SCHOOL OF BIO AND CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

HEAT AND MASS TRANSFER FOR BIOLOGICAL SYSTEMS

SCHA1311

UNIT – 1 PRINCIPLES OF MASS TRANSFER- SCHA1311

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 UNIT 1

PRINCIPLES OF MASS TRANSFER

Introduction to Mass transfer and diffusion, Ficks law for molecular diffusion, Molecular
diffusion in gases, Molecular diffusion in liquid, Molecular diffusion in solids, Miolecular
diffusion in biological solutions and gels.

Introduction to convective mass transfer, Convective mass transfer coefficients. Analogy

between Mass, Heat and momentum transfer. Mass Transfer and its Applications

Air is a mixture of various gases. Whenever we have a multicomponent system with a

concentration gradient, one constituent of the mixture gets transported from the region of higher
concentration to the region of lower concentration till the concentration gradient reduces to zero.
This phenomenon of the transport of mass as a result of concentration gradient is called 'Mass
Transfer'.

The mass transfer phenomenon is analogous to heat transfer phenomenon. In heat

transfer - heat energy flows in a direction of decreasing temperature gradient and ceases when
the temperature gradient reduces to zero. In mass transfer - the transfer of mass takes place in the
direction of decreasing concentration gradient and ceases when the concentration gradient is
zero.

The. common examples of mass transfer in our everyday life and in many

industries are:

- diffusion of smoke discharged by tall chimney into the atmosphere,

- a drop of ink diffusing in a glass of still water,

- evaporation of a drop of perfume in a room,

- humidification of air flowing over a spray pond or cooling tower,

- mixing of diesel or petrol with air inside an internal combustion engine,

- diffusion welding of metals,

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 - diffusion of neutron in a nuclear reactor.

Different Modes of Mass Transfer

There are basically two modes of mass transfer:

(i) Mass Transfer by Diffusion - the transport of mass by random molecular motion in
quiescent or laminar flowing fluids is known as mass transfer by 'diffusion' and is analogous to
heat transfer by conduction. Mass transfer by diffusion occurs due to (a) concentration gradient,
(b) temperature gradient, and (c) hydrostatic pressure difference.

(ii) Convective Mass Transfer - the rate of molecular diffusion of mass can be
accelerated by the bulk motion of the fluid. Mass can be transported between the boundary of a
surface and a moving fluid (drying of clothes, molecular diffusion of a sugar cube in a cup of
coffee by stirring, moist air flowing over the surface of an ocean and precipitation on a dry land
etc.), or between two moving fluids which are relatively immiscible (formation of clouds,
vapourisation of water in a tea kettle). This mechanism of mass transfer is called 'convectIve
mass transfer' and is analogous to heat transfer by convection (free or forced).

Dalton's Law of Partial Pressure

Each constituent of a multicomponent system contributes to the total pressure by an

amount which is known as the 'partial pressure' of the constituent. The relationship between the
partial pressures of the constituents is expressed by Dalton's Law:

The pressure of a mixture of gases is equal to the sum of the partial pressure of the
constituents. The partial pressure of each constituent is that pressure which the gas would exert if
it occupied alone that volume occupied by the mixture at the same temperature.

For a mixture of ideal gases, we have

P = PA + PB + ....... + PK;

where PA is the partial pressure of the species A and so on.

  Pi (1)
i

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 Dalton's law was reformulated by Gibbs to include a second statement on the properties
of mixtures. The combined statement is Gibbs-Dalton law:

The internal energy. enthalpy and entropy of a gaseous mixture are respectively equal to
the sum of the internal energies, enthalpies, and entropies of the constituents. The internal
energy, enthalpy and entropy which a constituent would have if it occupied alone that volume
occupied by the mixture at the temperature of the mixture.

Molar Density, Mass Density, Mass Fraction and Mole Fraction

There are a number of ways by which the concentration for a species in a

multicomponent mixture can be defined:

(i) Molar Density or Molar Concentration, CA = number of moles of the species A per
unit volume of mixture, kg-mol/m3

(ii) Mass Density or Mass Concentration, A = mass of the species A per unit volume
of the mixture, kg/m3.

(iii) Mass Fraction, mA = mass concentration of component A / total mass density of the
mixture.

(iv) Mole Fraction, XA = number of moles of species A / total number of moles of the
mixture. = CA/C

Therefore, the following summation rules hold true:

CA + CB + .... + CK = C

A + B + ..... + K =

XA + XB + ..... + XK = I1

rnA + mB + ..... + mK = I (2)

Since the number of moles = mass of species/molecular weight, we have

CA  A / MA

For a perfect gas, we have:

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 PA V  n A R oT , where Ro is the universal gas constant,

and, CA  n A / V  PA / R oT

XA  CA / C  PA / P and C  p / R oT

Mass Average and Molar Average Velocities and Different Types of Fluxes

Velocities: In a multicomponent mixture, the bulk velocity of the mixture can be

defined on the basis of mass average or molar average velocity. Let V A be the velocity of the
species A and A is the mass density of the species A, then the mass average velocity would be:

A VA  B VB  .... A VA  B VB  ....
V 
A  B 

 mA VA  mBVB  ..... (3)

Similarly, the molar average velocity would be:

CA VA  CB VB  .... CA VA  CBVB  ...

U   X A VA  X B VB  ....
CA  CB C

Since mass transfer requires the diffusion of a species with respect to a plane moving
with an average velocity, diffusion will take place when the diffusion velocity is in excess of the
average velocity. Thus

Mass diffusion velocity of the species A : VA – V (4)

Molar diffusion velocity of the species A : VA - U (5)

Fluxes: The mass flux of species A can be expressed relative to either a fixed observer
or an observer moving with the bulk velocity. For a stationary observer, the absolute flux of any
species A will be equal to the sum of the flux due to the molecular diffusion and that due to the
bulk motion.

Thus, Absolute flux: A VA and, Diffusion flux: m / A

Flux due to bulk motion: A V

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 A VA  m / A  A V, or m / A  A  VA  V  (6)

Similarly, molar diffusion flux = CA(VA – V) (7)

Fick's Law of Diffusion*

The fundamental equation (one-dimensional) of molecular diffusion is known as Fick's

law. It has been derived from the kinetic theory of gases, and can be written for a binary mixture
as

JA = –DAB (d CA/dx) (8)

where DAB = diffusion coefficient of species A with respect to species B,

JA = molar flux in the X-direction relative to the molar average velocity,

dCA/dx = Concentration gradient in X-direction.

Let us consider a two compartment tank as shown in Fig. 5.1. One compartment
contains gas A and the other compartment contains gas B and both the compartments are initially
at a uniform pressure and temperature throughout. When the partition between the compartments
is removed, the two gases will diffuse through each other until equilibrium is established and the
concentration of the gases is uniform throughout the tank.

Fig. 1 Diffusion of species A in to species B

Fig 2 illustrates the dependence of diffusion on the concentration profile. The

concentration of the species A on the left side of the imaginary plane is greater than that on the
right side. As such, more molecules will cross the plane per unit time from left to right. This

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would lead to a net transfer of mass from the region of higher concentration to the region of
lower concentration.

Fig.2 Dependence of diffusion on concentration profile

* This law assumes that fluxes are measured relative to the coordinates that move with
the average velocity of the mixture.

Diffusion in Gases, Liquids and Solids

(i) Diffusion in Gases - the diffusion rates in gases are dependent on the molecular
speed which is a function of temperature and therefore, the diffusion coefficient depends upon
the temperature of gases.

Gilliland has proposed a semi-empirical equation for diffusion coefficient in a binary

gas mixture –

1/ 2
T3/ 2  1 1 
D  435.7    (9)
 
2
p VA1/ 3  VB1/ 3  MA MB 

where D is in square centimeters per second, T is in Kelvin, p is the total pressure of the
system in pascals, V A and VB are the molecular volumes of the species A and R as calculated
from the atomic volumes in Table 12.1, M A and MB are the molecular weights of species A and
B.
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 Diffusion coefficients for gases depend upon pressure, temperature and other molecular
properties of diffusing gases. At two different pressure and temperature, we have

D2 / D1   p1 / p2  .  T2 / T1 
3/ 2
(10a)

Table 1 Atomic volumes*

Air 29.9 In secondary amines 1.2

Bromine 27.0 Oxygen, molecule (O2) 7.4
Carbon 14.8 Coupled to two other elements:
Carbon dioxide 34.0 In aldehydes and ketones 7.4
Chlorine In methyl esters 9.1
Terminal as in R-Cl 21.6 In ethyl esters 9.9
Medial as in R-CHCl-R 24.6 In higher esters & ethers 11.0
Flourine 8.7 In acids 12.0
Hydrogen, molecule (H2) 14.3 In union with S, P, N 8.3
in compounds 3.7 Phosphorous 27.0
Iodine 37.0 Sulphur 25.6
Nitrogen, molecule (N2) 15.6 Water 18.8
in primary amines 10.5
*(For three numbered ring like ethylene oxide, deduct 6.0, for four numbered ring like
cyclobutane, deduct 8.5, for six numbered ring like benzene, deduct 15.6, for napthelene ring,
deduct 30.0.)

Example: Calculate the diffusion coefficient of CO2 in air at 30°C and at 1 atm
pressure.

Solution: the atomic volumes are:

CO2: Volume 34; molecular weight 44

Air: Volume 29.9; molecular weight 28.9

From Eq. (12.9), we get

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  273  30 1.5
D  435.7 1/ 44  1/ 28.9 1/ 2
1.0135 10 34 
2
5 1/ 3
 29.91/ 3

= 0.1 cm2/s

Estimate the diffusivity of ethyl alcohol (C2 Hs OH) in air at 25°C

and 1 atm pressure.

Solution: Kopp's law of additive atomic volumes applies in gases where compounds are
involved.

For ethyl alcohol, the volume would be: 2(14.8) + 6(3.7) + 7.4 = 59.2

From Eq. (9), we have for ethyl alcohol,

 273  30 1.5
D  435.7 1/ 46  1/ 28.9 1/ 2
1.0135 10 59.2 
2
5 1/ 3
 29.91/ 3

= 0.753 cm2/s

Similarly, for methane CH4, the volume would be: 14.8 + 4(3.7) = 29.6

Using Eq (9), for methane, 0 = 1.114 cm2/s.

(ii) Diffusion in Liquids and Solids - Diffusion in liquids occurs at much slower rate
than in gases. Since kinetic theory of liquids is not as much developed as that of gases, it is
usually assumed as a first approximation that equations of the same general form are applicable
to the diffusion of a solute in a solvel1t as to the diffusion in gases, i.e., Fick's law is assumed
valid for liquids.

Diffusion coefficient for most of the common organic and inorganic materials in the
usual solvents such as water, alcohol and benzene at room temperature lie m the range of 1.79 ×
10-3 to 1.075 × 10-7 cm2/s.

Diffusion in solids is much slower than in liquids. Diffusion of solids in solid has
limited engineering applications but diffusion of fluids in solids have extensive applications.

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Fick's law is sometimes used, with an empirically determined effective diffusivity which takes
care of the structure of solid. A typical problem of liquid transfer in a solid, of interest, is drying
of solids.

The Equivalence of Diffusion Coefficient

Fick's law (Eq.8) can also be expressed in terms of mass flux per unit area or mass
concentration or in terms of molal concentrations and fluxes. For gases, the law may be
expressed in terms of partial pressures by making use of the perfect gas equation of state:

= RT

Since the characteristic gas constant of a gas is: RA = Ro/MA

We have A = A MA/RoT

and mA / A  DAB  MA / R oT  dpA / dx for isothermal diffusion. (5.10b)

Similarly, the diffusion of the component B, for the system shown in Fig. 5.1, we can
write

mB M dp B
 DBA B (11)
A R o T dx

When we have equimolal counter diffusion, shown in Fig. 12.3 (a, b), the steady state
molal diffusion rates of the species A and B, represented by N A and NB will be given by

mA  A   dpA 
NA   DAB    (12)
MA  R oT   dx 

mB  A   dpB 
and NB   DBA    (13)
MB  R oT   dx 

The total pressure of the system remains constant at steady state,

or, p = pA + pB ; and dpA/dx + dpB/dx = 0

as dpA/dx = –dpB/dx

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 Since each molecule of A is replaced by a molecule of B, the molal diffusion rates must
be equal. Thus: NA = –NB, and

 A   dpA   A   dpA 
DAB     DBA    (14)
 R 0T   dx   R 0T   dx 

or DAB = DBA = D

This fact is known as the equivalence of diffusion coefficients or diffusivities in binary

mixtures, and is a property of the binary mixture.

By integrating Eq. (12.10), we can obtain the mass flux of the species A as;

mA
A

DM A
R 0T
 
 p A2  p A1 / x (15)

corresponding to the nomenclature used in Fig. 3 (a, b). Table 2 gives the values of the
binary diffusion coefficients.

Fig. 3(b) Equlmolal counter-diffusion (partial pressure profile)

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 Table 2 Values of binary diffusion coefficient

Component A Component B T(K) DAB(m2/s)

Solids

O2 Rubber 298 0.21 × 10–9

CO2 Rubber 298 0.11 × 10–9

He SiO2 293 0.4 × 10–18

Cd Cu 293 0.27 × 10–18

Al Cu 293 0.13 × 10–33

Dilute Solutions

Caffeine H2O 298 0.63 × 10–9

Ethanol H2O 298 0.12 × 10–8

Glucose H2O 298 0.69 × 10–9

Acetone H2O 298 0.20 × 10–8

O2 H2O 298 0.24 × 10–8

H2 H2O 298 0.63 × 10–8

N2 H2O 298 0.26 × 10–8

Gases

NH3 Air 298 0.28 × 10–4

H2O Air 298 0.26 × 10–4

CO2 Air 298 0.16 ×10–4

H2 Air 298 0.41 × 10–4

O2 Air 298 0.21 × 10–4

Acetone Air 273 0.11 × 10–4

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Naphthalene Air 300 0.62 × 10–5

H2 O2 273 0.70 × 10–4

H2 N2 273 0.68 × 10–4

H2 CO2 273 0.55 × 10–4

CO2 N2 293 0.16 × 10–4

CO2 O2 273 0.14 × 10–4

O2 N2 273 0.18 × 10–4

Main Points of Fick's Law of Diffusion

These can be summarised as:

(i) It cannot be derived from first principles because it is based on experimental

evidence.

(ii) It is valid for all phases of matter. Since mass transfer is strongly influenced by
molecular spacing, diffusion is maximum in gases and minimum in solids.

(iii) It is analogous to Fourier law for conduction heat transfer.

(iv) It does not tell about diffusion due to temperature or pressure gradient or due to
external forces.

Convective Mass Transfer Coefficient

When the mass is transported between the boundary of a surface and a moving fluid or
between two moving fluids which are relatively immiscible, we have mass transfer by
convection. The convective process can be either natural or forced, depending upon the existence
of density or pressure gradient respectively, in the .medium. The convective mass transfer
coefficient is defined in a manner similar to that for convective heat transfer.


Or, mA  h DA A CA1  CA2  (1)

where m A = diffusive mass flux of species A, h DA = mass transfer coefficient, and

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CAi , CA2 , are the concentrations through which diffusion takes place. The convective mass

transfer coefficient depends upon the fluid properties, the mechanism of fluid flow, and the
geometry of the flow system and is analogous to the convective heat transfer coefficient.

For a steady-state diffusion across a layer of thickness L,

  
mA  DA CA1  CA2 / L  h DA A CA1  CA2 
therefore, h DA  D / L , m/s (2)

Dimensionless umbers Used in Mass Transfer

The following dimensionless numbers are of significance in convective mass transfer:

Schmidt Number, Sc = momentum diffusivity/mass diffusivity = /D = / D.

This number is analogous to Prandtl number and when Sc = I, there would be complete
similarity between momentum and concentration equations and the hydrodynamic results may be
applied directly to convective mass transfer problems.

Sherwood number, Sh = hDx/D, and IS analogous to Nusselt number. Lewis Number,

Le = aID, the temperature and concentration profiles will be similar when the Lewis number is
equal to unity.

gL3  Cs  C 
Mass Grashof number, Grm 
v 2 C

Cs = mass concentration at surface `

C = free stream mass concentration

An Expression for the Convective Mass Transfer Coefficient for Laminar Flow
Over a Flat Plate

Let us consider a flat plate where the concentration at the surface of the species A is
different than its concentration in the free stream. The species A will diffuse into the fluid and a
concentration boundary layer will develop as shown in Fig.8. The thickness of the concentration
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boundary layer is defined ill the same manner as that of the hydrodynamic boundary layer or
thermal boundary layer.

Fig. 8 Concentration boundary layer on a flat plate

Since there is a remarkable similarity between the laws governing the boundary layer
growth of the three processes: momentum, heat and mass, the governing equation far the
concentration boundary layer can be written as:

u . CA / x  v. CA / y  D.  2CA / y2 (3)

And for laminar flow over the flat plate, the average values for the convective mass
transfer coefficient can be obtained from the relation:

Sh L  h DL / D  0.664 Re0.5
L Sc
1/ 3
(for Sc  0.6 ) (4)

When the boundary layer is partly laminar and partly turbulent, transition occuring at Re
= 5 × 105, the correlation for mass transfer would be, similar to heat transfer, and is given by


Sh L  0.037 Re0.8
L  870 Sc
1/ 3
(5)

For flow over smooth flat plates, the Colburn analogy predicts:

(a) Laminar flow: Cf / 2  0.664ReL0.5  h D / USc2/ 3

(b) Turbulent flow: Cf / 2   h D / U  Sc  0.0296 ReL

2/3 0.2
(6)

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Expressions for Convective Mass Transfer Coefficient for Flow through Tubes,
Flow over Spheres and Cylinders

We have forced convection mass transfer when a liquid evaporates from the wetted
walls of a tube into the gas flowing through that tube. A concentration boundary layer develops
inside the tube, similar to the hydrodynamic boundary layer, as shown in Fig. 12.9.

Fig. 9 Concentration profile for mass transfer in a tube

For fully developed velocity and concentration profiles in a laminar flow through a tube,
the following equations have been suggested for the evaluation of mass transfer coefficients:

hDd/D = Sh = 3.66 for uniform wall mass concentration (7)

Sh = 4.34 for uniform wall mass flux (8)

In turbulent flow, the concentration of the diffusing component varies with time and
space and as such mass transfer coefficients are evaluated either experimentally or with the help
of empirical equations. These equations are based on analogy with heat transfer.

Gilliland has proposed the following equation for the vapourization of liquids from the
walls of smooth circular tubes when air is forced to flow through the tube: Sh = 0.023(Re)0.83
(v/D)0.44; 2000 < Re < 35,000;

and for gases 0.6 < Sc < 2.5 (9)

The Reynolds and Colburn analogy can also be used to calculate the mass transfer
coefficient from the friction factor. Or,

hD C
.Sc 2 / 3  f / 8  f (10)
U 2

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 When the coefficient of friction C f is eliminated from Colburn analogy for heat and
mass transfer, we get

St  Pr   St m Sc 
2/3 2/3

h
or,  Pr 2 / 3  St m Sc 2 / 3
Cp U

2/3 2/3
h  Sc  
 Cp  Le 
2/3
  Cp    Cp   (11)
hD  Pr  D

Eq. (11) gives a relation between the mass transfer and heat transfer coefficients. That
is, the coefficient of mass transfer can be evaluated from the data available for heat transfer
coefficients. Eq. (11) is known as Lewis Equation. Lewis Equation Le  1 in gas-vapour mixture.

Analysis among Mass, Heat and Momentum Transfer

Analogies among mass, heat and momentum transfer have their origin either in the mathematical
description of the effects or in the physical parameters used for quantitative description.

To explore those analogies, it could be understood that the diffusion of mass and conduction of
heat obey very similar equations. In particular, diffusion in one dimension is described by the
Fick’s Law as

dCA
J A   D AB
dz
Similarly, heat conduction is described by Fourier’s law as

dT
q  k
dz

Where k is the thermal conductivity.

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The similar equation describing momentum transfer as given by Newton’s law is

d
 
dz
Where  is the momentum flux (or shear stress) and  is the viscosity of fluid.

At this point it has become conventional to draw an analogy among mass, heat and momentum
transfer. Each process uses a simple law combined with a mass or energy or momentum balance.

In this section, we shall consider several analogies among transfer phenomenon which has been
proposed because of the similarity in their mechanisms. The analogies are useful in
understanding the transfer phenomena and as a satisfactory means for predicting behaviour of
systems for which limited quantitative data are available.

The similarity among the transfer phenomena and accordingly the existence of the analogies
require that the following five conditions exist within the system

1. The physical properties are constant

2. There is no mass or energy produced within the system. This implies that there is no
chemical reaction within the system
3. There is no emission or absorption of radiant energy.
4. There is no viscous dissipation of energy.
5. The velocity profile is not affected by the mass transfer. This implies there should be a
low rate of mass transfer.

Reynolds Analogy

The first recognition of the analogous behaviour of mass, heat and momentum transfer was
reported by Osborne Reynolds in 1874. Although his analogy is limited in application, it served
as the base for seeking better analogies.

Reynolds postulated that the mechanisms for transfer of momentum, energy and mass are
identical. Accordingly,

kc h f
 
    C p 2
Here h is heat transfer coefficient

f is friction factor

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  is velocity of free stream

The Reynolds analogy is interesting because it suggests a very simple relation between different
transport phenomena. This relation is found to be accurate when Prandtl and Schmidt numbers
are equal to one. This is applicable for mass transfer by means of turbulent eddies in gases. In
this situation, we can estimate mass transfer coefficients from heat transfer coefficients or from
friction factors.

Chilton – Colburn Analogy

Because the Reynold’s analogy was practically useful, many authors tried to extend it to liquids.
Chilton and Colburn, using experimental data, sought modifications to the Reynold’s analogy
that would not have the restrictions that Prandtl and Schmidt numbers must be equal to one.
They defined for the j factor for mass transfer as

kc
jD  Sc  2 3

The analogous j factor for heat transfer is

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j H  St Pr

Nu h
where St is Stanton number = 
Re Pr C p
Based on data collected in both laminar and turbulent flow regimes, they found

f
jD  jH  ----------------------------- (4.38)
2
This analogy is valid for gases and liquids within the range of 0.6 < Sc < 2500 and 0.6 < Pr <
100.

The Chilton-Colburn analogy has been observed to hold for many different geometries for
example, flow over flat plates, flow in pipes, and flow around cylinders.

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TEXT / REFERENCE BOOKS

1. Treybal R.E., Mass Transfer Operations, 3rd Edition, McGraw Hill, 2009.

2. McCabe and Smith, Unit Operations of Chemical Engineering, 7th Edition, McGraw Hill,
2009.

3. Coulson J.M. and Richardson J.F., Chemical Engineering, 6th Edition, Pergamon Press, 2002.

4. Anantharaman N., MeeraSheriffa Begum K.M., Mass Transfer Theory and Practice, 1st

Edition, PHI, 2011.

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 SCHOOL OF BIO AND CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

HEAT AND MASS TRANSFER FOR BIOLOGICAL SYSTEMS

SCHA1311

UNIT – 2 BASIC SEPARATION PROCESSES-1- SCHA1311

 UNIT 2

BASIC SEPARATION PROCESSES

Introduction to separation processes, Distillation, Types of distillation – Simple, Steam,

Vacuum, Continuous distillation,absorption-packed and plate columns, Adsorption-
chemisorption, physical adsorption, isotherms, membrane separation process –
Electrodialysis, Reverse osmosis, Ion exchange, Extraction – Batch and Continuous
operations.

INTRODUCTION

The separation processes are divided in equilibrium and rate governed separation process. In
equilibrium governed separation processes, the product phases are in equilibrium with the inlet
phases. In rate governed separation processes, difference of rate of physical transport of species
brings the separation. Some of the specific separation processes under these two categories are
elaborated below.

EQUILIBRIUM GOVERNED PROCESS

Four popular and quite common equilibrium governed separation processes are described.

Distillation

Distillation is based on the differences in boiling points of the constituents in a mixture. The
component having the lower boiling point will go to the vapor phase earlier, leaving behind the
other component in the residual mixture. In this process, external heating is required to heat up
the system. Therefore, the top vapor phase is condensed and is rich in one component and the
residual liquid phase is rich in other component. This is known as flash distillation. In another
process, a part of the condensed stream from the top is recycled down the column. This is known
as reflux. In this case, there is intimate mixing of the liquid stream coming down and vapor
going up. This operation is carried out in counter current fashion and this enhances the efficiency
of the process. This is generally used for separation of aqueous mixture of various organic
solvents, like, toluene, benzene, acetone, ethyl benzene, etc.

Absorption

In this process, a vapor in an inert gas is absorbed in a liquid stream. The vapor is soluble in the
liquid. The liquid stream rich in solubilized vapor components is separated by distillation or
some other suitable techniques. The liquid can be recovered and reused in the process itself. An
example is removal of ammonia from ammonia – water mixture using water as solvent. Removal
of carbon di oxide from a mixture of air and carbon dioxide using a solvent like primary or
secondary or tertiary amines is another example. Typically this operation is carried out in counter
current manner to enhance the efficiency of this process. Sometimes, the packed beds or staged
beds like trays are used to have better mixing during the transfer process. It may be mentioned
that absorption is a bulk phenomena, i.e., the gaseous solutes are transported to the bulk of the
liquid stream. It may be noted that to effect separation, a matter is introduced in the system.

Adsorption

Separation of solutes by transporting it from gaseous or liquid streams on a solid surface is

known as adsorption. As opposed to absorption it is a surface phenomenon. The solute is fixed
on the solid surface only. Typically, the solid surface is specific for a particular component
present in the feed stream. For example, in a liquid stream having organic as well as inorganic
components, the organics are preferentially adsorbed on the surface of activated carbon.
Typically, in a bed, the adsorbent particles are kept and the fluid is pumped through the system
for intimate mixing. In the process, the solute is transferred to the solid phase. After sometime,
the solid phase is completely saturated and the transfer of species becomes extremely slow due to
lack of driving force. In such case, the bed has to be replaced by new adsorbents or the bed has to
be regenerated by a suitable washing protocol. It may be noted, that a reasonably lower particle
size of adsorbents provides sufficient surface area for separation. Removal of organics from an
aqueous mixture using activated carbon is an example of adsorption. It may be noted that to
effect separation, a matter is introduced in the system.

Drying

In drying, water vapors from a solid material are removed by using a vapor stream to an
acceptable small limit. Generally it is carried out by applying thermal energy as compared to
introduction of a matter in case of absorption or adsorption. The process efficiency depends on
the temperature, relative humidity and other thermo physical properties of the drying vapor as
well as the temperature and other thermo-physical properties of the solid.

RATE GOVERNED PROCESS

Most of the membrane based processes are the rate governed. The main crux of the separation
lies in the difference of transport of various species through the membrane. The driving force of
such transport is generally gradient of chemical potential. If we recall the definition of gradient
of chemical potential, it is composed of four parts. These are concentration gradient, pressure
gradient, temperature gradient and electrochemical potential gradient. Presence of these causes
(one or more of such gradients) results into effects (the difference in separation and hence
effects). Some of these systems are described below.

Osmosis

Osmosis is observed when a solution is separated from the solvent by a semipermeable (only
solvent is permeable species) membrane. Apparently, difference in osmotic pressure across the
membrane causes the transport of the solvent. Actually, osmotic pressure is a colligative property
and it is a function of concentration. Therefore, the concentration (or more generally activity)
gradient of the solvent is the main driving force in osmosis. In this case, the solvent flows from
the solvent side to the solution side until, the solvent activity becomes almost equal in both the
sides. This results in generation of hydrostatic pressure difference between the two sides, known
as osmotic pressure. If the initial concentration of solute is more in the solution side, more
solvent will flow in from the solvent side to equalize the solvent activity on both the sides,
resulting in more osmotic pressure difference.

Reverse Osmosis

It must be understood that osmosis is a natural phenomenon. In case of reverse osmosis, pressure
is applied on the solution side externally (using a pump or a compressor), so that the osmotic
pressure is overcome and the solvents are forced out of the solution side. The efficiency of this
process depends on the porosity, morphology and thickness of the membrane. These factors
influence the transport of the solvent through the membrane immensely and thereby, dictating
the throughput of the process and the quality of the product. Since, reverse osmosis membranes
have very small pore size, this is used for separation of lower molecular weight species, like,
salts. A salt having very osmotic pressure, the operating pressure in the feed side of a reverse
osmosis process is therefore extremely high. This will lead to deposition of salts near the
membrane surface, leading to build up of a concentration boundary layer. Therefore, the pressure
gradient in this system leads to concentration difference.

Dialysis

In this case, two liquid streams are separated by a permeable barrier or membrane. In the feed
side, a specific set of solutes are permeated through the membrane to the other side. The
upstream feed is known as the feed side and the downstream is known as the dialysate.
Typically, dialysate stream is pure distilled water. Thus, the concentration gradient between the
two streams is the maximum. The transport is effected by the concentration gradient between
two streams. The duration of separation entirely depends on the rate
DISTILLATION

DEFINITION

Distillation may be defined as the separation of the constituents of a mixture including a

liquid by partial vaporization of the mixture and separate and collect the vapor.

Such separation may include

(i) one liquid from non-volatile impurities.

(ii) one liquid from one or more other liquids, with which it may be miscible, partially-
miscible or immiscible

N.B.

In practice it is difficult to distinguish between evaporation, distillation and drying.

