Chemical Engineering:

Chemical plant III

MODULE A

Only study guide for

CHP311-A/1/2006±2007

Complied byM.L. Janse van Rensburg

Moderated by:M.A Smit

UNIVERSITY OF SOUTH AFRICA

PRETORIA
# 2005 University of South Africa

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CHP311±A/1/2006±2007

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 (iii) LCP409-R/2/2006-2008

Contents

Chapter Page

1 MATERIALS
Introduction 00
1.1 Crystal structures 00
1.2 Different crystal structures 00
1.3 The mechanism of crystallisation 00
1.4 Single crystals 00
1.5 Imperfections in crystal structures 00
1.6 Examination of crystal structures 00
1.7 Mechanical properties 00
1.8 Mechanical testing 00
1.9 Phase diagrams 00
2 CORROSION 00
Introduction 00
2.1 Definition 00
2.2 Corrosne environments 00
2.3 The consequences of corrosion 00
2.4 Corrosion categories 00
2.5 Corrosion forms 00
2.6 Corrosion rate 00
2.7 Thermodynamics 00
2.8 Polarisation 00
2.9 Passivity 00
2.10 Factors influencing the corrosion rate 00
2.11 Cathodic protection 00
2.12 Anodic protection 00
2.13 Materials selection for corrosion resistance 00
3 WATER & WASTEWATER TREATMENT 00
Introduction 00
3.1 Water quality 00
3.2 Water treatment processes 00
3.3 Typical water treatment operations 00
3.4 The water Act 00
Appendix A 00
Bibliography 00
4 AIR POLLUTION 00
Introduction 00
4.1 Air pollution 00
4.2 Natural purification processes 00
4.3 Systems for air pollution control 00
4.4 Control devices for gaseous and particulate contaminants 00
Bibliography 00
Revision questions 00
5 SOLID WASTE MANAGEMENT 00
Introduction 00
5.1 Solid waste 00
5.2 Environmental management 00
5.3 Environmental legistlation 00
Bibliography 00
Revision questions 00
 1 CHP311-A/1

CHAPTER 1

Materials

OBJECTIVES
After completion of this chapter the student should be able to:
. Define the basic terms needed to understand material science
. Discuss the following crystal forms with relation to their structure an properties:
Face centred cubic
Body centred cubic
Close packed hexagonal
. Discuss the mechanism of crystallisation
. Discuss point, linear and interfacial defects in crystal structures
. Describe the basic techniques used to determine crystal structures
. Calculate physical properties from crystallographic data
. Define the following mechanical properties and describe the methods of testing
for these properties:
Yield strength
Tensile strength
Ductility
Hardness
Failure
Creep
. Interpret mechanical testing data
. Interpret simple binary and binary eutectic phase diagrams in relation to:
The phases present
The composition of these phases
The relative amounts of these phases
. Discuss, compare and select various engineering materials with regards to their
properties, appearance and applications.

INTRODUCTION
This chapter will be divided into two parts. The first section will deal with the theory of
materials science as it is relevant to the understanding of the properties of materials. The
second section will deal with the properties of specific engineering materials and their
applications in the engineering industry. Chemical engineers and engineering
technologists are mainly concerned with the properties of materials for specific
applications. You would want to know what material is best suited to withstand certain
chemicals or certain process conditions. In some cases it is a combination of these
factors that is important. For instance, a certain material might be resistant to a corrosive
 2

acid at room temperature, but at an elevated temperature it might corrode. Behaviour

such as this can often be foreseen with a little knowledge of the material properties and
behaviour.

There is a certain amount of prior knowledge required before we plunge into the study of
material structure. Information on basic atomic theory is readily available and the
student is advised to review his/her knowledge on the topic if necessary. A list of key
words is provided that you need to know in order to understand the materials structure
section. You should be able to define these basic terms or easily find them in any basic
matric level science book. If problems are encountered, please contact your tutor.

Make sure that you know what each of the following terms mean or refer to:
. Atomic Number
. Atomic Weight
. Bohr Atomic Model
. Bonding Energy
. Coulombic Force
. Covalent Bond
. Electric Dipole
. Electron Configuration
. Electron State
. Electronegative
. Ground State
. Ionic Bond
. Isotope
. Metallic Bond
. Mole
. Molecule
. Periodic Table
. Polar Molecule
. Quantum Mechanics
. Valence Electron
. Wave - Mechanical Model

1.1 CRYSTAL STRUCTURES

The structures of metals are divided into two main groups, namely crystalline and
amorphous.

You might have encountered the concept of crystal structure before. All metals are
crystalline, as well as many ceramic materials and some polymers. A crystal can be
described as a regular configuration of atoms that repeats itself throughout the structure
of the material. The way in which the various atoms of such a material configure
themselves is therefore dictated by the crystal structure. If a material is not arranged in
any kind of atomic pattern, it is called amorphous. The crystal structure can also be
made up of ions or molecules. The crystal structure of a material is important because
many of the physical properties of the material will be dependent on the crystal
structure. If the crystal structure of a material is known, then some of the physical
properties of the material can be inferred. In the discussion that follows the assumption
was made that all the building blocks of these crystal structures are atoms, and that they
are hard; in other words, they cannot be compressed.
 3 CHP311-A/1

The crystal structure is repeated on groups of atoms. A group of atoms will be bound in
a certain way and this grouping will be repeated to give the total crystal. Each of these
groups is called a unit cell. A unit cell is the smallest group of atoms (or, of course,
molecules or ions) that form the characteristic structure of that material. Metals arrange
themselves according to three categories of crystal structures namely:

1. Face Centred Cubic

2. Body Centred Cubic
3. Close Packed Hexagonal

Before we proceed to discuss each of these crystal structures in more detail, there are a
few terms that we have to define. The first of these terms is called the co-ordination
number. This can be defined as the number of atoms nearest to any particular atom. The
second is the atomic packing factor, which is the fraction of the solid volume of a unit
cell to the total volume of that cell. These numbers are calculated for various crystal
structures and it supplies a basis on which these structures can be compared. Let us look
at the structures in a bit more detail.

1.1.1 Face Centred Cubic

In the face centred cubic (FCC) crystal structure the unit cells have a cubic
configuration. It is easy to imagine the cube as a box, with an atom at each of the
eight corners. In the middle of each of the six sides of the box is another atom, making a
total of 14 atoms. It is not that simple, and the borders of this unit cell have been defined
as the centre of each of the corner atoms. If you imagine the atom as a sphere at the
corner of this box, only one eighth of this sphere belongs to the unit cell. This atom is a
part of eight adjacent unit cells and they all share an equal part of the atom. This is the
case for all the corner atoms. Each of the atoms on the sides of the box model shares one
other unit cell, so in essence only half of this atom belongs to the unit cell. Each unit cell
therefore needs 14 atoms to form its structure, but it only comprises 4 atoms.
   
1 1
 8 ‡  6 ˆ 4
8 2

Examples of metals that have a face centred cubic crystal structure are aluminium,
copper, gold, lead, nickel, platinum and silver.

1.1.2 Body Centred Cubic

The body centred cubic (BCC) crystal structure resembles the face centred cubic
structure in that there are eight atoms at the corners of a cube, but in this case the atoms
in the sides of our imaginary box are absent. There is a single atom right in the middle of
the box (or in the centre of the ``body'' of the unit cell). In the case of a body centred unit
cell, the cell consists of two atoms, one being made up of the one eighths of each of the
eight corners as in the case of the FCC structure and one in the centre of the unit cell.
The corner positions and the centre positions are equivalent because each centre atom is
in turn a corner atom for another unit cell. The co-ordination number for each of the
atoms in the BCC structure is eight, because each atom is surrounded by eight closest
neighbours. This is easy to understand if one imagines oneself in the position of being in
the centre of the unit cell, being surrounded by the eight corner atoms. The atomic
packing factor in the case of the body centred cubic crystal structure is 0.68. This is
lower than in the case of the FCC crystal structure which has an atomic packing factor of
 4

0.74. Remember that the packing factor is the volume of atoms per unit cell, and in the
case of the body centred cubic crystal structure there are more atoms per unit cell than in
the case of the face centred unit cell.

Metals with a body centred cubic crystal structure are chromium, iron, tungsten,
tantalum and molybdenum.

1.1.3 Hexagonal Close Packed

The third important crystal structure found in metals is the hexagonal close packed
(HCP) structure. It comprises of layers of atoms arranged in hexagons (six atoms, one
forming each corner) with an atom in the centre. This hexagon is packed on top of
another one, which is shifted so that the atoms of the second hexagon are half way
between the atoms of the first one. At the bottom is a third layer with atoms
corresponding to the first one. The resulting unit cell therefore consists of two of these
seven atom hexagonal structures on top of each other with a section of one of these
consisting of three atoms in between.

The co-ordination number and the packing factor for the HPC structure is the same as
for the FCC structure, namely 12 and 0.74. Metals that have this crystal structure are
cadmium, titanium and zinc.

