ChE 411: Unit Operations II (3 units)

Text book and notes

Grading: PBL,Homework, Test,
Midterm and Final

Teaching Philosophy
What I hear I forget, What I see I remember,
What I do, I understand Confucius (~200 BC)
Lecturing is not teaching, & Listening is not learning You
learn by doing Educational psychologists
Examples: Riding bicycle, driving car, etc.
Our philosophy: teach, tell, show you what to do and make you do
it & test if you know how to do it.
Home works, tutorials, quizzes, tests, EXAMS
You cannot put the same shoe on every foot. We learn
differently: individualistic, group, etc. Work together but answer
individually.

Objectives

Types of SP and underlying principles

Equilibrium in SP, equations, tables, graphs
Types of distillation and equipment used
Number of stages for given separation
Feed plate and Reflux on economics of process

Solvent extraction and other SP

Separation in packed tower/column
NTU & HTU ( number and height of transfer unit)

Reading Materials
C. J. Geankoplis Transport Processes
and Unit Operations, Prentice Hall,
1993
C. J. Separation Processes, McGraw
Hil,l 1980
G. F. Nalven ed. Distillation and other
Industrial Separations, AIChE, 1997.
R. E. Treybal, Mass transfer
Operations, McGraw Hill, 1980

Introduction: Separation
in process industry
removal of contaminants from feed, wastes,
and recycle streams
separation of valuable products from
wastes, impurities and by-products.
separation processes account for 50 to 90%
of the capital costs of most chemical plants
and about 70% of the ultimate product cost.
Separation processes also important in
biological organisms, ecosystems, and
environmental engineering.

Introduction: Separation
Process-1
a separation process, is any
mass transfer process used to convert a
mixture of substances into two or more
distinct product mixtures, at least one of
which is enriched in one or more of the
mixture's constituents.
done by contacting the mixture with
another phase.
Such two phases are generally only
partially miscible in one another.
The two phases in contact may be Gas-

Introduction: Separation
Process-2

When such two phases are

brought into contact
there is the transfer of one or
more solutes (components)
from one phase to the other
due to the difference in
concentration, temperature or
pressure of the solutes in the
two phases.

Separation process
.

Feed/mixt
ure to be
separated
Contactin
g device

Another
product
phase poorer
in a solute

A product
phase
richer in a
solute

Another
phase brought
in to contact
feed

Introduction: Separation
Process-3
After the contacting, the two phases may
now be separated
The choice of phase and conditions will
ensure that one of the phases in contact
will be depleted or enriched in one or
more components of the original mixture.
Several separations may be required to
achieve the level of purification desiredmultiple separation stages

Two Phases in Contact: Liquid and Gas

Name of separation
process

Phases in
contact

Direction of
transfer of
solute(e)
Gas to liquid

eg

Absorption

liquid and
gas

humidification

liquid and
gas

Liquid(water) to
gas(air)

Water into pure

air

dehumidification

liquid and
gas

Gas(air) to liquid

Drying of moist
air

Stripping or
desorption (reverse
absorption)

liquid and
gas

Liquid to gas

Steam to
remove volatile
components
from nonvolatile oils

SO2 in air to
water
NH3 in air to
water

L-V, L-L, S-L contacting

phases
Distillation
Volatile
Liquid to
Ammonia(aqueous) to vapour

Liquid-liquid
(solvent)extra
ction

vapour and
liquid that
vapourises

vapour;
vapour to
liquid

richer in ammonia

Liquidliquid

Liquidliquid

Acetic acid from aqueous

solution
to isopropyl ether

Solid-Liquid
extraction

Liquid- Solid

Solid to Liquid extracting copper from ores using

H2SO4 sol

crystallization

Liquid- Solid

Liquid to Solid Sugar from conc. sugar solutions

Other separation
processes
Adsorption, Crystallization,
cyclonic separation
Centrifugation , Chromatography,
Decantation, Demister (vapor), Drying,
Electrophoresis, Elutriation, Evaporation,
Flotation, Flocculation, Filtration,

Distillation processes:
most popular chemical separation
process,
capable of producing pure
substance from mixture
requires two phases: liquid and
vapor,
uses energy to accomplish
separation.

Production processes using distillation

oil production,
air separation,
distillation of wine
to cognac and
spirits.

Absorption/stripping
processes
popular in environmental
applications
transfer gas component from gas
to liquid or vice versa
requires two phases: liquid and gas
uses the different affinity gas
component for gas and liquid.

Production processes using

absorber

scrubbing smokestacks
removal of ammonia from
refinery
remove CO2 from air.

liquid-liquid extraction:
used for processes that requires low
temperature operation
transfer soluble component from one
liquid to another
requires two phases: two immiscible
or partially miscibleliquids
uses the different affinity
components for separation.

Production processes using extraction

food processing
pharmaceutical
separation,
oil purification.

solid-liquid extraction:
used liquid to extract component
from a solid matrix
transfer soluble component from
solid to liquid
requires two phases: solid and liquid,
uses the solubility of the component
for separation.

Production processes using leaching

mining
food processing,
pharmaceutical.

TYPICAL CASES
Gold from ore: mixture of solids
flotation, roasting (chemical
reaction) and electrolytic refining

Crude oil :mixture of many

components
Desalting + several stages of
distillation steps to obtain
gasoline, kerosene, diesel etc

Processing methods:
Several

single-stage process: mixture to be

separated and contacting phase are mixed
in a vessel and separated
multiple-stage process: after mixing and
separation the phases are contacted again
continuous contacting: contacting of
the phases is continuous throughout
contacting device

Equilibrium between
phases1

When two phases(V-L) of different

compositions are brought into
contact there is transfer of solute or
redistribution of solutes between the
phases.
The composition of the phases as a
result changes with time until
equilibrium is attained.
The compositions of the phases at
equilibrium is a measure of the

Vapour Liquid Separation Processes

Distillation
reliability, simplicity, and low-capital
cost
But energy consuming

Absorption
Stripping
Humidification
dehumidification

Vapour-liquid Separation Process:

DISTILLATION

Process in which a liquid or vapour or a vapour -liquid

mixture of two or more substances is separated into its
component fractions of desired purity, on the basis of
difference in relative volatility(or boiling point),
by the application and removal of heat
relies on differences in the concentrations of components
in the liquid and vapour phases at equilibrium.
This is related to components differences in the
1. Volatilities 2. vapour pressures 3. boiling points
The components that make up the mixture
distribute themselves unequally in both the vapour and liquid

Applications of distillation
1. separate crude oil into fractions for specific uses
such as transport, power generation and heating.
2. Water is distilled to remove impurities-salt from
sea water.
3. Air is distilled to separate its components - notably
oxygen, nitrogen and argon- for industrial use.
4. Distillation of fermented solutions- used since
ancient times to produce distilled beverages with a
higher alcohol content-whiskey, gin etc
5. Small-scale Purification of liquid mixtures:

i. benzene-toluene; Acetic acid acetone

ii. methanol or ethanol from water
iii. production of deuterium(heavy water)

Equilibrium between phases.