Based on the intention:

(i) when condensation vapor is required the operation is called distillation

(ii) when the concentrated liquid residue is required the operation is called evaporation.
(iii)when the dried solid residue is required as product the process is called drying

BOILING POINT DIAGRAM OF A BINARY MIXTURE

The figure represents the boiling

point and equilibrium-composition
relationship, at constant pressure.
tB
. a
Pressure is constant

Two liquids A (b.p. t A) and B (b.p. d e

tB) are taken in a chamber of
constant pressure. Now at any
t
Temperature . c

temperature the vapor composition

and liquid composition will give two . b
tA

lines when plotted vs. temperature. x y

0 100
In boiling point diagram, Mole % of component A
temperatures are plotted as ordinates
and compositions as abcissas.

 The diagram consists of two curves, the ends of which coincide with the b.p. of two
components (t A and tB).
 The upper-curve describes vapor composition and lower-curve liquid composition.
 At any temperature t the horizontal line cuts the vapor composition curve at ‘e’ which
corresponds to vapor composition of y (mole%A) and cuts the liquid composition curve at
‘d’ which corresponds to liquid composition of x (mole% of A). So any two points on the
same horizontal line (such as d and e) represent compositions of liquid and vapor in
equilibrium at temperature ‘t’.
 For all points above the top line (such as point ‘a’) the mixture is entirely vapor.
 For all points below the bottom line (such as point ‘b’) the mixture is completely liquefied.
 For all points between the two curves (such as point ‘c’) the system consists partly of liquid
and partly of vapor.

RAOULT’S LAW

Raoult’s law states that, any particular

temperature, the partial pressure of one
component of a binary mixture is equal to the
mole fraction of that component multiplied by
its vapor pressure in the pure state at this
temperature.

e.g. to illustrate Raoult’s law, let us consider

the case of benzene and toluene mixture.

At a temperature of 1000C toluene has a vapor pressure of 556 mm. Consequently, if partial
pressure is plotted against composition, the partial pressures of toluene at various compositions
will fall along a straight line from 556 mm for pure toluene to zero for pure benzene. At this
same temperature benzene has vapor pressure of 1350 mm, and its vapor pressure will change
linearly from zero for 0% benzene to 1350 mm for pure benzene.

The total pressure for any composition will be the sum of the two partial pressures at that
composition.

If the partial pressures are straight lines i.e. Raoult’s law holds then the total pressure will
be a straight line between 556 m for pure toluene and 1350 mm for pure benzene.

Derivation

Two liquids A and B are at constant temperature.

Liquid A is more volatile than B.

If Raoult’s law holds for this binary mixture then

from Raoult’s law pA = PA x (1)

and pB = PB (1 – x)
where pA and pB = partial pressure of A and B respectively

PA and PB = vapor pressure of pure A and B

x = mole fraction of A in the solution

If P represents the total pressure, then

P= pA + pB (2)

= PA x + PB (1 – x)

From Dalton’s law

pA
y where y = mole fraction of A in vapor phase
p A  pB
PA x
 [from (1) and (2)]
P
RELATIVE VOLATILITY

For a more volatile phase in equilibrium with a liquid phase, the relative volatility of component
A (the more volatile component) with respect to component B is defined by the equation:

yA / xA
 AB 
yB / xB 1.0 x
x
where x
x
AB = relative volatility of component A with respect to x
YA x
component B x

y = mole fraction of component A in vapor phase x

x = mole fraction of component in liquid phase 0

0 XA 1.0
In case of binary system, yB = 1 – yA and xB = 1 – Equilibrium curve
xA.

Substituting,

 y A   1 x A 
 AB    
 1  yA   xA 
  AB X A
Rearranging we get YA 
1  ( AB  1) X A

Equilibrium curve

If AB is given then from the above equation a set of XA and YA can be calculated. When YA is
plotted against XA the curve is called equilibrium curve.

If the liquid phase obeys Raoult’s law and the vapor phase obeys Dalton’s law then,

PA x A
yA 
P
PA x A / P 1  x A P
So  AB   A
PB (1  x A ) / P x A PB

HENRY’S LAW

The partial pressure of a component over a solution is proportional to its mole fraction in
the liquid . This can be expressed as pA = C x

where pA = partial pressure of component A

x = mole fraction of A in liquid phase

C = Henry’s law constant; C is constant only at constant temperature

N.B. Raoult’s law is essentially a special case of Henry’s law where the constant C in equation is
the vapor pressure of the pure component.

DISTILLATION METHODS
A. Distillation methods for miscible liquid systems

1. Equilibrium or Flash Distillation

2. Simple or Differential Distillation
3. Fractional Distillation
4. Distillation under reduced pressure (e.g. Molecular Distillation)
5. Special Distillation Methods for non-ideal mixtures
(a) Distillation of Azeotropic Mixtures
(b) Extractive Distillation
(B) Distillation of immiscible liquids (e.g. Steam Distillation)

1. EQUILIBRIUM DISTILLATION
/ FLASH DISTILLATION Vapor to condenser, y .

There are two types of

distillations that do not involve
rectification
Feed
(a) Equilibrium distillation or
Steam
flash distillation and Heating
chamber
(b) Simple or differential
Liquid, x
distillation.

(a) Equilibrium distillation or flash distillation

This is a single stage operation where a liquid is partially vaporized, the vapors are allowed to
come in equilibrium with the residual liquid and the resulting vapors and liquid are separated.

Use: This method is used only when the difference between volatilities of two components is
very large

Let us consider a binary system whose components are A and B. A is more volatile.

 Feed: WF = number of moles of liquid fed

xF = mole fraction of component A in feed

 Suppose V moles are vaporized in an equilibrium-distillation process.

Now in

Liquid phase Number of moles left in liquid phase = (WF – V) moles

Let the composition of the residual liquid = x mole fraction

of A

Vapor phase Composition of vapor phase = y mole fraction of A

Number of moles gained = V

Form material balance equation with respect to A
Material balance line
Moles of A at start = Moles of A in vapor phase y=c-mx

+ Moles of A in liquid phase

Intersection
point
y
WF xF = V y + (WF – V) x
(i)
Equilibrium line
In this case all the parameters are known except x and y .
x
2nd equation required for solving is obtained from Equilibrium curve of A-B system
equilibrium curve of the A, B system.

Eqn(i) is a straight line,

V y = WF xF – (WF – V) x

 W x   W  V
or, y  F F    F  x
 V   V 
or, y =c – mx

Plotting this equation in the equilibrium curve the point of intersection is obtained. The value of
x and y can be obtained form the point of intersection.

2. SIMPLE / DIFFERENTIAL DISTILLATION

In this process vapor is removed from the system as soon

as it is formed and condensed.

Use:
W x
dW y
 This method is commonly used in laboratory
 In industries it is only used for systems having high relative volatilities.

Derivation of Raleigh’s equation

Let us consider a batch of W0 moles of liquid was taken at the beginning.

Suppose at any given time during distillation there are W moles of liquid left in the still.

At this time let the mole fraction of A in liquid is x.

Suppose a very small amount of liquid dW is vaporized. In the vapor phase the mole fraction of
component A is y.

At a given time After a moment

Total moles of liquid present W W – dW
Moles of A present in liquid Wx (W – dW)(x – dx)
Total moles of liquid dW
removed
Moles of A present in the y
vapor

Therefore a material balance equation with respect to A will be

xW = (W – dW) (x – dx) + ydW

or, xW = xW – xdW – Wdx + dWdx + ydW

dWdx is very small hence ignoring the term the equation will be

ydW – xdW = Wdx

or, (y – x)dW = W dx

dW dx
or, 
W y x
Now, integrating between the limits

W1 X1 X
dW dx W1 1 dx
W W  X y  x or, ln
W0 X0 y  x

0 0

This equation is known as Raleigh’s equation. It relates the amount of material distilled with
instantaneous composition of the liquid at that moment

dx
The function can be integrated graphically from the equilibrium curve, since the curves
yx
gives the relationship between x and y.
N.B.

x y y–x 1/(y – x)

-- -- ----- -----------
1
y-x
-- -- ----- -----------
x0 x1
x

Application of Raleigh’s Equation

1. By using the Raleigh’s equation the effectiveness of simple distillation for a given system
can be estimated. [Ref: A.B.Paradkar, Introduction to Pharmaceutical Engineering, p. 247]
2. It is used in determination of cut-off point when we can stop distillation as soon as the vapor
composition falls below the required purity of the product.

SIMPLE DISTILLATION

Objective

Simple distillation is the process of converting a liquid into its vapors which, are passed through
a cooling surface to condense the vapors. The condensed vapors are reformed into liquid which,
is collected in a receiver.

Apparatus for laboratory scale

It consists of a distillation flask with a side arm sloping downward that is connected to a
condenser. The condensed vapors are collected in a flask called ‘receiver’. The whole apparatus
is made of glass.
Escape for
A thermometer is fitted in the distillation gases
flask to note down the temperature at which,
the vapors are distilled.

Bumping is avoided by adding small pieces Heating coils Constant level

of porcelain or porous pot before device
distillation.
Water
Apparatus for preparation of purified Jacket outlet
water

The boiler may be made of cast iron but the

baffles and the condenser tubes that comes Water
inlet

Distillate

Fig. Distillation unit for purified water

into contact with product are made of stainless steel or monel metal.

The cold water from the water tap enters the still through the inlet, which rises in the jacket fitted
with a constant level device, the excess of water over flow through the outlet.

A portion of hot water at 90 to 950C enters into the boiler through a narrow opening – the level
of water is maintained in the boiler up to overflow level.

The water is boiled in the boiler by means of heating coils. On heating, the dissolved gases in the
condenser are allowed to escape through a small opening and only the steam escapes into the
condensing tubes.

Since the dissolved gases are more volatile than water they escape in the first portion of the
distillate, therefore, must be rejected. Similarly, the last portion may contain volatile portion of
the dissolved solid substances in tap water – hence, discarded.

Application of simple distillation in pharmacy

1. It is used for the preparation of distilled water and water for injection.
2. Many volatile oils and aromatic waters are prepared by simple distillation e.g. Spirit of
nitrous ether and Aromatic Spirit of Ammonia
3. Concentration of liquid and to separate non-volatile solid from volatile liquids such as
alcohol and ether.
3. FRACTIONAL DISTILLATION / RECTIFICATION

A rectifying unit consists primarily of

(a) a still or reboiler, in which vapor is C

O
N S
generated, V
A
L
I
D E
E R

(b) a rectifying or fractionating column P

O
Q
U
N

U I
through which this vapor rises in counter- R D
REFLUX
current contact with a descending stream
of liquid, and PRODUCT
(c) a condenser, which condenses all the FEED
STILL
vapor leaving the top of the column, RESIDUE
HEAT
sending part of this condensed liquid (the
reflux) back to the column to descend
counter to the rising vapors, and
delivering the rest of the condensed liquid Diagram of still and fractionating column
as product.

As the liquid stream descends the column, it is progressively enriched with the less volatile
constituent.

The top of the column is cooler than the bottom, so that the liquid stream becomes
progressively hotter as it descends and the vapor stream becomes progressively cooler as it rises.
This heat transfer is accomplished by actual contact of liquid and vapor, and for this purpose
effective contact is desirable.

CONSTRUCTION OF RECTIFYING COLUMN

There are different varieties of equipments for rectification

(a) Plate column (i) Bubble cap column

(ii) Sieve-plate column

(b) Packed column

BUBBLE-CAP COLUMN
 Vapour

Reflux
Bubble cap Down pipe
(C) (F)

Rectification Plate
column (A)

Slot
Down pipe Cap (C)
(G) Layer of
Liquid
FEED Liquid Vapour
STILL Plate (A) Down pipe
(F)
Nipple (B) Vapour

 The column is divided into sections by means of a series of horizontal plates A.

 Each plate carries a number of short nipples B (or riser). Each nipple is covered by a bell-
shaped cap C that is secured by a spider and bolt with the plate. The edge of the cap is
serrated or the sides may be slotted.
 Vapor rises from the plate below through the nipple, is diverted downward by the cap, and
bubbles out under the serration or through the slots.
 A layer of liquid is maintained on the plate by means of an overflow or down-pipe (F) and the
depth of the liquid is such that the slots are submerged.
 The down-pipe, (G) from the plate above, is sealed by the liquid on the plate below, so that
the vapor cannot enter the down-pipe.
 Ordinarily, the liquid is delivered at one end of a diameter by the down-pipe from the plate
above, flows the other end of the same diameter.
Types of down-comers

F F
G
G
Baffle

F F F F

G G G G

Cross flow Split flow Reverse Flow Radial Flow

(a) Cross flow

The liquid flows across the plate from right to left on plate F and left to right on plate H and so
on down the column.

(b) Split flow

On plate F the liquid flows form the two sides to the center. On plate H it flows from the center
to the two sides and so on down the column. This arrangement is commonly known as split flow.

(c) Reverse flow

Liquid comes down the space on one side of the baffle and flows across the plate from right to
left, around the end of the baffle, from left to right and down the space behind the weir. This
arrangement is called reverse flow.

(d) Radial flow with circular down-take

One plate will have four or more down-comers around the circumference, and the next plate will
have a down-comer at the center so that on the upper plate the flow is from the circumference
towards center and on the next plate the flow is from the central down-take to the circumference.
Specification of bubble cap rectification column

Column diameter 2 to 15 ft

Height few feet to over 100 ft

Bubble cap diameter 3 to 6 inches

Slots in a 3 inches bubble cap may be 1/8 to 3/32 inch wide

½ to 1 inch height

SIEVE PALTE COLUMNS

All the constructions are same as bubble cap columns. Instead of bubble cap plates, flat plates
with a large number of relatively small perforations, drilled in them are used. These perforations
are usually 3/16 to ¼ inch in diameter.

The velocity of the vapor through these holes is sufficient to produce the liquid running down the
holes.

PACKED COLUMNS

The column is entirely filled with some sorts of material that offers a large surface area
supposedly wetted by the liquid.

A large variety of materials are used among which Raschig rings are popular. A Raschig ring is
a hollow cylinder whose length is equal to its diameter. This may be made of metal (by sawing
sections off a pipe), stone ware, ceramics, carbon, plastics, or other materials. Raschig rings are
usually dumped at random in the column.

Raschig Ring Lessing Ring Pall Ring Berl Saddle Intalox Saddle

Advantages
(i) Have a low pressure drop per unit of height than bubble cap
(ii) For very small diameters of column, where it would be difficult to get in more than two
or three bubble caps, a packed column can be used.
(iii)Since Raschig rings can be made of any material, hence packed columns can be used for
corrosive materials.
(iv) The amount of liquid held up in the column is low so thermolabile liquid remains in
contact with high temperature for a short time than bubble cap method.
Disadvantages
(i) They are relatively inflexible.
(ii) Distribution of liquid uniformly in such packed column is difficult. It is found that, as the
liquid passes down the tower it tends to concentrate at the walls and leave the center dry.
4. DISTILLATION UNDER REDUCED PRESSURE / VACUUM DISTILLATION

Theroy

Liquid boils when its vapor pressure is

equal to the atmospheric pressure. Liquids,
Condenser
... . . . . ... Mean free
which are decomposed at their boiling
point under atmospheric pressure, can be
Evaporating
surface
.. . . . path (

distilled at a much lower temperature than

its boiling point if the pressure is reduced on the surface of the liquid. Boiling under reduced
pressure will also increase the rate of distillation.

Molecular Distillation

Theory / Principle of Molecular Distillation

In a high vacuum distillation operation, where the material distills from an evaporating surface to
a relatively cool condensing-surface. The conditions are such that, the mean free path of the
distillating molecules is greater than the distance between the evaporating and condensing
surface.

 The vacuum applied in these types of apparatus is about 1 m Hg pressure or less.

Mean free path is defined as the average distance traveled by the molecules in a straight line
without any collision. It can be calculated by Clausius law:

1

2 d 2 N
where,  = mean free path (cm)

d = diameter of the molecules (cm)

N = number of molecules in 1 cm3 volume.

It is clear from the above equation and chart that, mean free path can be increased, by reducing
the number of molecules per cm3 volume. The molecules evaporate from the surface and travel
few cm without colliding with the molecules of the residual gas in the space above. If now the
condensing surface is placed within distance, a major fraction of the molecules will condense
and will not return to the distilland. Thus each molecule distills itself and hence called
“Molecular Distillation”.

Characteristics of molecular distillation

1. Molecules having molecular weight within the range of 300 to 1100 dalton can be distilled
by this method. [N.B. Low molecular weight (below 300 dalton) molecules will re-evaporate
 again from the condenser surface. High molecular weight molecules (greater than 1100
dalton) will not have sufficient volatility.]
2. The molecules to be distilled should reach the Feed
surface and evaporate. The molecules at the
bottom of the distilland have to overcome the
pressure of the layer above, to come to the
surface. Hence, the layer should be thin and
should be in a state of turbulent motion to
facilitate the molecules to reach the surface.
3. The distilland should be degassed before
entering in the still, because at very low
pressure the dissolved gas will occupy all the
Heating
space and rate of distillation will be reduced. Jacket

Condenser

Falling Film Molecular Still PTFE

Vacuum Wiper
The vessel has a diameter of the order of 1 m and the Residue pump
walls are heated suitably by a heating jacket. Product
Vacuum pumps are connected by a large diameter Fig. Falling film Molecular Still
pipe. The feed flows down the walls and is spread to
a film by the polytetrafluoroethylene (PTFE) wipers which move about 3 m/s giving a film
velocity of about 1.5 m/s. The residue is collected at the bottom of the vessel and it is re-
circulated (through the feed line).

The evaporated molecules are then condensed on the condenser surface. The condensate is taken
out as product.

Centrifugal molecular still

The distilland (feed) is introduced on to Vacuum

the center of a bucket-shaped vessel (1 Condenser pump
to 1.5 m in diameter) that rotates at
high speed. The film of liquid that is
formed moves outwards over the
surface of the vessel to the residue-
collection pipe. The vessel is heated by O O
radiant heaters. Condensers and a
collection device are located close to
the inner surface of the rotor.

Product
Feed
Radiant Residue
Bucket
Heat
Source

Fig. Centrifugal molecular stilll

Application of vacuum distillation in pharmacy

1. Vitamin concentrates

Vitamin A,D,E,K and tocopherols are obtained from vegetable and fish oils. The vitamin-A
concentrate produced by molecular distillation is very pure and has good stability. As no
chemical is used in this method which could split the ester linkage, the vitamins are retained
in the natural ester form which is the most stable form of vitamin A. The stability of the
concentrates is further enhanced by natural antioxidants distilling over from the original oil.

2. The fractionation of oil

The fractionation of oils into various components is carried out by molecular distillation.

Components Molecular Weight Temperature Range

(a) Fatty acids, 150 – 300 50 – 1400C
unsaponifiable matter of
low molecular weight.
(b) Unsaponifiable matter
like sterols, vitamins, 300 – 600 150 – 1900C
dyes, waxy alcohols,
monoglycerides
(c) Triglycerides, sterol
esters, vitamin esters, 600 – 900 Above 1900C
resins, waxes

3. Purification and fractionation of lanolin

It is used to get various fractions from Lanolin like, cetyl alcohol, cholesterol, ceryl alcohol,
lanopalmitic acid,isocholesterol etc.

4. Separation of Poly Ethylene Glycol (PEG)

On laboratory scale it is used to separate PEG according to the degree of polymerization.

5. SPECIAL DISTILLATION METHODS FOR NON-IDEAL MIXTURES

Industrial scale distillation of Azeotropic Mixture

The liquor from fermentation process is a common source of ethanol and contains approximately
8–10% ethanol.

After simple distillation an azeotrope will form containing 95.6% (96E+4W) ethanol and boiling
at 78.150C at atmospheric pressure.
In this type of system a reboiler is used instead of boiler. The feed liquor is introduced into the
system and must occur at a point where the equilibrium will not be disturbed. Hence, feed will
take place, at a place part of the way up the column, where the equilibrium composition on the
plate is similar to the feed composition.

The plate below the feed plate form the stripping section where the rising vapor strips the more
volatile component (ethanol) from the feed liquor while the upper section is known as the
rectifying section.

The binary azeotrope produced at this stage is freed from water by making use of ternary
azeotrope – ethanol, benzene, and water.

The ethanol/water azeotrope, with sufficient benzene (only required at start-up) is fed to column
A and the pure ethanol is obtained as bottom product, since the ternary azeotrope takes off the

E = ethanol 67E + 33B

W = water
B = benzene 18.5E
7.4W
74.1B

14.5E 84 Vol
1.0W
Feed 96E + B A 84.5B B C
16 Vol E+B
96E
Liq-liq 53E 4W
separator 36W
11B

100 E 100 W

96E + 4W
Fig. Plant for manufacture of Absolute ethanol (100% ethanol)
water.

 The azeotrope (E+B+W) is taken from the top of the column A, condensed and separated (in
liquid-liquid separator) into two layers, having the compositions given in the diagram.
 The upper layer predominates and, being rich in benzene (14.5E+1.0W+84.5B), is returned
to column A. The lower layer (53E+36W+11B) is taken to column B, where the benzene is
recovered as the ethanol/benzene binary azeotrope (67E+33B) and is mixed with the vapor
from ethanol.
 The ethanol / water residue passes to column C, where the ethanol is recovered as the
ethanol/water binary azeotrope (96E+4W), which can be incorporated with the original feed.
 The final product from column A is 100% ethanol and from column C is 100% water.

6. DISTILLATION OF IMMISCIBLE LIQUIDS

Steam distillation

Steam distillation is used for the distillation of two immiscible liquids one of which is water.

Application:

(i) Separation of volatile oil e.g. eucalyptus oil, rose oil, clove oil etc. and
(ii) Preparation of some aromatic water e.g. concentrated rose water..
Theory

Volatile oils are mixtures of high molecular weight compounds having low vapour pressure (i.e.
high b.p.). To separate these from the natural sources like petals of flowers, barks etc. it is not
possible to take them to their boiling points around 2000C. If these oils are distilled with water
(low molecular weight but high vapour pressure i.e. low b.p.) then volatile oil will be distilled
out at a temperature below 1000C.

Weight of volatile oil in distillate M P

 V V
Weight of water in distillate M W PW
Where, MW and MV are molecular weights of water and volatile oil respectively.

PW and PV are vapor pressure of water and volatile oil respectively.

 The aqueous phase of distillate that is collected is water saturated with volatile oil i.e. called
aromatic water.

Absorption

In this process, a vapor in an inert gas is absorbed in a liquid stream. The vapor is soluble in the
liquid. The liquid stream rich in solubilized vapor components is separated by distillation or
some other suitable techniques. The liquid can be recovered and reused in the process itself. An
example is removal of ammonia from ammonia – water mixture using water as solvent. Removal
of carbon di oxide from a mixture of air and carbon dioxide using a solvent like primary or
secondary or tertiary amines is another example. Typically this operation is carried out in counter
current manner to enhance the efficiency of this process. Sometimes, the packed beds or staged
beds like trays are used to have better mixing during the transfer process. It may be mentioned
that absorption is a bulk phenomena, i.e., the gaseous solutes are transported to the bulk of the
liquid stream. It may be noted that to effect separation, a matter is introduced in the system.
Adsorption

Separation of solutes by transporting it from gaseous or liquid streams on a solid surface is

known as adsorption. As opposed to absorption it is a surface phenomenon. The solute is fixed
on the solid surface only. Typically, the solid surface is specific for a particular component
present in the feed stream. For example, in a liquid stream having organic as well as inorganic
components, the organics are preferentially adsorbed on the surface of activated carbon.
Typically, in a bed, the adsorbent particles are kept and the fluid is pumped through the system
for intimate mixing. In the process, the solute is transferred to the solid phase. After sometime,
the solid phase is completely saturated and the transfer of species becomes extremely slow due to
lack of driving force. In such case, the bed has to be replaced by new adsorbents or the bed has to
be regenerated by a suitable washing protocol. It may be noted, that a reasonably lower particle
size of adsorbents provides sufficient surface area for separation. Removal of organics from an
aqueous mixture using activated carbon is an example of adsorption. It may be noted that to
effect separation, a matter is introduced in the system.

PHYSISORPTION

Molecules and atoms can attach to surface in two ways .

One is Physisorption ( Physical Adsorption ) in which there is a van der Waals interaction
between the adsorbate & the substrate. Examples , A dispersion or dipolar-dipolar interaction .
Van der Waals interactions are long range but are weak. Energy released when a particle is
physisorbed is of the same order of magnitude as the enthalpy of condensation . Such small
energies can be absorbed as vibrations of the lattice & dissipated as thermal motion, & a
molecule bouncing across the surface will gradually lose all its energy & finally adsorb to it.

CHEMISORPTIONS

Chemisorption (Chemical Adsorption) in which the molecules or atoms stick to the surface of
adsorbent by forming a chemical bond ( usually covalent ),& tend to find sites that maximize
their coordination number with the substrate. The distance between the surface & the closest
adsorbate atom is also typically shorter for chemisorption . A chemisorbed molecule may be torn
apart at the demand of the unsatisfied vacancies of the surface atoms, & the existence of
molecular fragments on the surface as a result of chemisorption is one reason why solid surface
catalyse reactions

FACTORS AFFECTING ADSORPTION

TEMPERATURE

Adsorption is an exothermic process. Therefore in accordance with Le Chatelier's principle, the

magnitude of adsorption should increases with decrease in temperature. It is in the case of
physical adsorption . Chemical adsorption first increases with rise in the temperature and then
starts decreasing
 PRESSURE

With increase of pressure, adsorption increases up to certain extent till saturation level is

achieved no more adsorption takes place no matter how high the pressure applied.

SURFACE AREA It’s a surface phenomenon therefore adsorption capacity of adsorbent

increases with increase in its surface area. Smaller the size of particles of solid adsorbents
more is the extent of adsorption at its surface interface

ACTIVATION OF SOLID ADSORBENT Activation of adsorbent surface done so as

to provide more vacant sites on surface. This can be done by breaking solid crystal in small
pieces, breaking lump of solid into powders or sub- dividing the adsorbent

ADSORPTION ISOTHERMS

Adsorption process is usually studied through graphs known as Adsorption Isotherm. The
amount of adsorbate on the adsorbent as a function if its pressure (gas) or concentration
(liquid) at constant T

According to Le Chatlier’s principle, on application of excess pressure , the equilibrium will

shift in the direction where number of molecules decreases.

Since no. of molecules decreases in forward direction i.e.direction of Adsorption , with

increase of pressure , forward direction equilibrium will be achieved

In the given Adsorption Isotherm , after saturation pressure Ps adsorption does not
increases

Vacancies on the surface of the adsorbent are limited, at Ps a stage is reached when all the
sites are occupied and further increase in pressure does not increases adsorption extent.

Types of Adsorption Isotherms :

1- Freundlich Isotherm

2- Langmuir Isotherm

3- Temkin Isotherm

4- Brunauer, Emmett And Teller (BET) Isotherm

• Equilibrium adsorption isotherm

– Adsorption isotherm relates the volume or mass adsorbed to the partial pressure
or concentration of the adsorbate
 – Quantity of adsorbate adsorbed (from gas phase) per unit adsorbent is
measured against partial presence of the adsorbate (in gas phase) at
equilibrium at given temperature (very sensitive to T)
– Incase of adsorbate in liquid/solution the measurement is against concentration
of adsorbate in the solution

Many equations are proposed to fit the experimental adsorption result

Which model/equation to be used to describe the adsorption process is determined through

experimentation

V cP

Vm ( Po  P)[1  (c  1)( P / Po )
V is the amount of adsorbed gas at a given pressure and temperature

Vm is the amount adsorbed if one molecule thick layer fills the surface

Po is vapor pressure of the adsorbate at the system’s temp.

P is partial pressure of the adsorbate

C is a parameter of adsorption process

When P/P0 is <0.05 and >0.35 then the plot is not linear and this approach for estimating
Vmono and C values can not be followed
Langmuir Adsorption Isotherm
Fruendlich adsorption isotherm

Temkin Isotherm
Temkin Isotherm takes into account all the indirect adsorbate adsorbate interactions on
adsorption isotherms

where c1 and c2 are constants, corresponds to supposing that the adsorption enthalpy changes
linearly with pressure Drying

In drying, water vapors from a solid material are removed by using a vapor stream to an
acceptable small limit. Generally it is carried out by applying thermal energy as compared to
introduction of a matter in case of absorption or adsorption. The process efficiency depends on
the temperature, relative humidity and other thermo physical properties of the drying vapor as
well as the temperature and other thermo-physical properties of the solid.

RAATE GOVERNED PROCESS:

Most of the membrane based processes are the rate governed. The main crux of the separation
lies in the difference of transport of various species through the membrane. The driving force of
such transport is generally gradient of chemical potential. If we recall the definition of gradient
of chemical potential, it is composed of four parts. These are concentration gradient, pressure
gradient, temperature gradient and electrochemical potential gradient. Presence of these causes
(one or more of such gradients) results into effects (the difference in separation and hence
effects). Some of these systems are described below.

Osmosis

Osmosis is observed when a solution is separated from the solvent by a semipermeable (only
solvent is permeable species) membrane. Apparently, difference in osmotic pressure across the
membrane causes the transport of the solvent. Actually, osmotic pressure is a colligative property
and it is a function of concentration. Therefore, the concentration (or more generally activity)
gradient of the solvent is the main driving force in osmosis. In this case, the solvent flows from
the solvent side to the solution side until, the solvent activity becomes almost equal in both the
sides. This results in generation of hydrostatic pressure difference between the two sides, known
as osmotic pressure. If the initial concentration of solute is more in the solution side, more
solvent will flow in from the solvent side to equalize the solvent activity on both the sides,
resulting in more osmotic pressure difference.