1.2 DIFFERENT CRYSTAL STRUCTURES

We have now seen that different metals have different crystal structures. This is true, but
it is also a slight oversimplification. It is possible that one metal may have more than one
of these crystal structures. Which of these crystal structures it has will depend on the
temperature and the pressure. This property is called polymorphism. If an elemental
solid is found in more than one crystal structure it is called allotropy. One of the more
well known polymorphs is carbon. At room temperatures and normal pressures carbon is
found in graphite form, and at high temperatures and pressures diamond is formed.
Another example is iron, which has a BCC crystal structure at around 15388C. As it
cools to about 14018C it becomes face centred cubic (FCC) and at around 9108C it
becomes BCC again.

1.3 THE MECHANISM OF CRYSTALLISATION

Before we look at the different ways in which these crystal structures can be distorted,
let's look at the process of crystallisation. You should know that crystallisation is a
solidification process - in other words a mechanism of forming a solid from a liquid. It
happens according to a specific mechanism which distinguishes it from ordinary
solidification. Crystallisation takes place in two stages, which are called nuclei
formation and crystal growth.

The internal energy of atoms or molecules in any given state is dependent on the
temperature of the material. In the liquid phase the internal energy is dependent on the
temperature of the liquid. The higher the temperature (and thus the internal energy), the
faster the movements of the atoms in the liquid with regards to each other. In some cases
the atoms arrange themselves in groups that resemble sections of a unit cell or unit cells.
In these groups the atoms are the correct distances from each other to be able to form a
 5 CHP311-A/1

unit cell, and they are in the correct orientation. If the temperature of the liquid is high
this process of spontaneous group formation is being inhibited by the random
movements of the different particles because of their internal energy.

The groups are often destroyed because some of the particles break away. If the number
of particles that belongs to the group is small the group might be unstable and break up.

As the temperature of the melt (liquid) starts to decrease, the kinetic energy drops and
the movements of these particles become slower. When the temperature has dropped
enough these groups become more stable because less particles break off them. Sections
of crystals start to form spontaneously. These sections are called nuclei and the crystal
structure starts to grow around these nuclei. More and more atoms attach themselves to
these nuclei and gradually crystals start to form. These crystals continue to grow in three
dimensions. The atoms have a preference to attach themselves to this crystal structure in
certain directions and this results in treelike structures which are called dendrites. All
these dendrites have different shapes and different orientations in relation to the others,
even though they are constructed from the same unit cells. This is easy to imagine,
because one can use the same shape and size of bricks and build many different shapes
of houses.

These dendrites keep growing until the majority of the liquid has crystallised. The gaps
between the different dendrites will be filled up and the growth of these dendrites will be
obstructed in these areas. These areas are called grain boundaries and they are areas of
mismatch between the different crystals. They lead to various deficiencies in the
material, but crystal imperfections will be discussed in the next section. The grain
boundaries sometimes have an amorphous structure because the atoms there do not
assume any fixed structure.

Once you understand the mechanism of crystallisation it is easy to explain why some
materials have a larger grain size than others. In some materials there are many fine
grains while others have fewer, coarser grains. What could affect this? There are two
things that influence the size of the grains formed, namely the rate of growth of the
grains and the number of nuclei formed. If the number of nuclei formed is high there
will be many grains and they will be smaller. In the case of a few nuclei the grains will
be less and bigger. What determines how many nuclei form?

The main factor is the rate of cooling. If the cooling is done fast then many different
nuclei will form and as a result of that the grains formed will be small. If the rate of
cooling is slow (for instance, when cooling is done in air) then a few nuclei will form
and the grains will have a lot of time to grow. As a result the grains will be larger. The
number of nuclei formed will also be affected by impurities. Often impurities in metal
melts act as nuclei for crystallisation, and as a result of that the number of nuclei that
will be formed increases as the impurities increase. Stirring or upsetting the melt during
crystallisation will break up the grains and will also reduce the grain size.

1.4 SINGLE CRYSTALS

In some isolated cases it is possible to grow a crystal that is perfect throughout, without
any dendrites producing areas of mismatch. This can be done by keeping the melt at a
constant temperature, just around its freezing point (in other words, making sure it does
not cool too fast) and touching the surface of the melt with a tiny crystal (called a seed).
When this happens the solution will tend to crystallise around this one seed and not form
new crystallisation nuclei. If this crystal is removed from the melt slowly one crystal is
produced. In cases such as these all the unit cells are interlinked perfectly and in the
 6

same orientation. Such a crystal is called a single crystal. Single crystals are sometimes
found in nature and they can be grown under extremely well controlled laboratory
conditions. The edges of single crystals would be smooth and they would not exhibit the
dendritic structure of granules (crystals consisting of different grains). Single crystals
find wide application in the electronics industry in relation to semi conductor
development. When a crystal has developed from various crystallisation nuclei, it is
called a polycrystalline material.

1.5 IMPERFECTIONS IN CRYSTAL STRUCTURES

We have now discussed perfect crystal orientations and a perfect single crystal. As you
might be well aware the real world is far from perfect and the same is true for real
crystals. There are various imperfections in real crystals and we are going to look at a
few of these. They are important because they change the nature of the crystal and
anything that changes the nature of the crystal changes its properties and is therefore the
concern of the material scientist and engineer.

1.5.1 Point Defects

Point defects are imperfections that occur at a single point in the crystal. The first two
point defects appear in pure crystals.

1.5.1.1 Vacancies
Vacancies are, as the name describes, empty sites in the crystal structure where an atom
is supposed to be. These vacancies are formed when the crystals solidify, or they can be
formed by lattice vibrations inside the crystal. Normally the concentration of vacancies
is such that one lattice site (position in the crystal structure) in 10 000 will be empty in
the crystal when it is just below its melting point. Figure 1 shows a schematic
representation of a vacancy.

FIGURE 1: Point defects

1.5.1.2 Self interstitial

A self interstitial develops when one of the atoms in the crystal wedges itself in between
the normal arrangements of atoms. This often causes quite a bit of distortion because the
atom is normally larger than the space it moves into. Figure 1 also shows a
representation of a self ± interstitial.
 7 CHP311-A/1

1.5.2 Impurities
We have now seen how a pure metal can be distorted by its own atoms. Now let's take a
look at the crystallographic defects one can find that are caused by atoms other than that
of the pure metal. The chance of a metal being 100 % pure is almost zero. So we can
safely assume that most metals have some atoms of other substances in their crystal
structures. In some cases different atoms are added to a pure metal intentionally. By
adding one metal to another one will alter the properties of the pure metal. This
technique is used extensively to produce materials with certain desired properties. For
instance if a metal is very soft another one can be added to it to make it harder. The same
applies in the case of metals that are attacked by certain corrosive environments. For
example, copper is normally added to silver to make it harder.

When impurities are added to a metal two things can happen. It can form a solid solution
or it can form a second or a new phase. The difference between these two types of
material can be imagined as follows. If metal A is added to metal B and a solid solutions
forms it is in effect a mixture of two metals, with the one dissolved into the second one.
The particles of the one are distributed more or less at random through the structure of
the second metal. In the case of a new phase forming the atoms of the original metal and
that of the new metal merge to form a new type of structure. This structure then consists
of particles of this new type and not merely a mixture of the two previous types. Alloys
are examples of cases where two or more metals were mixed and a new phase formed.
This new phase will then have its own characteristic physical properties (such as melting
and boiling point, etc.).

You might wonder under which circumstances a solid solution will form when two
metals are brought into contact with each other and when a new phase such as an alloy
will form. There are a few things that will help us in predicting whether a solid solution
or a new phase will form. They are:

1. Size.
2. Electronegativity of the atoms.

The first of these is size. There are two types of solid solution structures possible. The
one is called a substitutional solid solution and this one occurs when the two atoms that
are in contact with each other have more or less the same diameter (within about 15%).
The atom of the second metal just takes up a place in the lattice structure of the original
metal and it is absorbed in the crystal structure without changing it. In cases where the
atoms of the impurity metal are much smaller than that of the original metal an
interstitial solid solution can be formed. In this case the smaller atoms just position
themselves between the larger ones in the lattice structure. This will only happen in
crystal structures where there is a relatively low packing factor; otherwise there would
not be space for the smaller atoms to fit in between the others in the crystal lattice.

In the case of a solid solution the structure is basically the same as in the case of the pure
metal, with the atoms of the second metal acting mainly as impurities. Figure 2 gives a
representation of how this would look.

If the two atoms are different in size but the difference is not large enough to allow the
one atom to fit into the lattice structure of the larger one, the chances are that the two
atoms will form a new compound.

The second factor that needs to be considered is the electronegativity of the two different
atoms. From chemistry it is known that the bonding of metals depends on their
electronegativities. A large difference in electronegativity between the two atoms
 8

FIGURE 2: Different kinds of solid soutions

favours the formation of a new substance. This happens because the one would donate
an electron and the other would absorb an electron and so form an ionic bond. The
crystal structures of the two metals also determine whether a solid solution or a new
phase will be formed. If the two materials have a similar crystal structure they would be
likely to form a solid solution because the atoms are inclined to stay in the same crystal
structure and they would just dissolve into each other. If the metals have different crystal
structures they would form a new compound crystal structure that can accommodate
both metals.