At equilibrium the compositions,
temperature and pressure of the
contacting phases remain constantno change with time.
The relationship between the
compositions of a V and a L at
equilibrium at some constant
pressure/temperature is the vapourliquid equilibrium (VLE)data.
Data may tabulated or presented

Equilibrium between
phases2

The important variables affecting the

compositions at equilibrium of a solute in
the contacting phases are:
Temperature of phase
pressure of phase
Composition-in vapour, y and in
liquid, x

Experimental VLE Data for Binary

Systems
The VLE data for binary systems obtained
experimentally by mixing:
two liquid components(A & B) and
allowing the vapour-liquid system to
equilibrate
by changing temperature and/or
pressure

vapour phase and liquid phase

temperature and pressure are measured.
Samples of the vapour phase and liquid
phase are taken and analyzed.

Distribution of components between vapour

and liquid phases at equilibrium

Volatility Of Components1;

The components distribute differently because of

differences in their readiness to vaporize.
This readiness to vapourise is termed the volatility of the
substance.
substances with the lower boiling points will vaporize
more easily than those with a higher boiling point.
Volatile substances have higher vapour pressure at a given
temp.
a volatile substance will have a low boiling point and vice
versa.
substance with lower boiling point is known as the more
volatile component (MVC)

Vapour Pressure And Volatility

Some molecules with above average energy are able to
break away from the surface of the liquid into space above

gaseous molecules bounce around, some of them will hit the

surface of the liquid again, and be trapped there
Equilibrium set up -when the number of molecules leaving
the surface is exactly balanced by the number rejoining it.
number of the gaseous molecules in the space above the
liquid at equilibrium is fixed .

Vapour pressure2
molecules hit the walls of the container-exert a
pressure.
This pressure is called the saturated vapour
pressure (also known as saturation vapour
pressure) of the liquid
saturated vapour pressure increases with
temperature
Increasing temperature, increases the average
energy of the molecules which hit walls with more
energy
-more of them are likely to have enough energy to

Vapour pressure3
The higher the vapour pressure, the higher the tendency
of the molecules to escape from the liquid and hence the
higher the volatility.
higher the vapour pressure >> Intermolecular forces
holding liquid molecules together are relatively weak.
>> Less supply of heat to break them completely and boil
the liquid.

A liquid boils when its saturated vapour

pressure equals the external pressure on the
liquid.
On Mount Everest the pressure is so low that water
boils at about 70C.
Atop a 10,000mountain the boiling point of
water would be 90 C.
Liquid with the higher vapour pressure at a
particular temperature is the one with the lower
boiling point.
more volatile substance escapes to form a vapour
more easily than the less volatile ones.

volatility of components3
substance with the higher boiling point is
known as the less volatile component (LVC).
If we let A = MVC and B = LVC,
Composition of components in the phases are
expressed in terms of mole fractions:
yA = mole fraction of component-A in the
vapour phase
xA = mole fraction of component-A in the liquid
phase
At a different temperature and/or pressure, the
2 components will distribute differently
yB =1- yA
x =1- x

Distribution of components at different

temperatures

same initial compositions but different phase

compositions at different equilibrium temperatures but

Distribution of components
At higher temperature T2 but at the same pressure P,
equilibrium is attained, with different phase
compositions than at temperature T1.
mole fractions of A in the vapour and liquid are yA2 and
xA2 respectively.
components A and B are distributed in vapour and
liquid phases at different temperatures. Such a
diagram is called the phase diagram.
Such data at different temperatures but constant
pressure will constitute the T-x-y diagram or
constant pressure phase diagram or Boiling
point-concentration diagram
Also called boiling point diagram-gives the boiling
point of liquids of different compositions

Changes in distribution of
components in the phases with
temperature1

saturated vapour
subcoole
d liquid

saturated liquid

changes in distribution of components in the

phases with temperature3

Super heated
vapour

subcooled liquid

changes in distribution of components in

the phases with temperature.3
(a): Liquid-phase; no vapour Temperature 86 oC Concentration of benzene
Liquid: x = 0.40; Vapour: y = 0.00
(b): Liquid-phase; first bubble of vapour produced. Temperature 95.2 oC
(Bubble Point - solution about to boil). Concentration of benzene Liquid: x
= 0.40; Vapour: y = 0.61
(c): Vapour-Liquid Mixture; continued vaporization of liquid as heat is
added Temperature 98.0 oC Concentration of benzene Liquid: x = 0.31;
Vapour: y = 0.52
(d): Vapour-phase; last droplet of liquid remains Temperature 101.6 oC
(dew point) Concentration of benzene Liquid: x = 0.21; Vapour: y = 0.40
(e): Vapour-phase only, no liquid Temperature 108 oC .The process is
unsteady-state in nature.
NOTE: from the above Fig.
As heating continues, vaporization occurs over a range of boiling
points.
At any time when 2 phases - vapour and liquid - are present, the
concentration of benzene (more volatile component) in the vapour (y) is
always higher than that in the liquid (x). The reverse is true for toluene
(less volatile component).

2 types of phase diagrams:

Constant-pressure phase diagrams

called
T-x-y diagram
boiling point diagram
boiling point-concentration diagram

commonly used for distillation

calculations
Constant-temperature- phase diagrams
P-x-y diagram
Isothermal phase diagram
commonly used to depict deviations

PHASE DIAGRAMs1:T-x-y
the distribution of components in the liquid and
vapour phases is a function of temperature
the bubble-point and the dew-point of a binary
mixture at constant pressure.
Liquids of different composition at the same
pressure will boil at different temperatures- bubblepoint curve
Vapours of different composition at the same
pressure will condense at different temperaturesdew-point curve
boiling of a liquid mixture takes place over a range
of boiling points.
Condensation of a vapour mixture takes place over
a range of condensation points

Constant Pressure Phase

Diagram

VLE for Benzene toluene at 1 atm

Acetone water system

P=101.3k
P=344.7
P=344.7
Pa

T [K]
T [K]
T [K]
x1
y1
x1
y1
x1
y1
[mol/mo [mol/mo
[mol/mo [mol/mo
[mol/mo [mol/mo
l]
l]
l]
l]
l]
l]
368.25

0.008

0.138

395.65

0.017

0.349

423.85

0.014

0.249

363.25

0.016

0.277

393.15

0.024

0.398

415.45

0.036

0.395

355.25

0.033

0.479

385.15

0.055

0.518

409.55

0.078

0.507

349.35

0.052

0.604

379.15

0.107

0.608

404.25

0.144

0.582

345.35

0.072

0.675

375.95

0.194

0.67

402.75

0.229

0.618

342.65

0.094

0.719

374.45

0.273

0.695

402.15

0.341

0.65

340.75

0.117

0.738

373.05

0.388

0.718

401.45

0.444

0.665

338.15

0.171

0.776

372.15

0.545

0.747

399.75

0.559

0.7

336.45

0.237

0.8

371.95

0.633

0.768

398.85

0.754

0.781

PHASE DIAGRAM: features

bubble-point curve or saturated liquid line.
dew-point curve or saturated vapour line
Subcooled liquid region
Superheated vapour region
vapour-liquid region
bubble-point and dew-point temperatures

PHASE DIAGRAM2

The boiling point of A(MVC) is that at which the

mole fraction of A is 1.0
The boiling point of B(LVC) is that at which the
mole fraction of A is 0.
In this example, A is therefore has a lower boiling
point than B.
The dew-point is the temperature at which the
saturated vapour starts to condense.
The bubble-point is the temperature at which the
liquid starts to boil.