Reverse Osmosis

It must be understood that osmosis is a natural phenomenon. In case of reverse osmosis, pressure
is applied on the solution side externally (using a pump or a compressor), so that the osmotic
pressure is overcome and the solvents are forced out of the solution side. The efficiency of this
process depends on the porosity, morphology and thickness of the membrane. These factors
influence the transport of the solvent through the membrane immensely and thereby, dictating
the throughput of the process and the quality of the product. Since, reverse osmosis membranes
have very small pore size, this is used for separation of lower molecular weight species, like,
salts. A salt having very osmotic pressure, the operating pressure in the feed side of a reverse
osmosis process is therefore extremely high. This will lead to deposition of salts near the
membrane surface, leading to build up of a concentration boundary layer. Therefore, the pressure
gradient in this system leads to concentration difference.

Dialysis

In this case, two liquid streams are separated by a permeable barrier or membrane. In the feed
side, a specific set of solutes are permeated through the membrane to the other side. The
upstream feed is known as the feed side and the downstream is known as the dialysate.
Typically, dialysate stream is pure distilled water. Thus, the concentration gradient between the
two streams is the maximum. The transport is effected by the concentration gradient between
two streams. The duration of separation entirely depends on the rate

Ion exchange

Is defined as the process where an insoluble substance remove ions of positive or negative
charge from an electrolytic solution and releases other ions of the same charge into the solution
in a chemically equivalent amount. That means here exchange of ions will be taking place. So
one type of ions will be getting removed from the solution but equivalent amount or equivalent
amount of ions will be coming from the resin that is why it is known as ion exchange process

THEORY OF EXTRACTION OF DRUGS

Mass transfer

Consider a crystal of soluble material (e.g sugarcube) is immersedin asolvent in which it is

dissolving. The crystal will be surrounded by a stationary boundary layer of the solvent, with the
bulk of the fluid able to move.

The transport of molecules will take place in two stages:

1. The molecules will move through the boundary layer by molecular diffusion, with no
mechanical mixing or movement.
2. Once material has passed through the boundary layer, mass transfer takes place by bulk
movement of the solution, known as eddy diffusion.

Since there is no limit to the vigor of the movement of the bulk of the fluid, so the rate
controlling step is the molecular diffusion.

Mass transfer by molecular diffusion can be represented by an equation, similar to conduction of

heat transfer, in which
 m DA(C1 C2)

t h

where m = mass transferred in time t

D = diffusion coefficient of the solute

A = area of the solute exposed to the solvent

C1 = concentration of the solute at solid / liquid interface

C2 = conentration of solute in the bulk phase

h = thickness of the stagnant layer

Theory of extraction of drugs

Examination of the extraction processes will show that all have certain stages in common:

(i) Suitable size reduction of the drug

(ii) Penetration of the drug by the solvent
(iii)Solution of the soluble material within the cells.
(iv) Escape of the soluble material through the cell walls and through the solvent boundary layer
surrounding the particles of the drug.
(v) Separation of the solution and the exhausted drug.

(I) Suitable size reduction of the drug:

From the mass transfer equation it is evident that m/t is proportional to A. If the area (A) is
increased then rate of dissolution also increases. So if the size of the drug (plant or animal parts
containing the active constituents) is reduced surface area will increase, the consequence of
which is the increase of the dissolution rate (m/t) of the active constituent. The ideal size
reduction would be at cellular level but it poses the following disadvantages:

(i) It is difficult to reduce the size of a drug to its cellular dimension. It requires costly
instruments which may not be cost effective.
(ii) Obviously it will take more time to reduce the size to such a level. Thus prolonged
comminution (size reduction) will produce heat that may damage the heat labile constituents
of the drug.
(iii)After extraction of such small particles they will make a suspension which will be difficult to
filter.
(iv) While reducing the size to cellular level it is most probable that the cell walls will be broken
and breakage of cell walls will release unwanted cellular materials like gums, starch, proteins
etc. which may produce the filtrate cloudy by the release of colloidal material.
So the degree of size reduction to be used will depend, therefore, on the botanical structure of the
drug.

(II) Penetration of the solvent into the drug:

Before drying the fresh drugs are surrounde by a thin film of water. After drying that water film
evaporates and becomes porous due to shrinkage. The pores are then occupied by air. To
penetrate the cell wall the solvent must have to displace the air first.

When the dry drug is moistened, the liquid film is again renerated and then the cells imbibe the
solvent and swell.

Sometimes to facilitate the removal of air from the pores the solvent and the drug is first taken in
a vessel, vacuum is applied - thus air is removed from the pores. Then, when the vacuum is
released, pressure of the atmosphere forces the solvent into the drug and penetration is facilated
considerably.

(III) Solution of constituents:

Once the solvent has penetrated into the cells solution of the constituents takes place and is
governed by the solubility of the constituents in the solvent and again solubility depends on the
temperature. So if the temperature is increased the solubility will also enhance.

(IV) Escape of the solution from the cells:

The solute molecules are transferred through the boundary layer or stagnant layer. Factors
controlling mass transfer will show that the rate of extraction can be affected in the following
ways:

(i) m / t  1 / h i.e. if the thickness of the boundary layer can be reduced rate will ne
increased. h can be reduced by agitating the mixture occassionally which disperses local
concentrations of the solution, thereby, increasing the concentration gradient.
(ii) By suspending the drug in a cloth bag or placing it on a perforated plate near to the surface of
the liquid the escape of the solution can be hastened. As the constituents dissolve, the density
of the solution increases, so that convection currents are established, leading to circulation of
the solution followed by the reduction of local concentration surrounding the cloth.

(V) Separation of solution and exhausted drug:

After dissolution the solid materails has to be strained off. Since, the drug absorbs solvent and
there is a residue of soluble constituents in that solvent, so the drug is subjected to pressure and
sometimes under hydraulic pressure.

PROPERTIES OF SOLVENTS USED FOR EXTRACTING DRUGS

The ideal solvent would be:

1. It must be cheap.
2. Non-toxic
3. It should be stable chemically and physically.
a) neutral to reaction
b) not too volatile
c) non-inflammable
4. Selective, i.e. it should remove the desired constituents with minimum amount of the
inert materials.

Water as a solvent for extraction:

Advantages:

(i) It is cheap.
(ii) It has a wide solvent action (e.g. protein, coloring maters, gums, antharaquinone derivatives,
most alkaloidal salts, glycosides, sugars and tanins).
(iii)It is non-toxic and can be taken internally.

It is non-inflammable. In industry handling of large volume of volatile solvents may cause

accident. Hence the inflammability of a solvent is very important from the point of view of
industry.

Disadvantages:

(i) It is not selective. It dissolves a wide range of substances that may interfere with the
extract’s clarity e.g. gum, protein (coagulated).
(ii) Water is good medium for mold and bacterial growth. Generally most preparations are
preserved with a small amount of glycerine, chloroform or by sterilization.
(iii)Water promotes hydrolysis of many substances and allows enzymatic actions to take place
[e.g glycosides such as digitalis].
(iv) Concentration of aqueous solution requires more heat than for most other solvents due to its
higher latent heat of evaporation (537 cal / gm).

Ethanol as solvent:

Advantages:

(i) Reasonably selective, e.g. in a drug containing gum, albuminous matter and a glycoside or an
alkaloidal salt, ethanol in a suitable dilution with water would dissolve only the glycoside or
the alkaloidal salt, whereas water would usually dissolve all of the constituents.
(ii) Molds cannot grow in solvent mixture containing more than 20 % ethanol.
(iii)Non-toxic in the quantities prescribed in the medicinal preparations.
(iv) It is neutral, hence compatible with other products .
(v) Latent heat of vaporization is less than water , so less heat will be consumed to make an
extract concentrated.
(vi) Can be mixed in any combination with water.
Disadvantage:

Cost due increases due to the duty imposed by the Government on it

TEXT / REFERENCE BOOKS

1. Treybal R.E., Mass Transfer Operations, 3rd Edition, McGraw Hill, 2009.

2. McCabe and Smith, Unit Operations of Chemical Engineering, 7th Edition, McGraw Hill,
2009.

3. Coulson J.M. and Richardson J.F., Chemical Engineering, 6th Edition, Pergamon Press, 2002.

4. Anantharaman N., MeeraSheriffa Begum K.M., Mass Transfer Theory and Practice, 1st

Edition, PHI, 2011.

 SCHOOL OF BIO AND CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

HEAT AND MASS TRANSFER FOR BIOLOGICAL SYSTEMS

SCHA1311

UNIT – 3 BASIC SEPARATION PROCESSES-2 SCHA1311

 UNIT 3

BASIC SEPARATION PROCESSES – 2

Drying, -Tray dryer, Vacuum dryers, rotary dryers, drum and spray dryers. Equilibrium
moisture content of materials. Bound and unbound moisture. Free and equilibrium
moisture, Rate of Drying curves, Freeze drying and Sterilization of Biological materials,
Crystallization theory, Equipments for crystallization, Tank, DTB Crystallizer, circulating
–magma vacuum crystallizer, Swenson walker crystallizer.

Drying is defined as the removal of liquid from a solid by thermal method.

When large amount of liquid is evaporated from a solution /suspension / slurry the process is
called ‘evaporation’. The final product is a concentrated liquid / slurry.

When very small amount of liquid is evaporated from solids the process is called ‘drying’.
The final product is a ‘dried solid’.

PURPOSE OF DRYING

1. Drying is most commonly used in pharmaceutical industries in the preparation of granules,

which can be packed in bulk or compressed into tablets or filled in capsules.
2. Drying is required for processing of materials like, drying of aluminium hydroxide, spray
drying of lactose and preparation of powdered extracts.
3. Drying is used to reduce the bulk weight that lowers the transportation and storage costs of
that material.
4. Drugs obtained from plant and animal sources, when dried, becomes more friable. Thus
drying helps in size reduction of natural drugs.
5. Animal and vegetable drugs are preserved against mold growth in dried condition.
6. Dried products often are less more stable than moist ones as in the case of effervescent salts,
aspirin, hygroscopic powders, ascorbic acids and penicillin.

SOME DEFINITIONS

Moisture content (MC)

weight of water in sample

% Moisture Content  x 100
weight of dry sample

Loss on drying (LOD)

weight of water in sample

% LOD  x 100
total weight of wet sample
THEORY OF DRYING
A

MC I B
A typical drying cycle shows the following
phases: II
C
III D
IV
Time
A B
Phase-I: Initial adjustment period

Phase-II: Constant rate

Rateperiod
of
I II
drying
III C
Phase-III: First falling rate period
IV D
Phase-IV: Second falling rate period Time
B A

The rate of drying of a sample can be Rate of II I

determined by suspending the wet material on drying C III
a scale or balance in a drying cabinet and D IV
measuring the weight of the sample as it dries MC
as a function of time. B: Critical Moisture Content (CMC)
D: Equilibrium Moisture Content (EMC)
Phase-I: Initial adjustment period

A wet material when kept for drying it begins to absorb the heat and the temperature of the
material increases. At the same time, the moisture begins to evaporate and thus cools the drying
solid. After a period of initial adjustment, the rates of heating and cooling become equal and the
temperature of the drying material reaches the wet-bulb temperature of the drying air.

Phase-II: Constant rate period

During this period there is continuous liquid film over the surface of the solid. Evaporation from
the film (at wet bulb temperature) proceeds at a constant rate and the film is continuously
replaced by the underlying moisture. As long as the delivery of water from the interior of the
material is sufficient to keep the surface completely wet, the drying rate remains constant.

Drying rate at this phase is given by:

dW Ah c (t d - t w )

d L
 dW  kg of water 
where, = Rate of drying in  
d  kg of dry solid 

A = Area exposed to drying

td, tw = Dry bulb and wet bulb temperature of the drying air respectively

 = Bulk density of solid

L = Thickness of solid bed

 = Latent heat of vaporization of water

hc = Convection heat transfer coefficient

Phase-III: First falling rate period

Due to dry spots on the surface, the area of constant mass transfer decreases and the heat
transferred to the dry spots will be utilized to raise the temperature of the material to the dry bulb
temperature. Thus as the number of dry spots increase, heat transfer and mass transfer rates fall
which is called the first falling rate period. The point from which Phase-II starts is called critical
point (B). Moisture content at which this point appears is called critical moisture content
(CMC).

Phase-IV: Second falling rate period

In this period the capillaries are empty, no film is present on the surface. The moisture movement
takes place only by diffusion. In this phase the rate of drying falls and it is lesser than first falling
rate. The starting of second falling rate period is called second critical point (C).

At the end the drying rate becomes zero. The moisture content at this point is called
Equilibrium Moisture Content (EMC). EMC may be defined as the moisture content of the
solid when drying limit has attained by use of air at a given temperature (dry bulb) and humidity
of air. EMC depends on the nature of the material, temperature and humidity.
Utility of drying curve

1. From the drying curve the time for drying a batch of material in a certain dryer can be
estimated.
2. The size of a particular dryer can be determined for drying a substance from one moisture
level to the desired moisture content.

CLASSIFICATION OF DRYERS

Classification based on solid handling

Material Not Agitated Material Agitated

Static bed dryers Moving bed dryer Fluidized bed dryer Pneumatic dryer

Batch Continuous Batch Continuous Batch Continuous Continuous

type type type type type type type

Tray & Truck Tunnel dryers Vacuum Rotary dryers Vertical Horizontal Spray dryers
dryers tumble dryers vibrating
Belt dryers Turbo tray Flash dryer
dryers conveyor
Vacuum shelf dryers
dryers
dryer Festoon dryers
Pan Vibrating
Drum dryers conveyor dryers Vertical
Freeze dryers dryers
dryers
Tower & cascade
dryers
Screw conveyor
dryers

Classification of dryers, based on methods of solids handling

Classification based on heat transfer mechanism

A. Convection dryers

(a) Tray or shelf dryers (b) Tunnel dryers(c) Rotary dryers (d) Fluidized bed dryers

B. Conduction dryers

(a) Vacuum oven (b) Freeze dryers

C. Radiant heat dryers

(a) Infra-red dryers

TRAY DRYER / TRUCK DRYER / SHELF DRYER / CABINET DRYER / COMPARTMENT

DRYER

Construction
It consists of a small cabinet or a large Direction Air outlet
compartment in which trays containing wet vanes Fan
materials are placed. The compartment wall is
insulated to reduce heat loss.

 In tray dryers the trays are directly placed Heater

inside the cabinet.
 The truck dryer the trays are loaded on to Fresh air
the trucks (shelves on wheel) and then the inlet
trucks are introduced inside the heating
cabinet. Truck carrying
trays
The bottom of the trays are either perforated or Wheel
Fig. Truck dryer
having wre-mesh bottom.

 The material is heated by hot air circulated by means of fans that removes the humid air from
the cabinet.

The trays containing the load remain in the dryer until drying is complete, after which they are
withdrawn, emptied and recharged for drying the next batch.

Energy sources: Dry air can be heated either by electricity or steam.

Applications

 Drying of crude drugs, chemicals, powders, tablet granules etc.

 It is a batch process and materials can be handled separately.

ROTARY DRYERS

Construction
 Feed inlet

Drive gear Dryer shell

Air outlet Air heater

Air
inlet

Motor
Dry product
Fig. Rotary dryer outlet
It is a cylindrical shell (10 m length) mounted with a slight slope so that the material will move
through the shell as it is slowly rotated at about 10 rpm. To improve contact the shell contains
baffles or flights, which lift the solids and spill the particles through the air stream.

The hot air flows counter current to the flow off material.

Application

It is used for continuous drying on a large scale of any powdered or granular solid.

FLUIDIZED BED DRYER

C E
Principle D
B

Let us consider a situation where a bed of granules is placed log(P)

over a perforated bottom container and hot air is flown from
A
bottom through the bed. The pressure drop (P) across the
bed and the air velocity (V) are measured. If the air velocity log(V)

is gradually increased and P is plotted against V then the following curve is observed.

 Point A: When the air velocity is very low flow takes place between the particles without
causing any disturbance.
 Point B: When the velocity is increased to a certain value the frictional drag on the particles
become equal the force of gravity of the particle.
 Point C: Rearrangement of the particles occurs to offer least resistance.
 Point D: Eventually the particles are suspended in the air and can move, P decreases
slightly because of greater porosity.
 Further increase in the air velocity causes the particles to separate and move freely, and the
bed is fully fluidized. Any additional increase in velocity separate the particles further, i.e. the
bed expands, without appreciable change in P until E.
 In the D-E region the air flows through the bed
in the form of bubbles – the term boiling bed is Air Inlet
Air outlet
Fan
generally used for this stage.
 Above point E the solid particles entrain into the
gaseous phase and the particles float in the gas.
Filter
bag
Construction Air
heaters
Two types of fluidized bed dryers are there Fluidized
solids
(i) vertical fluidized bed dryer – for batch
process
(ii) horizontal fluidized dryer – for continuous Fig. Fluidized bed dryer
process

The dryer consists of:

(a) Air handler: This is a source of dry and hot air. It is also attached by means of heating and
dehumidifying air, if necessary.
(b) Plenum: It consists of a screen or plate to distribute the incoming air as it enters the dryer.
(c) Product container: This container holds the product that is to be dried.
(d) Expansion chamber: This chamber is situated above the product container and holds the
suspended material.
(e) Filter: The upper part of the expansion chamber has bag filters. It prevents fines from
escaping into the atmosphere or collecting on the blades that pulls the air through the dryer.

Applications

1. Wet granulation:

(a) Fluidized bed dryers are used to dry the previously prepared wet granules.
(b) Powders are agglomerated in the drying chamber by spraying liquid binder over it,
while the hot air dries the agglomerates to form dry granules.

2. Coating of tablets

The fluidized bed dryer can be used for coating granules also. This technique is called Wurster
technique. Three basic designs are employed

(a) top spray(b) bottom spray(c) tangential spray

In fluidized condition the powder is coated by coating solution sprayed from the nozzles. As the
particles are coated they become heavier. When the mass developed becomes higher than the
drag force given by the fixed air velocity the particles no longer floats. They fall back, which is
then collected as product.
Advantages

1. Efficient heat and mass transfer facilitate high drying rates. Heating time of thermolabile
materials is minimized.
2. Individual particles of the bed get dried in the fluidized state. So, most of the drying will be
at constant rate and the falling rate period is very short.
3. Temperature can be controlled uniformly.
4. A free-flowing product is obtained.
5. Since the bed is not static, free movement of individual particles eliminates the risk of
soluble materials migrating.
6. Short time yields a high output from a small floor space.

Disadvantages

1. Turbulence of fluidized state may produce fine particles due to attrition.

2. Fine particles lead to segregation, so they must be collected by bag filters.
3. Static charges may be produced due to vigorous movement of particles in hot dry air.

VACUUM DRYER

Conduction is used as the

principle method of heat transfer
in dryers that are operated under
vacuum. Convection cannot take Condenser
place when air is nearly absent. Water or
steam jacket Condensate
receiver
Construction

It is a jacketed vessel through

Connection to
which steam or hot water is vacuum pump
passed. The vessel can be closed Fig. Vacuum dryer
airtight. The oven is connected
through a condenser and receiver to a vacuum pump. The supports of the shelves form part of the
jacket, giving a larger area for heat conduction. Materials to be dried are kept in a tray and placed
on the shelves. Hot water or steam is passed through the jacket, a vacuum pump is connected to
the chamber.

Advantages:

1. Drying takes place at low temperature, so thermolabile materials can be dried.

2. It reduces the risk of oxidation during drying.
3. It produces porous and friable granules. [N.B. Because under vacuum the vapor forms
bubbles and in this condition the material is dried.]
4. The solvent can be recovered from the condenser.

Disadvantages
1. Heat coefficients are low. Most of the heating takes place by conduction, some is from
radiation from the wall of the jacket around. So the drying rate is slow.
2. Labor and running costs are high.

Applications:

1. To dry a thermolabile material like Penicillin.

2. To produce porous form such as dry extract.
3. To recover the solvent, for example to recover ethanol from ethanol extractives.

FREEZE DRYER

Principle

The temperature and pressure of the material is reduced

below the triple point of solvent to be dried. Under these Liquid
conditions, any heat transferred is used as latent heat and
the ice sublimes directly to vapor state (without formation Pressure
of liquid state). Solid Triple point

Vapor
Triple point of pure water is 4579 m of Hg and 0.00990C.
Pharmaceutical products remain in solution. In this case
Temperature
the pressure and temperature below which water
evaporates directly from ice to vapor state is called eutectic point. In freeze dryer the pressure
and temperature is maintained well below the eutectic point. Generally it is carried out at –100C
to –400C, and at pressure of 2000 to 100 m Hg.

Construction

Freeze dryer consists of

1. a chamber for vacuum drying:

Two types of chambers are there, one for batch type and another for continuous type
operation.

2. a vacuum source:

Vacuum is achieved either by vacuum pump or by steam ejector or a combination of two.

3. a heat source:

Heat is provided by conduction or radiation.

4. a vapor removal system:

 For removal of water vapor condensers, desiccants, pumps or scrapper blades are employed.

Stages of freeze drying process

(a) Preparation and pretreatment: Drying Shelves

chamber
Protein solutions take 8 to 10 times longer Condenser
period than pure water. Therefore, in such
cases, it is desirable to concentrate the
solution under normal vacuum tray dryer. Door
Vacuum
pump

(b) Pre-freezing

The aqueous solutions to be dried are Heating

System
packed in vials, ampoules or bottles. Refrigerator
They are then cooled to solidify the
Fig. Industrial freeze dryer
water. Cooling can be done by using
cold-shelves (–500C), alcohol baths (–500C) or liquid nitrogen bath (–1950C).

 Thinner the layer of frozen material higher is the drying rate. The usual thickness is kept at
0.5 to 0.75 inches.
 Low freezing rates produces larger crystals of ice. Sublimation of water from this material
leaves large pores. So freezing rate is generally maintained at 3 to 25 0C/min resulted in a
product having pore size of 1 to 45 m.

(c) Primary drying (Sublimation of ice under vacuum)

A vacuum of 0.5 bar is applied on the frozen materials. The temperature is increased to 30 0C
within 2 hours. Then the temperature is kept constant. During this stage around 98 to 99%
water is removed from the materials.

(d) Secondary drying (Removal of residual moisture under high vacuum)

Temperature is maintained at 300C continuously and vacuum is lowered to a pressure of 0.07

bar. The rate of drying is very low it takes 10 to 20 hours to dry 1% moisture.

(e) Packing

Inert gas is introduced inside the dryer to break the vacuum. Then the vials and ampoules are
sealed within the dryer to reduce the contact of atmospheric gases.

Advantages

1. Drying takes place at a very low temperature, so that the enzyme action is inhibited, and
decomposition (e.g. hydrolysis) is minimized.
2. The solution is frozen, so that the final dry product is a network of solid occupying the same
volume as the original solution. Thus there is no case-hardening and the product is light and
porous.
3. The dried products are readily re-dissolved or re-suspended by the addition of water prior to
use (this procedure is termed as reconstitution).
4. The solutions do not concentrate during drying (like in other drying methods). Hence salts do
not concentrate and denature the proteins present in the same solution.
5. Under high vacuum there is no contact with air, and oxidation is minimized.

Disadvantage

1. It produces a very hygroscopic product, hence should be sealed in the final package within
the dryer.
2. The process is very slow.
3. The instruments are very costly.

Applications:

1. Maintenance and preservation of microbial culture.

2. Solution of penicillin can be stored at 0 – 20C and used within two-three days, but if freeze
dried then it is stable for several months.
3. To produce fibrin foam [N.B. Fibrinogen is dissolved in sodium chloride injection and
whipped into a foam that is then clotted by addition of human thrombin. The foam is then
freeze dried].
4. To prepare gelatin sponge [N.B. A solution of gelatin containing traces of formaldehyde is
foamed, freeze dried, sterilized and used as surgical dressing.]
5. Used to dry sera, blood products, certain enzymes, plant extracts, diagnostics, mammalian
tissues useful in skin and bone graft surgery.

SPRAY DRYING

In spray dryer the liquid is sprayed in small droplets by atomizer in a drying chamber so that
each droplet dries to a solid particle. The feed may either Tangential
air inlet Liquid
be solution, suspension or paste. feed
Hot air

Construction and working

Atomiser

The spray drying process involves four basic stages: Drying

chamber
(A) Atomization of feed into spray

When a feed is atomized into small droplet its specific

surface area increases many folds. So drying takes place at
a very fast rate. The instrument that produces small
Air outlet
Dry product

Fig. Spray dryer

droplets is called atomizer. Atomizers are classified as follows on the mechanisms involved in
breaking the bulk of the liquid.

(a) Centrifugal atomizer

e.g. Rotary atomizer. In rotary atomizer the liquid is distributed centrally on a wheel disc
or cup that is rotated at high speed. Due to centrifugal force the liquid gets high velocity
in the radial direction. The liquid is extended as a thin film over the disc. Then the liquid
films disintegrate to produce fine droplets.

Use: Used for slurries or pastes having thermolabile, abrasive, corrosive or high viscous
properties.

(b) Pressure atomizer

e.g. Centrifugal pressure nozzle. The liquid is fed through a nozzle under pressure. The
feed is issued from the nozzle as a thin film that readily disintegrates into a spray. The
feed rotates inside the nozzle so that a cone shaped spray pattern is obtained.

Use: Used to obtain coarse particles.

(c) Pneumatic atomizer

e.g. Two fluid Nozzle atomizer. It involves impact of liquid with a high velocity gas or
air. The high velocity gas creates a high frictional force over the liquid surfaces leading to
disintegration of liquid into droplets. The stream of gas is rotated inside the nozzle and
may come in contact with the liquid wither within the nozzle or after emerging of liquid
from the nozzle.

Use: Feed of high viscosity feed produce coarse and less uniform product. Feed of low
viscosity produces smaller size particles and more uniform particles.

(B) Spray-Air contact

The spray and hot air can flow in two ways: (i) co-current flow, (ii) in counter-current
flow.

In co-current flow the spray and the hot air is passed in the same direction. Here fresh droplets
come in contact with the hottest air. Solvent evaporates and the droplet temperature falls to wet
bulb temperature. So heat labile materials can be dried.

In counter-current flow the spray and hot air flows in opposite directions. Here the dried product
comes in contact with the hottest air hence this type of flow is suitable for thermostable
materials.

(C) Droplet drying

Heat is transferred to droplets by convection from air. The moisture from the interior migrates to
the surface and evaporation takes place from the surface. The air temperature is so high that
migration of moisture from the interior of the droplet cannot provide the moisture necessary to
keep the surface wet. So the surface becomes dried quickly and the moisture in the interior
produces vapor that expands the droplets. The final product depends on the nature of the surface
layer:

Layer is porous and rigid  No change

Layer is less porous and rigid Broken particles

Layer is non-porous and plasticExpanded hollow particles

(D) Separation and recovery of dried products

Majority of dried product falls to the base of the chamber where primary separation takes place.
The particles entrained in the air is recovered by any one of the separation equipment like
cyclone separator, bag filters, electrostatic precipitators or wet scrubbers.

Applications

1. For drying pharmaceutical products three types of spray dryers are used:

(i) Standard open cycle type: Used from drying infusions, extracts, adrenaline etc. Air is
used for drying.
(ii) Aseptic open cycle type: Used to dry antibiotics, vitamins, destrans, hormones,
enzymes etc. in aseptic condition. The air is made sterile by passing through HEPA
filter.
(iii)Closed cycle type: This type is commonly used to remove organic solvent by using
nitrogen instead of air. This type is used for inflammable solvents, for drying toxic
substances and for complete recovery of solvent.

2. For spray congealing: In this process solid drug particles are suspended in molten waxes (or
congealing polymers) and sprayed in a chamber containing cool air. The droplets of wax
congeal around the drug particles. Thus the taste of unpalatable drugs can be masked and
sustained release products can be produced.

3. Spray coating: Solid drug particles are suspended in a coating solution (containing polymer)
and the slurry is sprayed in a drying chamber. The solvent of the coating solution evaporates
leaving a coating on the solid drug particles. Liquids can also be coated by this method. An
emulsion is prepared with the liquid drug as internal phase and coating solution as the external
phase. The emulsion is sprayed in the drying chamber. Solvent is evaporated from the external
phase leaving a coating over the dispersed liquid drug.

STERILISATION
INTRODUCTION

Among the many facets of patient care is that of the sterilization of a range of materials.
These include bacteriologically contaminated glassware and Petri dishes, dressings, sutures,
ligatures, surgical instruments, etc., as well as certain raw materials and forms of pharmaceutical
dosage. It is considered necessary to sterilise all of these as they could constitute a potential
health hazard to patients.

Sterilization is the process of killing or removing microorganisms. A sterile material is

one that contains no living organisms at all and the term sterile is therefore an absolute one.
However, the killing or removing of microorganisms follows a probability function, there always
being a finite chance of leaving some live microorganisms intact in the system so that
sterilization process are designed to minimize the probability of leaving survivors.

However, with all articles to be sterilized there is the chance that the sterilizing treatment
will have a detrimental effect. This is particularly true of pharmaceutical dosage forms where it
is important that the chosen process should not cause changes in the formulation, which would
reduce its therapeutic efficacy or patient acceptability. For this reason, with the design of all
sterilization processes a balance has to be achieved between the maximum acceptable risk of
failing to achieve sterility and the maximum permissible concomitant damage caused to the
treated articles.