1.5.3 Dislocations
All the defects in crystal structures we have dealt with up to this point have been limited
to a single point within a crystal structure. Dislocations are linear defects within the
lattice structure. They deform the crystal structure and thus cause internal stresses. There
are two main types of dislocations or dislocation lines, namely an edge dislocation and a
screw dislocation. As you can see in figure 3, an edge dislocation forms if a section of a
row in the crystal structure is inserted in the normal crystal structure. This causes the
crystal structure around the dislocation to distort. The further away you are from the
dislocation, the less apparent is the distortion until at a point it is eliminated entirely.

FIGURE 3: Crystal structure of an edge dislocation

 9 CHP311-A/1

A screw dislocation is formed by a shear stress and it appears as if the lattice structure
has moved up one place and is distorted as a result of that. A typical screw dislocation is
shown in figure 4. In some cases a mixed dislocation is found, which is a combination of
screw and edge dislocations.

FIGURE 4: Crystal structure of a screw dislocation

The various dislocations have a definite effect on the properties of the materials. Both
interstitial and substitutional defects, whether by the same or a different substance,
introduce strain into the crystal structure. Dislocations have the tendency to "move"
through the metal or compound. It is in effect the atoms that just move into the empty
spaces left by the dislocation, but it causes the dislocation to "move up". If this happens
continuously it can lead to the concentration of dislocations, because the atoms will find
it harder to move across more than one empty space. These concentrated dislocations
weaken the metal because this dislocation area can be the beginning of a fracture. In
places of increased strain, such as in the interstitial and substitutional point defects
mentioned above, the energy needed to move the atoms in the lattice structure is
increased because of the increased strain. This then serves to strengthen the metal. Very
often a pure metal is strengthened by the addition of an impurity.

In order to reduce lattice strain to minimum, solute atoms (the less abundant metal
atoms) sometimes move in the direction of a dislocation line. When these solute atoms
are larger than the atoms in the lattice structure they will prefer to move to below the
dislocation line, and if they are smaller than the atoms in the lattice structure they will
move to spaces above the dislocation line. The result is that there is a concentration of
solute atoms in the region of dislocation lines.

1.5.4 Interfacial Defects

We have considered linear defects that can be found in crystals. In this section we are
going to take a look at the multidimensional defects that can be found in crystals.

1.5.4.1 External Surfaces

Although there is no way that we can grow or manufacture a crystal that does not have
an external surface (because then it would have to have an infinite or a zero volume) it is
none the less considered to be an imperfection in the crystal structure of a metal. The
atoms on the surface of the metal are bound to fewer atoms than the ones in the middle
 10

of the lattice structure. They are less stable because they are bound to fewer atoms than
the internal ones and because of that they are more reactive or they are said to have a
higher energy state.

1.5.4.2 Grain Boundaries

We have touched on grain boundaries before. When a crystal forms, it starts forming
around several crystallisation nuclei. Around each nucleus a crystal starts forming
according to the crystal structure favoured for that particular metal. At the end of the
crystallisation process all these crystals have to be connected and the grains of the
different crystals cannot grow freely in the last section of solidification because of other
crystals competing for space. All the boundaries of these grains are therefore areas of
imperfect crystal structure. These grain boundaries contain impurities as well as atoms
that are imperfectly bound. The fact that the grain boundaries are less stable once again
leads to a state of higher energy. This energy is called grain boundary energy

1.6 EXAMINATION OF CRYSTAL STRUCTURES

At the beginning of this section we said that the reason why we study the crystal
structure of materials is the fact that it gives us an indication of what the relationship is
between the microstructure of the material and its physical properties. Once it is known
how the microstructure of the material affects the physical properties we can predict
certain things about the materials. This section takes a brief look at the most common
methods by which the structures of materials are observed.

Observations of crystal structure can be made on either a macroscopic or a microscopic

level. On a macroscopic level it is sometimes possible to see grains in certain materials,
but material structures are better observed on a microscopic level. The way in which this
is most often done is microscopy. There are two main microscopic techniques, namely
electron microscopy and optical microscopy.

1.6.1 Optical Microscopy

An optical microscope operates by shining a light on the surface of a material and
magnifying the reflection of the light. The surface of any material reflects light that falls
on it according to the composition and properties of the material. The difference in the
reflection from different areas on the surface of the metal gives us an image of the
surface. Normally the surface has to be treated to make the best observation possible.
The preparation is done by grounding the surface of the sample. After it has been ground
it is polished with increasingly finer abrasive papers or powders. Lastly the surface of
the specimen is treated with a chemical substance, normally an acid.
This treatment is the last step used to reveal the microstructure of the metal. In our
discussion on crystallographic defects we have said that the grain boundaries have a
higher energy state than the other regions in the grain because the atoms are bound to
less than the maximum number of adjacent atoms. This also implies that the grain
boundaries are more reactive to chemical substances than the rest of the structure.

Under treatment with chemical substances the grain boundaries are affected at a greater
rate than the rest of the surface and it makes it easier to see the grain structure of the
metal. The different phases in the metal also react at different rates with this chemical
and this makes them more visible. The procedure of treating a metal with an agent that
reveals the surface is called etching.
 11 CHP311-A/1

Optical microscopes can enlarge objects up to about 2000 times. Above that more
sophisticated techniques are required to determine the crystal structure of materials. It is
here we enter the field of electron microscopy.

1.6.2 Electron Microscopy

This technique allows us to enlarge specimens up to 1 000 000 times. Electron
microscopy can be done either by a transmission electron microscope (TEM) or by a
scanning electron microscope (SEM). We have seen that, in the case of an optical
microscope, light was reflected off the sample and that was magnified to give us an
image of the specimen. In the case of an electron microscope electrons are aimed at the
sample. It can be proven that an electron moving at a high velocity will possess certain
wave properties, and the higher the velocity of an electron, the shorter the wavelength.
The beam of electrons is focussed on the sample with magnetic lenses.
In the case of a transmission electron microscope (TEM) the beam of electrons passes
through the sample. It is important that the samples used in this apparatus be very thin
because if not the beam of electrons will be absorbed by the sample. The electrons pass
through the sample and are scattered according to the structure of the sample. They fall
on a photographic film or a fluorescent screen and this image can be interpreted to give
an indication of the structure of the sample. In the case of a transmission electron
microscope magnifications of up to 1 000 000 magnifications are possible and this
makes it possible to study the dislocations and imperfections in the crystal structure.
In the case of a scanning electron microscope the sample is scanned with a beam of fast
moving electrons and the electrons are reflected off the surface of the sample. These
scattered electrons are collected and the image displayed on a cathode ray tube. The
image resembles a television screen image. The surface of the sample must be
electrically conductive for this technique to work, and therefore the samples are coated
with an atomic layer of gold or carbon to make them electrically conductive. The surface
of the sample can be magnified from 10 times to 50 000 times and it can also be
examined to considerable depth. The scanning electron microscope is often used to do
qualitative and semi-quantitative analyses of chemical composition.
For instance, the SEM can determine that, in a given sample, there is carbon, aluminium
and zinc, and that there is 50%, 30% and 20% of each of these substances on any
particular spot in the sample. It can be put to extensive use in the manufacturing of
alloys or ceramics where the specific composition of the substance is important, as well
as the form in which the components occur. In the manufacture of ceramics, for instance,
it is often important that a certain substance be present in a whisker form rather than in a
granular form in order to contribute towards a specific physical property. This
information can be supplied by a SEM.

Example 1.1
Crystalline polythene has a unit cell which contains two molecules of C2H4. The unit
cell dimensions are 2.53 AG 6 4.93 AG 6 7.40 AG. Calculate the density of 100%
crystalline polythene.

Answer
4 Catoms 6 l2g/mol + 8 Hatoms 6 1g/mol
Mass/unit cell = ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
6.023 6 1023 atoms / mol

= 9.30 6 10-23 g
 12

Volume/unit cell = (2.53 AG 6 4.93 AG 6 7.40 AG)(10-8 AG/cm)3

= 9.23 6 10-23 cm3

9.30 6 10-23g
Density = ÐÐÐÐÐÐÐ
9.23 6 10-23cm3

= 1.01 g/cm3

The experimental density is 0.92±0.96, depending on degree of crystallinity, due to less

than perfect packing.

1.7 MECHANICAL PROPERTIES

We have now dealt with the basic crystal structures as well as techniques used to detect
and evaluate these structures. The mechanical properties of a material produce a
terminology in which the physical structure of the material can be described.
At this stage we are dealing mainly with the mechanical properties of metals. We will get
to other engineering materials a bit later in the chapter. As said before there is a
correlation between the crystal structure of a metal and the mechanical properties of that
metal. We need different terms to be able to describe the mechanical properties of a
material properly, because this will enable us to specify the type of material for a specific
application very precisely.
Materials in use are continuously subjected to forces. There are four basic ways in which
a force can act on a body. Invariably the material will be affected by these forces acting
on them and the extent to which they are affected will be determined by their mechanical
properties. The basic forces are:

. Tension
. Compression
. Shear
. Torsion

Tension and compression forces are fairly straight forward and are illustrated in figures 5
(a) and (b). A shear force will have the effect of moving two parallel sides of the
specimen in opposite directions to one another, and torsion is similar to a shear force, but
the surfaces are now turned or twisted with respect to each other. Shear and torsion can
be seen in figure 5 (c) and (d).