PHASE DIAGRAM3

a subcooled liquid with mole fraction of

A=0.4 (point A) is heated at constant
pressure, its concentration remains
constant until it reaches the bubble-point
(point B), when it starts to boil.
The vapour evolved has the equilibrium
composition given by point C,
approximately 0.8 mole fraction A. This is
approximately 50% richer in A than the
original liquid

Constant
(Isothermal)/PConstantTemperature
Temperature (Isothermal)
Phase
Diagram
x-y
Phase
Diagram

Constant Temperature
(Isothermal) Phase Diagram:P-x-y
Diagram

Data at constant temperature (isothermal) are plotted as

two curves:
pressure versus x and pressure versus y,
more volatile liquid will have a higher vapour pressure
(i.e. pA at xA = 1.0) at a fixed temperature.

Unlike in the constant pressure phase diagram, the

bubble point curve is above that of the dew point
higher pressure required to maintain in liquid state
At lower pressure more vapour is formed
vapour-liquid mixture region is between the two curves.

Constant P vs. Constant T phase

Diagrams

The constant pressure phase diagram is

more commonly used in the analysis of VLE
but the constant temperature phase
diagram is also useful in the analysis of
solution behaviour that deviates from
Raoult's Law
the more volatile liquid will have a higher
vapour pressure (i.e. pA at xA = 1.0).
Note also the regions in the two phase diagram of
vapour-only,
liquid-only
vapour-liquid mixtures.

Vapour-Liquid Equilibrium[VLE] curve

Constant pressure Equilibrium Curve can
be obtained from boiling point diagrams or
phase diagrams.
VLE Curve of binary mixtures are often
presented as shown i.e. y vs. x
The VLE plot expresses the bubble-point
and the dew-point of a binary mixture at
constant pressure.
The curved line is called the equilibrium
line and describes the compositions of the
liquid and vapour in equilibrium at some
fixed pressure.

Equilibrium Curve (at constant

pressure)

The Figure shows a typical equilibrium

curve for a binary mixture on x-y plot.
contains less information than the phase
diagram (i.e. temperature is not
included),
but it is most commonly used.
It is useful for graphical design in
determining the number of theoretical
stages required for a distillation column
Has line y=x for MVC

Equilibrium Curve: example

Ideal liquid system

Equilibrium Curve: more complicated1

Equilibrium Curve: azeotropic

systems

Equilibrium Curve from Phase Diagram

Equilibrium Curve from Phase Diagram

By drawing horizontal lines (constant T) like DF and
HJ on the phase diagram
obtain the corresponding mole fractions x and y at the
intersections with the horizontal lines.
With a set of x-y values, a graph of y vs. x can be
plotted i.e. the equilibrium curve

Effects of Increased Pressure on

phase diagram
Although most distillations are carried out at
atmospheric or near atmospheric
pressure,
it is not uncommon to distill at other pressures.
High pressure distillation (typically 3 - 20
atm) usually
occurs in thermally integrated processes or
when the normal boiling point of the
vapour product is lower than the
temperature of the cooling water
required to condense it.
normally cheaper to pressurize the column in

Effects of Increased Pressures

At Higher Pressures

the phase diagram becomes narrower

and the corresponding bubble point and dew point
temperatures also become higher.
Relative volatilities and hence Separability becomes
less at higher pressures.
At elevated pressures, the vapour phase tends to
deviate from ideal gas behaviour, and modifications to
the VLE data is required (e.g. through the use of the
compressibility factor).
Above the critical pressure of the more volatile
component there is no longer a distinction between
vapour and liquid. Distillation is no longer possible
beyond this point.
The vast majority of distillations are carried out at
pressures below 70% of the critical pressure.

Relative Volatility of A with respect to B

a measure of separability of A and B.

volatility of component-A defined as:
partial pressure of component-A in vapour
divided by mole fraction component-A in
liquid
For a binary mixture of A and B, therefore:
Volatility of A = pA / xA
Volatility of B = pB / xB
where Pi is the partial pressure of component i
and xi is mole fraction of i in the liquid.
Relative volatility is the ratio of volatility of A
Volatility of A
PA / x A

(MVC)
toABvolatility
of B (LVC):
Volatility of B

PB / x B

Relative Volatility of A with respect to B

Since xB = 1 xA

AB

PA = y A P T ; P B = ( 1 - y A ) P T

PA / x A
PA (1 x A )

PB /(1 x A ) PB x A

AB

y A (1 x A )

x A (1 y A )

y (1 x )

x (1 y )

With the understanding that concentrations are in terms of the MVC and
simplifying,

in general, relative volatility of a mixture

Effect of Relative Volatility on VLE

 1
At y=x (straight line through the origin)
A and B have the same volatility and will vapourise together
when heated
Vapour and liquid will have the same composition.
No separation is possible
The larger the value of above 1.0, the easier the
separation.

Therefore, separation by distillation is only feasible within

the region bounded by the equilibrium curve and the 45o
diagonal line.
From the equilibrium curve, we see that the greater the
vertical distance between the equilibrium curve and the
diagonal line( y = x ), the greater the difference in liquid and
vapour compositions and therefore the easier the
separation by distillation.

Ease of separation

Equilibrium Curve From Constant Relative

Volatility
If relative volatility is constant it can be used to
obtain the equilibrium curve data
more usually, the average relative volatility, ( ave) is
known:
The composition of the vapour y, in equilibrium
with liquid of composition,
x is calculated from :
x
y

1 ( 1) x

where is assumed constant

Substituting values of x between 0 and 1will yield
the equilibrium curve predictions

Equilibrium Curve From constant Relative

Volatility
examples of binary mixtures whose VLE
can be accurately represented with a
constant relative volatility values:

x
1 ( 1) x

Effect of non-constant relative volatilities

on predicted VLE data
benzene-toluene (ideal solution)

ethanol-water (non-ideal solution

Effect of Non-constant Relative Volatilities on

Predicted Equilibrium Curve Data
benzene-toluene (ideal solution)

ethanol-water (non-ideal solution

1. Less variation in
relative volatilities
with composition

1. More variation in
relative volatilities
with composition

2. Lower levels of
2. Higher levels of
deviation from actual
deviation from actual
VLE data
VLE data
3. Cannot be used to
predict VLE
3. Can be used to
accurately
predict VLE
accurately

Calculating Constant Relative Volatility And

Equilibrium Temperature, T
Binary Mixtures :Constant Relative Volatility

where TA and TB are the boiling points (in K)

of pure components A and B at the system
pressure
R = 8.314 J/g-mole.K, and
is the average heat of vapourization of the
2 pure components at the system pressure
equilibrium temperature T at liquid
concentration x (for MVC)

Equilibrium Curve and T-x-y diagram from

Vapour Pressure data-valid for ideal solutions
Combining Raoult's Law with Dalton's Law:
Raoults law:

Dalton's Law: PT = PA +PB

xA=1-xB

Since:

Vapour Pressure =f(T),

Calculate xA and yA between Boiling Points of A and Boiling
Point of B yields the data for T-x-y and hence the equilibrium
curve

Equilibrium Curve using vapour

pressure data

Temperat
ure,
T

T1
T2
T3

PA0

PB0

xA

yA

Note that from Raoults law:

The partial pressure PA varies linearly with xA.
the partial pressure PB varies linearly with xA.
total pressure PT varies linearly with xA.
shown as PT vs. x; PA vs. x and PB vs. x
respectively in the Figure.
Temperatures should be between the boiling
points of the pure components

Antoine Equation for Vapour Pressure in SI units:

Pi0 in kPa, T in K )

Log(10) Pi0 =A- [B/(T+C)]

Antoines
equation is
Antoine constants A, B and C for some typical liquids are provided in the Table

Constant-temperature(P-x-y) phase diagram

for an ideal solution
From Raoults law the partial pressures PA and PB vary
linearly with xA as shown
The total pressure varies linearly with xA . This is shown
as PT vs. x in the Figure
Substituting for XA

Solving for PT yields

from

P = P P / [P - y (P P )]
T

0
A

0
B

We note that xA is between 0 and 1.0 .

