole fractions as a
measure of concentrations of the components in the 2 phases:
yA = mole fraction of component-A in the vapour
xA = mole fraction of component-A in the liquid phase
ChE 334: Separation Processes

phase.

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
At

and/or

different

temperature

pressure,

components

will

the

2-

distribute

differently. For example, the

Figure shows equilibrium at
pressure P and temperature T1.
The mole fraction of A in the
vapour and liquid are yA1 and
xA1 respectively.
ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
At another higher temperature T2
but at the same pressure P,
another equilibrium is attained,
with different mole fractions than
at temperature T1. As shown in the
Figure, the mole fractions of A in
the vapour and liquid are yA2 and
xA2 respectively.
ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM

ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM
NONIDEALITY IN VAPOR-LIQUID EQUILIBRIUM

At low and moderate pressures, nonideal vapor-liquid equilibrium

can be described by modified raoults law

This equation assumes that most of the nonideal behavior is caused

by liquid phase effects.

In the liquid phase, molecules are much more closely spaced than in
the vapor phase. Therefore, attraction and repulsion among
molecules have larger effects.
ChE 334: Separation Processes

Dr Saad Al-Shahrani

BINARY VAPOR-LIQUID
EQUILIBRIUM

(Ideal solution)

It is useful for graphical design in

determining the number of theoretical
stages required for a distillation
column.
ChE 334: Separation Processes

(nonideal solution)

(nonideal solution)

Dr Saad Al-Shahrani