The methods currently used to kill microorganisms involve exposing the preparation to
an inimical physical agent or condition for a known period of time. The agents used are of three
different types, namely elevated temperature, ionizing or UV radiation, and toxic gases. The
fourth way of achieving sterility is restricted to solutions and gases and involves passing the
solution through a filter that will retain the microorganisms.

DEFINITIONS

1. Antiseptic: A substance that arrests or prevents the growth of microorganisms by inhibiting

their activity without necessarily destroying them. Can be applied on human body.
2. Bactericide: Anything that kills bacteria.
3. Bacteriostat: Anything that arrests or retards the growth of bacteria.
4. Disinfection: A process that removes infection potential by destroying microorganisms but
not ordinarily bacterial spores. Disinfectants are generally meant for application on
inanimate objects.
5. Germicides: A substance that kills disease microorganisms (i.e. pathogens / germs) but not
necessarily bacterial spores.
6. Sterility: The absence of viable organisms.
7. Sterilization: A process by which all viable forms of microorganisms are removed or
destroyed.
8. Viable = growing bacteria (or microorganisms) + spores
9. Vegetative microorganisms = growing organism
DEFINITION OF STERILISATION

Sterilization is a process whereby all the viable life forms are either killed or removed
(by filtration) from a product.

‘Sterilisation’ and ‘Sterility’ are two absolute terms i.e. a sterile product should be absolutely
free from viable (vegetative + spores) microorganisms.

METHODS OF STERILISATION

STERILISATION METHODS

PHYSICAL CHEMICAL MECHANICAL

Gaseous sterilization Filtration through

with ethylene oxide bacteria proof

filter units

Dry heat Moist heat Radiation

i)Heating in i) Moist heat in i) By exposure i) Berkefeld filter (could be
hot air oven autooclave to UV - rays porcelain, keiselguhr)

ii)Flaming ii) Heating with a ii) By ionising ii)Sietz filter (Asbestos

bactericide radiation. pads)
iii)Infra-red (i.e gamma
radiation iii) Heating at rays) iii) Sintered glass filter
1000C
iv) Sintered metallic filter
iv)Pasteurization
v) Membrane filters
v)Tyndalization
or Fractional
sterilisation.

vi) Heating at 55
to 600C

DRY HEAT STERILIZATION

Principle:

The killing of microorganisms by heat is a function of the time-temperature combination used. If

the temperature is increased then the time required for killing all the bacteria will be decreased.

Condition: Cycles recommended as per BP 1988 are:

A minimum of 1800C for not less than 30 minutes.

A minimum of 1700C for not less than 1 hour.

A minimum of 1600C for not less than 2 minutes.

Mechanism of killing the bacteria:

The vital constituents of cells such as proteins (enzymes) and nucleic acids are denatured by
oxidation.

Biological indicator: Spores of Bacillus subtilis var. niger. or,

Spores of Bacillus globigii or,

Spores of Clostridium tetani (atoxigenic)

Application of dry heat sterilization:

Dry heat is used to sterilize

1. Glass ware e.g. test tubes, Pasteur-pippettes, petridishes, flasks, glass syringes etc. The glass
wares should be prewashed with apyrogenic water.
2. Porcelain and metal equipment such as forceps, scalpels, scissors etc.
3. Dry materials in sealed container like powders.
4. Fats, oils and greasy materials (like petroleum jelly) those are impermeable to moisture.

Dry heat sterilization is not used in the following cases:

1. Aqueous solution cannot be sterilized by dry heat beacause the water will evaporate if the
container is kept open. If the container is kept close then it may burst due to pressure
developed by the steam.
2. Surgical dressings cannot be sterilized by dry heat because cotton or other cellulosic
material will get chared at the high temperature.
3. Powders that cannot withstand the high temperature are not sterilised by dry heat method.
HEATING IN A HOT AIR OVEN

 A hot air oven is a double walled chamber made up of mild steel or aluminium. The door is
insulated with asbestos gasket to minimize the heat loss. To reduce heat loss by conduction
insulating material (glass fibre or puff) is used in between two walls.
 The inner surface is made reflecting to reduce heat loss by radiation.
 It consists of one or more shelves.
 It is thermostatically controlled. Heaters are fitted to heat the air inside. The heat is circulated
by normal convection. To spread the heat uniformly forced convection is arranged by fitting
fans in strategic places.
 For effective utilization of the oven and to obtain correct results it should be uniformly
packed or loaded so that all the objects are exposed to sterilization temperature for the
required period of time.
 Care should be taken so that once in operation the oven is not opened in the middle of the
cycle.

FLAMING

This is an emergency method, the forceps-tips, the surfaces of the scalpels and the
needles may be sterilized by holding the items directly in the flame of a Bunsen burner. This
method is generally done in microbiology.

INFRARED RADIATION

 Infrared radiation (IR) is a thermal radiation, i.e. when absorbed by some article its energy is
converted to heat and therefore it is often known as radiant energy.
 A tunnel having an IR source is used for this purpose. The instruments and glass wares are
kept in trays are passed through this tunnel keeping on the conveyor belt, at a controlled
speed exposing them to a temperature of 1800C for 17 minutes, thereby achieving the
sterility. This is a continuous process and is used in hospitals for regular supply of sterile
syringes and other apparatus.
 Heating at or above 2000C by IR in vacuum is employed as a means of sterilizing surgical
instruments.
 Cooling is hastened, (after the heating cycle) during the cooling period, by admitting filtered
N2 to the chamber.

MOIST HEAT STERILIZATION

Principle:

Mechanism of killing of microorganisms:

Bacterial death by moist heat is due to denaturation and coagulation of essential protein
molecules (enzymes) and cell constituents.

Conditions:
The USP XXI and BP 1988 recommended the following condition:

 Pressure: 15 lb / square inch (psi)

 Temperature: 1210C
 Time: 15 minutes
 The following combinations of temperature and holding time are normally employed for
sterilizing by heat in autoclave:
Holding temperature (0C) Holding time (min)
115 to 118 30

121 to 124 15

126 to 129 10

134 to 138 3

Biological indicator: Spores of Bacillus stearothermophilus or

Spores of Clostridium sporogenes.

Principles of sterilization by steam under pressure:

Pressure itself has no sterilizing power. Steam is used under pressure as a means of
achieving an elevated temperature.

Steam production: This may be achieved in two ways:

1. In a small scale, steam may be generated from water within the sterilizer and since water is
present this steam is known as ‘wet saturated steam’.
2. For large scale sterilizers dry saturated steam may be piped from a separate boiler.

Penetration of steam:

Steam flows quickly into every article in the load ( and into porous articles). This is due
to its condensation creating a low-pressure region into which more steam flows.

Rapid heating: The saturated steam heats the load rapidly due to the release of its considerable
amount of latent heat.

Moist heat: The condensate produced on cooling hydrates the microorganisms and thus helps in
coagulating microbial proteins.

No residual toxicity: The product is free from toxic contamination.

The design and operation of autoclave:

 A portable autoclave is an elaborate pressure cooker. It is a hollow cylindrical vessel
fitted with a lid that can be tightly secured in a position by nut-bolts or screws. The body is made
up of aluminium or steel or gun metal.

The lid is provided with a steam vent, a safety valve and a pressure or temperature gauge.
It is heated electrically or gas operated. The electrical element is fitted at the bottom of the
autoclave. First water is added so that the heating element is fully immersed in water. Then the
materials to be sterilized are placed over a perforated platform.

Heater is switched on. Initially the steam-vent (outlet) is opened. The displaced air is first
removed, then the vent is closed. The pressure will then rise to 15 lb/sq inch (psi) and as a result
the temperature inside will rise to 1210C. At this condition the autoclave is kept for 15 minutes,
then the heater is switched off. When the pressure inside and outside the autoclave equals, the
steam-vent is opened and the lid is removed to take out the sterilized articles.

Application of autoclave:

It is used to sterilize anything, which is not injured by steam and high temperature of

sterilization. These includes:

1. Aqueous parenteral solutions e.g. distilled water, saline solutions.

2. Aqueous liquid media e.g. liquid media with or without carbohydrate and gelatin.
3. Surgical dressings and fabrics.
4. Plastic and rubber closures.
5. Metal instruments.
6. Glass apparatus and containers.

HEATING WITH A BACTERICIDE

This method is used for sterilizing aqueous solutions that are thermolabile to withstand
normal autoclaving temperature.

Condition:

Temperature: 98 to 1000C boiling water

Time: 30 minutes

Bactericides: Bactericide that is compatible with the product,

container and closure:

e.g. for injection

 Chlorocresol 0.2%(w/v)

Phenylmercuric nitrate (PMN) 0.002%(w/v)

Phenylmercuric acetate (PMA) 0.002%(w/v)

e.g. for eye drop

Thiomersal 0.01%(w/v)

Chlorhexidine acetate 0.01%(w/v)

PMA and PMN 0.002%(w/v)

Benzalkonium chloride (BAC) 0.01%(w/v)

Applications:

In the following cases this method can be used:

1. Injection fluids in the final container (i.e. terminal sterilization).

2. Eye drops.

**In the following cases this method cannot be used:

1. Solution of medicaments intended for intrathecal, intra-atrial, peridural, intra-peritoneal,

intra-cisternal and any other route of injection giving access to the cerebro-spinal fluid and
for intracardiac and intra-ocularly.
2. Large volume parenteral fluids having a volume greater than 15 ml is not recommended to
use bactericide because, though the concentration of the bactericide in the solution is less but
the total amount entering into the system may be considerable due to large volume. e.g.
bactericides are not used in saline solutions.

TYNDALISATION or FRACTIONAL STERILIZATION

Instrument used : Arnold’s sterilizer

Condition: Arnold’s sterilizer employs streaming steam at a temperature of approximately

1000C for a period of 20 minutes for three consecutive days.

e.g. Agar media is sterilized by this method.

Principle:

In this process it is presumed that on the first day all the vegetative cells will be killed
and some spores may germinate in the following day. So the second day’s sterilization cycle will
kill the vegetative cells. Similarly some spore may still remain. Therefore for an additional 24
hours period is allowed to elapse to make sure all ‘spores’ have germinated into vegetative cells.

N.B.

1000C,20min Incubation
Spores + Veg. cells Spores Veg. cells 1000C,20min
24 hr
Incubation
24 hr Sterile
Incubation 0
Spores + Veg. cells 0
Spores Veg. cells 100 C,20min
100 C,20min 24 hr

Causes of failure in this process:

It may be seen unless the spores are germinated the method will fail to sterilize. Failure may be
due to the following reasons:-

1. The media may be unsuitable for the germination of the spores, e.g. distilled water is not a
favorable environment for the growth of bacteria and will not permit spores to germinate into
vegetative cells.
2. Spores of anaerobic bacteria, if present, will not germinate in a media in contact with air.
3. If any preservatives are present in the product it may not allow to germinate the spores.
4. If a product has intrinsic antimicrobial properties then it will not allow to spore germination.

Application of Arnold’s sterilizer (Tyndallization)

The Arnold’s sterilizer is used principally for the sterilization of gelatin, milk and
carbohydrate media. Higher temperature in the autoclave, larger single exposure in the Arnold’s
sterilizer may hydrolyze or decompose carbohydrates and prevent gelatin from solidifying.
Obviously such media would then be unsuitable for use.

PASTEURIZATION

Pasteur developed the procedure of gentle heating (Pasteurization) to prevent spoilage of

beers, wines by undesired contaminating microbes. This process has no pharmaceutical
application. This is used for processing of milk in order to kill the pathogenic bacteria without
affecting the taste and nutritional value of the milk. Following two methods are used:

Holding method:
 The milk is heated in tanks at 620C for 30 mins while it is gently stirred and the steam is
flown on the surface to disperse the foam.

High temperature short time method (H.T.S.T. / Flash method):

In this process the milk is rapidly raised to 71.60C held at this temperature for at least 20
seconds and quickly cooled.

The common milk born pathogens (Mycobacterium tuberculosis, M. bovis, Brucella

abortes) do not form spores and are reliably sterilized by this procedure. In addition to this, total
bacterial count is generally reduced by 97 - 99%. therefore in true sense this technique is not an
absolute sterilization process.

Advantages of moist heat sterilization:

1. High heat content plus rapid heat transfer.

2. Destroys micro-organism more efficiently than dry heat.
3. It can be used for a large number of injections, ophthalmic solutions, irrigants, dialysis fluids
etc.
4. It rapidly penetrates porous materials and is therefore very suitable for sterilizing surgical
dressings and materials.
5. The process is adaptable for plastic containers and some other special dosage forms.
6. It is more suitable than dry heat for sharp instruments.
7. Accurate control and monitoring of the process is possible.
8. No toxic contaminants are left in the materials sterilized.

Disadvantages of moist heat sterilization:

1. It is not suitable for anhydrous materials such as powders and oils.

2. It cannot be used for thermolabile substances.
3. It does not destroy pyrogens.
GASEOUS STERILIZATION

This process involves exposure of materials to sterilize gasses such as ethylene oxide,
formaldehyde, glutaraldehyde, propylene oxide.

ETHYLENE OXIDE

Ethylene oxide is the only gas that is successfully used on a large scale of industrial and
medical applications.

Structure:

HCHO CH2 CH2 CH2 H2C CH2 H2C CH CH3

.
CHO CHO O O
Formaldehyde Glutaraldehyde Ethylene oxide Propylene oxide
Mechanism of action: Ethylene oxide acts by alkylation.

Biological indicator: Bacillus subtilis var. niger.

Factors affecting sterilization:

Sterilization efficiency is influenced by

1. the concentration of ethylene-oxide

2. the humidity of the sterilizing atmosphere
3. the temperature of sterilization
4. time of exposure
5. physical nature and permeability of the load.
6. atmospheric preconditioning of the load before sterilization.

FORMALDEHYDE

Like ethylene oxide this is an alkylating agent but it is generally inferior for use as a sterilizing
agent. Because

 formaldehyde has poor penetrating power and is readily inactivated by organic matter.
 High concentrations are difficult to maintain in the atmosphere because it tends to deposit in
the form of solid polymers on contact with cool surfaces.

Condition:

Input concentration: 2 g/L of HCHO in subatmospheric steam

Temperature: 900C

Exposure time: 3 hours

Formaldehyde can be obtained as :

1. Formaldehyde solution (Formalin) B.P.

Approximately 37%w/w containing stabilizers to prevent deposition of solid polymers

2. Tablets of paraformaldehyde

* In case of formalin addition of KMnO4 produces heat by oxidation and the gas will be
vaporized.

Use: Dressing packs.

Disadvantages:
1. Low penetrability. It cannot penetrate polymeric packaging.
2. Polymerize to inactive forms on the surface of low exposure temperature.
3. Can fall in the active concentration
4. Cannot sterilize narrow lumen.

Solution of the above problems:

1. Reducing the size of the load.

2. Increasing exposure temperature.

STERILIZATION BY RADIATION

Radiation can be divided into two groups:

1. Electromagnetic waves: (i) infra-red radiation (IR) (iii)

X-rays

(ii) ultraviolet radiation (UV) (iv) gamma rays

2. Streams of particulate matter (i) alpha ra

For sterilization infrared, ultraviolet, gamma radiation and high velocity electrons (a type of beta
radiation) are used for sterilization.

Radiation Wave length Energy

UV-radiation 190 to 370 nm 5 eV

Gamma radiation 1 to 10-4 nm 1.3 MeV*

High velocity electrons 4MeV

* MeV = Million electron volt

ULTRAVIOLET RADIATION

Source: Low current of high voltage is passed through mercury vapor in an evacuated tube made
of borosilicate glass.

Dose of sterilizing radiation: 10 to 60 microwatts / cm2 reduce the populations of vegetative

cells by 90% in a short period.

Mode of action: Only a narrow range of wavelength (220 to 280 nm) is effective in killing
micro-organisms, and wavelengths close to 253.7 nm are the most effective. It has been
found that a maximum biological efficiency exists at 253.7 nm, which is also the
 absorption peak of isolated DNA, this suggests strongly therefore that DNA or the
nucleic acid is the target for UV-induced lethal events.

Use: (i) Surface sterilization

(ii) Sterilization of clean air and water in thin layers.

Disadvantages:

1. It has very poor penetration power.

[N.B. UV radiation does not penetrate normal packaging material, such as glass or plastic
and hence, it is not used to sterilize pharmaceutical dosage forms.]

2. UV-light sterilization is not absolutely reliable because DNA may get repaired in some
favorable condition.

3. Bactericidal UV -light causes eye problems and erythema (reddening) of the skin if those
parts are exposed to UV- radiation for a prolonged period of time.

IONISING RADIATION

Mode of action of ionizing radiation:

Ionizing radiation can cause excitations, ionization and where water is present free
radical formation. Free radicals are powerful oxidizing ( OH, HO 2) and reducing (H) agents,
which are capable of damaging essential molecules (enzymes and DNAs) in living cells. This
results in cell death.

Biological indicator: Bacillus pumilis.

HIGH SPEED RADIATION

Source: This type of sterilizing radiation is most widely used in Denmark and the USA. In a
machine known as a van de Graph accelerator electrons are generated from a suitable source and
then accelerated along a highly evacuated tube by a tremendous potential difference between the
ends.

Dose: 5 MeV to 10 MeV (Million electron Volt).

Use: The beam, which is narrow and intense, is used to irradiate articles on a conveyor-belt.

GAMMA RAYS
60
Source: Radiation from the radioactive isotope of Cobalt Co, is used as a source of gamma
emission.
Dose: 1.25 MeV,

Some users take the adequate dose as 2.5 Mrad (Mega radiation unit)

Procedure: Articles for sterilization by radiation are packed in boxes of standard size, which are
suspended from a monorail and sterilized by slow-passage around the gamma-ray source.

Uses:

 Articles regularly sterilized on a commercial scale include plastic syringes, catheters,

hypodermic needles and scalpel blades, adhesive dressings, single-application capsules of
eye-ointment and catgut
 Containers made of polyethylene and packaging materials using aluminum foil and plastic
films.

Disadvantages:

 The damage of the cells is mediated through radiation-induced free radicals in water, hence
the extent of degradation is found to be maximum in pharmaceuticals in aqueous solutions.
Practically the amount of degradation in aqueous solution is so great that this sterilization
method is only confined to sterilize surgical sutures, instruments etc.
 The necessary apparatus is much expensive for installation in hospital. It is employed
commercially for the sterilization of large amount prepackaged disposable items such as
plastic syringes and catheters, which are unable to withstand heat.
STERILIZATION BY FILTRATION

This method is used for sterilizing thermolabile solutions, which will otherwise be
degraded by other conventional heating methods.

The drug solutions are passed through the sterile bacteria proof filter unit and
subsequently transferring the product aseptically into the sterile containers which are then sealed.

The process involves considerable hazards. Hence IP and BP require that the tests for
sterility be carried out on the filtered product.

Biological indicator: Micromonospora diminuta.

Procedure:

The solutions to be sterilized is passed through the filter and collected in the sterile receiver by

the application of positive pressure to the nonsterile compartment or negative pressure to the

sterile side..]
Advantages of sterilization by filtration:

1. Thermolabile solutions can be sterilized.

2. It removes all the living microorganisms.

Disadvantages of sterilization by filtration:

1. Filters may break down suddenly or gradually on use.

2. Sterility testing is obligatory on the filtered solution.

3. Filter media may be absorbed on the filter surface.

4. Viruses are not removed by filtration.

5. Suspensions and oils cannot be sterilized by this method due to their heavy load of
particulate matters and viscosity.

Mode of action:

The filters are thought to function by one or usually a combination of the following:

1. Sieving or screening,

2. Entrapment,

3. Electrostatic attraction.

When a particle is larger than the pore size of the filter the particle is retained on the filter
- this known as sieving or screening.

Entrapment occurs when a particle smaller than the size of the pore enters into the pore
channel and lodges onto the curves of the channel while passing through it.

Electrostatic attraction causes particles, opposite in charge to that of the surface of the
filter pore, to be held or adsorbed onto the surface.

MEMBRANE FILTERS

 Membrane filters are made of cellulose-derivative (acetate or nitrate). They are very fine.
They are fixed in some suitable holders.
 Nominal pore size is 0. 22  0. 02 m or less is required.
 The membranes are brittle when dry. In this condition they can be stored for years together.
They become very tough when dipped in water.
  They are sterilized by autoclaving or by ethylene oxide gas. They cannot be sterilized by
dry heat as they decompose above 1200 C.
 They are suitable for sterilizing aqueous and oily solutions but not for organic solvents
such as alcohol, chloroform etc.
 Membrane filters are generally blocked by dirt particles and organisms. Pre-filtration
(through glass-fibre paper prefilter) reduces the risks of blockage of the final filter.

Examples of membrane filters:

MF-Millipore – it is a mixture of cellulose esters

Sartorius Regular – it is made of cellulose nitrate

Gelmen Triacetate Metricel – cellulose triacetate

SINTERED (or FRITTED) GLASS FILTERS

Borosilicate glass is finely powdered in a ball-mill and the particles of

required size are separated. This is packed into disc mounted and heated till the
particles get fused. The disc thus made have pore size of 2 m and are used for
filtration.

They are cleaned with the help of sulfuric acid.

SIETZ FILTER: They are made of asbestos pad.

[For further details see Cooper & Gunn Dispensing pp. 582]

CERAMIC FILTERS: They are made of either porcelain or keiselghur. These are supplied in the
shape of candles mounted to metallic joint.

TESTING OF FILTERS:

The BP requires that the integrity of an assembled sterilizing filter be verified before use and
confirmed after use by means of a suitable test.

Bacteriological test:

A diluted solution of broth culture of Serratia marcescens is passed though the filter and
the filtrate is collected aseptically and incubated at 250C for 5 days. The filter passes this test if
no growth is found after 5 days of incubation.

Bubble point test:

The bubble point of a test filter is the pressure at which the largest pore of a wetted filter
is able to pass air.
Objectives:

1. Filtration should normally be performed at pressures lower than the bubble point of a
membrane. This prevents gas from passing through the filter at the end of a filtration cycle
and thereby prevents excessive foaming.

2. For testing membrane efficiency and integrity.

INTRODUCTION

Crystallization

Crystallization is the formation of solid particles within a homogeneous phase. It may occur as
the formation of solid particles in a z
vapor, as in snow; as solidification
from a liquid melt, as in the
manufacture of large single crystals; or
as crystallization form liquid solution.
g b x
a
Crystal
y (b) Unit cell
A crystal is a regular polyhedral form,
bounded by smooth faces, which is
assumed by a chemical compound, due (a) Lattice structure in crystal
to the action of its interatomic forces, when passing, under suitable conditions, from the state of a
liquid or gas to that of a solid.

[N.B. A polyhedral form simply means a solid bounded by flat planes (we call these flat planes
CRYSTAL FACES). "A chemical compound" tells us that all drugs are chemicals. The last half
of the definition tells us that a crystal normally forms during the change of matter from liquid or
gas to the solid state. In the liquid and gaseous state of any compound, the atomic forces that
bind the mass together in the solid state are not present. Therefore, we must first crystallize the
compound before we can study it's geometry. Liquids and gases take on the shape of their
container, solids take on one of several regular geometric forms. These forms may be
subdivided, using geometry, into six systems. ]

Crystal Lattice
Crystal lattice is defined as a
three dimensional network of c
+C c c
imaginary lines connecting the
-A b
atoms, ions or molecules. b a b
-B +B a a
The distance between the center +A
of two atoms (or ions, or -C
molecules) is called length of unit Crystallographic Cubic Tetragonal Orthorhombic
cell and the angle between the axes a = b =c a = b =c a = b =c
edges of a unit cell is called as = 90 0 = 90 0 = 90 0
lattice angle. c
c
b
 The units that constitute the a
b a
crystal structure are atoms,
ions or molecules.
Triclinic
 Ions with opposite charges Monoclinic a = b =c
are bonded together by a = b =c 0
bc = ac = ab = 90
electrostatic attraction e.g. bc = 90 0 ac = ab = 90 0
Na+ and Cl– ions bonded in
NaCl crystals.
 Atoms are bonded together by covalent bonds e.g. C atoms are bonded by covalent bonds in
diamond and graphite.
 Molecules of organic compounds are bonded by van der Waal’s force and / or hydrogen
forces. E.g. Naphthalene, p-hydroxy benzoic acid.

Crystal Forms

Crystal lattice can be classified according to the angles between the faces. There is only finite
number of symmetrical arrangements possible for a crystal lattice, this is termed as crystal forms.

The ability of a compound to exist in different crystal forms is known as polymorphism.

[N.B. The types of crystal-forms has no relationship to the relative sizes of the faces since the
relative development of the faces are not constant, only the angles between the faces remain
constant. ]

There are six types of crystal forms, depending on the arrangement of the faces expressed as
crystal axes and angles between the axes.

1. Cubic - The three crystallographic axes are all equal in length and intersect at right angles
(90 degrees) to each other. [a = b = c] e.g. Sodium chloride and potassium chloride crystals.
2. Tetragonal - Three axes, all at right angles, two of which are equal in length (a and b) and
one (c) which is different in length (shorter or longer). Note: If c was equal in length to a or
b, then we would be in the cubic system. Urea and potassium dihydrogen phosphate crystals.
3. Orthorhombic - Three axes, all at right angles, and all three of different lengths. Note: If
any axis was of equal length to any other, then we would be in the tetragonal system e.g.
Barium sulphate crystals.
4. Hexagonal - Four axes, three of the axes fall in the same plane and at 60 0 to each other.
These 3 axes, labeled a1, a2, and a3, are the same length. The fourth axis, termed c, may be
longer or shorter than the ‘a’ axes set. The c axis also passes through the intersection of the a
axes set at right angle to the plane formed by the a set. Ice and thymol crystals.
5. Monoclinic - Three axes, all unequal in length, two of which (a and c) intersect at an oblique
angle (not 90 degrees), the third axis (b) is perpendicular to the other two axes. Note: If a and
c crossed at 90 degrees, then we would be in the orthorhombic system. Sucrose and
Ephedrine chloride crystals.
6. Triclinic - The three axes are all unequal in length and intersect at three different angles (any
angle but 90 degrees). Note: If any two axes crossed at 90 degrees, then we would be
describing a monoclinic crystal. Phenolphthalein and Copper sulphate.

Crystal Habits

Crystal is a polyhedral solid with number of

Needle or Acicular
planar faces. The arrangement of these faces
is termed as habit. The crystal habit may Platy
Tabular
change due to changes in rate of deposition,
shielding of certain faces, presence of
impurities in mother liquor. Bladed
Equant or Massive
e.g. NaCl crystallizes out from aqueous Fig. 1 Prismatic
solution with cubic faces only. On the other
hand, if NaCl is crystallized from aqueous solution containing a small amount of urea, the
crystals are found to have octahedral faces.

Different crystal habits are

Acicular e.g. Nalidixic acid

Columnar e.g. Fluorocortisone acetate

Blade e.g. Resorcinol

Plate e.g. Naphthalene

Tabular e.g. Tolbutamide

Equant e.g. Sodium chloride etc.

Purity of crystals
A well formed crystal is nearly a pure chemical. Some times it retains mother liquor when
removed from the final magma. If the product contains crystal aggregates then considerable
amount of impure mother liquor may be entrapped inside the product. When this mother liquor is
dried on the crystals, contamination results.

In practice most of the mother liquor is removed from the crystals by centrifuging or filtration
and the balance is removed by washing with fresh solvent.

IMPORTANCE OF CRYSTALLIZATION

 Crystallization from solution is important industrially because of the variety of materials that
are marketed in the crystalline form.
 Crystallization affords a practical method of obtaining pure chemical substances in a
satisfactory condition for packaging and storing. A crystal formed from an impure solution is
itself pure (unless mixed crystals occur).
 A drug may remain in different crystalline forms, some are stable, and rests are metastable.
The metastable forms have greater solubility in water, thus have better bioavailability. By
controlling the conditions during crystallization the quantity of metastable to stable forms
may be controlled.
 After crystallization water or solvent molecules may be entrapped within the crystal structure
and thus form hydrates or solvates which have different physical properties that may be
utilized in various pharmaceutical purpose.
 Particles with various micromeritic properties, compressibility and wettability can be
prepared by controlling the crystallization process.
 Desalination of seawater by crystallization method requires only 1/7 th of the energy required
by distillation process.
Factors affecting the crystal habit

1. Presence of another substance in the mother liquor:

Sodium chloride crystallized from aqueous solutions produces cubic crystals. If sodium
chloride is crystallized from a solution containing a small amount of urea, the crystals
obtained will have octahedral faces. Both types of crystals belong to the cubic crystal
form but differ in habit.

2. Solvent:

Griseofulvin crystallized out from acetone has different crystal habit than when
crystallized from benzene or chloroform.

3. Rate of cooling:

Acicular or needle-like crystals are produced when the solution is cooled very slowly.
Fluffy and small crystals are produced when the solution is cooled very fast.
THEORY OF CRYSTALLIZATION

Mechanism of crystallization

The formation of crystals from solution involves three steps:

A. Supersaturation
B. Nucleation (or nucleus formation)
C. Crystal growth
A. Supersaturation

When the concentration of a compound in its solution is greater than the saturation solubility of
that compound in that solvent the condition is known as supersaturation. This is an unstable
state. From this supersaturates solution the escess compound may be precipitated out or
crystallize.

Supersaturation can be achieved by the following methods:

1. Evaporation of solvent from the solution.

2. Cooling of the solution.
3. Formation of new solute molecule as a result of chemical reaction in situ
4. Addition of a substance, which is more soluble in solvent than the solid to be crystallized.
B. Nucleation

Nucleation refers to the birth of very small bodies of molecules from which the crystal forms.