Hence yA can also be calculated and substituted
into equations for PT vs. xA and PT vs. yA
PT varies linearly with xA
variation of PT with yA is given by equation

VLE Data(P-x-y) from vapour

pressure data

Ideal
behavio
ur

Ideal Solution & Raoult's Law

Ideal Solution: obeys Raoult's Law:
Raoult's Law:PA =PA0 XA
Where
PA =equilibrium partial pressure of a component A,
at a fixed temperature T
PA0 =vapour pressure of pure liquid A at temperature
T
xA = mole fraction of A in the liquid
Note1: The vapour pressure is constant at constant
temperature.
Note2: PA0 =f(T)

Characteristics of Ideal Solutions

The average intermolecular forces of attraction and

repulsion in the solution are unchanged on mixing the pure
liquids
The volume of the solution varies linearly with
composition
There is neither absorption nor evolution of heat in
mixing the liquids
The total vapour pressure of the solution varies linearly
with composition (in mole fraction)
Ideality requires that molecules be similar in size,
structure, and chemical nature:
the nearest approach is the optical isomers. In practice, for
engineering purposes, many solutions or organic
compounds in a homologous series are considered

VLE Data : Non-Ideal Solutions

do not obey Raoult's Law
Most solutions show, at least to some
extent, non-ideal behaviour-show
deviations from ideal
equation for describing non-ideal
solutions: Henry's Law:
PA=HxA
H=Henrys constant
mole fraction of A in liquid
Henry's Law also used to determine
solubility of gases in liquids

Deviation from Raoult's Law:

activity coefficients

Deviation from Raoult's Law can be

accounted for by the use of activity
coefficients
most of the non-ideal behaviour is caused
by liquid-phase effects.
In the liquid-phase, the molecules are
much more closely spaced together
than in the vapour space
attractive and repulsive forces among the
molecules have larger effects than
vapour-phase

Deviation from Raoult's Law:

activity coefficients
When chemically dissimilar components are mixed
together, there can be repulsion or attraction between
dissimilar molecules.
If the molecules repel each other, they exert a higher
partial pressure than if they were ideal.
In this case the activity coefficients are greater than unity
(called a positive deviation from Raoults law).

If the molecules attract each other, they exert a lower

partial pressure than if they were ideal.
Activity coefficients are less than unity (negative
deviations).

Activity coefficients are usually calculated from

experimental data

general guidelines for vapourliquid mixtures in

terms of their nonideality
a. Mixtures of isomers usually form ideal solutions.
b. Mixtures of close-boiling aliphatic hydrocarbons
are
nearly ideal below 10 bar.
c. Mixtures of compounds close in molar mass and
structure:
frequently do not deviate greatly from ideality
(e.g. ring compounds, unsaturated compounds,
naphthenes etc.).
d. Mixtures of simple aliphatics with aromatic
compounds:
deviate modestly from ideality

Deviation from Raoult's Law:

activity coefficients

PA= PA0 xA A

PB=PB= PB0 xB B
where
A is the (liquid-phase) activity coefficient of
component, A
A is the (liquid-phase) activity coefficient of
component, B
Activity coefficient=f(T & composition)
1. determined experimentally
2. predicted using various equations

PT=PA+PB= PA0 xA A +PB0 xB

Deviation from Raoult's Law: activity

coefficients

For ideal solutions: A= B =1

Deviations can be either positive or negative

non-ideal solutions display distortions in their
phase diagrams.
equilibrium curves show marked deviations
from the uniform curves that are typical of
constant relative volatility systems.
azeotropes typical of deviations:
1. minimum-boiling and
2. maximum-boiling (less common).

Deviations: Minimum-boiling azeotropes

carbon-disulfide-acetone (61.0 mole% CS2, 39.25 oC, 1 atm)

When the positive deviations from ideality are

sufficiently large,
the mixture is said to form a minimum-boiling
azeotrope.
characteristic of such mixture in constant-temperature
phase diagram:
total pressure goes through a maximum
in constant-pressure phase diagram therefore
temperature goes through a minimum (39.250C),
shown as point L.

Minimum-boiling azeotrope: carbondisulfide- acetone

(61.0 mole% CS2, 39.25 oC, 1 atm)

Minimum-boiling azeotrope
Mixtures less composition than azeotropes
produce vapour richer than liquid.
Remaining liquid becomes poorer in mvc and moves
away from L

Liquid richer than azeotrope produces vapour that

is poorer in mvc on boiling.
Remaining liquid becomes richer in mvc and moves
away from L

Azeotropic composition and boiling pionts depend

on the pressure of the system
azeotrope may be eliminated by simply changing
the pressure of system
Azeotropes can not be easily separated by
ordinary distillation

Minimum-boiling azeotrope: carbon-disulfide

acetone
(61.0 mole% CS2, 39.25 oC, 1 atm.)

At point L, the concentration in the vapour

phase is the same as the concentration in
the liquid phase ( y = x ), and a = 1.0.
known as the azeotropic composition
(0.61 mole fraction CS2).
At this point, the mixture boils at a constant
temperature (39.25 oC under 1 atm.) and
without change in composition.
On the equilibrium diagram, it can be seen
that at this point, the equilibrium curve
crossed the 45o diagonal.

Maximum-boiling azeotrope: acetone chloroform

(65.5 mole% chloroform, 64.5 oC, 1 atm.)

It occurs when the negative deviations

are very large:
total pressure on constanttemperature phase diagram passes
through a minimum,

giving rise to a maximum in the

temperature (i.e. boiling point)on
constant-pressure phase diagram
On the equilibrium diagram, it can be
seen that at this point, the equilibrium
curve crossed the 45o diagonal.

Maximum-boiling azeotrope: acetone

chloroform
(65.5 mole% chloroform, 64.5 oC, 1 atm)

Maximum-boiling azeotropes: acetone chloroform

(65.5 mole% chloroform, 64.5 oC, 1 atm)

The azeotropic composition is 0.345 mole

fraction acetone.
Point L in the Fig. is now a minimum on
the constant temperature phase diagram
a maximum (64.5 oC, under 1 atm) on the
constant-pressure phase diagram.
These azeotropes are less common than
the minimum type.
Azeotropic mixtures cannot be easily
separated by ordinary distillation
methods

Azeotrope= azeotropic mixture, or

constant-boiling mixtures
a special class of liquid mixture that boils at a
constant temperature at a certain composition.
it behaves as if it was one component with one
constant boiling point.
A boiling liquid mixture at the azeotropic
composition produces a vapour of exactly the
same composition,
the liquid does not change its composition as it
evaporates
Very large deviations from ideality lead to azeotropes

Azeotropic mixtures cannot be easily separated by

ordinary distillation

Types of distillation
methods
1. Distillation without reflux1. boiling of liquid mixture to be separated
and separating the vapour generated
without allowing any liquid to return to
the still

2. Continuous Distillation with reflux

returning part of condensate to still in
such a way that it runs counter to the
vapour rising to the condenser

Distillation without
reflux
Two types :
a. Simple (differential )distillation:
vapour generated by boiling of liquid
mixture to be separated is condensed
without allowing any liquid to return to
the still
b. Flash or equilibrium distillation:
vapourizing a fraction of the liquid in
such a way that the vapour produced is
in equilibrium with the residual liquid and
then separating the two phases

DISTILLATION:
binary mixture of A (MVC) and
The system consists
of a batch of liquid
B (LVC)
(fixed quantity) inside a kettle (or still)
fitted with heating element or steam jacket
a condenser to condense the vapour
produced.
The condensed vapour is known as the
distillate. The distillate is collected in a
condensate receiver.
The liquid remaining in the still is known
as the residual.