FIGURE 5: (a) Compression (b) Tension (c) Shear (d) Torsion

 13 CHP311-A/1

1.7.1 Stress and Strain

When an engineering material is subjected to an external force there is an internal
resistance to that force. This internal resistance prevents the material from falling apart
and is caused by the bonding forces in the material. This internal resistance is called a
stress. The larger the area over which the external force is applied the smaller is the
internal force required to counter that force. This internal force is called a stress and it
can be defined as follows:

force
stress = ÐÐÐ
area

The normal result of any force applied to a material is that the dimensions will be
changed. A tensile force will elongate the material along the axis at which the force is
applied, a compressive force will make it shorter along the axis at which the stress is
applied and the shear stress and torsion will result in the material being twisted. The
internal force experienced when, for example, a tensile (pulling) force is applied to the
material is called a tensile stress. Similarly there are compressive, torsional and shear
stresses.

Strain is related to the elongation of a material. Strain tests are normally performed on
cylindrical or rectangular samples. A load is applied to these specimens and this load is
increased gradually. If we are performing a tensile test the load will have the effect of
increasing the length of the sample. Typical sample diameters are of the order of
12.8 mm, and the length should be at least four times the diameter. The apparatus is
designed so that the rate at which the sample is elongated is constant. Typically the
sample will elongate in the centre and eventually the sample will snap. This type of
testing leads to the destruction of the sample and is thus termed destructive testing.

The load applied as well as the elongation is recorded and the strain c is calculated as:

li ÿ lo
" ˆ
lo

where li is the instantaneous length (the length at any particular time) and lo is the
original length of the sample.

A compressive force causes a reduction in length so that the strain for a compressive
force will be negative. You should know that the negative convention in science
indicates an opposite in direction, so a compressive strain is a strain in the opposite
direction to the tensile strain. The application of a shear force causes the sample to twist.
Figure 6 shows a shear force applied to a rectangular prism that is twisted through an
angle cp. In this case the force creates a shear stress, 'c, which is given by

F
 ˆ
A

as usual. The shear strain, , is calculated from the amount of displacement x of two
x
elements separated by a distance y, ˆ (see fig. 6). Y
y

1.7.2 Yielding and Yield Strength

When the applied force is relatively small, the metal can return to its original shape once
the force has been removed. Some material such as ceramics can return to their original
 14

FIGURE 6: calculation of shear strain

shape up until the point where the material snaps. In the case of most metals, however,
there is a region where the metal can be deformed, but it does not return to its original
shape. This is easy to see if one pulls on both ends of a plastic drinking straw. Initially
the straw just gives way and then, once left, returns to its original shape. After a while,
as the force increases, the deformation is permanent and it cannot be returned to the
original shape. The phenomenon that allows the straw to elongate and then return to its
original shape is called elasticity. When the straw can still be stretched but cannot be
returned to its original shape it is called plasticity. The point where the plastic
deformation begins is called the yield point and the stress applied at that particular point
is called the yield stress.

Figure 7 shows a graph of the applied force against the linear extension for a metal. As
can be seen, the first section of the graph is linear, so the strain (elongation) is
proportional to the stress (internal force to overcome external one). At point A the metal
extends faster than the rate at which the force is increased and this is the point where the
elastic limit is crossed and some permanent deformation takes place. Point A is thus
called the limit of elasticity or the elastic limit.

For a fully elastic material (no plastic deformation) the ratio of the stress to the strain
will be a constant for that particular material.

stress ()
E = ÐÐÐÐÐ where E is just a numerical constant.
strain (")

This proportionality is an expression of Hooke's law. E is also sometimes called the

modulus of elasticity. This elastic limit is also applicable in the case of shear stresses.

shear stress ()

G = ÐÐÐÐÐÐÐ where G is called the modulus of rigidity.
shear strain ( )

1.7.3 Anelasticity
Under normal elastic behaviour a metal is deformed when a load acts on it and once the
load is removed the metal returns to its original shape. In some cases the metal takes a
while longer to respond to the stress. This results in the elastic deformation of the metal
continuing after the load has been applied and, once the load has been removed, the
metal does not return to its original state immediately. This time dependant elastic
behaviour is called anelasticity or anelastic deformation. This anelastic behaviour is
 15 CHP311-A/1

FIGURE 7: Elastic vs. Plastic deformation

related to the microscopic changes in the metal. Anelastic deformation is reversible, so

although the metal does not respond to the removal of the load instantaneously, it will
return to its original shape completely in due time.
In the case of metals, however, the anelastic behaviour is small compared to the elastic
and plastic deformations and it is often ignored.

1.7.4 Tensile Strength

We have seen that yielding is the point at which we go from the region of elastic
deformation to the region of plastic deformation. In any typical stress - strain test, if the
load is applied after the yield point the stress needed to continue further plastic
deformation increases to a maximum. After this maximum point the stress decreases
again. Figure 8 shows this phenomenon.

The maximum stress is at point TS on the graph. This stress is called the tensile strength.
It is measured in psi or in MPa. This is the maximum stress that a structure can withstand
when it is subjected to a load. If this stress is applied for a long enough period the given
structure or sample will fracture. This is also the point in the stress ± strain test that
``necking'' occurs. Up to this point all the deformation that takes place in the sample was
uniform throughout the whole sample.

FIGURE 8: Typical stress-strain curve for metal

 16

At the tensile strength a section of the sample becomes thinner to form a neck. All the
deformation that occurs after this point occurs at this neck. If the structure eventually
fractures it will also do so at the neck. The fracture strength of the metal corresponds to
the stress applied at the point at which the metal fractures. In figure 8 the point TS
represents the tensile strength and the point F represents the fracture strength. You will
see that the fracture occurs at a stress lower than the tensile stress.
In designing a structure the strength that the structure must be able to withstand has to be
specified. With knowledge of yield, tensile and fracture strengths at your disposal, which
of the possible strengths would you specify? If you said the yield strength you agree
with most engineers. This is done because, if the tensile strength is specified the metal or
structure will suffer a great deal of plastic deformation under normal loading conditions,
and that is irreversible.

1.7.5 Ductility
Ductility is another physical property that you should be familiar with. Ductility is the
degree of plastic deformation that a material undergoes before it fractures. In an extreme
case a material will break without deforming, or without deforming very much. This
material is termed brittle. If a material is deformed a lot before it fractures it is termed
ductile Ductility can be expressed as the percentage elongation a material undergoes
before fracturing, or as the percentage area reduction that a sample undergoes. The
percentage elongation can be calculated as follows:

100…lf ÿ lo †
%EL ˆ
l0

where lf is the final length of the sample and lo is the original length.
The percentage area reduction can be calculated in a similar way. The original length is
replaced by the original area and the final length is replaced by the final area.
Most metals possess some degree of ductility at room temperature. This physical property
is affected quite dramatically by a change in temperature. The effect of temperature on
mechanical properties will be discussed later in this section. In some cases a ductile metal
is used in design because it can deform quite a bit before it fractures. This allows for
small tolerances in design. In most cases a metal that has less than 5% ductility is
considered to be brittle. Figure 9 shows the typical tensile stress ± strain behaviours for a
brittle and a ductile metal. In the one case there is a large area of plastic deformation and
in the other the metal fractures early on the plastic deformation line.

FIGURE 9: Typical stress strain behaviour for brittle and ductile

 17 CHP311-A/1

1.7.6 Resilience
Resilience measures the capacity of a material to absorb energy when it is deformed in
the elastic deformation range. This energy is stored and can be recovered from the
material when the load is removed. Resilience is usually expressed as the modulus of
resilience. The modulus of resilience is the energy that is needed to stretch a unit volume
of a sample up to the point of yielding. The modulus of resilience can easily be
determined from the stress ± strain curve. It is given by the area under the curve. The
units of resilience are the product of the two units on the axes of the stress- strain plot.
kg m
The units of stress are Pa, or N2 or 2 and the units for strain are or dimensionless.
m ms m
kgm2
The units for energy are Joules, or Nm or 2 , so the area under the curve has the units
s
Joule
of Pascals, or similarly . Thus the resilience of a material is the energy absorption
m3
per unit volume of material.

Resilient materials have high yield strengths and low moduli of elasticity. They are often
used in spring applications. The modulus of elasticity for a material gives an indication
of the rate at which the elastic deformation of a metal takes place. It is also given by the
slope of the stress ± strain curve. For most metals the stress and the strain in the elastic
range are proportional to each other, and the stress ± strain graph is a straight line in that
region. Figure 10 shows the graphical determination of the modulus of resilience.