 In solution, solute molecules, ions or atoms remain in constant random motion. This is due
thermodynamic energy of the solution system.
 When the solute particles (molecules, atoms or ions) moves and collide over each other they
may form aggregates. This aggregates are called clusters. These are loose aggregates, which
usually disappear quickly.
 Some clusters may become so big that they may arrange themselves in lattice arrangement.
These bodies of aggregates are called embryo. However, embryos are unstable and they may
break into clusters again.
 Some embryo may grow to such a size that it remains in thermodynamic equilibrium with the
solution. They do not revert back to clusters. These bodies are called nucleus (plural is
nuclei).

C. Crystal growth

Crystal growth is a diffusion process and a surface phenomenon. Every crystal is surrounded by
a layer of liquid known as stagnant layer. From the bulk solution a solute particle (molecule,
atom or ion) diffuse through this stagnant layer and then reaches the surface of the crystal. This
particles then organize themselves in the crystal lattice. This phenomenon continues at the
surface at a slow rate. This process will happen if the bulk solution is supersaturated.
Mier’s Supersaturation theory

Mier and Issac proposed a theory explaining a relationship between supersaturation and
spontaneous crystalization.

Mier’s theory points out that

(i) the greater the degree of supersaturation, the more chance is of nuclei formation,
(ii) if the super-saturation passes a certain range of values, nuclei formation is extremely rapid.

Assumption:

1. The solute and the solvent must be pure.

2. The solution must be free from solid solute particles.
3. The solution must be free from foreign solid particles.

The theory can be explained with the help of solubilty -

SUPER SOLUBILITY
supersolubility diagram. F A
SOLUBILITY CURVE
CURVE
 Here the curve AB is the ordinary solubility D C
(equilibrium) curve. It represents the maximum CONCEN G
concentration of solutions that can be obtained by TRATION
E
bringing solid solute into equilibrium with solvent. B
 If a sample of solution having a temperature and
composition of point C is cooled in the direction of
TEMPERATURE
CD, it first crosses the solubility curve AB, but no
nucleus will be formed. When it reaches some where in the neighbourhood of the point D
(according to Mier’s theory) crystallization begins. As the crystallization proceeds the
concentration of the solution follows roughly according to the curve DE and reaches the
solubility curve.
 In the absence of any solid particles the curve FG represents the limit at which nucleus
formation begins spontaneously and, consequently crystallization starts – this line (FG) is
called the super-solubility curve. According to Mier’s theory at any point between C and D
points nuclei cannot form and crystallization cannot start.

Limitations of the Mier’s theory

1. According to Mier’s theory, crystallization starts at super-solubility curve (FG). But the
general tendency is that crystallization takes place in an area rather than a line.
2. If the solution is kept for long periods, nucleation starts well below the super-solubility
curve.
3. If the solution is available in large volume, nucleation starts well below the super-solubility
curve.
4. Mier’s theory is applicable only when pure solute and pure solvent is taken. In practice, it is
impossible to get them in pure state.
 [N.B. Mier’s theory is base on the postulation that the solution consists of pure solvent
and pure solute without the presence of any solid particles, whether of solute itself or of
any foreign material. In presence of any such solid particles it has been found that
crystallization occurs well before the line FG.]

5. During crystallization the solution may become contaminated with dust, particles from
container etc. Nucleation may be initiated from these foreign particles also.
Solubility curves

Solubility of a solute depends on the temperature. When the solubility (of a saturated solution) of
a solute is plotted against temperature the curve is known as solubility curve. Temperature is
plotted in X-axis and solubility is plotted in Y-axis. The metastable condition is shown by dotted
line.

The following solubility curves may be observed with various solutes:

1. Curve-1 represents potassium nitrate (KNO3). This is most common type in which the
solubility of a substance increases with temperature.
2. Curve-2 represents sodium chloride (NaCl). The solubility increases with increase in
temperature, but to a marginal extent.
3. Curve-3 represents sodium thiosulphate (Na2S2O3). Here solubility increases rapidly with
temperature. But inflections are observed in the curve to represent different hydrates.
4. Curve-4 represents sodium carbonate
(Na2CO3). This curve is unusual. Here
solubility of sodium chloride increases
with temperature, if it is in hydrated form..
Once the compound turns in to mono-
hydrate form, its solubility decreases.
Calculation of yields

A solution of a substance is taken. The

concentration of the solute in the solution is
noted.

The solution is evaporated or cooled to make it

supersaturated solution. The excess solute
crystallizes out of the solution and the mother
liquor at the end of the crystallization process
is nothing but a saturated solution. The
solubility is the saturation solubility at that
temperature. This saturation solubility at that
temperature is determined from the solubility
curve.

During evaporation some amount of solvent is evaporated.

Material may crystallize out in pure form or as hydrates.

Problem:

A solution containing 30% MgSO4 and 70% H2O is cooled to 180C. During cooling 5% of the
total water in the system evaporate. How many kilograms of crystals are obtained per kg of
original mixture? Crystals formed are MgSO4, 7H2O. Concentration of mother liquor is 24.5%
anhydrous MgSO4.

Solution
In the original mixture

MgSO4 30% x 1000kg = 300kg

Free water 70% x 1000kg = 700kg

Total = 1000kg

Water evaporated = 5% of free water in the original mixture = 5% x 700kg = 35kg

MgSO4 crystallizes out in the form of MgSO4, 7H2O (7 molecules of crystal water)

Let, m kg of (MgSO4, 7H2O) crystal forms from 1000kg of original mixture.

Molecular weight of MgSO4 = 120.4 and MgSO4, 7H2O = 246.5

120.4
Therefore, m kg MgSO4, 7H2O crystal contains mx kg of MgSO4. = 0.488 m kg
246.5
MgSO4.

7x18
and mx kg water = 0.511 m kg H2O
246.5
In the final mixture

MgSO4, 7H2O crystal = m kg

MgSO4 left in the mother liquor = (300 – 0.488m) kg

Water left in the mother liquor = (700 – 35 – 0.511m) kg = (655 – 0.511m) kg

From the solubility curve of MgSO4 in water it is found that at 180C the solubility of MgSO4 is
24.5%.
So in the final mixture at 600F MgSO4 = 24.5kg

Free water = (100 – 24.5) kg = 75.5 kg

300  0.488m 24.5

Therefore,  Solving this equation will yield, m = 261 kg
655  0.511m 75.5
CRYSTALLIZERS
Classification of crystallizers

Crystallization equipment is classified by the methods by which supersaturation is bought about.

These are as follows:

1. Supersaturation by cooling alone

A. Batch processes

(i) Tank crystallizers

(ii) Agitated batch crystallizers

B. Continuous processes

(i) Swenson-Walker

(ii) Other

2. Supersaturation by adiabatic cooling

A. Vacuum crystallizers

3. Supersaturation by evaporation

A. Salting evaporators

B. Krystal evaporators

TANK CRYSTALLIZER

Procedure
Cover
Hot , nearly saturated solutions are kept in open Crystals
rectangular tanks in which the solution stood while it Tank
cooled and crystals are deposited. No seed is given.
Some times rod or strings are hung in the tanks to String
give the crystals additional surfaces on which the Mother liquor

Fig. Tank crystallizer

crystals may grow and to keep major part of the product above the bottom of the tank where the
sediment is collected (actually the sediment is the source of impurity).

Disadvantages

1. Crystal growth is very slow.

2. Crystals formed are large and interlocked, so mother liquor along with impurity gets
entrapped within the crystals.
3. The floor space required and the amount of material tied up in this process are both large.

AGITATED BATCH CRYSTALLIZER

Procedure

It is a tank with a central shaft Cooling water Cooling coil

running through it. Water is circulated outlet
through the cooling coils, and the
solution is agitated by the propellers on Propeller
the central shaft. Product is collected at
the bottom of the crystallizer. It is a
batch process.
Cooling water
Advantages inlet

 The agitation increases the rate of

heat transfer and keeps the
temperature of the solution uniform Product
through out the crystallizer.
 Agitation keeps the smaller crystals in suspension and allows them to grow uniformly– thus
finer crystals can be obtained.

Disadvantages

 It is a batch process or a discontinuous one.

 Since the solubility is least at the cooling surface hence the crystals growth is more rapid on
the cooling coils. Thus the crystals deposited on the cooling coils reduces the heat transfer
rate.

SWENSON-WALKER CRYSTALLIZER
 TOP VIEW
10 ft Unit Spiral agitator

10 ft Unit
2 ft Trough

SIDE VIEW
Jacket

Construction: It consists of an open trough (A) 2 ft wide, with a semicylindrical bottom. A water
jacket (B) is welded to the outside surface of the trough. Inside the trough a slow speed, long
pitch, spiral agitator (C) is fitted as close as possible to the bottom of the trough. The agitator
rotates at a speed of 7 rpm.

This apparatus is built in units of 10 ft length. Several such units are joined together to give
increased capacity.

Working principle: This is continuous type crystallizer. The hot supersaturated solution is fed
at one end of the trough, and the cooling water is flows in the jacket, but in counter current (i.e.
opposite to the flow ) to the solution. As the hot solution flows along the trough it is cooled and
crystals are formed. Agitator prevents an accumulation of the crystals on the cooling surface and,
lift the crystals and shower them through the solution. In this manner perfectly individual
crystals are formed.

At the end of the crystallizer there may be an over flow gate where the mother liquor and
the crystals are overflowed in a draining table or drain box,, from which the mother liquor is
separated and fed in the crystallizer again. The crystals are sent to centrifuge.

In another method an inclined screw conveyor lifts the crystals and the wet crystals are
send to the centrifuge.

VACUUM CRYSTALLIZER
Vacuum
Principle: Under vacuum the boiling point of a C
liquid reduces. So under vacuum a liquid boils under
its normal boiling point. If a warm saturated solution
Crystallize (A).
is introduced into a vessel in which a vacuum is
maintained and the feed temperature is above the Feed (B)
(reduced) boiling point of the solution then the
solution so introduced must flash (sudden
evaporation) and be cooled due to adiabatic Propeller (F)F
evaporation (taking the latent heat from the
solution). Cooling will cause supersaturation and Discharge pipe (D)
Pump (E)
thus crystallization. Evaporation will increase the yield.

Vacuum crystallizers are often operated continuously, but they can also be operated batch-wise.

Construction

A simple vacuum crystallizer contains no moving parts. The crystallizer is a cone-bottomed

vessel (A). The feed enters at any suitable point (B) of the crystallizer and the vapor leaves at
point C to go to the vacuum producing equipment. Under vacuum the feed flashes (rapid
evaporation) and due to ebullition (formation of bubbles) in the crystallizer the crystals are kept
in suspension until they become large enough to fall into the discharge pipe (D), from which they
are removed as slurry by a pump (E).

There is sometimes a tendency for the feed to short-circuit to the discharge pipe without being
flashed (i.e. the feed enters and directly flows into the discharge pipe). For this reason two
propellers (F) are installed in the crystallizer to keep the solution thoroughly stirred to prevent
the feed solution from reaching the discharge pipe without flashing.

KRYSTAL CRYSTALLIZER
Vacuum
Construction and working principle
Vapor head (A)
Here A is the vapor head, and B is the
crystallizing chamber. For the first time
solution is fed into the suction end of the Crystal growth
pump (C). Pump sends the feed solution to chamber (B) .
the heater or cooler (D). The feed then is
introduced in the vapor head (A). The vapor Heater / Cooler D
F
is discharged to a condenser and vacuum
pump. The operation is so controlled that
the crystals are not formed in the vessel A,
but the vessel A is prolonged into tube E
extended almost to the bottom of vessel B.
At the lower part of the vessel B the X Product
Feed outlet
crystals are formed and are suspended in
the liquid. The supersaturated liquid formed O
Pump
in nozzle E passes to vessel B and an
upward flow maintains the suspension at the bottom of vessel B.

At the bottom coarser crystals remain and becomes finer at the top. The coarser crystals are
drawn out form time to time through G. The finest crystals, remaining at the top flows again
through connection F to the pump which is sent again into the heater or cooled D.

Use:
Krystal crystallizer is preferred when large quantities of crystals of controlled size is required.
For example in sodium chloride and magnesium sulphate crystallization.

CAKING OF CRYSTALS
What is caking?

Caking can be defined as the process of formation of clumps or cakes when crystals are
improperly stored.

Crystal powders can absorbs moisture when the humidity of the air is above the critical humidity.
Below this critical humidity the crystals do not absorbs moisture while above the critical
humidity the crystals absorbs moisture and forms a saturated solution on the surface of the
crystals. When temperature of the crystals are cooled (due to some reason) or the water is
evaporated from the surface, the extra solute crystallize out and thus may form solid bridges in
between two adjacent crystals, called crystal bridges. Thus the crystal particles will join together
to form hard aggregate. This aggregates or lumps are called caking.

Problems of caking

After caking the flow properties of the powder decreases. Powder will not flow uniformly from
the hopper into the die-cavity of tablet punch machine. Capsule filling will not be uniform.
Filling of pouches will not be uniform.

Factors affecting caking

1. Size of the crystals: Smaller crystals have a greater tendency of caking than larger crystals
because powder of smaller crystals have less void so greater number of contact points. More
the number of contact points greater number of crystal bridges will be formed.
2. Shape of the crystals: Spherical shape posses the least possible points of contacts than any
other form. Hence, the distorted crystals tends to more caking than spherical particles.
3. Humidity: The higher the humidity of the atmosphere to which crystals are exposed, more
will be the rate of caking.
4. Time of exposure to moisture: The higher the time of exposure, the more will be the caking,
provided that the atmosphere has humidity more than critical humidity.
5. Impurities in the crystals: The crystals may be coated with impurities from the mother liquor.
This may increase the value of critical humidity. For example MgCl2 and CaCl2 alters the
critical humidity of NaCl crystals.
6. Melting points of crystals: If the melting point of the crystals are near room temperature then
at slightly high temperature they will melt and at low temperature they will fuse to form
crystals and thus increases caking.
7. Temperature fluctuations: When temperature is increased solubility of crystals increases.
Subsequent decrease of temperature will produce a supersaturated solution from which
crystals will be precipitated. So fluctuations of temperature produce crystals rapidly.

Prevention of caking
1. Crystals must be more spherical in shape, with least points of contact.
2. Crystals must be larger in size with more voids ad must be of a narrow size distribution (i.e.
must be more uniform in size).
3. Crystals are packed and stored in atmosphere where the humidity is less than critical
humidity.
4. Crystals may be coated with powdery inert material to prevent absorption of moisture like
NaCl is coated with magnesia (MgO) or tricalcium phosphate

TEXT / REFERENCE BOOKS

1. Treybal R.E., Mass Transfer Operations, 3rd Edition, McGraw Hill, 2009.

2. McCabe and Smith, Unit Operations of Chemical Engineering, 7th Edition, McGraw Hill,
2009.

3. Coulson J.M. and Richardson J.F., Chemical Engineering, 6th Edition, Pergamon Press, 2002.

4. Anantharaman N., MeeraSheriffa Begum K.M., Mass Transfer Theory and Practice, 1st

Edition, PHI, 2011.

 SCHOOL OF BIO AND CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

HEAT AND MASS TRANSFER FOR BIOLOGICAL SYSTEMS

SCHA1311

UNIT – 4 PRINCIPLES OF HEAT TRANSFER - SCHA1311

UNIT 4 PRINCIPLES OF HEAT TRANSFER

Introduction to various modes of heat transfer, Conduction- Fourier’s law of heat

conduction, thermal conductivity,conduction through liquids. Convection, individual and
overall heat transfer coefficient, LMTD, radiation.

Introduction
Heat transfer is a science, which deals with the flow of heat from a higher temperature to lower
temperature. Heat cannot be stored and it is defined as the energy in transit due to the difference
in the temperatures of the hot and cold bodies. The study of heat transfer not only explains how
the heat energy transports but also predicts about the rate of heat transfer. When a certain amount
of water is evaporated or condensed, the amount of heat transferred in either of the processes is
same. However, the rate of heat transfer in both the cases may be different.

At this point, it is very important to understand about the basic information that the phases of a
substance (solid, liquid, and gas) are associated with its energy content. In the solid phase, the
molecules or atoms are very closely packed to give a rigid structure (fig.1.1a). In the liquid
phase, sufficient thermal energy is present, which keeps the molecules sufficiently apart and as a
result the rigidity looses (fig.1.1b). In the gas phase, the presence of additional energy results in a
complete separation and the molecules or atoms are free to move anywhere in the space
(fig.1.1c). It must be noticed that whenever a change in phase occurs, a large amount of energy
involves in the transition.

Fig. 1.1: Relative molecular distance of different phases of a substance at a fixed

temperature (a) gas/vapour, (b) liquid, and (c) solid

As we are dealing with the heating and cooling of materials in almost our all the processes, the
heat transfer is an indispensable part of any of the industries. Therefore, heat transfer is a
common subject in many engineering disciplines, especially mechanical and chemical
engineering. Study of heat transfer has a vital role in the chemical process industries. Chemical
engineers must have a thorough knowledge of heat transfer principles and their applications.
The study of heat transfer is directed to (i) the estimation of rate of flow of energy as heat
through the boundary of a system both under steady and transient conditions, and (ii) the
determination of temperature field under steady and transient conditions, which also will provide
the information about the gradient and time rate of change of temperature at various locations
and time. i.e. T (x, y, z, τ) and dT/dx, dT/dy, dT/dz, dT/dτ etc. These two are interrelated, one
being dependent on the other. However explicit solutions may be generally required for one or
the other.

The basic laws governing heat transfer and their application are as below:

1. First law of thermodynamics postulating the energy conservation principle: This law
provides the relation between the heat flow, energy stored and energy generated in a given
system. The relationship for a closed system is: The net heat flow across the system bondary +
heat generated inside the system = change in the internal energy, of the system. This will
also apply for an open system with slight modifications.

The change in internal energy in a given volume is equal to the product of volume density and
specific heat ρcV and dT where the group ρcV is called the heat capacity of the system. The
basic analysis in heat transfer always has to start with one of these relations.

2. The second law of thermodynamics establishing the direction of energy transport as heat.
The law postulates that the flow of energy as heat through a system boundary will always be in
the direction of lower temperature or along the negative temperature gradient.

3. Newtons laws of motion used in the determination of fluid flow parameters.

4. Law of conservation of mass, used in the determination of flow parameters.

5. The rate equations as applicable to the particular mode of heat transfer.

There are three different modes in which heat may pass from a hot body to a cold one. These
modes are conduction, convention, and radiation. It should be noted that the heat transfer takes
place in combination of two or three modes in any of the real engineering application. In this
chapter, we will briefly discuss about the different modes of heat transfer along with the various
basic information that will help us as a building block for further study.

Mode of heat transfer

In this section, we will discuss about the three different modes of heat transfer. The discussion
will help us to understand about the conduction, convection, and radiation. Moreover, we would
be able to understand the basic difference between the three modes of heat transfer.

Conduction
Conduction is the transfer of heat in a continuous substance without any observable motion of
the matter. Thus, heat conduction is essentially the transmission of energy by molecular motion.
Consider a metallic rod being heated at the end and the other end of the rod gets heated
automatically. The heat is transported from one end to the other end by the conduction
phenomenon. The molecules of the metallic rod get energy from the heating medium and collide
with the neighbouring molecules. This process transfers the energy from the more energetic
molecules to the low energetic molecules. Thus, heat transfer requires a temperature gradient,
and the heat energy transfer by conduction occurs in the direction of decreasing temperature.
Figure 1.2 shows an illustration for the conduction, where the densely packed atoms of the rod
get energized on heating and vibration effect transfers the heat as described in fig.1.2.
 Fig.1.2: Different stages during conduction in a metallic rod

Convection
When a macroscopic particle of a fluid moves from the region of hot to cold region, it carries
with it a definite amount of enthalpy. Such a flow of enthalpy is known as convection.
Convection may be natural or forced. In natural convection, the movement of the fluid particles
is due to the buoyancy forces generated due to density difference of heated and colder region of
the fluid as shown in the fig.1.3a. Whereas, in forced convection the movement of fluid particles
from the heated region to colder region is assisted by some mechanical means too (eg., stirrer) as
shown in fig.1.3b.

Fig.1.3: Heat transfer through convection (a) natural, and (b) forced

Radiation
We have seen that a medium is required for the heat transfer in case of conduction and
convection. However, in case of radiation, electromagnetic waves pass through the empty space.
Electromagnetic waves travel at the velocity of light in vacuum. These waves are absorbed,
reflected, and/or transmitted by the matter, which comes in the path of the wave. We will limit
our discussion (in this NPTEL course) to the thermal radiation. Thermal radiation is the term
used to describe the electromagnetic radiation, which is observed to be emitted by the surface of
the thermally excited body. The heat of the Sun is the most obvious example of thermal
radiation.

There will be a continuous interchange of energy between two radiating bodies, with a net
exchange of energy from the hotter to the colder body as shown in the fig.1.4.

Fig.1.4: Heat transfer through radiation

Material properties of importance in heat transfer

Before understanding heat transfer laws, we have to understand various properties of the
material. This section is devoted to a brief discussion of some of the important properties of the
material.

Thermal conductivity
As discussed earlier, the heat conduction is the transmission of energy by molecular action.
Thermal conductivity is the property of a particular substance and shows the ease by which the
process takes place. Higher the thermal conductivity more easily will be the heat conduction
through the substance. It can be realized that the thermal conductivity of a substance would be
dependent on the chemical composition, phase (gas, liquid, or solid), crystalline structure (if
solid), temperature, pressure, and its homogeneity.
The thermal conductivity of various substances is shown in table-1.1 and table 1.2.

Table-1: Thermal conductivities of various substances at 0oC

Table-2: Thermal conductivity of mercury at three different phases
 The general results of the careful analysis of the table-1.1 and 1.2 are as follows,

 Thermal conductivity depends on the chemical composition of the substance.

 Thermal conductivity of the liquids is more than the gasses and the metals have the highest.
 Thermal conductivity of the gases and liquids increases with the increase in temperature.
 Thermal conductivity of the metal decreases with the increase in temperature.
 Thermal conductivity is affected by the phase change.

These differences can be explained partially by the fact that while in gaseous state, the molecules
of a substance are spaced relatively far away and their motion is random. This means that energy
transfer by molecular impact is much slower than in the case of a liquid, in which the motion is
still random but in liquids the molecules are more closely packed. The same is true concerning
the difference between the thermal conductivity of the liquid and solid phases. However, other
factors are also important when the solid state is formed.

Solid having a crystalline structure has high thermal conductivity than a substance in an
amorphous solid state. Metal, crystalline in structure, have greater thermal conductivity than
non-metal (refer table-1.1). The irregular arrangement of the molecules in amorphous solids
inhibits the effectiveness of the transfer of the energy by molecular impact. Therefore, the
thermal conductivity of the non-metals is of the order of liquids. Moreover, in solids, there is an
additional transfer of heat energy resulting from vibratory motion of the crystal lattice as a
whole, in the direction of decreasing temperature.

Many factors are known to influence the thermal conductivity of metals, such as chemical
composition, atomic structure, phase changes, grain size, temperature, and pressure. Out of the
above factors, the temperature, pressure, and chemical composition are the most important.
However, if we are interested in a particular material then only the temperature effects has to be
accounted for.

As per the previous discussion and the table it is now clear that the thermal conductivity of the
metal is directly proportional to the absolute temperature and mean free path of the molecules.
The mean free path decreases with the increase in temperature so that the thermal conductivity
decreases with the temperature. It should be noted that it is true for the pure metal, and the
presence of impurity in the metal may reverse the trend. It is usually possible to represent the
thermal conductivity of a metal by a linear relation k = ko(1 + bT), where ko is the thermal
conductivity of the metal at 0oC, Tis the absolute temperature, and b is a constant.

In general the thermal conductivity of the liquids is insensitive to the pressure if the pressure is
not very close to the critical temperature. Therefore, in liquids (as in solids) the temperature
effects on the thermal conductivity are generally considered. Liquids, in general, exhibit a
decreasing thermal conductivity with temperature. However, water is a notable exception. Water
has the highest thermal conductivity among the non-metallic liquids, with a maximum value
occurring at 450oC.

The thermal conductivity of a gas is relatively independent of pressure if the pressure is near 1
atm. Vapours near the saturation point show strong pressure dependence. Steam and air are of
great engineering importance. Steam shows irregular behaving rather showing a rather strong
pressure dependence for the thermal conductivity as well as temperature dependence.

The above discussions concerning thermal conductivity were restricted to materials composed of
homogeneous or pure substances. Many of the engineering materials encountered in practice are
not of this nature like building material, and insulating material. Some material may exhibit non-
isotropic conductivities. The non-isotropic material shows different conductivity in different
direction in the material. This directional preference is primarily the result of the fibrous nature
of the material like wood, asbestos etc.

Specific heat capacity

Now we know that the thermal conductivity facilitates the heat to propagate through the material
due to the temperature gradient. Similarly, specific heat capacity or specific heat is the capacity
of heat stored by a material due to variation in temperature. Thus the specific heat capacity (unit:
kJ/kg·oC) is defined as the amount of thermal energy required to raise the temperature of a unit
amount of material by 1 oC. Since heat is path dependent, so is specific heat. In general, the heat
transfer processes used in the chemical process plant are at constant pressure; hence the specific
heat capacity (co) is generally used.

Conduction: One Dimensional

The fundamentals of heat conduction were established over one and a half century and its
contribution goes to a French mathematician and physicist, Jean Baptiste Joseph Fourier. You
may be aware that any flow whether it is electricity flow, fluid flow, or heat flow needs a driving
force. The flow is proportional to the driving force and for various kinds of flows the driving
force is shown in the table 3.

Table 3. Various flows and their driving forces

Thus the heat flow per unit area per unit time (heat flux, ) can be represented by the following
relation,

where, proportionality constant k is the thermal conductivity of the material, T is the temperature
and x is the distance in the direction of heat flow. This is known as Fourier’s law of conduction.

The term steady-state conduction is defined as the condition which prevails in a heat conducting
body when temperatures at fixed points do not change with time. The term one-dimensional is
applied to a heat conduction problem when only one coordinate is required to describe the
distribution of temperature within the body. Such a situation hardly exists in real engineering
problems. However, by considering one-dimensional assumption the real problem is solved
fairly upto the accuracy of practical engineering interest.

Steady-state conduction through constant area

A simple case of steady-state, one-dimensional heat conduction can be considered through a flat
wall as shown in the fig.2.1.
 Fig.2.1: Steady-state conduction through a slab (constant area)

The flat wall of thickness dx is separated by two regions, the one region is at high temperature
(T1 ) and the other one is at temperature T2 . The wall is very large in comparison of the thickness
so that the heat losses from the edges are negligible. Consider there is no generation or
accumulation of the heat in the wall and the external surfaces of the wall are at isothermal
temperatures T1 and T2 . The area of the surface through which the heat transfer takes place is A.
Then the eq.2.2 can be written as,

The negative sign shows that the heat flux is from the higher temperature surface to the lower
temperature surface and is the rate of heat transfer through the wall.

Now if we consider a plane wall made up of three different layers of materials having different
thermal conductivities and thicknesses of the layers, the analysis of the conduction can be done
as follows.

Consider the area (A) of the heat conduction (fig.2.2) is constant and at steady state the rate of
heat transfer from layer-1 will be equal to the rate of heat transfer from layer-2. Similarly, the
rate of heat transfer through layer-2 will be equal to the rate of heat transfer through layer-3. If
we know the surface temperatures of the wall are maintained at T1 and T2 as shown in the fig.2.2,
the temperature of the interface of layer1 and layer 2 is assumed to be at T' and the interface of
layer-2 and layer-3 asT".
 Fig.2.2: Heat conduction through three different layers

The rate of heat transfer through layer-1 to layer-2 will be,

and,
The rate of heat transfer through layer 2 to layer 3 will be,

and,
The rate of heat transfer through layer 3 to the other side of the wall,

On adding the above three equations,

Where, R represents the thermal resistance of the layers. The above relation can be written
analogous to the electrical circuit as,

Fig 2.3: Equivalent electrical circuit of the fig.2.2

The wall is composed of 3-different layers in series and thus the total thermal resistance was
represented by R (= R1 + R2 + R3 ). The discussed concept can be understood by the illustrations
shown below.

The unit of the various parameters used above is summarized as follows,

Lecture 4

Illustration 2.1
The two sides of a wall (2 mm thick, with a cross-sectional area of 0.2 m2) are maintained at
30oC and 90oC. The thermal conductivity of the wall material is 1.28 W/(m· oC). Find out the
rate of heat transfer through the wall?
Solution 2.1
Assumptions
1. Steady-state one-dimensional conduction
2. Thermal conductivity is constant for the temperature range of interest
3. The heat loss through the edge side surface is insignificant
4. The layers are in perfect thermal contact
Given,

Fig. 2.4: Illustration 2.1

Illustration 2.2
Solution 2.2
Assumptions:
1. Steady-state one-dimensional conduction.
2. Thermal conductivity is constant for the temperature range of interest.
3. The heat loss through the edge side surface is insignificant.
4. The layers are in perfect thermal contact.

On putting all the known

values,

Fig. 2.5: Illustration 2.2

Thus,
The previous discussion showed the resistances of different layers. Now to understand the
concept of equivalent resistance, we will consider the geometry of a composite as shown in
fig.2.6a.

The wall is composed of seven different layers indicated by 1 to 7. The interface temperatures of
the composite are T1 to T5 as shown in the fig.2.6a. The equivalent electrical circuit of the above
composite is shown in the fig 2.6b below,
 Fig.2.6. (a) Composite wall, and (b) equivalent electrical circuit

The equivalent resistance of the wall will be,

where,

Therefore, at steady state the rate of heat transfer through the composite can be represented by,

where, R is the equivalent resistance.