SIMPLE (DIFFERENTIAL) DISTILLATION

SIMPLE DISTILLATION:
Condensate Composition vs. time

Repeated partial distillation of

collected condensates

Repeated partial distillation of

collected condensates2
The distillate product from the
second stage will be purer in A
compared to the first stage
but the quantity of distillate
collected in the second stage is
lower than that of the first stage.
As more stages are added, purer
distillate product can be obtained,
but the quantity collected will be
lower than the previous stage

Rayleigh Equation: concentration vs.

quantity in simple distillation
useful in the analysis of simple distillation
total moles remaining vs. the mole fraction
MVC in the still.
L1 = initial moles of liquid originally in still
L2 = final moles of liquid remained in still
x1= initial liquid composition in still (mole
fraction of A)
x2 = final liquid composition in still (mole
fraction A)
At any time t, the amount of liquid in the still

Rayleigh Equation:
concentration vs. quantity in
simple
distillation
After time (t + dt) , vapour dL is produced,

composition of A in the vapour is y

The vapour is assumed to be in equilibrium
with the residue liquid.
The liquid in the still is thus reduced from L to
(L - dL), liquid composition changed from x to (x
- dx).

Rayleigh Equation: material

balance on A

Initial moles in still(at t) = moles left in

still(at t+dt) + moles vaporized(within dt)
i.e. amt. in still at t=amt. in still at t+dt +
amt. vapourised within dt
Moles of A=total moles x mole fraction of A
Since
xL = (x - dx) (L - dL) + y dL
xL = xL - x dL - L dx + dx dL + y dL
Neglecting the term dx dL(product of 2
small quantities), the equation reduces to:

Rayleigh Equation: material

balance on A

Simplifying

Integrating from L1 to L2, and from x1 to x2, we

obtain the Rayleigh Equation

or ideal mixture: constant relative volatili

yA
xA
AB
yB
xB
Suppose there are LA moles of A and LB moles of B of liquid
dL moles of liquid ( containing dLA moles of A and dLB moles of B)
are distilled off: hence

dLA / dL dLA
dLB / dL dLB

LA / L
AB
LB / L

Separating variables and Integrating

LA
LB
ln
AB ln
LA0
LB 0

LB
LA

LA 0
LB 0

AB

LB = total mole of B left in still,

LA = total mole A left in still.
LB0 = total initial mole of B in
still,
LA0 = total initial mole A in still

EXAMPLE
A batch of crude pentane contains 15 mole
percent n-butane and 85 percent n-pentane. If a
simple batch distillation at atmospheric
pressure is used to remove 90 percent of
butane, how much pentane will be removed?
What will be the composition of the remaining
liquid?
average value of 3.5

Simple Batch or Differential Distillation

with reflux
The pot is filled with
liquid mixture and
heated.
Vapour flows upwards
though the column and is
condensed at the top.
Part of the liquid is
returned to the column
as reflux, and the
remainder withdrawn as
distillate.
Nothing is added or
111
withdrawn from the still

FLASH (EQUILIBRIUM) DISTILLATION

A single-stage continuous operation

where a liquid mixture is partially
vaporized:
the vapour produced and the residual
liquid are in equilibrium, which are
then separated and removed.

FLASH (EQUILIBRIUM) DISTILLATION

yA
Separat
or

heater

xA

Equilibrium or Flush Distillation

Total mass balance:

F V L
Separator

FxF V y A Lx A
Component A balance:

yA

heater

where
F, V and L are flow rate of feed, vapor and liquid phases.
xF, yA and xA are mole fraction of component A in feed,
vapor and liquid.

xA

Material balance for more volatile component :

Where

( f 1)
xF
yA
xA
f
f

f = V/F = molal fraction of the feed that is vaporized and withdrawn

continuously as vapor.
1-f = molal fraction of the feed that remains as liquid

114

Homework
1. 100 kg mols of a mixture which contains 60 mol% n-pentane (A)
and 40 mol% n-heptane (B) is vaporized at 101.32 kPa pressure
under differential conditions until 40 kg mol are distilled. What is
the average composition of the vapour formed and of liquid
remaining in the still.
2. If 100 kg mols of the same mixture is flash distilled such that 40
kg mol are vapourised, what are the compositions of the vapor
and liquid left?
3.
100 kg mols of a binary mixture (n-pentane and n-heptane ) is
distilled until the % composition of n-heptane in the still increases from
40% to 70% at 101.32 kPa pressure and under differential conditions . What
is the average composition of the vapour formed and of liquid remaining in
the still. How much liquid remains in in the still

Equilibrium data for n-pentane-n-heptane, x and y are mole fraction

of n-pentane
x 0.0 0.059 0.145 0.254 0.398 0.594 0.867 1.000
y 0.0 0.271 0.521 0.701 0.836 0.925 0.984 1.000

Homework No.7
1. A mixture containing 50 g mol of benzene and 50 g
mol of chlorobenzene is distilled by simple distillation
without reflux until 40 percent of the initial charge is
taken off as overhead. The system benzenechlorobenzene may be considered ideal, with an
averge relative volatility of 5.3
(a) What are the compositions of overhead and residue
after distillation is complete?
(b) The overhead from the first distillation is subjected to
a second simple distillation. Again 40 percent of the
charge is taken overhead. What is the composition of
the second over head product? What is its mass in
grams? How many grams of chlorine does it contain?

Homework No.7 (continue)

2. A mixture of 50 g mol of liquid benzene and 50 g mole
water. Determine the boiling at 101.32 kPa pressure.
Liquid benzene is immiscible in water. Determine the
boiling point of the mixture and the composition of the
vapor. Which component will first be removed
completely from the still? Vapor pressure data of the
pure components are as follows:
Temperature
K

Pwater
(mm Hg)

Pbenzene
(mm Hg)

308.5

35.3

43

150

325.9

52.7

106

300

345.8

72.6

261

600

353.3

80.1

356

760

FLASH (EQUILIBRIUM) DISTILLATION:

mixture of A (MVC) and B (LVC)
The feed is preheated before entering the separator
As such, part of the feed may be vaporized.
The heated mixture then flows through a pressurereducing valve to the separator.
In the separator, separation between the vapour and
liquid takes place.
A produced in the vapour depends on the condition
of the feed
i.e. how much of the feed is entering as vapour state,
which in turn is controlled by the amount of heating.
In other words, the degree of vapourization of the
feed affects the concentration (distribution) of A in
vapour phase and liquid phase.