FIGURE 10: Determination of the modulus of resilience

1.7.7 Toughness
The term toughness is related to the fracture behaviour of the metal. If considerable
energy is needed to fracture the metal, and a considerable amount of plastic deformation
foregoes the fracturing of the metal, then the metal is said to be tough. The type of
fracture that will occur in any particular case is dependant on the type of material, the
nature of the stress applied and the environmental conditions. In some cases materials
will fracture in a fast ``brittle like'' fashion at a tension well below the yield stress. This
occurs due to cracks in the material. The resistance of the material to this type of
fracturing is called fracture toughness.
 18

We have seen before that most materials contain some or other imperfections in their
crystal structures. Internal cracks are part of these standard imperfections in materials. A
material can fracture by means of two main mechanisms; tearing occurs in the case of
ductile materials and cleavage occurs more in brittle materials. In the case of tearing the
material fractures by undergoing plastic deformation just before the tip of the crack. A
lot of energy is used to bring about this plastic deformation. The plastic deformation also
has the effect of blunting the tip of the crack. Once the tip of the crack is less sharp, the
stresses that are concentrated at this tip are reduced.
This type of fracturing normally proceeds slowly and often the crack does not propagate
far before the process is terminated. In the case of brittle materials there is very little or
no plastic deformation possible. The edge or tip of the crack is very sharp and a lot of
internal tension is concentrated there. There is no mechanism by which these stresses
can be relieved and this stress is greater than the bonding energy of the atoms in the
crystal lattice. The interatomic or intermolecular bonds are severed and the material
splits extremely fast, resulting in a brittle fracture. Glasses, ceramics and brittle metals
fracture in this way.
Various methods can be employed to strengthen the material. One is the insertion of
fibres in the material. These fibres absorb some of the concentrated tensions in the tip of
the crack and they also keep the material together. The development of materials with
internal fibres is a growing field of research.

1.7.8 Hardness
The hardness of a material can be described as the resistance of the material to small
dents and scratches. There are various ways in which the hardness of a material can be
determined. These tests will be discussed in the next section.

1.8 MECHANICAL TESTING

This section deals with the various tests that can be performed on a specimen to
determine its physical properties. Some of these tests have been discussed briefly in the
previous sections and others we will deal with for the first time.

1.8.1 Tensile Test

Figure 1 1 shows the apparatus that is used to perform tensile stress- strain tests.

FIGURE 11: Tensile testapparatus

 19 CHP311-A/1

The sample is clamped in the apparatus and the moving crosshead is extended to exert a
tensile stress on the sample. The load cell measures the magnitude of the load (force)
applied and the extensiometer measures the degree of elongation of the sample. The
stress and the strain can then be calculated from this data. Compression tests can also be
conducted in a similar apparatus. In the case of a compression test the sample will
contract along the direction of the applied force. Compression tests are used in the case
of brittle materials.
Figure 12 shows typical stress- strain results for four different engineering materials. It
can be seen that the mild steel exhibited a large strain before fracture. This is due to the
high ductility of mild steel. Other materials that will also exhibit this behaviour are
aluminium and copper. Cast iron and glass fibre are brittle materials and they fracture
before exhibiting plastic deformation.

The interesting thing to note about concrete is that it has a bigger stress limit under
compression than under tension. This also corresponds with the fact that concrete is
usually used under compressive load, because that is where the greatest strength of the
material lies.

In the case of rubber we see quite an uncharacteristic stress - strain graph. Initially there
is a large region where the stress is extremely low, followed by sharp rise. This can be
explained if one remembers that rubber is made up of long polymer chains. When this
substance is put under load it initially absorbs the energy by elongating all these chains.
Thereafter the lattice structure begins to resist the external force with a rapid increase in
stress. This accounts for the last section of the graph.

Example 1.2
The following data were obtained from a high-strength aluminium alloy. A 12.8 mm
diameter tensile specimen with a 50.8 mm gauge length was used. The load and gauge
strength were obtained experimentally, whereas the stress and strain were calculated.
Plot the engineering stress-strain curve. Calculate the tensile strength, the yield strength
at 0.2% offset, the percent elongation and the percent reduction in area.

Gauge length Stress,

Load, lb in Strain MPa
0 2 0 0
4000 2.0041 0.002 138
8000 2.0079 0.004 276
10000 2.0103 0.005 345
12000 2.0114 0.006 414
13000 2.0142 0.007 449
14000 2.0202 0.01 483
16000 2.0503 0.025 552
16000 2.099 0.05 552
15600 2.134 0.067 538
 20

Answer

Tensile strength = 552 MPa

Yield strength at 0.2 percent offset (0.002 strain) = 475

MPa E = 276 MPa / 0.004 = 6.9 6 104 MPa

Percent elongation = 0.067 6 100 = 6.7%

…=4†…0:0128†2 ÿ …=4†…0:0119†2
Percent reduction ofarea =  10 ˆ 14:1%
…=4†…0:0128†2

Example 1.3
We have a rectangular bar 25.4 mm 6 12.7 mm 6 254 mm long of the aluminium alloy
in Example 1.2. The bar is hung from one end and a 156250 N load is placed on the
other end. The bar undergoes an increase in length. Determine the stress, the elastic and
plastic components of strain, and the bar length when under load.

Answer
force 156250
Stress = ˆ = 484 MPa At this stress the total strain is
area …0:0254†…0:0127†
0.010 m/m

(Example 1.2). Therefore the strained bar length is

254 mm + (254 mm 6 0.010 mm/mm) = 256.5 mm

 21 CHP311-A/1

when the bar is unloaded, the stress follows a straight line that follows the modulus of
elasticity E. Therefore we can calculate the elastic component of strain

stress 484MPa
"el ˆ ˆ ˆ 0:007
E 6:9  104 MPa

Because "total ˆ "el ‡ "pl

"p1 = 0.010 ± 0.007 = 0.003

1.8.2 Hardness Test

There are two very well known tests for determining the hardness of materials, namely
the Rockwell and the Brinell hardness tests. In the case of the Rockwell hardness test a
hardened steel ball or a diamond indentor is driven into the specimen with a given force.
This produces a dent in the material and the depth to which this ball or indentor
penetrates the material indicates the hardness of the material. This test can be used for all
alloys and metals. The balls vary in diameter from about 1.6 mm to 12.7 mm. Each test
consists of the application of two loads, a light load and a heavier load. This is done to
provide a suitable standard for the test results. The difference in the penetration depth of
these two loads is used for the hardness determination.

The Rockwell test is subdivided into the Rockwell and the superficial Rockwell tests.
The difference between the two tests lies in the size of the loads applied. The table below
indicates the different loads applied in each of these tests.

Rockwell Test Superficial Rockwell Test

Minor = 10 kg Minor = 3 kg
Major = 60100150 kg Major = 15 30 45 kg

Each of these scales is represented by a letter of the alphabet, as well as the load. In the
case of the superficial test, and in the case of the Rockwell test, the letters of the alphabet
indicate the different loads and the indentors. The superficial test is applied to the softer
materials and the Rockwell test is applied to the harder materials. There is an area of
overlap between these two tests. These tests can be inaccurate in cases where the wrong
test is used for the specific application, where the test specimen is too thin, where the
indentation is made too close to the edge of the specimen, or where two or more
indentations were made too close to each other. The surface of the specimen to be tested
must also be smooth in order for the results to be useful.

The Brinell hardness test is similar to the Rockwell test. A hard spherical indentor is
forced into the specimen and this force is applied for between 10 and 30 seconds. These
indentors are made of either tungsten carbide or hardened steel. The loads applied are
between 500 kg and 3000 kg. The typical indentor diameter is 10 mm. The diameter of
the indentation left by this indentor gives the Brinell hardness. This hardness is affected
by the magnitude of the applied force.

There is an approximate relationship between the hardness of a material and the tensile
stress, because both these measures are indicative of the metal's resistance to plastic
deformation. The conversion from the hardness to the tensile stress can be done as
follows:
 22

FIGURE 12: Typical stress ± strain curves

Tensile Stress (MPa) = 3.54 6 Brinell Hardness

1.8.3 Fatigue and Creep Testing

These two mechanisms are the two most common reasons for metal failure. Before we
discuss the tests conducted to determine these, let's briefly define fatigue and creep.

Fatigue failures occur when a material is subjected to a load for a long period of time
.The load at which a material will fail is lower than the load that will result in fracture in
a single stress-strain test. Because the load at which failure occurs is lower than would
 23 CHP311-A/1

be predicted by normal stress strain tests, failure often occurs unexpectedly and causes
quite dramatic upsets in the operation of plants. During the fatigue process cracks appear
in the material, but they often go undetected because of their size and location (they are
often in corners or covered with dirt or corrosion products).

Creep occurs when a material is subjected to a constant stress over a long period of
time. This leads to the development of a strain. This strain is dependant on the
temperature. Most metals creep slowly at room temperature, but the rate of creep
increases rapidly with temperature increases.