Illustration 2.3
Consider a composite wall containing 5-different materials as shown in the fig. 2.7. Calculate the
rate of heat flow through the composite from the following data?

Solution 2.3
Assumptions:
1. Steady-state one-dimensional conduction.
2. Thermal conductivity is constant for the temperature range of interest.
3. The heat loss through the edge side surface is insignificant.
4. The layers are in perfect thermal contact.
5. Area in the direction of heat flow is 1 m2.

The height of the first layer is 4 m (h1 = h2 + h3 ).

The equivalent circuit diagram of the above composite is,
On calculating equivalent resistance with the given data (Note: thickness of layer 2 = thickness
of layer 3 and thickness of layer 4 = thickness of layer 5, in the heat flow direction),
Fig. 2.7: Composite of illustration 2.3; (a) composite, (b) corresponding electrical
circuit

Thus the heat flow rate through the composite,

2.2 Thermal contact resistance

In the previous discussion, it was assumed that the different layers of the composite have perfect
contact between any two layers. Therefore, the temperatures of the layers were taken same at the
plane of contact. However, in reality it rarely happens, and the contacting surfaces are not in
perfect contact or touch as shown in the fig.2.8(a). It is because as we know that due to the
roughness of the surface, the solid surfaces are not perfectly smooth. Thus when the solid
surfaces are contacted the discrete points of the surfaces are in contact and the voids are
generally filled with the air. Therefore, the heat transfer across the composite is due to the
parallel effect of conduction at solid contact points and by convection or probably by radiation
(for high temperature) through the entrapped air. Thus an apparent temperature drop may be
assumed to occur between the two solid surfaces as shown in the fig.2.8b. If TI and TII are the
theoretical temperature of the plane interface, then the thermal contact resistance may be defined
as,

where Rcrepresents the thermal contact resistance.

The utility of the thermal contact resistance (Rc ) is dependent upon the availability of the
reliable data. The value of Rc depends upon the solids involved, the roughness factor, contact
pressure, material occupying the void spaces, and temperature. The surface roughness of a
properly smooth metallic surface is in the order of micrometer. The values of Rc generally
obtained by the experiments. However, there are certain theories which predict the effect of the
various parameters on the Rc.

It can be seen in the fig.2.8, that the two main contributors to the heat transfer are (i) the
conduction through entrapped gases in the void spaces and, (ii) the solid-solid conduction at the
contact points. It may be noted that due to main contribution to the resistance will be through
first factor because of low thermal conductivity of the gas.
 Fig.2.8 (a) Contacting surfaces of two solids are not in perfect contact, (b) temperature
drop due to imperfect contact

If we denote the void area in the joint by Av and contact area at the joint by Ac, then we may write
heat flow across the joint as,

where, thickness of the void space and thermal conductivity of the fluid (or gas) is represented
by lgand kf, respectively. It was assumed that lg/2 is the thickness of solid-I and solid-II for
evenly rough surfaces.

Lecture 62.3 Steady-state heat conduction through a variable area

It was observed in the previous discussion that for the given plane wall the area for heat transfer
was constant along the heat flow direction. The plane solid wall was one of the geometries but if
we take some other geometry (tapered plane, cylindrical body, spherical body etc.) in which the
area changes in the direction of heat flow. Now we will consider geometrical configuration
which will be mathematically simple and also of great engineering importance like hollow
cylinder and hollow sphere. In these cases the heat transfer area varies in the radial direction of
heat conduction. We will take up both the cases one by one in the following sections.

2.3.1 Cylinder
Consider a hollow cylinder as shown in the fig.2.9a. The inner and outer radius is represented
by riand ro , whereas Ti and To (Ti > To ) represent the uniform temperature of the inner and outer
wall, respectively.

Fig. 2.9. (a) Hollow cylinder, (b) equivalent electrical circuit

Consider a very thin hollow cylinder of thicknessdr in the main geometry (fig.2.9a) at a radial
distancer. If dr is small enough with respect to r, then the area of the inner and outer surface of
the thin cylinder may be considered to be of same area. In other words, for very small dr with
respect to r, the lines of heat flow may be considered parallel through the differential element in
radial outward direction.

We may ignore the heat flow through the ends if the cylinder is sufficiently large. We may thus
eliminate any dependence of the temperature on the axial coordinate and for one dimensional
steady state heat conduction, the rate of heat transfer for the thin cylinder,
Where dT is the temperature difference between the inner and outer surface of the thin cylinder
considered above and k is the thermal conductivity of the cylinder.
On rearranging,

To get the heat flow through the thick wall cylinder, the above equation can be integrated
between the limits,

On solving,

Where , and the careful analysis of the above equation shows that the
expression is same as for heat flow through the plane wall of thickness (ro–ri ) except the
expression for the area. The ALM is known as log mean area of the cylinder, whose length

is L and radius is rLM (= ). The fig.2.9b shows the equivalent electrical circuit of the
fig.2.9b.

Now we have learnt that how to represent the analogous electrical circuit for the cylindrical case.
It will provide the building block for the composite cylinders similar to the plane composite we
have learnt earlier. The following fig.2.10a shows a composite cylinder with 4-layers of solid
material of different inner and outer diameter as well as thermal conductivity. The equivalent
electrical circuit is shown below in fig.2.10b.
 (a)

(b)

Fig.2.10.(a) Four layer composite hollow cylinder, (a) equivalent electrical circuit

The total heat transfer at steady-state will be,

where R1 , R2 , R3 , and R4 are represented in the fig.2.10b.

2.3.2 Sphere
The rate of heat transfer through a hollow sphere can be determined in a similar manner as for
cylinder. The students are advised to derive the following expression shown below.

The final expression for the rate of heat flow is,

convection.

The rate of heat transfer in a solid body or medium can be calculated by Fourier’s law.
Moreover, the Fourier law is applicable to the stagnant fluid also. However, there are hardly a
few physical situations in which the heat transfer in the fluid occurs and the fluid remains
stagnant. The heat transfer in a fluid causes convection (transport of fluid elements) and thus the
heat transfer in a fluid mainly occurs by convection.

3.1 Principle of heat flow in fluids and concept of heat transfer coefficient
It is learnt by day-to-day experience that a hot plate of metal will cool faster when it is placed in
front of a fan than exposed to air, which is stagnant. In the process, the heat is convected away,
and we call the process convective heat transfer. The term convective refers to transport of heat
(or mass) in a fluid medium due to the motion of the fluid. Convective heat transfer, thus,
associated with the motion of the fluid. The term convection provides an intuitive concept of the
heat transfer process. However, this intuitive concept must be elaborated to enable one to arrive
at anything like an adequate analytical treatment of the problem.

It is well known that the velocity at which the air blows over the hot plate influences the heat
transfer rate. A lot of questions come into the way to understand the process thoroughly. Like,
does the air velocity influence the cooling in a linear way, i.e., if the velocity is doubled, will the
heat transfer rate double. We should also suspect that the heat-transfer rate might be different if
we cool the plate with some other fluid (say water) instead of air, but again how much difference
would there be? These questiones may be answered with the help of some basic analysis in the
later part of this module.

The physical mechanism of convective heat transfer for the problem is shown in fig.3.1.
 Fig. 3.1: Convective heat transfer from a heated wall to a fluid

Consider a heated wall shown in fig.3.1. The temperature of the wall and bulk fluid is denoted
by respectively. The velocity of the fluid layer at the wall will be zero. Thus the
heat will be transferred through the stagnant film of the fluid by conduction only. Thus we can
compute the heat transfer using Fourier’s law if the thermal conductivity of the fluid and the
fluid temperature gradient at the wall is known. Why, then, if the heat flows by conduction in
this layer, do we speak of convective heat transfer and need to consider the velocity of the fluid?
The answer is that the temperature gradient is dependent on the rate at which the fluid carries the
heat away; a high velocity produces a large temperature gradient, and so on. However, it must be
remembered that the physical mechanism of heat transfer at the wall is a conduction process.

It is apparent from the above discussion that the prediction of the rates at which heat is convected
away from the solid surface by an ambient fluid involves thorough understanding of the
principles of heat conduction, fluid dynamics, and boundary layer theory. All the complexities
involved in such an analytical approach may be lumped together in terms of a single parameter
by introduction of Newton’s law of cooling,

where, h is known as the heat transfer coefficient or film coefficient. It is a complex function of
the fluid composition and properties, the geometry of the solid surface, and the hydrodynamics
of the fluid motion.

If k is the thermal conductivity of the fluid, the rate of heat transfer can be written directly by
following the Fourier’s law. Therefore, we have,
where, is the temperature gradient in the thin film where the temperature gradient is
linear.

On comparing eq.3.1 and 3.2, we have,

It is clear from the above expression that the heat transfer coefficient can be calculated
if k and δ are known. Though the k values are easily available but the δ is not easy to determine.
Therefore, the above equation looks simple but not really easy for the calculation of real
problems due to non-linearity of k and difficulty in determining δ. The heat transfer coefficient is
important to visualize the convection heat transfer phenomenon as discussed before. In fact, δ is
the thickness of a heat transfer resistance as that really exists in the fluid under the given
hydrodynamic conditions. Thus, we have to assume a film of δ thickness on the surface and the
heat transfer coefficient is determined by the properties of the fluid film such as density,
viscosity, specific heat, thermal conductivity etc. The effects of all these parameters are lumped
or clubbed together to define the film thickness. Henceforth, the heat transfer coefficient (h) can
be found out with a large number of correlations developed over the time by the researchers.
These correlations will be discussed in due course of time as we will proceed through the
modules. Table 3.1 shows the typical values of the convective heat transfer coefficient under
different situations.

Table-3.1: Typical values of h under different situations

3.2 Individual and overall heat transfer coefficient
If two fluids are separated by a thermally conductive wall, the heat transfer from one fluid to
another fluid is of great importance in chemical engineering process plant. For such a case the
rate of heat transfer is done by considering an overall heat transfer coefficient. However, the
overall heat transfer coefficient depends upon so many variables that it is necessary to divide it
into individual heat transfer coefficients. The reason for this becomes apparent if the above
situation can be elaborated as discussed in the following sub-sections.

3.2.1 Heat transfer between fluids separated by a flat solid wall

As shown in fig.3.2, a hot fluid is separated by solid wall from a cold fluid. The thickness of the
solid wall is l, the temperature of the bulk of the fluids on hot and cold sides are Th and Tc,
respectively. The average temperature of the bulk fluid is T1 and T4, for hot and cold fluid,
respectively. The thicknesses of the fictitious thin films on the hot and cold sides of the flat solid
are shown by δ1 and δ2. It may be assumed that the Reynolds numbers of both the fluids are
sufficiently large to ensure turbulent flow and the surfaces of the solid wall are clean.

Fig.3.2. Real temperature profile

It can be seen that the temperature gradient is large near the wall (through the viscous sublayer),
small in the turbulent core, and changes rapidly in the buffer zone (area near the interface of
sublayer and bulk fluid). The reason was discussed earlier that the heat must flow through the
viscous sublayer by conduction, thus a steep temperature gradient exists because of the low
temperature gradient of most of the fluids.

The average temperatures of the warm bulk fluid and cold bulk fluids are slightly less than the
maximum temperature Th (bulk temperature of hot fluid) and slightly more than the minimum
temperature Tc (bulk temperature of cold fluid), respectively. The average temperatures are
shown by T1 and T4, for the hot and cold fluid streams, respectively.

Figure 3.3 shows the simplified diagram of the above case, where T2 and T3 are the temperatures
of the fluid wall interface.

Fig.3.3. Simplified temperature profile for fig.3.2

If the thermal conductivity of the wall is k, and the area of the heat transfer is A, the electrical
analogy of the fig.3.3 can be represented by fig.3.4, where h1 and h2 are the individual heat
transfer coefficient of the hot and cold side of the fluid.
 Fig.3.4. Equivalent electrical circuit for fig. 3.3

Considering that the heat transfer is taking place at the steady-state through a constant area and
the heat loss from other faces are negligible, then the rate of heat transfer on two sides of the wall
will be represented by eq. 3.4-3.6.

Rate of heat transfer from the hot fluid to the wall,

Rate of heat transfer through the wall,

Rate of heat transfer from the wall to cold fluid,

At steady state, the rate of heat transfers are same and can be represented
by . Therefore,

On adding equations (3.7 to 3.9)

where,

Thus,

The quantity is called the overall heat transfer coefficient (can be calculated if
the are known). Thus from the system described is established that the overall
heat transfer coefficient is the function of individual heat transfer coefficient of the fluids on the
two sides of the wall, as well as the thermal conductivity of the flat wall. The overall heat
transfer coefficient can be used to introduce the controlling term concept. The controlling
resistance is a term which possesses much larger thermal resistance compared to the sum of the
other resistances. At this point it may be noted that in general the resistance offered by the solid
wall is much lower. Similarly, if a liquid and a gas are separated by a solid wall the resistance
offered by the gas film may generally be high.

he steady state temperature distribution in a wall is , where x (in meter) is the position in the
wall and T is the temperature (in oC). The thickness of the wall is 0.2 m and the thermal
conductivity of the wall is 1.2 (W/m·oC). The wall dissipates the heat to the ambient at 30 oC.
Calculate the heat transfer coefficient at the surface of the wall at 0.2 m.

Solution 3.1
The rate of heat transfer through the wall by conduction will be equal to the rate of heat transfer
from the surface to the ambient by convention at steady state,

Rate of heat transfer by conduction at x=0.2 is given by,

where Ta is the ambient temperature.

On putting the values and solving,

Log mean temperature difference (LMDT):

The log mean temperature difference (LMTD) is used to determine the temperature driving force
for heat transfer in flow systems, most notably in heat exchangers. The LMTD is a logarithmic
average of the temperature difference between the hot and cold streams at each end of the
exchanger. The larger the LMTD, the more heat is transferred. The use of the LMTD arises
straightforwardly from the analysis of a heat exchanger with constant flow rate and fluid thermal
properties.

We assume that a generic heat exchanger has two ends (which we call "A" and "B") at which the
hot and cold streams enter or exit on either side; then, the LMTD is defined by the logarithmic
mean as follows:

where ΔTA is the temperature difference between the two streams at end A, and ΔTB is the
temperature difference beween the two streams at end B.

This equation is valid both for parallel flow, where the streams enter from the same end, and for
counter-current flow, where they enter from different ends.

Once calculated, the LMTD is usually applied to calculate the heat transfer in an exchanger
according to the simple equation:
 Where Q = Heat transfer

 Once calculated, the LMTD is usually applied to calculate the heat transfer in an
exchanger according to the simple equation:

Where Q is the exchanged heat duty (in watts), U is the heat transfer coefficient (in watts per
kelvin per square meter) and A is the exchange area. Note that estimating the heat transfer
coefficient may be quite complicated.

It is to be noted that the following assumption have been considered for developing LMTD,

1. The overall heat transfer coefficient is constant throughout the exchanger

2. In case any fluid undergoes for phase change (e.g., in condenser), the phase change occurs
throughout the heat exchanger and the constant fluid temperature prevails throughout the
exchanger.
3. The specific heat and mass flow rate and hence the heat capacity rate, of each fluid is constant.
4. No heat is lost in to the surroundings.
5. There is no conduction in the direction of flow neither in the fluids nor in the tube or shell walls.
6. Each of the fluids may be characterized by a single temperature, at any cross section in the heat
exchanger that is ideal transverse mixing in each fluid is presumed.

FT, the LMTD correction factor can be directly obtained from available charts in the literature.
These charts were prepared from the results obtained theoretically by solving the temperature
distribution in multi-pass heat exchangers.

Figures 8.12 and 8.13 show the two generally used heat exchangers and their corresponding plots
for finding FT. It may be noted that the given figures have the representative plots and any
standard book on heat transfer may be consulted for the accurate results.
Fig. 8.12: FT plot for 1-2 exchanger; t: cold fluid in the tube; T: hot fluid in the shell; 1:
inlet; 2: outlet
 Fig. 8.13: FT plot for 2-4 exchanger; t: cold fluid in the tube; T: hot fluid in the shell; 1:
inlet; 2: outlet

It should be noted that in case of condensation or evaporation the correction factor becomes
unity (FT =1). While designing a heat exchanger, the rule of thumb is that the FT should not be
less than 0.8.

RADIATION

Now, if we observe the heat transfer from the Sun to the earth atmosphere, we can understand
that there is no medium exists between the source (the Sun) and the sink (earth atmosphere).
However, still the heat transfer takes place, which is entirely a different energy transfer
mechanism takes place and it is called thermal radiation.

Thermal radiation is referred when a body is heated or exhibits the loss of energy by radiation.
However, more general form “radiation energy” is used to cover all the other forms. The
emission of other form of radiant energy may be caused when a body is excited by oscillating
electrical current, electronic bombardment, chemical reaction etc. Moreover, when radiation
energy strikes a body and is absorbed, it may manifest itself in the form of thermal internal
energy, a chemical reaction, an electromotive force, etc. depending on the nature of the incident
radiation and the substance of which the body is composed.

In this chapter, we will concentrate on thermal radiation (emission or absorption) that on

radiation produced by or while produces thermal excitation of a body.

There are many theories available in literature which explains the transport of energy by
radiation. However, a dual theory is generally accepted which enables to explain the radiant
energy in the characterisation of a wave motion (electromagnetic wave motion) and
discontinuous emission (discrete packets or quanta of energy).

An electromagnetic wave propagates at the speed of light (3×10 8 m/s). It is characterised by its
wavelength λ or its frequency ν related by

c = λv (7.1)

Emission of radiation is not continuous, but occurs only in the form of discrete quanta. Each
quantum has energy

E = hv (7.2)

where, = 6.6246×10-34 J.s, is known as Planck’s constant.

Table 7.1 shows the electromagnetic radiation covering the entire spectrum of wavelength

Table 7.1: Electromagnetic radiation for entire spectrum of wavelength

 Type Band of wavelength (µm)

Cosmic rays upto 4×10⁻7

Gamma rays 4×10⁻7 to 1.4×10⁻4

X-rays 1×10⁻5 to 2×10⁻2

Ultraviolet rays 5×10⁻3 to 3.9×10⁻1

Visible light 3.9×10⁻1to 7.8×10⁻1

Infrared rays 7.8×10⁻1 to 1×103

Thermal radiation 1×10⁻1 to 1×102

Microwave, radar, radio waves 1×103 to 5×1010

It is to be noted that the above band is in approximate values and do not have any sharp
boundary.

7.1 Basic definition pertaining to radiation

Before we further study about the radiation it would be better to get familiarised with the basic
terminology and properties of the radiant energy and how to characterise it.

As observed in the table 7.1 that the thermal radiation is defined between wavelength of about
1×10-1 and 1×102 μm of the electromagnetic radiation. If the thermal radiation is emitted by a
surface, which is divided into its spectrum over the wavelength band, it would be found that the
radiation is not equally distributed over all wavelength. Similarly, radiation incident on a system,
reflected by a system, absorbed by a system, etc. may be wavelength dependent. The dependence
on the wavelength is generally different from case to case, system to system, etc. The wavelength
dependency of any radiative quantity or surface property will be referred to as a spectral
dependency. The radiation quantity may be monochromatic (applicable at a single wavelength)
or total (applicable at entire thermal radiation spectrum). It is to be noted that radiation quantity
may be dependent on the direction and wavelength both but we will not consider any directional
dependency. This chapter will not consider directional effect and the emissive power will always
used to be (hemispherical) summed overall direction in the hemisphere above the surface.

7.1.1 Emissive power

It is the emitted thermal radiation leaving a system per unit time, per unit area of surface. The
total emissive power of a surface is all the emitted energy, summed over all the direction and all
wavelengths, and is usually denoted as E. The total emissive power is found to be dependent
upon the temperature of the emitting surface, the subsystem which this system is composed, and
the nature of the surface structure or texture.
The monochromatic emissive power Eλ, is defined as the rate, per unit area, at which the surface
emits thermal radiation at a particular wavelength λ. Thus the total and monochromatic
hemispherical emissive power are related by

(7.3)

and the functional dependency of Eλ on λ must be known to evaluate E.

7.1.2 Radiosity
It is the term used to indicate all the radiation leaving a surface, per unit time and unit area.

(7.4)

where, J and Jλ are the total and monochromatic radiosity.

The radiosity includes reflected energy as well as original emission whereas emissive power
consists of only original emission leaving the system. The emissive power does not include any
energy leaving a system that is the result of the reflection of any incident radiation.

7.1.3 Irradiation

It is the term used to denote the rate, per unit area, at which thermal radiation is incident upon a
surface (from all the directions). The irradiative incident upon a surface is the result of emission
and reflection from other surfaces and may thus be spectrally dependent.

(7.5)

where, G and Gλ are the total and monochromatic irradiation.

Reflection from a surface may be of two types specular or diffusive as shown in fig.7.1.

Fig. 7.1: (a) Specular, and (b) diffusive radiation

Thus,

J = E + ρG (7.6)

7.1.4 Absorptivity, reflectivity, and transmitting

The emissive power, radiosity, and irradiation of a surface are inter-related by the reflective,
absorptive, and transmissive properties of the system.
When thermal radiation is incident on a surface, a part of the radiation may be reflected by the
surface, a part may be absorbed by the surface and a part may be transmitted through the surface
as shown in fig.7.2. These fractions of reflected, absorbed, and transmitted energy are interpreted
as system properties called reflectivity, absorptivity, and transmissivity, respectively.

Fig. 7.2: Reflection, absorption and transmitted energy

Thus using energy conservation,

(7.7)

(7.7)

where, are total reflectivity, total absorptivity, and total transmissivity. The
subscript λ indicates the monochromatic property.

In general the monochromatic and total surface properties are dependent on the system
composition, its roughness, and on its temperature.

Monochromatic properties are dependent on the wavelength of the incident radiation, and the
total properties are dependent on the spectral distribution of the incident energy.
Most gases have high transmissivity, i.e. (like air at atmospheric
pressure). However, some other gases (water vapour, CO2 etc.) may be highly absorptive to
thermal radiation, at least at certain wavelength.

Most solids encountered in engineering practice are opaque to thermal radiation Thus
for thermally opaque solid surfaces,

ρ+α=1 (7.6)

Another important property of the surface of a substance is its ability to emit radiation. Emission
and radiation have different concept. Reflection may occur only when the surface receives
radiation whereas emission always occurs if the temperature of the surface is above the absolute
zero. Emissivity of the surface is a measure of how good it is an emitter.

7.2 Blackbody radiation

In order to evaluate the radiation characteristics and properties of a real surface it is useful to
define an ideal surface such as the perfect blackbody. The perfect blackbody is defined as one
which absorbs all incident radiation regardless of the spectral distribution or directional
characteristic of the incident radiation.

A blackbody is black because it does not reflect any radiation. The only radiation leaving a
blackbody surface is original emission since a blackbody absorbs all incident radiation. The
emissive power of a blackbody is represented by , and depends on the surface temperature only.

Fig. 7.3: Example of a near perfect blackbody

It is possible to produce a near perfect blackbody as shown in fig.7.3.

Figure 7.2 shows a cavity with a small opening. The body is at isothermal state, where a ray of
incident radiation enters through the opening will undergo a number of internal reflections. A
portion of the radiation absorbed at each internal reflection and a very little of the incident beam
ever find the way out through the small hole. Thus, the radiation found to be evacuating from the
hole will appear to that coming from a nearly perfect blackbody.

7.2.1 Planck’s law

A surface emits radiation of different wavelengths at a given temperature (theoretically zero to
infinite wavelengths). At a fixed wavelength, the surface radiates more energy as the temperature
increases. Monochromatic emissive power of a blackbody is given by eq.7.10.

(7.7)

where, h = 6.6256 X 10-34 JS; Planck’s constant

c = 3 X 108 m/s; speed of light
T = absolute temperature of the blackbody
λ = wavelenght of the monochromatic radiation emitted
k = Boltzmann constant

Equation 7.10 is known as Planck’s law. Figure 7.4 shows the representative plot for Planck’s
distribution.
 Fig. 7.4: Representative plot for Planck’s distribution

7.2.2 Wien’s law

Figure 7.4 shows that as the temperature increases the peaks of the curve also increases and it
shift towards the shorter wavelength. It can be easily found out that the wavelength
corresponding to the peak of the plot (λmax) is inversely proportional to the temperature of the
blackbody (Wein’s law) as shown in eq. 7.11.

λmax T = 2898 (7.11)

Now with the Wien’s law or Wien’s displacement law, it can be understood if we heat a body,
initially the emitted radiation does not have any colour. As the temperature rises the λ of the
radiation reach the visible spectrum and we can able to see the red colour being height λ (for red
colour). Further increase in temperature shows the white colour indicating all the colours in the
light.

7.2.3 The Stefan-Boltzmann law for blackbody

Josef Stefan based on experimental facts suggested that the total emissive power of a blackbody
is proportional to the fourth power of the absolute temperature. Later, Ludwig Boltzmann
derived the same using classical thermodynamics. Thus the eq. 7.12 is known as Stefan-
Boltzmann law,
 Eb = σT4 (7.12)

where, Eb is the emissive power of a blackbody, T is absolute temperature, and σ (= 5.67 X 10-
8
W/m2/K4) is the Stefan-Boltzmann constant.

The Stefan-Boltzmann law for the emissive power gives the total energy emitted by a blackbody
defined by eq.7.3.

7.2.4 Special characteristic of blackbody radiation

It has been shown that the irradiation field in an isothermal cavity is equal to Eb. Moreover, the
irradiation was same for all planes of any orientation within the cavity. It may then be shown that
the intensity of the blackbody radiation, Ib, is uniform. Thus, blackbody radiation is defined as,

Eb = πIb (7.13)

where, is the total intensity of the radiation and is called the spectral
radiation intensity of the blackbody.

7.2.5 Kirchhoff’s law

Consider an enclosure as shown in fig.7.2 and a body is placed inside the enclosure. The radiant
heat flux (q) is incident onto the body and allowed to come into temperature equilibrium. The
rate of energy absorbed at equilibrium by the body must be equal to the energy emitted.

where, E is the emissive power of the body, is absorptivity of the of the body at equilibrium
temperature, and A is the area of the body.

Now consider the body is replaced by a blackbody i.e. E → Eb and = 1, the equation 7.14
becomes

Eb= q (7.15)

Dividing eq. 7.14 by eq.7.15,

 (7.16)

At this point we may define emissivity, which is a measure of how good the body is an emitter as
compared to blackbody. Thus the emissivity can be written as the ratio of the emissive power to
that of a blackbody,

(7.17)

On comparing eq.7.16 and eq.7.17, we get

(7.18)

Equation 7.18 is the Kirchhoff’s law, which states that the emissivity of a body which is in
thermal equilibrium with its surrounding is equal to its absorptivity of the body. It should be
noted that the source temperature is equal to the temperature of the irradiated surface. However,
in practical purposes it is assumed that emissivity and absorptivity of a system are equal even if
it is not in thermal equilibrium with the surrounding. The reason being the absorptivity of most
real surfaces is relatively insensitive to temperature and wavelength. This particular assumption
leads to the concept of grey body. The emissivity is considered to be independent of the
wavelength of radiation for grey body.

7.3 Grey body

If grey body is defined as a substance whose monochromatic emissivity and absorptivity are
independent of wavelength. A comparative study of grey body and
blackbody is shown in the table 7.2.

Table-7.2: Comparison of grey and blackbody

Blackbody Grey body

Ideal body Ideal body
Emissivity (∈) is independent of Emissivity (∈) is independent of
wavelength wavelength
Absorptivity (α) is independent of Absorptivity (α) is independent of
wavelength wavelength
ε=1 ε<1
α=1 α<1
Illustration 7.1
The surface of a blackbody is at 500 K temperature. Obtain the total emissive power, the
wavelength of the maximum monochromatic emissive power.

Solution 7.1

Using eq. 7.12, the total emissive power can be calculated,

Eb = σT4

where, σ (= 5.67 X 10-8 W/m2/K4) is the Stefan-Boltzmann constant. Thus at 500 K,

Eb = (5.67 X 10-8)(50004) W/m2

Eb = 354.75 W/m2

The wavelength of the maximum monochromatic emissive power can be obtained from the
Wien’s law (eq. 7.11),

λmaxT = 2898

7.4 Radiative heat exchanger between surfaces

Till now we have discussed fundamental aspects of various definitions and laws. Now we will
study the heat exchange between two or more surfaces which is of practical importance. The two
surfaces which are not in direct contact, exchanges the heat due to radiation phenomena. The
factors those determine the rate of heat exchange between two bodies are the temperature of the
individual surfaces, their emissivities, as well as how well one surface can see the other surface.
The last factor is known as view factor, shape factor, angle factor or configuration factor.

7.4.1 View factor

In this section we would like to find the energy exchange between two black surfaces having
area A1and A2, respectively, and they are at different temperature and have arbitrary shape and
orientation with respect to each other. In order to find the radiative heat exchange between the
bodies we have to first define the view factor as

F12 = fraction of the energy leavings surface 1 which reaches surface 2

F21 = fraction of the energy leaving surface 2 which reaches surface 1 or in general,
Fmn = fraction of the energy leaving surface m which raches surface n
Thus the energy leaving surface 1 and arriving at surface 2 is E b1A1 F12 and the energy leaving
surface 2 and arriving at surface 1 is Eb2A2F21. All the incident radiation will be absorbed by the
blackbody and the net energy exchange will be,

Q = Eb1A1F12 - Eb2A2F21

At thermal equilibrium between the surfaces Q12 = 0 and Eb1 = Eb2, thus

0 = Eb1 (A1F12 - A2F21)

A1 F12 - A2F21 (7.19)

Equation 7.19 is known as reciprocating relation, and it can be applied in general way for any
blackbody surfaces.