Separation in Flash Distillation1

If no vapourization takes place, then the liquid
leaving the separator will have the same
composition as the feed.
If total vapourization occurs, the vapour will also
have the same composition as the feed.
Clearly, for effective separation, there must be some
vapour-liquid mixture present.
This means that there exists a certain relationship
between the extent of heating, and the concentration
in the vapour and liquid streams.
f =molal fraction of the feed that is vaporized
and withdrawn continuously as vapour
Therefore, for 1 mole of binary feed mixture, (1- f) is
the molal fraction of the feed that leaves continuously
as liquid

Separation In Flash Distillation2

yD = mole fraction of A in vapour leaving

xB = mole fraction of A in liquid leaving
xF = mole fraction of A in feed entering
the greater the heating, the larger the
value of f.
If the feed is completely vapourised, then
f = 1.0
Thus, the value of f can vary from

0 (no vapourization) to
1 (total vapourization).

Flash Distillation: material

balance for the MVC (A)[1mole of
feed]
1. x = f y + (1 - f) x
F

f yD = xF - (1 - f) xB
Re-arrange to yield:
fraction f depends on the enthalpy of the liquid
feed, the enthalpies of the vapour and liquid
leaving the separator
for a given value of f, we will obtain certain
values for yD and xB.

Flash Distillation: material balance for

the MVC (A)[1mole of feed]
For a given feed condition, and hence the
known value of f and xF, equation is a straight
line with slope [-(1-f)/f and intercept xF / f.
The operating line crosses the point (xF, xF) for
all values of f
Since the liquid and vapour are assumed to be
in equilibrium, the intersection of this line with
the equilibrium curve is the solution of the
material balance
the intersection of straight line with slope [-(1f)/f, through (xF, xF)and intercept xF / f is
drawn to obtain the solution

Solution to flash distillation

Case of constant relative volatility

the intersection point can be
determined mathematically by
simultaneously solving the operating
line equation and equilibrium curve
equation as given below:

The quadratic equation is solved for x

y is solved from equilibrium curve

CONTINUOUS DISTILLATION
Distillation process, in its simplest form,
can be represented in a block diagram as
Distillate:D:
shown
Feed:F

Bottoms:B

Binary Distillation: A (more

volatile) and B (less
volatile)
1 feed stream F:mixture
of 2 components
separated into 2 product streams:
D:distillate (top product or overhead product)
B:bottoms.
The more volatile component will vaporize more and is
removed mainly in the distillate stream
the less volatile component will remain mainly in the
bottoms stream.
bottoms stream is in liquid phase
distillate stream is produced by condensing the vapour
phase.

Separation by distillation

Some industrial-scale binary

distillation processes.
Note the general inverse relationship
between the relative volatility and the
number of trays

Equipment for Continuous Distillation

A:column
This is the main equipment where the separation
process described above is carried out.
In general, column has 3 sections:
1. rectifying (or enriching) section: the more
volatile component is removed through
contacting the rising vapour with the downflowing liquid. located above feed entry;
2. stripping section: the down-flowing liquid is
stripped of the more volatile component by the
rising vapour. located below feed entry.
3. feed (or flashing) section.
. column may be equipped with trays or packings
or both.

Tray Column or Packed Column

Overhead condenser
a heat exchange equipment for condensing the hot
vapour leaving the top of the distillation column.
Either cooling water (e.g. using shell-and-tube heat
exchanger) or air (using fin-fan condensers) can be
used as the cooling medium.
In either case, partial or total condensation may be
achieved.
In the case of total condensation (as in the analysis
above), all the vapour is converted into liquid.
For partial condensation, there remain in the
vapour state the most volatile components.
The condensed liquid is partially returned to the
distillation column as reflux and partially withdrawn
as distillate product.

Accumulator/ Pump
Overhead accumulator
This is a horizontal (usually) pressure
vessel whereby the condensed vapour is
collected.
Pumps :
for returning the reflux liquid back to
the distillation column,
for pumping out the bottoms product for
storage,
for pumping the feed into the
distillation column.

Reboiler
Reboiler :
to produce the vapour stream in the distillation
column, called the reboiled vapour or the boil-up
vapour.
Reboilers can be both external or internal (stab-in).
Steam reboilers or fired reboilers can be used. Fired
reboilers typically uses fuel gas or fuel oil or
combination of both

Feed/Bottom Exchanger
used for heat conservation: the hot bottoms
stream is used to heat up the feed stream before
it enters the distillation column.
As a result the bottoms product is cooled and
then rundown to storage.
For better temperature control of the feed stream,
a separate preheater or charge heater (both not
shown in the above diagram) may be used.
This is usually located downstream of the
feed/bottom exchanger for final temperature
adjustment.
Steam may be used for the preheater, and fuel
gas-fuel oil is used for the charge heater.

Charge Heater / Steam Preheater

This can be a fuel gas/fuel oil-fired

heater or steam-heated exchanger for
final temperature control before the
feed enters the column.
Other distillation columns: different
set-ups
depends on the types of mixtures to be
separated and the complexity of the
operation.

- more than 1 feed inlet, as well as one

or more sidedraws.

Tray/plate columns

Binary Distillation- A (MVC) and B (LVC):

nomenclature
Feed stream F
with mole fraction xF

Distillate D
with mole fraction xD

Bottoms B
with mole fraction xB

The Reflux Liquid is L.

For a total condenser, it has the same
concentration as the distillate.

Tray/plate columns
The feed usually enters somewhere near
the middle of the column.
Distillate D is richer in the more volatile
component
Bottoms B is richer in the less volatile
component,
want the distillate to be as pure in MVC
as possible (maximum xD = 1.00), and
the bottoms to be as pure in LVC as
possible (minimum xB = 0.00).

Tray/plate columns:
types
3 major types:
1. sieve Trays
2. valve Trays
3. bubble cap Trays

(a)
(b) valve cap(c) bubble cap
perforation

(d) Tray with valve caps

Figure 6.4 Three types of tray openings for

passage of vapor up into liquid

Analysis of Continuous Tray Columns

With a tray column, the vapours
leaving the tray will be richer in the
MVC than the vapour entering the tray
by one "step" change

Enrichment of Vapour Occurs

Continuously Over Entire Height of
Packing Used

RANDOM PACKING DESIGNS

SHAPES
RINGS
SADDLES
OTHERS

MATERIALS
METAL
CERAMIC
PLASTIC
http://www.koch-glitsch.com/koch/products/plastic_random_packing.asp

More surface area for mass transfe

Higher flow capacity
Lower pressure drop

Packing Materails

(b)
(a) Structured
Random Packing
Packing
Materials
Expensive
Far less pressure drop
Higher efficiency and capacity

Figure 6.7 Typical materials used in a packed column

STRUCTURED PACKING
PACKING IS MADE IN SECTIONS
AND FILLS ENTIRE COLUMN
DIAMETER

http://www.sulzerchemtech.com/DesktopDefault.aspx/tabid-232/

The McCabe-Thiele
Method
uses the equilibrium curve diagram to
determine the number of theoretical
stages (trays) required to achieve a
desired degree of separation.
It is a simplified method of analysis making
use of several assumptions,
very useful tool for the understanding of
distillation operation.
The VLE data must be available at the
operating pressure of the column.

The McCabe-Thiele Method.2

Information required :
feed condition (temperature, composition)
distillate compositions
bottom compositions
the reflux ratio - the ratio of reflux liquid over the
distillate product.
to determine number of theoretical stages required
for a given separation
Main assumption
1) Equimolar overflow through the tower between the
feed inlet and the top tray and the feed inlet and bottom
tray.
2) Liquid and vapor streams enter a tray, are
equilibrated, and leave.