Fatigue tests can be carried out in a laboratory. The sample is clamped and one of the
following types of loads is applied to it over a prolonged period of time:

. Push ± pull
. Rotating bending
. Reverse bending
. Torsion

These loads are usually applied sinusoidally and the amplitude of the applied force is
kept constant. In a real life situation the load changes applied to the structure would be
random, but the sinusoidal forces used in the tests are a fair approximation. For any
particular material a series of specimens are tested until failure for different values of
stress amplitude. The results of a failure analysis are reported as a graph. Each of these
tests represents one point on the graph. The stress amplitude is plotted on the y axis and
the number of cycles before failure is plotted on the x axis.

Creep tests are done in an apparatus such as in figure 13.

FIGURE 13: Test apparatus for determining creep

The weight hanging on the beam applies a tensile force to the sample. This force is kept
constant throughout the test. The elongation of the sample is measured with the
extensiometer. The strain is not very large and the extensiometer must be able to pick up
small strains. Figure 14 shows a typical strain vs. time result for a creep test.
 24

FIGURE 14: Typical creep test results

1.9 PHASE DIAGRAMS

We have now discussed the basic mechanical properties of materials and we have also
shown that the mechanical properties of a material are dependent on the microstructure
of that material. We have also briefly touched on alloys and solid solutions. In this
section we will take a brief look at phase diagrams.
Phase diagrams are a simple graphical way to represent the different alloys in any
particular system, their formation and properties. Phase diagrams are set up for different
materials to illustrate the different phases that a combination of these materials can enter
into and also to display the temperature regions in which these phases will occur. Phase
diagrams are usually drawn for two materials, but, in some cases, they can be drawn for
more than two. We will restrict ourselves to phase diagrams that are drawn for two
materials only. These are called binary phase diagrams. In essence a phase diagram is a
graph that shows the solubility of two materials in each other over a range of
temperatures. Let's illustrate this by means of a simple example. You are aware that
various salts (such as table salt) are soluble in water up to a certain point. After a certain
amount of salt is added the solution will be saturated and if additional salt is added it will
not dissolve. The amount of salt that can dissolve in a certain amount of water is
dependent on the temperature of the water. This solubility can be represented in figure
15 below.

FIGURE 15: Solubility curve (salt)

 25 CHP311-A/1

Once the salt content is 70% by mass the solution is saturated with salt at 0Å Celsius. As
the temperature rises the solubility of salt in water increases. The curve therefore
represents the solubility limit of the salt in water. To the left of the curve there is an
unsaturated solution of salt in water. On the curve we have a saturated solution of salt in
water and to the right of the curve we have a saturated solution of salt and water as well
as some undissolved salt. The salt water solution is one phase and the undissolved salt in
the case of the section to the right of the graph is another phase. The left hand section is
thus made up of one phase and the right hand section of two phases. A system that has
only one phase is called homogeneous and one with more than one phase is called
heterogeneous. The term phase equilibrium refers to a system with more than one
phase, where the composition of the two phases stays constant with time. If we cool
down a saturated salt water mixture, the amount of salt the solution can hold decreases.

Thus some of the dissolved salt will have to crystallise in order to leave the solution.
During this process the composition of both the solution and the crystallised phase will
change, so the system is not in equilibrium. Phase diagrams represent the equilibrium
that exists between different systems. As stated before, phase diagrams represent
valuable information about materials. Let's look at these phase diagrams. Figure 16
shows a simple phase diagram for two metals, A and B.

FIGURE 16: Phase diagram for two completely solble metals

Point FB is the freezing point for pure B and point FA is the freezing point for pure A.
The line connecting these two points at the top is called the liquidus line. Above this
line both these metals are in the liquid form and they are completely soluble in each
other. The lower line connecting these two points is called the solidus line. Below the
line both metals are in the solid form and they are completely soluble in each other in all
concentrations. The region between the two lines will represent the section of
crystallisation. In this section there will be part liquid and part solid phase. If we move
up this diagram at the very extreme left hand side (where we have 100% B and 0% A)
we will see that the solidus line and the liquidus line meet. Pure B will therefore melt or
freeze at one constant temperature. The same holds on the other end of this phase
diagram for pure A. For all intermediate compositions the melting or freezing will occur
over a range of temperatures. If we cool down a mixture of A and B the first point at
which freezing will occur is when the mixture reaches the temperature indicated on the
liquidus line. The last liquid will freeze when the solidus line is reached. In the
temperature region between these points the liquid and the solid phase of the specified
 26

composition will be present simultaneously. This also implies that for any composition
between 0% A and 100% A freezing takes place over a range of temperatures. The main
categories of information found on an equilibrium diagram are:

. The phases that are present between the various materials

. The compositions of these phases
. The relative percentages of these phases

We have seen from graph 16 above that it is relatively simple to locate which phases are
present at each point on the phase diagram. We will repeat this at a later stage. The next
step is to determine the relative compositions of the phases. If we take a look at the
dotted line in the graph we see that at that composition the mixture contains 60% of
metal A and 40% of metal B. We also know that in the region between the solidus line
and the liquidus line there are two phases, a solid phase and a liquid phase. But how do
we find out what the compositions of the solid and the liquid phases are? Are they the
same or is there a difference in composition between the two phases? To determine this,
a tie line needs to be drawn. A tie line is a horizontal line drawn at the temperature at
which we need to determine the relative phases. This line is drawn across the two phase
region. A tie line is drawn above for a temperature X. Where this tie line cuts the two
boundaries of the two phase region (the liquidus line on the one side and the solidus line
on the other side) two lines are drawn to the base axis. The tie line meets the solidus line
at about 33% A. From this we can deduce that the solid phase present at this point
contains 33% A and 67% B. The same can be done on the liquidus line. The tie line
intersects the liquidus line at 96% A, so we can deduce that the liquid present contains
96% A and 4% B.
The next thing to determine is the relative amount of each of the phases present in the
two phase region. In other words, we would like to know what percentage of any given
mixture is made up of the solid phase and what percentage is made up of the liquid
phase. This is also determined with the aid of the tie line, and a procedure that is referred
to as the lever rule. To make this explanation easier to follow, let's label the tie line
MPN, with point P being the point at which we want to determine the relative phases.
We have the following compositions for points N, M and P:

%A %B
Point M 33 67
Point P 60 40
Point N 96 4

If we were to calculate the ``length'' of the tie line in terms of % A, it would be 96 ± 33 =

63. Now the relative presence of each phase is computed by taking the length of the
section of the tie line from the point desired (P) to the opposite side and expressing it as
a fraction of the total length.

Example 1.4
If 60 g of A and 40 g of B are heated to temperature T, two phases form. What are the
relative amounts of the liquid phase and the solid phase?
 27 CHP311-A/1

Answer
MP
ˆ 100 
MN
Mass % of liquid phase 60 ÿ 33
ˆ 100 
96 ÿ 33
ˆ 42:86%

The mass of the liquid phase is determined by taking the length between point P and the
solidus line. We can conclude that 42.86% (or in this case 42.86g) of the alloy at point P
will be in the liquid phase and the remaining 57.14% will be in the solid phase. We
could, of course, determine the mass % of solid phase first.

Example 1.5
Given the solid phase in example 1.4 contains 33% A and 67% B, and the liquid phase
contains 96% A and 4% B, calculate the masses of the liquid phase and solid phase
without using tie lines.

Answer
If the grams of solid phase equal x, then the grams of liquid phase = 100 ± x

Total g of A = (g solid)(mass fraction A in solid) + (g liquid)(mass fraction A in liquid)

60 = (x)(0.33) + (100±x)(0.96)

Likewise for B

40 = (x)(0.67) + (100±x)(0.04)

Solving either of the above equations gives x = 57.14g as before.

1.9.1 Binary Eutectic Systems

We have discussed the phase diagram for a system consisting of two metals that was
completely soluble in each other in both the solid and liquid phases in the previous
section. Systems that show such behaviour are, for instance the nickel, copper phase
diagram. The second common type of phase diagram that we are going to consider is the
eutectic system, such as found in the copper silver phase diagram.

Many other systems, such as Fe-C, have phase diagrams that can be divided into various
eutectic systems, each with its own characteristics. Figure 17 shows a typical phase
diagram for a binary eutectic system.