AiFij - AjFji (7.20)

Though the relation is valid for blackbody it may be applied to any surface as long as diffuse
radiation is involved.

7.4.1.1 Relation between view factors

In this section we will develop some useful relation of view factor considering fig. 7.5

Fig. 7.5: Exchange of energy between area A1 and A2 (A is area of blackbody)

View factor for radiation from A1 to the combined area A2,

F12 = F13 + F14 (7.21)

and using the reciprocating relations for surface 1 and 4,

 A1F14 = A4F41 (7.22)

Using eq. 7.21 and 7.22,

Thus the unknown view factor F14 can be estimated if the view factors F12 and F13, as well as
their areas are (A1, A2) known.

Now, consider a flat plate (for eg.) which is emitting the radiation, it can be understood that the
radiation of the flat plat cannot fall on its own surface (partly or fully). Such kind or surfaces are
termed as “not able to see itself”. In such situations,

F11 = F22 = F33 = F44 = 0

However, if the surface can see itself like concave curved surfaces, which may thus see
themselves and then the shape factor will not be zero in those cases.

Another property of the shape factor is that when the surface is enclosed, then the following
relation holds,

(7.23)

where, Fij is the fraction of the total energy leaving surface i which arrives at surface j.

In case of N-walled enclosure, some of the view factors may be evaluated from the knowledge of
the rest and the total N2 view factors may be represented in square matrix form shown below,

Illustration 7.2
A pipe having 10 cm of diameter is carrying saturated steam at 8 bar of absolute pressure. The
pipe runs through a room. The wall of the room is at 300 oK. A portion around 1 m of the pipe
insulation is damaged and exposed to the room atmosphere. Calculate the net rate of heat loss
from the pipe by radiation.

Solution 7.2

The emissivity of the pipe surface is not given so it may be considered black. Moreover, since
the room may be big compared to the surface area of the pipe, the room may also be considered
to be a blackbody.
We can write F11 + F12 = 1.
The value of F11 = 0, as the pipe cannot see itself.
Thus F12, the view factor (1-pipe, 2-room) will be 1.
The net rate heat loss due to radiation,

Tpipe can be obtained by the temperature of the steam at the prevailing pressure with the help of
steam table = 450 K.

σ (= 5.67 X 10-8 W/m2/K4)

On putting the value,

Q12 = {π(0.1)(1)}(1)(1)(5.67 X 10-8){4504 - 3004}

Q12 = 586 W

7.5 Heat exchange between non blackbodies

Evaluation of radiative heat transfer between black surfaces is relatively easy because in case of
blackbody all the radiant energy which strikes the surface is absorbed. However, finding view
factor is slightly complex, but once it can be done, finding heat exchange between the black
bodies is quite easy.

When non blackbodies are involved the heat transfer process becomes very complex because all
the energy striking on to the surface does not get absorbed. A part of this striking energy
reflected back to another heat transfer surface, and part may be reflected out from the system
entirely. Now, one can imagine that this radiant energy can be reflected back and forth between
the heat transfer surfaces many times.

In this section, we will assume that all surfaces are in the analysis are diffuse and uniform in
temperature and that the reflective and emissive properties are constant over all surfaces.
 Fig. 7.6: (a) Surface energy balance for opaque surface (b) equivalent electrical circuit

It is also assumed that the radiosity and irradiation are uniform over each surface. As we have
already discussed that the radiosity is the sum of the energy emitted and the energy reflected
when no energy is transmitted (as opaque body), or

(7.24)

where, is the emissivity and Eb is the blackbody emissive power. Because the transmissivity is
zero due to opaque surface and absorptivity of the body (grey) will be equal to its emissivity by
Kirchhoff’s law.

Thus, eq.7.24 becomes

(7.25)

The net energy leaving the surface is the difference between the radiosity and the irradiance
(fig.7.6a),
 (7.26)

The eq.7.26 can be analogous to the electrical circuit as shown in fig.7.6(b). The numerator of
the eq.7.26 is equivalent to the potential difference, denominator is equivalent to the surface
resistance to radiative heat, and left part is equivalent to the current in the circuit.

In the above discussion we have considered only one surface. Now we will analyse the exchange
of radiant energy by two surfaces, A1 and A2, as shown in the fig.7.7a.

Fig. 7.7: (a) Energy exchange between two surfaces, (b) equivalent circuit diagram

The radiation which leaves surface 1, the amount that reaches surface 2 is

J1A1F12

Similarly, the radiation which leaves system 2, the amount that reaches surface 1 is

J2A2F21

The net energy transfer between the surfaces,

Reciprocity theorem states that

(7.27)

It also resembles an electrical circuit shown in fig.7.7b. The difference between eq.7.26 and 7.27
is that in eq.7.27 the denominator term is space resistance instead of surface resistance.

Now, to know, the net energy exchange between the two surfaces we need to add both the
surface resistances along with the overall potential as shown in the fig.7.8. Here the surfaces see
each other and nothing else.

Fig. 7.8: Radiative nature for two surfaces which can see each other nothing else

(7.28)

7.6 Radiation shield

Till now we have discussed about the radiative heat transfer from one surface to another without
any interfering surface in between. Here we will discuss about an interfering shield in between,
which is termed as radiation shield. A radiation shield is a barrier wall of low emissivity placed
between two surfaces which reduce the radiation between the bodies. In fact, the radiation shield
will put additional resistance to the radiative heat transfer between the surfaces as shown in
fig.7.9.
Fig. 7.9: Radiation between two large infinite plates (a) without and (b) with radiation
shield

Considering fig.7.9(b) and the system is at steady state, and the surfaces are flat (F ij because each

plate is in full view of the other). Moreover, the surface are large enough and may be
considered and the equivalent blackbody radiation energy may be written as Eb = σT4.

Thus, eq. 7.28 becomes

(7.29)

In order to have a feel of the role of the radiation shield, consider that the emissivities of all the
three surfaces are equal.

Then it can be seen that the heat flux is just one half of that which would be experienced if there
were no shield present.
In similar line we can deduce that when n-shields are arranged between the two surfaces then,

(7.30)

7.7 Electrical network for radiation through absorbing and transmitting medium
The previous discussions were based on the consideration that the heat transfer surfaces were
separated by a completely transparent medium. However, in real situations the heat transfer
medium absorbs as well as transmits. The examples of such medium are glass, plastic film, and
various gases.
Consider two non-transmitting surfaces (same as in fig. 7.8) are separated by a transmitting and
absorbing medium. The medium may be considered as a radiation shield which see themselves
and others. If we distinguish the transparent medium by m and if the medium is non-reflective
(say gas) then using Kirchhoff’s law,

(7.31)

The energy leaving surface 1 which is transmitted through the medium and reaches the surface 2
is,

and that which leaves surface 2 and arrives at surface 1 is,

Therefore, the net exchange in the transmission process is therefore,

Using eq. 7.31,

Thus the equivalent circuit diagram is shown in fig. 7.9

Fig. 7.9. Equivalent electrical circuit for radiation through gas

7.8 Radiation combined with conduction and convection

In industrial processes, in general, the heat transfer at higher temperature has significant portion
of radiation along with conduction and convection. For example, a heated surface is shown in the
fig. 7.10 with all the three mechanism of heat transfer.
 Fig. 7.11: Radiation combined with conduction and convection

At steady state

Heat flux by conduction = heat flux by convention + heat flux by radiation

where, h is the heat transfer coefficient at the surface in contact (outer surface) with atmosphere
due to natural and forced convection combined together, is the emissivity of the outer surface,
andTatm is the atmospheric temperature.

TEXT / REFERENCE BOOKS

1. Treybal R.E., Mass Transfer Operations, 3rd Edition, McGraw Hill, 2009.

2. McCabe and Smith, Unit Operations of Chemical Engineering, 7th Edition, McGraw Hill,
2009.

3. Coulson J.M. and Richardson J.F., Chemical Engineering, 6th Edition, Pergamon Press, 2002.

4. Anantharaman N., MeeraSheriffa Begum K.M., Mass Transfer Theory and Practice, 1st

Edition, PHI, 2011.

SCHOOL OF BIO AND CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

UNIT – 5 HEAT TRANSFER OPERATIONS -SCHA 1311

1
 UNIT 5

HEAT TRANSFER OPERATIONS

Evaporators- natural circulation, forced-circulation and agitated-film evaporators.

Methods of operation of evaporators-single-effect and multiple-effect evaporators,
Evaporation of Biological materials- fruit juices, sugar solution and paper-pulp waste
liquors.

Definition:

Theoretically, evaporation means simply vaporization from the surface of the liquid.

N.B. Thus no boiling occurs and the rate of vaporization from the depends on the diffusion of
vapor through the boundary layers above the liquid. The partial pressure of vapor is the driving
force here. In practice rate of heat transfer by this process is very slow.

Practically, evaporation is defined as the removal of liquid from a solution by boiling the
liquor in a suitable vessel and withdrawing the vapor, leaving a concentrated liquid residue.

Objective of evaporation:

To make a solution more concentrated. Generally extracts are concentrated in this way.

Factors affecting evaporation:

(i) Temperature:

Heat is necessary to provide the latent heat of vaporization, and in general, the rate of
evaporation is controlled by the rate of heat transfer. Rate of heat transfer depends on the
temperature gradient.

Many pharmaceutical agents are thermolabile. So the temperature that will cause the least
possible decomposition should be used.

e.g. Many glycosides and alkaloids are decomposed at temperature below 1000C.

e.g. Hormones, enzymes and antibiotics are extremely heat sensitive substances. e.g. Malt extract
(containing enzyme) is prepared by evaporation under reduced pressure to avoid loss of
enzymes.

2
 Some antibiotics are concentrated by freeze-drying.

(ii) Temperature and time of evaporation

Exposure to a relatively high temperature for a short period of time may be less
destructive of active principles than a lower temperature with exposure for a longer period.

Film evaporators used a fairly high temperature but the time of exposure is very short.

An evaporating pan involve prolonged heating.

(iii) Temperature and moisture content

Some drug constituents decompose more rapidly in the presence of moisture, especially
at a raised temperature (by hydrolysis). Hence, evaporation should be carried out at a low
controlled temperature, although the final drying can be performed at higher temperature when
little moisture remains.

e.g. Belladonna Dry Extract is an example of this type.

(iv) Type of product required

Evaporating pans or stills will produce liquid or dry products, but film evaporators will
yield only liquid products. So a dilute extract can be first concentrated in a film evaporator and
then the concentrated extract may be died in an evaporating pan.

(v) Effect of concentration

As the liquor becomes concentrated, the increasing proportion of solids results in

elevation of the boiling point of the solution. This leads to a greater risk of damage to
thermolabile constituents and reduction of the temperature gradient.

In general concentrated solutions will have increased viscosity, causing thicker boundary
layers, and may deposit solids that may build up on the heating surface that reduce heat transfer.

All these problems may be minimized by turbulent flow condition.

EVAPORATORS

Evaporators are classified according to the form of the movement,

(i) Natural circulation evaporators.

3
 (ii) Forced circulation evaporation

(iii) Film evaporators

(i)Natural Circulation Evaporator

EVAPORATING PAN

Description
STEAM AIR VENT
In these evaporators the
movement of the liquid results
from convection currents set up by
the heating process.

The apparatus consists of a CONDENSATION

PRODUCT OUTLET
hemispherical, or shallower pan, OUTLET
constructed from a suitable
material such as copper or stainless
steel and surrounded by a steam jacket.

The hemispherical shape gives the best surface/ volume ratio for heating, and the largest
area for disengagement of vapor.

The pan may have a mounting , permitting it to be tilted to remove the product, but the
shallow form makes this arrangement somewhat unstable, and an outlet at the bottom, is
common.

Advantages:

(a) It is simple and cheap to construct.

(b) It is easy to use, clean and maintain.

Disadvantages:

(a) Having only natural circulation, the overall coefficient of heat transfer will be poor and solids
are likely to deposit on the surface, leading to decomposition of the product and a further
deterioration in heat transfer.
(b) Also many products give rise to foaming.
(c) The total liquor is heated over all the time, which may be unsatisfactory with thermolabile
materials.
4
(d) The heating surface is limited and decreases proportionally as the size of the pan increases.
(e) The pan is open, so the vapor passes to the atmosphere which can lead to saturation of the
atmosphere.
(f) Only aqueous liquids can be evaporated in this pans.
(g) Pan evaporation cannot be done under reduced pressure.
(h) Can only be used for thermolabile products.

EVAPORATING STILLS

They are called

stills because it is
essentially a vessel similar
to the evaporating pan, with
a cover that connects it to a
condenser, so that the liquid
is distilled off. CONDENSER
COVER
Often a quick
release system of clamps
which allows the cover to
STEAM
be removed easily for AIR VENT

access to the interior of the

vessel for cleansing or
removal of the product may
CONDENSATE
be used. PRODUCT OUTLET
OUTLET

Advantages:

(a) Simple construction and easy to clean and maintain.

(b) The vapor is removed by condensation which

(i) speeds evaporation

(ii) reduces inconvenience and
(iii)allows the equipment to be used for solvents other than water e.g. ethanol.

(c) A receiver and vacuum pump can be fitted to the condenser, permitting operation under
reduced pressure and, hence, at lower temperature.

Disadvantages:

(a) Natural convection only

5
 (b) All the liquor is heated all the time

(c) The heating surface is limited.

Uses:

(i) Aqueous and other solvents may be evaporated

(ii) Thermolabile materials can be evaporated under reduced pressure.
(iii)Removing the still head it is convenient for evaporating extracts to dryness.

SHORT TUBE EVAPORATOR (Basket type vertical short tube evaporator)

Construction and Principle

Calendria

The lower portion of the evaporator consist of a nest of tubes with the liquor inside and steam
outside.

Tube length: 1–2m

VAPOUR TO
Tube diameter: 40 – 80 mm CONDENSER

Diameter of evaporator: 2.5 m

Number of tubes: 1000 LIQUOR LEVEL

This part of the evaporator is called the LIQUOR

calendria. INLET
STEAM STEAM
 The liquor is maintained at a level INLET OUTLET
slightly above the top of the tubes, the
CENTRAL CALENDRIA
space above this being left for the DOWNTAKE
disengagement of vapor from the
boiling liquor.
 The liquor in the tubes is heated by the
steam and begins to boil, when the
mixture of liquid and vapor will shoot CONDENSATE
up the tubes (in a similar manner to OUTLET
PRODUCT
that of a liquid that is allowed to boil OUTLET
to vigorously in a test-tube).
 This sets up a circulation, with boiling

6
 liquor rising up the smaller tubes of the calendria and returning down the larger central
downtake.

Advantages

1. Use of tubular calendria increases the heating area, possibly by a factor of 10 to 15 compared
to that of an external jacket.
2. The vigorous circulation reduces boundary layers and keeps solids in suspension, so
increasing the rate of heat transfer.
3. Condenser and receiver can be attached to run the evaporation under vacuum with
nonaqueous solvents.

Disadvantages

1. Since the evaporator is filled to a point above the level of the calendria, a considerable
amount of liquid is heated for a long time. The effect of this continual heating can be reduced
to some extent by removing concentrated liquor slowly from the outlet at the bottom of the
vessel.
2. Complicated design, difficult for cleaning and maintenance.
3. The head (pressure) of the liquor increases pressure at the bottom of the vessel and, in large
evaporators where the liquor depth may be of the order of 2 m; this may give rise to a
pressure of about 0.25 bar, leading to elevation of the boiling point by 5 to 60C.

FORCED CIRCULATION EVAPORATORS

7
 Forced circulation
evaporators are natural
VAPOUR OUTLET
circulation evaporators with
TANGENTIAL INLET
some added form of
mechanical agitation. Different
forms of forced circulation
evaporators can be designed.
STEAM
 An evaporating pan, in LIQUOR INLET
which the contents are INLET
agitated by a stirring rod or
pole could be described as
a forced circulation
CONDENSATE
evaporator. OUTLET
 A mechanically operated
propeller or paddle agitator
can be introduced into an PUMP
evaporating pan or still.
 Propeller or paddle agitator PRODUCT OUTLET
can be introduced into the
downtake of a short-tube evaporator.
 A typical forced circulation evaporator can be shown as follows:

Working Principle

 The liquor is circulated by means of the pump and as it is under pressure in the tubes the
boiling point is elevated and no boiling takes place.
 As the liquor leaves the tubes and enters the body of the evaporator there is a drop in pressure
and vapor flashes off from the superheated liquor.

Advantages

 Rapid liquid movement improves heat transfer, especially with viscous liquids or materials
that deposit solids or foam readily.
 The forced circulation overcomes the effect of greater viscosity of liquids when evaporated
under reduced pressure.
 Rapid evaporation rate makes this method suitable for thermolabile materials, e.g. it is used
in practice for the concentration of insulin and liver extracts.

8
FILM EVAPORATORS

Film evaporators spread the material as

a film over the heated surface, and the
vapor escapes the film. VAPOUR

Long tube evaporators (Climbing

SEPARATOR
film evaporators) STEAM
OUTLET

Construction and working principle

The heating unit consists of

steam-jacketed tubes, having a length
STEAM
to diameter ratio of about 140 to 1, so INLET
that a large evaporator may have tubes LIQUID
50 mm in diameter and about 7 m in CONCENTRATE
LIQUOR
length. INLET
CONDENSATE
OUTLET

The liquor to be evaporated is

introduced into the bottom of the tube, a film of liquid forms on the walls and rises up the tubes,
hence it is called climbing film evaporator.

At the upper end, the mixture of vapor and

concentrated liquor enters a separator, the vapor passing on
to a condenser, and the concentrate to a receiver.

Cold or pre heated liquor is introduced into the tube

(i). Heat is transferred to the liquor from the walls and
boiling begins, increasing in vigor (ii). Ultimately sufficient
vapor has been formed for the smaller bubbles to unite to a
large bubble, filling the width of the tube and trapping a
‘slug’ of liquid above the bubble (iii).
(i) (ii) (iii) (iv)
As more vapor is formed, the slug of liquid is blown
up the tube, the tube is filled with vapor, while the liquid
continues to vaporize rapidly, the vapor escaping up the tube and, because of friction between
the vapor and liquid, the film also is dragged up the tube upto a distance of 5 to 6 metres.

Long tube evaporators (Falling film evaporators)

9
Construction and working
principle
LIQUOR
INLET STEAM
Construction is same
OUTLET
as climbing film evaporator
but is inverted as shown in
the figure. STEAM
INLET

The liquor to be evaporated

is introduced at the top of the
evaporator tubes and the
liquor comes down due to
gravity.

The concentrate and VAPOUR

CONDENSATE OUTLET
vapor leaves the bottom.
OUTLET
They are separated in a
chamber where the SEPARATOR
.
concentrate is taken out
through product outlet out LIQUID
through product outlet and CONCENTRATE
vapor from vapor outlet.

Advantages of long tube evaporator

Since the movement of the film is assisted by gravity, more viscous liquid can be handled
by falling film evaporator.

(i) Very high film velocity reduces boundary layers to a minimum giving improved heat
transfer.
(ii) The use of long narrow tubes provides large surface area for heat transfer.
(iii)Because of increased heat transfer efficiency, a small temperature gradient is necessary with
less risk of damage to thermolabile materials.
(iv) Although the tubes are long, they are not submerged, as in the short-tube evaporator; so that
there is no elevation of boiling point due to hydrostatic head.

Disadvantages

(i) Expense to manufacture and install the instrument is high.

(ii) Difficult to clean and maintain.
(iii)From the operational point of view the feed rate is critical. if too high, the liquor may be
concentrated insufficiently, where as if the feed rate is to low, the film cannot be maintained
and dry patches may form on the tube wall.

10
Multiple effect evaporator

TO VACUUM PUMP

VAPOR VAPOR VAPOR

CONDENSER

1st Effect 2nd Effect 3rd Effect

p1 T1 p2 T2 p3 T3
FEED
STEAM
ps Ts
CONDENSATE

STEAM PRODUCT
CONDENSATE

Triple-effect evaporator: ps, p1, p2, p3 vapor pressures, Ts, T1, T2, T3 temperatures

where ps> p1> p2 >p3 .

In a single effect evaporator steam is supplied for heating the liquor. The total heat is not
transferred form the steam. So the rest of the heat is wasted. to use that heat efficiently.
Connections are made so that the vapor from one effect serves as the heating medium for the
next effect.

(i) The dilute feed (liquor) enters the first effect, where it is partly concentrated; it flows to the
second effect for additional concentration and then to the third effect for final concentration.
This liquor is pumped out of the third effect.
(ii) In the first effect raw steam is fed in which the vapor pressure in the evaporator is the
highest, p1. the second effect has the intermediate vapor pressure; i.e. p1>p2>p3. This pressure
gradient is maintained by drawing the vapor through a vacuum pump and condensing after
the final effect.
(iii)Depending on the lowering of vapor pressure boiling point of the liquids of 2nd and 3rd
effect will also be lowered; i.e. T1 > T2 > T3.
(iv) In the 2nd effect vapor from the 1st effect (T1 ) is heating the liquor (having temperature T2).
So there is a temperature gradient (T1 – T2); consequently the liquor will be heated.

Similar heating will be there in the 3rd effect also.

11
Methods of feeding

VAPOR
CONDENSER

FEED
STEAM Forward Feed.

Condensate

PRODUCT

VAPOR
CONDENSER

FEED
STEAM
Backward Feed .

Condensate

PRODUCT

VAPOR
CONDENSER

FEED
STEAM
Mixed Feed .

Condensate

PRODUCT

12
 VAPOR
CONDENSER

FEED FEED FEED FEED

STEAM
.
Parallel Feed

Condensate

THICK LIQUOR THICK LIQUOR THICK LIQUOR THICK LIQUOR

Forward feed

Advantages:

1. Feed moves from high pressure (in effect-2) to low pressure (in effect – 4) chambers, so
pumping of liquor is not required.
2. Product is obtained at lowest temperature.
3. This method is suitable for scale-forming liquids because concentrated product is subjected
to lowest temperature.

Disadvantages

It is not suitable for cold feed because, the steam input in effect-1 raises the temperature of the
feed, and a small amount of heat is supplied as latent heat of vaporization. Therefore, amount of
vapor produced will be less than the amount of steam supplied. Lower amount of vapor in effect-
1 produces lower amount of vapor in the subsequent effects. Therefore, the overall economy is
lower.

Backward feed

In backward-feed the feed enters in the last effect and moves towards first effect (i.e
IVIIIIII).

Advantages

 It is suitable for cold feed, because the heat used for increasing the temperature in IV effect is
already used for heating 3 times. This will give more economy.
 The method is suitable for viscous products, because highly concentrated product is at
highest temperature, hence lower viscosity ( higher heat transfer  higher capacity)

Disadvantages

13
The liquid moves from low-pressure (IV) to high-pressure chambers (III  II  I) pumping is
requierd.

Mixed feed method

The feed enters in the intermediate effect, moves forward and then backward to effect-I
(IIIIVIII).

Advantages
 Liquid moves from high pressure (III) to low pressure (IV), hence no pump is required.
Liquid moves from IVIII requires pump.
 Product is obtained from highest temperature (I) hence lowest viscosity.

Parallel feed

It is suitable where the feed has to be concentrated slightly.

A heat exchanger is a device built for efficient heat transfer from one medium to another,
whether the media are separated by a solid wall so that they never mix, or the media are in direct
contact. Typical applications involve heating or cooling of a fluid stream of concern and
evaporation or condensation of single- or multicomponent fluid streams. In a heat exchanger
there is no direct contact between the two fluids. The heat is transferred from the hot fluid to the
metal isolating the two fluids and then to the cooler fluid.

In other applications, the objective may be to recover or reject heat, or sterilize, pasteurize,
fractionate, distill, concentrate, crystallize, or control a process fluid. They are widely used in
Space Heating, Refrigeration, Air Conditioning, Power Plants, Chemical Plants, Petro-chemical
Plants, Petroleum Refineries, and Natural Gas Processing. One common example of a heat
exchanger is the Radiator in a car.

14
Different Terminologies of Heat Transfer Equipment

Heat exchanger: both sides single-phase and process streams

Cooler: one stream a process fluid and the other cooling water or air.
Heater: one stream a process fluid and the other a hot utility, such as steam or hot oil.
Condenser: one stream a condensing vapor and the other cooling water or air.
Chiller: one stream a process fluid being condensed at sub-atmospheric temperatures and the
other a boiling refrigerant or process stream.
Reboiler: one stream a bottoms stream from a distillation column and the other a hot utility
(steam or hot oil) or a process stream.
a. Multiple pass heat exchangers

If fluids pass each other more than once then it applies the principle of multiple pass heat
exchangers .Reverse flow are common in these heat exchanger as there are designed with
“U”bend tubes. These tubes provide a pathway for back and forth movement of fluid across the
length of the heat exchanger.Another way for establishing a multiple pass is to insert baffles on
the shell side of the heat exchanger. Baffles directs shell sides the fluid back and forth across the
tubes to achieve multiple pass effect. Tubes are sometimes arrayed within the shell in order to
shorten the overall exchanger length of the heat exchanger in the opposite direction using the
other half of the tube bundle. The exchanger would then be said to have two side tube passes. It
has an advantage that the tube side velocities are doubled for the same flow rate thus the heat
transfer coefficient increases. Longitudinal baffles are placed in the shell such that the number of
shell sides passes can be increased and a shell side coefficient increase consequently. The more
complex and costly, the more complex and costly construction and the higher pressure drops for
each fluid is off set of multiple pass heat exchanger.

15
Advantages of Multiple Pass Heat Exchangers

 It has wide ranges of pressure thus pressure can be varied over large drops
 Thermal stresses can be accommodated inexpensively.
 Use of materials is diverse and it take into consideration corrosion and other disruptive
concerns .shell and tubes can be made with different material.
 Extended heat transfer surfaces can be used to enhance heat transfer.
 Cleaning and repair are relatively straightforward, because the equipment can be
dismantled for this purpose
b. Plate heat exchangers
It’s a type of Heat Exchanger which consists of many corrugated stainless-steel sheets
separated by polymer gaskets and clamped into a steel frame.Plate heat exchangers
transfer heat by placing thin, corrugated metal sheets side by side and connecting them by
gaskets. Flow of the substances to be heated and cooled takes place between alternating

16
 sheets allowing heat to transfer through the metal sheets.

The parts and function

The heat exchangers frame is made up of thick steel pressure retaining parts, the fixed cover
and the movable cover, that when pulled together with the tightening bolts form the pressure
retaining structure for the plates / plate pack. The carrying bar and guide bar act as a carrier and
guide to both the plates and the movable cover.The heat exchanger plates, which make up the
heat transfer surface, are clamped between two plates of steel with the use of the tightening bolts.
The heat exchanger construction allows a plate heat exchanger to be easily opened for inspection
and cleaning. Each plate has a gasket that produces a sealing and channel system through the
entire plate pack in which the two heat exchanging media flow in a counter-current direction.
The circular portion of the gasket stops the fluid from going across the heat transfer plate and
sends it to the next open channel. The remaining portion or field gasket directs the opposing fluid
across the heat transfer surface. The heat transfer plates with gaskets are arranged in an
alternating pattern of left hand flow and right hand flow to direct the fluids in an opposing
direction within the heat exchanger. The completed assembly of all the plates and gaskets is
called the “plate pack.”

Plate heat exchangers are used because there have high heat transfer area, high heat transfer
coefficient. There are compact and have lower floor space requirements. By increasing the
number of plates the area of heat exchange can be increased. They are most suitable type heat
exchangers for lower flow rates and heat sensitive substances. They can perform multiple
duties that can be performed by a single unit. There are classified into gasketed plate heat
exchanger, brazed plate heat exchanger, welded plate heat exchangers.

Benefits of plate heat exchangers are lightweight: The PHE unit is lighter in total weight
than other types of heat exchangers because of reduced liquid volume space and less surface
area for a given application. High-viscosity applications: Because the PHE induces
turbulence at low fluid velocities, it has practical application for high-viscosity fluids. Saves
space and servicing time: The PHE fits into an area one-fifth to one-half of that required for
a comparable shell and tube heat exchanger. The PHE can be opened for inspection,
maintenance. Lower liquid volume: Since the gap between the heat transfer plates is
relatively small, a PHE contains only low quantities of process fluids. The benefit
is reduced cost due to lower volume .Lower cost: PHEs are generally more
17
economical than other types of equivalent duty heat exchangers due to the higher
thermal efficiency and lower manufacturing costs. Quick process control: Owing to the thin
channels created between the two adjacent plates, the volume of fluid contained in PHE is
small; it quickly reacts to the new process condition and is thereby easier to control.

The limitations of plate heat exchangers are the maximum allowable working pressure is
also limited by the frame strength and plate deformation resistance. Commonly stated limits
have been 300°F (149°C) and 300 psi .Because of the narrow gap between the plates, high
liquid rates will involve excessive pressure drops, thus limiting the capacity. Large
differences in fluid flow rates of two streams cannot be handled. The gaskets cannot handle
corrosive or aggressive media. Gaskets always increase the leakage risk. The standard PHEs
cannot handle particulates that are larger than 0.5 mm.