McCabe-Thiele Method:
assumptions of the method
a. Constant Molal Overflow. The molar flow rates of
the vapor and liquid are nearly constant in each
section of the column. This also ensures the operating
lines are straight lines.
b. Heat Effects are negligible. For example, heat
losses to and from the column are small and neglected
.
c. For every mole of vapor condensed, another mole of
liquid is vaporized.
d. The liquid and vapor leaving the tray is in
equilibrium with the vapor and liquid entering the tray.

number of theoretical
stages

method involves the plotting on the equilibrium

diagram and 3 straight lines:
rectifying section operating line (ROL)
feed line (or q-line)
stripping section operating line (SOL) .
These operating lines represent the relationship
between the concentrations in the vapour
phase (y) and the liquid phase (x) flowing
counter currently between the stages
The number of theoretical stages required for
a given separation is then the number of
triangles that can be drawn between these
operating lines and the equilibrium curve.

The McCabe-Thiele Method 3

number of theoretical
stages

McCabe-Thiele Method-number of theoretical

stages: the steps

1. Analysis of the Rectifying section, and determine

the ROL using xD and R
2. Analysis of the Feed section, and determine the
feed condition (q)
3. Determination of the feed line (q-line) using xF
and q
4. Locate the intersection point between ROL and qline
5. Analysis of the Stripping Section, and determine
the SOL using (4) and xB
6. Usually the SOL is the last line to draw, after both
ROL and q-line are drawn

Rectifying Section Operating Line (ROL):

(total condenser and the reflux is at bubble
point)

 Overall Balance (Total): Vn+1 = Ln +D

balance around the envelope at steady
Component (MVC):V
n+1 yn+1 = Ln xn + D xD
state:
Rate of flow IN = Rate of flow OUT:ROL
Combining: (Ln + D) yn+1 = Ln xn + D xD
Under constant molal overflow
assumption:
L1 = L2 = .......... Ln-1 = Ln = Ln+1 = L =

Operating Line Eqn. for the

rectifying section: ROL
*

Reflux Ratio R = L /
D

ROL Characteristics:
i. Straight Line Equation
ii. Slope= R/(R+1),
Intercept =(xD /R+1),
iii. In addition, if xn = xD, then yn+1 = xD .
iv. Thus, the operating line passes through the
point (xD , xD) on the 45o diagonal line.

R changes, the slope and intercept

of the ROL

Rectifying Section: ROL

Introduction of Feed : the q-line

Consider the tray where the feed is introduced
(known as the feed tray location), say tray f :

The feed may consists of:

liquid, vapour or a mixture of both.
The quantities of the liquid stream and
vapour stream in the rectifying and stripping
sections may change abruptly because of the
addition of the feed stream.

q = moles of liquid flow in the

stripping section that results from the
introduction of each mole of feed.
The value of q can be controlled by adjusting the
amount of preheat the feed stream is subjected to
before entering the column.
For different feed conditions, numerical limits :
cold feed (below bubble point): q > 1
feed at bubble point (saturated liquid): q =
1
feed partially vapour: 0 < q < 1
feed at dew point (saturated vapour): q = 0
feed superheated vapour: q < 0
If the feed is a mixture of liquid and vapour, then
q is the fraction of the feed that is liquid

Effect of various feed conditions on

vapour and liquid loading in column
As an example, consider the Figure above
whereby the feed is a cold liquid.
In this case, all the liquid feed will go to
the stripping section.

q vs. feed condition

Q=1q=
1

1>q>0

q=0

0>q

Relating q with L and L; Vand

V

In addition, because the feed is cold, it will

also condense some of the rising vapour.
As a result, the amount of liquid flow in the
stripping section L' is much larger than the
liquid flow in the rectifying section L.
The vapour flow in the rectifying section V,
is lower than the vapour flow in the
stripping section V' because of the
condensation into the liquid.
Hence for case (a), we have L' > L and V' >
V.

Feed Section Operating Line (q-line

F moles/hr of feed, with fraction q of

liquid
By definition:
liquid flow = q F moles/hr
vapour flow = (1-q) F moles/hr
Overall material balance:
L' = L + q F
V = V' + (1-q) F
Component balance for the
more volatile component

Operating Line Equation :

Stripping Section , SOL
Analysis not really required, as SOL can be
automatically fixed once ROL and q-line are
drawn.
The SOL is the last line drawn:
by connecting xB on the diagonal to the point of
intersection between the ROL and q-line
With ROL fixed, when the q-line changes the SOL
changes as well.

3 different SOL that correspond to 3 different qlines, for a given ROL (i.e. fixed R and x D)is shown
.
Thus, the operating line passes through the
point (xB , xB) on the 45o diagonal line.

Equation for stripping section

Material balance over dashed-line

section:
A component A
balance:

Vm 1 Lm B

Vm1 ym 1 Lm xm Bx B

167

Solving for ym+1, the enriching-section operating

line is

Lm
Bx B
ym 1
xm
Vm 1
Vm 1

Again, since equimolal flow flow is assumed,

Lm LN
Vm 1 VN

= constant and
Lm Vm 1

= constant,

SOL eqn. is a straight line when plotted as y

versus x:
Lm

slope of Lm/Vm+1
It intersects the y = x line at x = xB.

y Bx B / Vm 1

168

SOL: equation
Substituting, and re-arrange

Substituting V' = L' - B: stripping operating line (SOL)

straight line: slope= L' / (L' - B) ;

intercept= B xB /( L' - B )
passed through ( xB, xB ) on the 45o diagonal line.
the stripping section operating line can be drawn on
equilibrium diagram and the number of theoretical
stages in the stripping section can be done in the same
manner
The last "stage" on the graphical construction
represents the reboiler

Intersection of operating lines

Rectifying section : V y = L x + D xD
Stripping section : V' y = L' x - B xB
At the feed point where the two lines operating lines
intersect:
( V - V' ) y = ( L - L' ) x + D xD + B xB
we have also:
V - V' = ( 1 - q ) F
L - L' = - q F
In addition, from component balance around the
entire column:
F xF = D x D + B xB
Thus, y = - q/ ( 1 - q ) x + xF /( 1 - q )
This gives the loci of points of intersection as a
function of q

For a given feed condition, xF and q

are fixed, therefore the q-line is a
straight line
slope =-q/(1-q) and
Intercept = xF / (1-q).
q-line passes
the point (xF, xF)

Effect of q on the intersection of

operating lines
this also marks the end of each of the
operating lines
q = 0 (saturated
vapor)
q = 1 (saturated
liquid)
q > 1(subcooled
liquid)
q < 0 (superheated
vapor)

The q-values: not certain of the feed condition

If the condition of the feed is known to be either
saturated liquid or saturated vapour, then the value
of q is either 1 or 0 value of q.
Using enthalpy balance around the feed plate f. :
F HF + L HL,f-1 + V' HV,f+1 = L' HL,f + V HV,f
where
HF = enthalpy of feed, evaluated at TF
HV = enthalpy of vapour, and
HL = enthalpy of liquid

Tbp= bubble point of the feed

Tdp is the dew point of the feed

Feed Plate Location

Optimum location would be the one represented by the

triangle that has one corner on the rectifying line
and the other corner on the stripping line.
In transferring from the rectifying section to the
stripping section, the steps on the diagram should be
kept as large as possible, and the transition is made at
the first opportunity after passing the intersection
point.
the optimum feed location is stage no.5 that results in
the least number of stages.
Any other location would
result in more than 5 trays

If "staircase" construction is continued beyond

tray 5 along the ROL to tray 6 and tray 7 instead
of down to SOL, note that the triangles become
smaller, which means that the driving force for
mass transfer is smaller.
As a result, more trays will be required to
achieve the desired separation.
tray 6 for the first case is more effective than
that for the second case - the triangle is larger.