This diagram has three regions where single phases occur. The first of these phases is the
liquid phase, similar to the previous phase diagram. On the left hand side of the phase
diagram there is a region of solid solution which is rich in copper, called the a phase. In
this particular case this phase has a face centred cubic crystal structure. On the right hand
side of the phase diagram we find the  phase, also a face centred cubic crystal structure
and also a solid solution, but now the copper is dissolved in silver, which is the main
constituent. In these solid solutions the concentration of the ``impurity'' is so low that
the  phase can be considered to be pure copper and the phase can be considered to be
pure silver. This means that there is a limit up to which silver will dissolve in copper
and, likewise, a limit up to which copper will dissolve in silver.
 28

FIGURE 17: Binary eutectic phase diagram for Cu ± Ag

These ``solubility lines'' are denoted by lines ABC and line EFG respectively. As you
can see from line ABC the solubility of silver in copper increases from 4008C to a
maximum at about 8008C and then decreases again so that the solubility of silver in pure
copper at its melting point (point A) is zero. The same happens for the pure silver. The
maximum solubility of copper in silver occurs around 8008C, and the solubility of
copper in pure silver is zero (point E). The sections of these solubility lines below line
BDF are called solvus lines and the section above the line BDF is called the solidus line.
Line BDF connects the two points of maximum solubility. This line also represents the
lowest temperature where a liquid phase for any copper ± silver alloy will exist. In this
phase diagram there are three regions where two phases exist simultaneously. On the
phase diagram you can identify them as the +L, the + and the +L areas, where L
represents the liquid phase. In all these regions of two phases the compositions of the
phases and the relative amounts of the phases can be determined with tie lines and the
lever rule that was discussed in the previous section. Lines AD and DE are liquidus
lines. As we add silver to copper you can see that the melting temperature of the alloy
decreases. If we add copper to silver (in other words, move from the other side) the
melting point of the initially pure silver also decreases. These liquidus lines meet at
point D on line BDF. This is the lowest melting point for any copper-silver alloy. For
this system it occurs at a composition of 71.9 % silver. This point is called the invariant
point. The interesting thing about this point is the fact that, if an alloy of this
composition (71.9%) is cooled down to the temperature on line BDF (in this case, 780
C). The phase change from the liquid phase to the two solid phases happens at one
Å
temperature. When heating the solid phases the melting will also occur at one fixed
temperature. This is called a eutectic reaction (meaning ``easily melted''), and the
composition and temperature at which this reaction occurs is called the eutectic
composition and eutectic temperature respectively. Note that the solid product of
eutectic solidification is always two solid phases. Phase diagrams that have this type of
reaction are thus called eutectic phase diagrams. Once a phase diagram has been
generated the different stages of cooling an alloy goes through can be easily determined
from the phase diagram. This also gives us valuable information about the grain
structure of the alloy at different temperatures.

Say we are cooling an alloy of set composition along the dotted line in the graph below.
At point a the whole alloy will consist of a single liquid phase of the set composition.
 29 CHP311-A/1

Once we cross the liquidus line AD, solidification of the a phase starts. At point b we
have a liquid that is a mixture between copper and silver and solid pieces of pure a. The
relative amounts of the two phases and the composition of the phases can be determined
from the lever rule and tie lines. When cooling continues to point c, a solid solution of
pure a exists. The last section is reached as solvus line BC is crossed, and now the a
phase separates and pieces of solid start to form in the gaps.

FIGURE 18: Cooling of a set composition alloy

1.10 ENGINEERING MATERIALS

We have now discussed the basics of the theory of material science. The next section
deals with the different engineering materials, their properties and their specific
applications. Under the heading Engineering Materials we can list the following
categories:

. Metals
. Composites and Alloys
. Plastics/ Polymers
. Ceramics

Each of these categories will now be discussed in more detail. Some alloys will be
discussed together with the metals they consist of.

1.10.1 Metals

1.10.1.1 Aluminium
Aluminium occurs in nature in the oxide form. The most common form is called bauxite.
Bauxite is hydrated aluminium oxide. It also contains iron oxide and other minerals. The
 30

ore is purified and the aluminium oxide is reduced to form aluminium metal. The
aluminium metal produced is of a very high purity (99.5%±99.8%). The main impurities
contained in aluminium are iron, silicon and manganese. Aluminium has a melting point
of 6608C. It has a face centred cubic crystal structure and a fairly low density (2.7 6 103
kg/m3). Because it has such a low density it is very light, and it is said to have a good
strength to weight ratio. This means that the metal is very strong for its weight. It also
has high corrosion resistance.

These properties make it particularly suited to applications in the transport industry.

Aeroplanes, boats and road transportation are more efficient the lighter they are, and the
high strength of the metal ensures that the safety regulations are met. Pure aluminium is
very soft and not very strong, but the strength can be increased dramatically when it is
alloyed with other metals. Due to the face centred cubic nature of the aluminium metal it
is very ductile and can easily be shaped by different methods. The metal also has good
electrical conductivity and good heat conductivity. This lends it to applications in the
electronics industry. Although it was said that aluminium has good corrosion resistance
it is not as simple as that. Aluminium itself oxidises very rapidly when it comes into
contact with oxygen. The layer of aluminium oxide, which is only a few atoms thick,
sticks to the surface of the metal. This layer is very corrosion resistant and oxygen
cannot penetrate it. This increases the corrosion resistance of the metal and protects it
from further attack. The thickness of this film can be increased by anodising the
aluminium metal. Anodising the metal means that it is made the anode of an
electrochemical cell.

Aluminium also shows a rapid decrease in mechanical properties at elevated

temperatures. Pure aluminium is too weak to use for structural applications so its
main use is as a coating for vessels in the food and other industries. The corrosion
product of aluminium is not poisonous so it is widely applied as a lining for food
containers. Most aluminium products that we see (such as aluminium foil, thermal
insulation, electronic components, kitchenware, wires and armature windings) are
manufactured from commercial grade aluminium. Commercial grade aluminium is
manufactured by adding 0.5% iron to the pure metal.

1.10.1.2 Aluminium alloys

Aluminium alloys can be divided into two main categories, namely the alloys which can
be heat treated and the alloys which cannot be heat treated.

The alloys that cannot be heat treated are aluminium-manganese, aluminium-

magnesium and aluminium-silicon. Manganese infiltrates the Aluminium crystal
structure to form a solid solution of Mn-Al. The commercial alloy of Mn-Al contains
1.25 % manganese. Manganese is stronger than aluminium and the addition thereof
increases the strength of the alloy by about 15%. It also increases the corrosion
resistance somewhat. Some uses for Al-Mn are for the manufacture of pressure cookers
and for sheets that are used to clad buildings.

Magnesium enters the aluminium structure in the same way as manganese and, apart
from strengthening the metal, it also improves the corrosion resistance, especially in sea
water. Aluminium-magnesium alloys normally contains up to 10% magnesium. These
alloys are used in manufacturing processes where a high strength is required, such as in
the manufacture of metal crates or construction materials for ship building.
 31 CHP311-A/1

Silicon forms a eutectic mixture (fine grained crystal mixture) with aluminium. The
addition of silicon improves the fluidity of the molten mixture. Alloys that contain
silicon are used to manufacture cast pieces in both sand and die casting procedures.
Aluminium-silicon alloys contain between 10% and 13% silicon.

The alloys of aluminium that can be heat treated are aluminium-copper, aluminium-
coppernickel, aluminium-magnesium -silicon, aluminium-zinc-copper and aluminium-
lithium. All these systems are partially soluble in each other in the solid state.

Aluminium-copper alloys are used for structural applications such as the manufacture of
aircraft. The presence of copper reduces the corrosion resistance of the alloy. This is
treated by coating the outside of the alloy with a thin layer of aluminium, where the
oxide film will provide corrosion resistance.

Aluminium-copper-nickel alloys can be used at elevated temperatures without a loss in

strength. The body of the Concorde aeroplane is made of this type of alloy. These alloys
are also used for the manufacture of parts for internal combustion engines.

Magnesium and silicon form a compound, Mg2Si, and when aluminium is alloyed with
magnesium and silicon, it is in fact an alloy of aluminium and Mg2Si. These alloys are
relatively strong and they have a good corrosion resistance. They are used for structural
applications and for the manufacture of containers to transport goods by road.

Aluminium-zinc-copper alloys are the aluminium alloys with the highest strengths. They
are, as a result, hard to form and they are also subject to stress corrosion cracking. Their
main application is in aircraft construction.

Aluminium alloyed with tin is used for the manufacture of bearings.

1.10.1.3 Copper
Copper occurs in nature as a mixture of copper and iron sulphides and the copper is
removed from the ore either by means of electrolysis or by means of electrolytic
extraction. Copper is best known for its high heat and electrical conductivity. It has a
face centred cubic crystal structure and it melts at 10838C. Copper has a high corrosion
resistance and it is easy to form and to machine into various shapes. It also has a high
resistance to urban, industrial and sea water, and this explains its extensive use in water
piping.

It is also used for wire (because of the high electrical conductivity), water tanks,
materials for vessels in the food industry, and heat exchanger pipes. In general, copper
and its alloys are resistant to slightly alkaline solutions, as long as they do not contain
ammonia. Copper is alloyed with zinc, tin, aluminium and nickel. If a small amount of
beryllium or chromium is added to copper the strength of the alloy is increased. The
alloys of copper with tin, zinc and aluminium are complex, with a lot of different
structures being formed with changing copper composition. When the copper content of
the alloy is relatively high the structure is normally face centred cubic. In alloys with an
intermediate copper content the structure tends to be body centred cubic, and when the
majority of the alloy consists of a different substance with a low percentage of copper, it
tends to be very brittle.