In conclusion Plate heat exchangers are available in a wide variety of configurations to suit
most processes heat transfer requirements. The advantages of PHEs, and associated heat
transfer enhancement techniques, extend far beyond energy efficiency. Lower capital cost,
reduced plant size, and increased safety are typical of the benefits arising from the use of
PHEs. Plate heat exchangers can replace some normal size heat exchangers bringing
advantages and performance

c. Scraped surface heat exchangers

One type of heat exchanger, that finds considerable use in the food processing industry
particularly for products of higher viscosity, consists of a jacketed cylinder with an
internal cylinder concentric to the first and fitted with scraper blades. The blades rotate,
causing the fluid to flow through the annular space between the cylinders with the outer
heat transfer surface constantly scraped. Coefficients of heat transfer vary with speeds of
rotation but they are of the order of 900-4000 J m-2 s-1 °C-1. These machines are used in
the freezing of ice cream and in the cooling of fats during margarine manufacture. Liquid
foods that contain large solid particles are heated in scraped-surface heat exchangers.
These heat exchangers use blades to continuously scrape the inside surface of the heating
chamber. The scraping action protects highly viscous foods from being burned on the
heating surface.

18
The dynamic scraped surface heat exchanger (DSSHE) was designed to face some problems
found in other types of heat exchangers. They increase heat transfer by:

o removing the fouling layers,

o increasing turbulence in case of high viscosity flow,
o Avoiding the generation of ice and other process by-products.

The dynamic scraped surface heat exchangers incorporate an internal mechanism which
periodically removes the product from the heat transfer wall. The product side is scraped by
blades attached to a moving shaft or frame. The blades are made of a rigid plastic material to
prevent damage to the scraped surface. This material is FDA approved in the case of food
applications.

d. Double pipe heat exchangers

Two sets of concentric pipes, two connecting tees, and a return head and a return bend. A device
whose purpose is the transfer of thermal energy between two fluids. Common applications:
boilers, coolers, condensers, evaporators. Common design consists of tow fluids separated by a
conducting medium.

Simplest type has one tube inside another - inner tube may have longitudinal fins on the outside
However, most have a number of tubes in the outer tube - can have very many tubes thus
becoming a shell-and-tube.

Advantages of Double Pipe Heat Exchangers

1. Double pipe heat exchanger consists of two concentric pipes are hot fluid, cold fluid.
2. Economically adaptable to service differentials. Ideal for wide temperature ranges and
differentials.
19
 3. Provides shorter deliveries than shell and tube due to standardization of design and
construction.
4. Operates in true counter current flow permitting extreme temperature cross.

e. Tubular heat exchangers

This type of heat exchanger are categorized in following types: Double Pipes heat Exchanger,
Shell& Tube Heat Exchanger, Spiral Heat Exchanger, Cracked Surface Heat Exchanger.

Shell and Tube Heat Exchangers

• The shell and tube heat exchanger is the most common style found in industry.
• As the tube-side flow enters the exchanger, flow is directed into tubes that run parallel to
each other. these tubes run through a shell that has a fluid passing through it.
• Heat energy is transferred through the tube wall into the cooler fluid.
• Heat transfer occurs primarily through conduction and convection.

Baffles are used to establish a cross-flow and to induce turbulent mixing of the shell-side
fluid.

20
 One Shell Pass,Two Tube Passes

Two Shell Passes,Four Tube Passes

Main Parts:

1.Connections

2.Tube Sheets

3.Gaskets

4.Head

5.Mounting

21
6.Baffles

7. Shell

8.Tube bundle

Thermal design considerations

Thermal design of a shell and tube heat exchanger typically includes the determination of
heat transfer area, number of tubes, tube length and diameter, tube layout, number of shell
and tube passes, type of heat exchanger (fixed tube sheet, removable tube bundle etc), tube
pitch, number of baffles, its type and size, shell and tube side pressure drop etc.

Shell

Shell is the container for the shell fluid and the tube bundle is placed inside the shell. Shell
diameter should be selected in such a way to give a close fit of the tube bundle. The clearance
between the tube bundle and inner shell wall depends on the type of exchanger ( [2]; page 647) .
The shells are usually fabricated from standard steel pipe with satisfactory corrosion allowance.
The shell thickness of 3/8 inch for the shell ID of 12-24 inch can be satisfactorily used upto 300
psi of operating pressure.

Tube

Tubes OD of ¾ and 1'' are very common to design a compact heat exchanger. The most efficient
condition for heat transfer is to have the maximum number of tubes in the shell to increase
turbulence. The tube thickness should be good enough to withstand the internal pressure along
with the adequate corrosion allowance. The tube thickness is expressed in terms of BWG
(Birmingham Wire Gauge) and true outside diameter (OD). The tube length of 6, 8, 12, 16, 20
and 24 ft are preferably used. Longer tube reduces shell diameter with the expense of higher
shell pressure drop. Finned tubes are also used when fluid with low heat transfer coefficient
flows in the shell side. Stainless steel, admiralty brass, copper, bronze and alloys of copper-
nickel are the commonly used tube materials:

Tube pitch, tube-layout and tube-count

Tube pitch is the shortest centre to centre distance between the adjacent tubes. The tubes are
generally placed in square or triangular patterns as shown in the Figure 5 . The widely used tube
layouts are illustrated in Table 2.

The number of tubes that can be accommodated in a given shell ID is called tube count. The
tube count depends on the factors like shell ID, OD of tube, tube pitch, tube layout, number of
tube passes, type of heat exchanger and design pressure.

22
 Tube passes

The number of passes is chosen to get the required tube side fluid velocity to obtain greater heat
transfer co-efficient and also to reduce scale formation. The tube passes vary from 1 to 16. The
tube passes of 1, 2 and 4 are common in application. The partition built into exchanger head
known as partition plate (also called pass partition) is used to direct the tube side flow.

· Table 2 . Common tube layouts.

Figure 5 . Heat exchanger tube-layouts.

Tube sheet

The tubes are fixed with tube sheet to form the barrier between the tube and shell fluids. The
tubes are generally fixed with the tube sheet using ferrule and a soft metal packing ring. The tube
sheet thickness should be greater than the tube outside diameter to make a good seal. The
recommended standards (IS:4503 or TEMA) should be followed to select the minimum tube
sheet thickness.

Baffles

Baffles are used to increase the fluid velocity by diverting the flow across the tube bundle to
obtain higher transfer co-efficient. The distance between adjacent baffles is called baffle-spacing.
The baffle spacing of 0.2 to 1 times of the inside shell diameter is very common. The baffles are
positioned by means of baffle spacers. Closer baffle spacing gives greater transfer co-efficient by
23
inducing higher turbulence. The pressure drop is more with closer baffle spacing. The various
types of baffles are schematized in Figure 6 . In case of cut-segmental baffle, a segment (called
baffle cut) is removed to form the baffle expressed as a percentage of the baffle diameter. Baffle
cuts from 15 to 45% are normally used. A baffle cut of 20 to 25% provide a good heat-transfer
within the reasonable pressure drop.

Figure 6. Different type of heat exchanger baffles: a). Cut-segmental baffle, b). Disc and
doughnut baffle, c). Orifice baffle

Fouling Considerations

The most of the process fluids in exchanger foul the heat transfer surface. The material deposited
reduces the effective heat transfer rate due to relatively low thermal conductivity. Therefore, net
heat transfer should the increased to compensate the reduction in performance during operation.
Fouling of exchanger increases the cost of (i) construction due to oversizing, (ii) additional
energy due to poor exchanger performance and (iii) cleaning to remove deposited materials. The
duplicate exchanger may be required during cleaning for uninterrupted service.

Shell and tube heat exchanger

24
Shell and tube heat exchangers consist of a series of tubes. One set of these tubes contains the
fluid that must be either heated or cooled. The second fluid runs over the tubes that are being
heated or cooled so that it can either provide the heat or absorb the heat required. A set of tubes is
called the tube bundle and can be made up of several types of tubes: plain, longitudinally finned.
Shell and tube heat exchangers are typically used for high-pressure applications (with pressures
greater than 30 bar and temperatures greater than 260 °C). This is because the shell and tube heat
exchangersare robust due to their shape. Shell and tube heat exchanger units can be designed
for almost all condition of temperature and pressure. In extreme cases, high pressure may impose
a limitation by fabrication problems associate with material thickness

Double pipe heat exchanger

They consist of one pipe concentrically located inside a second larger pipe. In this heat
exchanger the fluid to be cooled or heated passes through the tube 2(green) and the other fluid is
passed through tube 1 (red) to absorb or release the heat.

Advantages: Cheap for both design and maintenance.

Disadvantages: Low efficiency and requires large space.

Mainly used in pasteurization, digester heating, heat recovery, pre-heating, effluent cooling.

25
Spiral heat exchanger

A spiral heat exchanger (SHE), may refer to a helical (coiled) tube configuration efficient use of
space. They can be easily cleaned.

A Spiral Heat Exchangers (or SHE) is a coiled tube arrangement, with two channels coiled one
around the other. These two channels operate in a counter-flow arrangement, offering excellent
turn down ratios, while optimizing flow patterns which in turn, enhance heat transfer. spiral heat
exchangers are mainly used in pasteurization, recuperators (Exhaust and Air Handling
Systems),sludge treatment (Thermal depolymerisation) Selection of spiral heat exchangers is
based on cost, high/low pressure limits, thermal performance, temperature ranges, product mix
(liquid/liquid, particulates or high-solids liquid),pressure drops across the exchanger, fluid flow
capacity, clean ability, maintenance and repair, materials required for construction, ability and
ease of future expansion Spiral heat exchangers can be used in most applications in the chemical
process industry
In many difficult applications where fouling and plugging are problems, a standard shell and
tube design may not be effective
While a spiral heat exchanger often has a higher initial cost, it may provide a lower life cycle
cost due to lower fouling rates and ease of maintenance

Contact type and Non-contact type

Contact type

In Direct Contact type of heat Exchanger heat is directly transferred between Hot and Cold
fluids.
There is no separating wall between the hot and cold fluids.
Most direct contact heat exchangers fall under the Gas- Liquid category, where heat is
transferred between a gas and liquid in the form of drops, films or sprays.
Properties of both fluids, such as viscosity, thermal conductivity, density, specific heat and
reaction on the metal in contact are essential to determine the pumping, thermal requirement and
material construction.
In a direct-contact exchanger, two fluid streams come into direct contact, exchange heat,
and are then separated.
26
 Common applications of a direct-contact exchanger involve mass transfer in addition to
heat transfer, such as in evaporative cooling and rectification.
However, the applications are limited to those cases where a direct contact of two fluid
streams is permissible.

However direct contact are in three classes

a) Immiscible Fluid Exchangers

b) Gas–Liquid Exchangers
c) Liquid–Vapor Exchangers
Immiscible Fluid Exchangers
In this type, two immiscible fluid streams are brought into direct contact.

These fluids may be single-phase fluids, or they may involve condensation or vaporization.

Condensation of organic vapors and oil vapors with water or air are typical examples.

Gas–Liquid Exchangers
In this type, one fluid is a gas (more commonly, air) and the other a low-pressure liquid (more
commonly, water) and are readily separable after the energy exchange.
In either cooling of liquid (water) or humidification of gas (air) applications, liquid partially
evaporates and the vapor is carried away with the gas.
In these exchangers, more than 90% of the energy transfer is by virtue of mass transfer (due to
the evaporation of the liquid), and convective heat transfer is a minor mechanism.
A ‘‘wet’’ (water) cooling tower with forced- or natural-draft airflow is the most common
application.
Other applications are the air-conditioning spray chamber, spray drier, spray tower, and spray
pond.
Liquid–Vapor Exchangers
In this type, typically steam is partially or fully condensed using cooling water, or water is
heated with waste steam through direct contact in the exchanger.
Noncondensables and residual steam and hot water are the outlet streams.
Common examples are desuperheaters and open feed water heaters (also known as
deaerators) in power plants.

Compared to indirect contact recuperators and regenerators, in direct-contact heat exchangers,

1. very high heat transfer rates are achievable,

2. the exchanger construction is relatively inexpensive, and
3. the fouling problem is generally nonexistent, due to the absence of a heat transfer surface
(wall) between the two fluids.

27
Non-Contact type

 In an Indirect Contact Type Heat Exchanger, the fluid stream remains separated.
There is separating wall between the hot and cold fluids.
 The heat transfer in this type of heat exchanger takes place continuously through a
dividing wall.
 Most indirect contact heat exchangers fall under those gases and liquids that are
soluble in nature.
 The fluid streams remain separate and the heat transfers continuously through a
dividing wall into and out of the wall in a transient manner.
Non-contact are in three classes
a) Direct transfer type heat exchanger
b) Storage type heat exchanger
c) Fluidized bed heat exchanger
a) Direct Transfer Type Heat Exchanger
 In this, type heat transfers continuously from the
hot fluid to the cold fluid through a dividing
wall.
 There is no direct mixing of the fluids because
each fluid flows in separate fluid passages.
 It is also known as recuperators. Examples,
tubular exchangers, plate and frame heat
exchangers and extended surface exchangers.

Tubular Plate and Frame

Exchanger Exchanger
b) Storage Type Heat Exchanger (Regenerative Heat Exchanger)
 In a storage type exchanger, both fluids flow alternatively through the
same flow passages, and hence heat transfer is intermittent.

28
  The heat transfer surface (or flow passages) is generally cellular in
structure and is referred to as a matrix, or it is a permeable (porous)
solid material, referred to as a packed bed.
 When hot gas flows over the heat transfer surface (through flow
passages), the thermal energy from the hot gas is stored in the matrix
wall, and thus the hot gas is being cooled during the matrix heating
period.
 As cold gas flows through the same passages later (i.e., during the
matrix cooling period), the matrix wall gives up thermal energy, which
is absorbed by the cold fluid.
 Thus, heat is not transferred continuously through the wall as in a
direct-transfer type exchanger (recuperator), but the corresponding
thermal energy is alternately stored and released by the matrix wall.

Fixed Bed Regenerator

29
 b) Storage Type Heat Exchanger (Regenerative Heat Exchanger)
a. Regenerative heating was one of the most important technologies
developed during the Industrial Revolution when it was used in the hot
blast process on blast furnaces.
b. It was later used in glass and steel making, to increase the efficiency of
open hearth furnaces, and in high pressure boilers and chemical and
other applications, where it continues to be important today.
c. Fluidized bed heat exchanger

In a fluidized-bed heat exchanger, one side of a two-fluid exchanger is

immersed in a bed of finely divided solid material, such as a tube
bundle immersed in a bed of sand or coal particles. The common
applications of the fluidized-bed heat exchanger are drying, mixing,
adsorption, reactor engineering, coal combustion, and waste heat
recovery

Difference between Direct and Indirect Heat Exchanger

Direct Heat Exchanger Indirect Heat Exchanger

Not have a separating wall between two fluids. Have a separating wall between two fluids.

Mostly used for those gases and liquids that Used for those gases and liquids that are
are not soluble in nature soluble in nature.

30
Mostly use drops and steam for heat transfer There is no use of steam and drops

Co-current and counter-current flow in heat exchangers

Co-current and countercurrent exchange mechanisms

the magnitude of the property to be exchanged, is represented by shading. The direction of
transfer across the barrier is from the greater to the lesser magnitude.

In the co-current flow exchange mechanism, the two fluids flow in the same direction.

As the Co-current and countercurrent exchange mechanisms diagram showed, a co-current

exchange system has a variable gradient over the length of the exchanger. With equal flows in
the two tubes, this method of exchange is only capable of moving half of the property from one
flow to the other, no matter how long the exchanger is.

If each stream changes its property to be 50% closer to that of the opposite stream's inlet
condition, exchange will stop when the point of equilibrium is reached, and the gradient has
declined to zero. In the case of unequal flows, the equilibrium condition will occur somewhat
closer to the conditions of the stream with the higher flow.

31
Co-current flow examples

Co-current and Countercurrent heat exchange

A co-current heat exchanger is an example of a co-current flow exchange mechanism.

Two tubes have a liquid flowing in the same direction. One starts off hot at 60 °C, the second
cold at 20 °C. A thermoconductive membrane or an open section allows heat transfer between
the two flows.

The hot fluid heats the cold one, and the cold fluid cools down the warm one. The result is
thermal equilibrium: Both fluids end up at around the same temperature: 40 °C, almost exactly
between the two original temperatures (20 and 60 °C). At the input end, there is a large
temperature difference of 40 °C and much heat transfer; at the output end, there is a very small
temperature difference (both are at the same temperature of 40 °C or close to it), and very little
heat transfer if any at all. If the equilibrium—where both tubes are at the same temperature—is
reached before the exit of the liquid from the tubes, no further heat transfer will be achieved
along the remaining length of the tubes.

A similar example is the co-current concentration exchange. The system consists of two tubes,
one with brine (concentrated saltwater), the other with freshwater (which has a low concentration
of salt in it), and a semi permeable membrane which allows only water to pass between the two,
in an osmotic process. Many of the water molecules pass from the freshwater flow in order to
dilute the brine, while the concentration of salt in the freshwater constantly grows (since the salt
is not leaving this flow, while water is). This will continue, until both flows reach a similar
dilution, with a concentration somewhere close to midway between the two original dilutions.
Once that happens, there will be no more flow between the two tubes, since both are at a similar
dilution and there is no more osmotic pressure.

Countercurrent flow

32
Spiral counter-current heat exchange schematic

In countercurrent flow, the two flows move in opposite directions.

Two tubes have a liquid flowing in opposite directions, transferring a property from one tube to
the other. For example, this could be transferring heat from a hot flow of liquid to a cold one, or
transferring the concentration of a dissolved solute from a high concentration flow of liquid to a
low concentration flow.

The counter-current exchange system can maintain a nearly constant gradient between the two
flows over their entire length of contact. With a sufficiently long length and a sufficiently low
flow rate this can result in almost all of the property transferred. So, for example, in the case of
heat exchange, the exiting liquid will be almost as hot as the original incoming liquid's heat.

Countercurrent flow examples

In a countercurrent heat exchanger, the hot fluid becomes cold, and the cold fluid becomes
hot.

In this example, hot water at 60 °C enters the top pipe. It warms water in the bottom pipe which
has been warmed up along the way, to almost 60 °C. A minute but existing heat difference still
exists, and a small amount of heat is transferred, so that the water leaving the bottom pipe is at
close to 60 °C. Because the hot input is at its maximum temperature of 60 °C, and the exiting
water at the bottom pipe is nearly at that temperature but not quite, the water in the top pipe can
warm the one in the bottom pipe to nearly its own temperature. At the cold end—the water exit
from the top pipe, because the cold water entering the bottom pipe is still cold at 20 °C, it can
extract the last of the heat from the now-cooled hot water in the top pipe, bringing its
temperature down nearly to the level of the cold input fluid (21 °C).

The result is that the top pipe which received hot water, now has cold water leaving it at 20 °C,
while the bottom pipe which received cold water, is now emitting hot water at close to 60 °C. In
effect, most of the heat was transferred.

33
Conditions for higher transfer results

It should be noted that nearly complete transfer in systems implementing countercurrent

exchange, is only possible if the two flows are, in some sense, "equal".

For a maximum transfer of substance concentration, an equal flowrate of solvents and solutions
is required. For maximum heat transfer, the average specific heat capacity and the mass flow rate
must be the same for each stream. If the two flows are not equal, for example if heat is being
transferred from water to air or vice versa, then, similar to co-current exchange systems, a
variation in the gradient is expected because of a buildup of the property not being transferred
properly.

Types of flows in heat exchangers

Co-current flow

where mc – mass flow rate in cold stream

mh – mass flow in hot stream

Countercurrent flow

Classification of Heat Exchangers

Heat exchangers are generally classified according to the relative directions of hot and
cold fluids:

34
 (a) Parallel Flow – the hot and cold fluids flow in the same direction. Fig 3.2 depicts
such a heat exchanger where one fluid (say hot) flows through the pipe and the other fluid (cold)
flows through the annulus.

(b) Counter Flow – the two fluids flow through the pipe but in opposite directions. A
common type of such a heat exchanger is shown in Fig. 3.3. By comparing the temperature
distribution of the two types of heat exchanger

Fig 3.2 Parallel flow heat exchanger with Fig 3.3 Counter-flow heat exchanger

temperature distribution with temperature distribution

we find that the temperature difference between the two fluids is more uniform in
counter flow than in the parallel flow. Counter flow exchangers give the maximum heat transfer
rate and are the most favoured devices for heating or cooling of fluids.

When the two fluids flow through the heat exchanger only once, it is called one-shell-
pass and one-tube-pass as shown in Fig. 3.2 and 3.3. If the fluid flowing through the tube makes
one pass through half of the tube, reverses its direction of flow, and makes a second pass through
the remaining half of the tube, it is called 'one-shell-pass, two-tube-pass' heat exchanger,fig 3.4.
Many other possible flow arrangements exist and are being used. Fig. 10.5 depicts a 'two-shell-
pass, four-tube-pass' exchanger.
35
 (c) Cross-flow - A cross-flow heat exchanger has the two fluid streams flowing at right
angles to each other. Fig. 3.6 illustrates such an arrangement An automobile radiator is a good
example of cross-flow exchanger. These exchangers are 'mixed' or 'unmixed' depending upon the
mixing or not mixing of either fluid in the direction transverse to the direction of the flow stream
and the analysis of this type of heat exchanger is extremely complex because of the variation in
the temperature of the fluid in and normal to the direction of flow.

(d) Condenser and Evaporator - In a condenser, the condensing fluid temperature

remains almost constant throughout the exchanger and temperature of the colder fluid gradually
increases from the inlet to the exit, Fig. 3.7 (a). In an evaporator, the temperature of the hot fluid
gradually decreases from the inlet to the outlet whereas the temperature of the colder fluid
remains the same during the evaporation process, Fig. 3.7(b). Since the temperature of one of the
fluids can be treated as constant, it is immaterial whether the exchanger is parallel flow or
counter flow.

(e) Compact Heat Exchangers - these devices have close arrays of finned tubes or plates
and are typically used when atleast one of the fluids is a gas. The tubes are either flat or circular
as shown in Fig. 10.8 and the fins may be flat or circular. Such heat exchangers are used to a
chieve a very large ( 700 m2/mJ) heat transfer surface area per unit volume. Flow passages are
typically small and the flow is usually laminar.

Fig 3.4: multi pass exchanger one shell pass, two shell pass

36
 Fig 3.5: Two shell passes, four-tube passes heat exchanger (baffles increases the
convection coefficient of the shell side fluid by inducing turbulance and a cross flow velocity
component)

Fig 3.6: A cross-flow exchanger

37
 Fig. 3.8 Compact heat exchangers: (a) flat tubes, continuous plate fins, (b) plate fin
(single pass)

Condenser

The change from liquid phase to vapor phase is called vaporization and the reverse phase transfer
is condensation. The change from liquid to vapor or vapor to liquid occurs at one temperature
(called saturation or equilibrium temperature) for a pure fluid compound at a given pressure. The
industrial practice of vaporization and condensation occurs at almost constant pressure; therefore
the phase change occurs isothermally.

Condensation occurs by two different physical mechanisms i.e. drop-wise condensation and
film condensation .

The nature of the condensation depends upon whether the condensate (liquid forms from vapor)
wets or does not wet the solid surface. If the condensate wets the surface and flows on the
surface in the form of a film, the process is called film condensation. When the condensate does
not wet the solid surface and the condensate is accumulated in the form of droplets, the
mechanism is drop-wise condensation. Heat transfer coefficient is about 4 to 8 times higher
for drop wise condensation. The condensate forms liquid film on the bare-surface in case of

38
 film condensation. The heat transfer coefficient is lower for film condensation due to the liquid
film resistance.

Dropwise condensation occurs usually on new, clean and polished surfaces. The equipment used
for condensation heat transfer is called condenser. In industrial condensers, film condensation
normally occurs.

Types of condensers

There two general types of condensers:

 i. Vertical condenser

Downflow vertical condenser: The vapor enters at the top of condenser and flows down
inside tubes. The condensate drains from the tubes by gravity and vapor induced shear
(Figure 7) .

Upflow vertical condenser: In case of upflow condenser, the vapor enters at the bottom
and flows upwards inside the tubes. The condensate drains down the tubes by gravity
only.

ii. Horizontal condenser: The condensation may occur inside or outside the horizontal
tubes ( Figure 8 ). Condensation in the tube-side is common in air-cooled condensers.
The main disadvantage of this type of condenser is that the liquid tends to build up in the
tubes. Therefore the effective heat transfer co-efficient is reduced significantly.

39
Figure 7 . Downflow vertical condenser with condensation inside tube [5] .
40
Figure 8. Horizontal condenser with condensation outside horizontal tubes [5] .

Condenser design considerations

The design of condenser is similar to a typical shell and tube exchangers. A condenser must have
a vent for removal of non-condensable gas. The non-condensable gas decreases the heat transfer
rate by reducing condensation temperature. Condenser usually uses a wider baffle spacing of B =
Ds (ID of shell). Vertical cut-segmental baffles are generally used in condensers for side to side
vapor flow not for top to bottom. An opening at the bottom of the baffles is provided to allow
draining of condensate.

Mean temperature difference

The condensation occurs almost at a fixed temperature (isothermally) at constant pressure for a
pure saturated vapor compound. The logarithmic mean temperature difference can be used for
condenser design. No correction factor for multiple pass condensers is required . The
logarithmic mean temperature difference:

Where, T sat = Saturation vapor temperature

t1 = Coolant inlet temperature

t2 = C oolant outlet temperature

41
 Reboilers

Classification of reboilers

There are three major types of reboilers:

i. Thermosyphon natural circulation reboiler: The boiling occurs inside the tubes in vertical
thermosyphon reboiler and inside shell in horizontal thermosyphon reboiler ( Figure 10) . In
vertical thermosyphon reboiler, the liquid circulation occurs due to density difference between
vapor-liquid mixture (two phase) in the exchanger from the reboiler and the liquid through the
downcomer to the reboiler.

Advantages: most economical because no pump is required.

Limitations: not suitable for heavily viscous fluid; high construction cost for the installation of
the column base at suitable elevation to get thermosyphon effect; not suitable for low
temperature difference processes due to boiling point elevation imposed by static head.

Figure 10. Thermosyphon reboiler [5] .

ii. Forced circulation reboiler : The liquid is fed by means of a pump. Forced circulation
reboilers with inside vertical or horizontal tubes boiling may be designed. Forced circulation
reboilers are similar to vertical thermosiphon reboilers, except the pump is used for the
recirculation of the liquid. To calculate the heat transfer coefficient it is generally assumed that,
heat is transferred only by forced convection. The usual method of shell and tube exchanger
design can be used.

42
Advantage: suitable for viscous and highly fouling fluids.

Disadvantage: high pumping and maintenance cost; pump is required to circulate the boiling
liquid through the tubes and back into the column.

iii. Kettle reboiler : The tube bundle is immerged in a pool of liquid at the base in an oversize
shell ( Figure 11 ). Kettle reboiler is also called a “submerged bundle reboiler”. The height of
the tube bundle is usually 40-60% of the shell ID. The submergence of the tube bundle is assured
by an overflow weir at height of typically 5-15 cm from the upper surface of topmost tubes.

Advantage: suitable for vacuum operation and high vaporization rate upto about 80% of the feed.

Limitations: low heat transfer rate than other types as there is no liquid circulation (low
velocity); not appropriate for fouling fluids; kettle reboiler is not suitable for heat sensitive
materials as higher residence time is required.

The bundle diameter Db , can be obtained from the empirical equation ([2] page 647-649 ) :

where, Db = bundle diameter [mm], nt = number of tubes, do = tube outside diameter [mm]. The
values of the constants k1 and n1 are in Table 5.

Table 5. Constants used to calculate the tube bundle diameter.

43
Figure 11 . Kettle type reboiler [1] .

REFERANCES

 Berk, Z. (2009). Food Process Engineering & Technology (1st Edition). Elsevier Inc.
 Hausbrand, E. (1933) Condensing and Cooling Apparatus, 5th ed, Van Nostrand, New
York.
 Heat Exchanger Design Handbook. Kuppan Thulukkanam, CRC Press.
 Jacobs, H. R. (1988) Direct Contact Heat Transfer for Process Technologies. ASME
Journal of Heat Transfer, Vol. 110, pp. 1259-1270.
 Jacobs, H. R. (1995) Direct Contact Heat Exchangers, Heat Exchanger Design
Handbook.
 Jacobs, H. R. (1995) Direct Contact Heat Transfer, Heat Exchanger Design
HandbookFundamentals of Heat Exchanger Design. Ramesh K. Shah and Dušan P.
Sekulic, John Wiley & Sons, Inc.
 Singh, P.R., Heldman, D. R. (2009). Introduction to Food Engineering (4th Edition).
Elsevier Inc.
 Smith, P. G. (2011). Introduction to Food Process Engineering. Springer Science &
Business Media
 Subramanian, R, S. Thermal Analysis of a Steady State Heat Exchanger. Department of
Chemical and Bimolecular Engineering Clarkson University Journal.
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 Toledo, R. T. (2007). Fundamentals of Food Process Engineering. (3rd Edition). Springer
Science Business Media, LLC. New York.
 Wilhelm, L. R., Suter, D. A., Brusewitz, G. H. (2005). Food & Process Engineering
Technology. (Revised Edition)

 Treybal R.E., Mass Transfer Operations, 3rd Edition, McGraw Hill, 2009.
 McCabe and Smith, Unit Operations of Chemical Engineering, 7th Edition, McGraw
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 Coulson J.M. and Richardson J.F., Chemical Engineering, 6th Edition, Pergamon Press,
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