If the change to SOL is made too soon, at tray 4. Again the result is less than opt

Steps/Procedure:
1. Draw VLE curve.
2. Draw 45" line.
3. Locate xB, xD, and ZF on y=x line.
4. Calculate slope of q line [ -q/( 1 - q)]
and draw q line from (zF, zF)
5. Calculate B and D from overall balances
6. Calculate liquid and vapour flow rates in
rectifying and stripping sections.

stepping off stages

Using Operating Lines and the Feed Line in

McCabe-Thiele Design

Slope = R/(R+1)
Slope = q/(1-q)
Slope = L/ V

Ex 4.7 A continuous fractioning column is to be designed to

separate 30,000 kg/h of a mixture of 40 percent benzene and
60 percent toluene into an overhead product containing 97
percent benzene and a bottom product containing 98 percent
toluene. These percentages are by weight. A reflux ratio of 3.5
mol to 1 mol of product is to be used. The molal latent heats of
benzene and toluene are 7,360 and 7,960 cal/g mol,
respectively. Benzene and toluene from a nearly ideal system
with a relative volatility of about 2.5. The feed has a boiling
point of 95C at a pressure of 1 atm.
a) Calculate the moles of overhead product and bottom product
per hour.
b) Determine the number of ideal plates and the position of the
feed plate (i) if the feed is liquid and at its boiling point; (ii) if
the feed is liquid and at 20C (specific heat 0.44 cal/g.C); (iii) if
the feed is a mixture of two-thirds vapor and one-third liquid.

Homework No.8
1. A saturated liquid feed of 200 mol/h at the boiling
point containing 42mol% heptane and 58% ethyl
benzene is to be fractionated at 101.32 kPa abs to give
a distillate containing 97 mol% heptane and a bottoms
containing 1.1 mol% heptane. The reflux ratio used is
2.5:1. Calculate the molar flow rate of the distillate and
the bottoms, theoretical number of trays required to
achieve the separation, and the optimum feed tray
location. Equilibrium data are given below at 101.32
kPa abs pressure for the mole fraction n-heptane x H
Temperature
Temperature
and yH.
K

xH

yH

xH

yH

409.3

136.1

383.8

110.6

0.485

0.730

402.6

129.4

0.08

0.23

376.0

102.8

0.790

0.904

392.6

119.4

0.25

0.514

371.5

98.3

1.000

1.000

Tempe
rature

Tempe
rature

2. Determine the minimum reflux ration Rm

and the minimum number of theoretical
plates at total reflux for the rectification of
a mixture of heptane and ethyl benzene as
given in problem 1. Do this by the graphical
methods of McCabe-Thiele.

 it can affect the separation

Importance
of
Reflux
Ratio,
R
efficiency
for given feed condition (xF and q):
higher reflux ratio (R) will results in
lesser number of theoretical trays
(N) required, and vice versa.
In other words:
there are many possible
combinations of reflux ratio R
and number of theoretical

ANALYSIS OF REFLUX RATIO CHANGES

inverse relationship between the reflux

ratio and the number of theoretical
stages.
new design, of course the reflux ratio
and number of theoretical stages can both
be varied to achieve an optimum balance.
For an existing column, the number of
trays used is fixed, hence:
higher distillate concentration (mole
fraction xD) can only be obtained by
increasing the reflux ratio.

 At a specified distillate concentration (i.e.

constant xD), when R changes, the slope and
intercept of the ROL changes. The ROL
therefore rotates around the point (xD, xD).
with a given feed condition (i.e. x F and q fixed),
and a specified product compositions (i.e. x D
and xB fixed) - increasing R will result in
lesser number of theoretical stages
required.
From the ROL equation, we can see that when
R increases (with xD constant), the slope of
ROL becomes steeper, i.e. (R/R+1) and the
intercept (xD/R+1) decreases.

Effect of R changes onthe slope and

intercept of the RO

Thus, as R increases, the ROL rotates

downwards around (xD, xD).
The SOL also moved down accordingly.
The area between the equilibrium curve and
ROL is now larger,
draw larger triangles between the operating
lines.
This means that there are now greater driving
force for separation,
this in turn means that lesser number of
theoretical stages are required.
The reverse is true when R decreases.

total reflux andminimum reflux ratio

at two extremes of the reflux

ratios,
how to find the most suitable
reflux ratio
minimum reflux ratio:
- results in infinite stages
total reflux or infinite reflux rati
o

Fenske equation at total reflux :Nmin

if the relative volatility of the two components
is approximately constant, we have the
calculate the minimum number of theoretical
steps when a total condenser and a reboiler
are used.

Nm= the minimum number of equilibrium

excluding the reboiler, at total reflux.

Nm at total reflux: graphical method

*

Operating line at minimum

reflux ratio:

Operating line and q-line intersect on the

equilibrium curve

Slope=Rm/(Rm+1)

XD/(Rm+1)

Minimum

total reflux and minimum reflux ratio

The minimum reflux ratio and the
infinite reflux ratio place a constraints
on the range of separation operation.
Any reflux ratio between Rmin and Total
R will produce the desired separation,
with the corresponding number of
theoretical stages varying from infinity
at Rmin to the minimum number (Nmin at
Total R).
The choice of reflux ratio to use is
governed by cost considerations

Steps/Procedure:
1. If the external reflux, Lo, is at its bubble point:
2. LR = Lo = (R) D
3. VR = LR + D
4. vs = VR - (1 - q ) F
5. Ls = LR + qF
. 7. Calculate slope of rectifying operating line:=[ R/(R+1)
. 8. Draw rectifying operating line from (xD , xD ) with slope= =[ R/(R+1) . 9. Draw stripping operating line from (xB , xB ) to the intersection
. of the q line with the rectifying operating line.
. 10. Check your calculations by seeing whether the slope of stripping operating
. line is Ls/Vs.
. 11. Start from the xB point on the 45 line and step up from the stripping operating line to
the VLE curve.
. The first step corresponds to the partial reboiler. The next step is tray above, the next is tray 2,
and so on.
. 12. When this stepping procedure crosses the intersection of operating lines, this is the
optimum feed tray (i.e.? any other feed tray would require a greater total number of
trays). Thus the feed tray NF has been determined.
. 13. Switch to the rectifying operating line and continue stepping.
. 14. When the xD point is crossed, this is the total number of trays NT.

Steps/Procedure:
13. Switch to the rectifying operating line and continue stepping.
14. When the xD point is crossed, this is the total number of trays
NT.
This last step may not go through the xD point exactly, implying a
noninteger
number of trays.
Dont let this worry you. In this procedure we have assumed perfect or
theoretical or 100 percent efficient trays;
that is, trays on which the vapour and liquid streams leaving the trays
are in perfect phase equilibrium.
Actual industrial columns seldom achieve this ideal situation, so an
efficiency factor must be used to determine the number of actual trays
installed in the column
this must be an integer number in an actual column.
Typical efficiencies run from 40 to 90percent, depending on the
system.