Alloys of copper and zinc are known as brasses. When zinc is introduced into pure
copper it forms a solid solution. The strength of the copper is increased and the ductility
increases until the zinc content is about 30%. These alloys (up to 30% zinc) are widely
used for tube manufacture because of their high ductility. If small amounts of aluminium
 32

or tin are added to these brasses the resistance to sea water is increased considerably.
Alloys with a higher zinc content (about 40%) can be hot worked and can be cast for
different applications. The addition of lead to the alloys will improve the machinability
while the addition of manganese, tin, aluminium, iron or nickel will increase the strength
of the alloy. These materials are cast to form ship's screws and machine fittings.

Bronzes are copper alloys with tin and zinc added to them. Copper can hold up to 14 %
tin in solid solution, but the tin content of the bronze is rarely greater than 5%. Bronzes
are used for the manufacture of springs, coins and sheet metal for decorative purposes.
In some cases phosphorous is added to this alloy. This serves to improve the strength. In
some combinations bronzes are used for the manufacture of bearings because they will
have a good resistance to shock and to wear. In some cases zinc and lead are added to
the material. The addition of zinc strengthens the material and improves the
machinability.

The aluminium bronzes are similar to the bronzes in strength. At low aluminium
contents the alloy can be cold worked and at higher temperatures the alloy can be heat
treated. Aluminium bronzes (aluminium + copper) have a high corrosion resistance,
especially in sea water and they are often used for applications such as heat exchanger
tubing, or condenser parts. When the aluminium content is about 10% these alloys are
used in screws for ships, and valves and pumps that is used in marine areas.

Nickel is soluble in copper in all concentrations and these alloys are strong and ductile.
They have a face centred cubic structure and they have excellent corrosion resistance.
Nickel ± copper alloys are used for the manufacture of coins as well as condenser tubing
and heat exchangers. Alloys of nickel in copper are often called cupronickels.

If zinc is added to an alloy of copper and nickel it is called a nickel silver. These alloys
have face centred cubic structures and they are very ductile. Nickel silver is used
extensively in the manufacture of decorative objects and cutlery. These objects are
generally coated with silver.

The copper alloy with the highest strength available is called beryllium-copper. These
alloys contain up to about 2.7% beryllium. They can be strengthened further by heat
treating them and they also have a high tensile strength. In some cases a little cobalt or
nickel is added to the alloy. Beryllium-copper is used for the manufacture of springs and
non sparking tools.

If cadmium is added to copper the alloy is called cadmium-copper and the tensile
strength of the copper is increased considerably. The electrical conductivity of the alloy
is still good enough that it can be used for the manufacture of wires and electrodes.

Chromium-copper is an alloy that contains in the region of 0.5% chromium and it has a
high strength as well as high electrical and thermal conductivity. It is used for the
manufacture of welding electrodes.

In some cases small amounts (0.3±0.7%) of tellurium are added to copper. Tellurium is
insoluble in copper and has an influence on the grain size of the metal.

Copper and most of its alloys are also subject to wear in corrosive environments (erosion
corrosion). Cupronickels with small amounts of iron added are, however, resistant
against erosion corrosion.
 33 CHP311-A/1

1.10.1.4 Lead
Lead is one of the metals that has been in use for engineering applications for the longest
time. Early water pipes have been made of lead because of its malleability and its
resistance to corrosion. Lead has a fairly low melting point (3278C) and this also makes
it easy to manufacture lead items without sophisticated equipment. It has a face centred
cubic structure and a density of 11340 kg/m3. This high density makes lead suitable for
use as a radiation shield.

Lead is very corrosion resistant. It forms corrosion films consisting of sulphates, oxides
and phosphates. These corrosion products form a protective film on the metal. Lead is
widely used for the manufacture of different alloys. If 1% antimony (Sb) is added it is
used for cable sheathing. Lead with about 6% antimony is used for the manufacture of
lead acid batteries. These batteries accounts for about 30% of the world's consumption
of lead. Lead and tin are alloyed to form soft solders. In some cases a little antimony is
added for extra strength. Alloys containing around 60% lead, 25% antimony and 15%
tin are used for casting printing type. Tin improves the flow characteristics of the melt
and antimony prevents any volume changes during solidification.

An alloy of lead, bismuth and tin has been manufactured that has a very low melting
point (718C). This alloy is used for the manufacture of fusible plugs for fire alarm water
sprinkler systems and also for the manufacture of castings. Lead is also used for the
manufacture of bearings, roofing, ammunition and as a lining for steel. Because of its
corrosion resistance, lead shows a high resistance to sulphuric acid, chromic acid,
hydrofluoric acid and phosphoric acid. It is also resistant to neutral solutions, sea water
and soil. Because lead is so soft it is not very resistant to wear, and it is subject to erosion
corrosion. Lead and its alloys lose their strength at elevated temperatures.

1.10.1.5 Tin
Tin melts at 2328C, and has a body centred tetragonal crystal structure. The most widely
known use for tin is in the tin can industry. Tin has an attractive appearance, a low
melting point and good corrosion resistance. It is also non toxic. It is used extensively to
coat other metals, such as steel. Tin coating is applied on steel by dipping the steel in a
melt or by electroplating the steel. The main advantage of electroplating is that the
coating can be applied in different thickness on the two sides of the plate. Tin also
provides a good base for organic coatings. About 40% of the world's tin production is
used for the manufacture of white metal bearings. Tin can also be rolled into thin foils
that can be used for packaging, especially in the food industry. The tin packaging was
replaced largely by aluminium, because aluminium foil is much cheaper. Tin can be
alloyed with zinc, nickel, cadmium or copper and these alloys can be plated onto other
metals to protect them against corrosion. Tin shows good corrosion resistance to
relatively pure water, dilute mineral acids and organic acids. It is not used for alkalis. Tin
is in general a weak metal which makes it unsuited for structural applications.

1.10.1.6 Magnesium
Magnesium is one of the lightest metals available. It has a melting point of 6498C and it
has a close packed hexagonal crystal structure. It has a density of 1740 kg/m3' which is
very low. Pure magnesium is weak and not of much use unless alloyed. Magnesium is
normally alloyed with aluminium, in proportions of up to 10%. This increases the
strength considerably. Thorium, zirconium and zinc are also used to produce alloys that
can be hardened by heat treatment.
 34

Manganese is added to increase corrosion resistance. Magnesium cannot be cold worked

because it has a low ductility. This is mainly due to the hexagonal crystal structure.
Magnesium is used for the manufacturing of trucks, car engines, ladders, saws, and
weaponry.

It has a low corrosion resistance. The corrosion resistance tends to decrease with
alloying and impurities. It is attacked by most acids, except for hydrofluoric and chromic
acid.

1.10.1.7 Nickel
Nickel is one of the most widely utilised metals for corrosion applications. It is used on
its own, and in a wide range of alloys. Pure nickel has a face centred cubic crystal
structure and a high melting point of 14558C. It has an excellent resistance to corrosion
by both alkalis and acids and, as a result, has many applications in chemical plants and
also in the food industry. It is particularly well suited to applications involving caustic
soda. The corrosion resistance of alloys to caustic soda is proportional to the nickel
content of the alloy. Pure nickel is also used to coat sheets of mild steel in order to
improve the corrosion resistance. Nickel is also electroplated onto a lot of other
materials for the same reason. The addition of nickel to another metal increases the
resistance to stress corrosion.

The Monel, Inconel and Nimonic series of alloys of nickel are those used most often.
Monel has very good resistance to corrosion and it is used in various plant applications,
amongst others steam turbine blades. Inconel, apart from having good corrosion
resistance also has good mechanical properties at elevated temperatures. This makes it
suitable for high temperature applications in chemical plants, such as heaters and
elements for electric cookers. The Nimonic series of alloys were developed for the
specific purpose of gas turbines. They are also very strong at elevated temperatures.

1.10.1.8 Titanium
Titanium is a fairly strong metal that was originally used for aircraft and missiles. It is
also utilised in the chemical process industries. Like aluminium, titanium forms a film of
TiO2 and it is this film that protects it against corrosive substances. The metal has the
tendency to absorb gases at high temperatures, and thus it needs to be welded and melted
in inert atmospheres. As far as corrosion resistance is concerned, titanium has excellent
resistance to chloride solutions and sea water, and also against hypochlorites and wet
chlorine. Titanium is resistant against nitric acid and fuming acids. Titanium is used in
the manufacture of cast pumps and valves. Titanium should not be used in environments
that contain sulphuric or hydrochloric acids or dry chlorine.

1.10.1.9 Zinc
Zinc has a relatively low melting point (4198C). This makes it a good metal for die
casting. The alloys used for die casting has 4% aluminium and 1±2% copper. These
additions improve the tensile strength of the die cast zinc. The zinc used for die casting
should contain no other impurities because that would cause the cast objects to fail. Zinc
alloy die castings are used for the manufacture of automotive components and model
toys.

Zinc sheets are produced at temperatures of about 1008C. Cold zinc metal is very brittle
and cannot be easily formed, therefore the elevated temperature. These sheets are used
 35 CHP311-A/1

for the manufacture of battery cases for dry cells, where the zinc also acts as the anode of
the battery. Zinc is used for galvanising where metal that is not corrosion resistant is
covered with zinc and thus protected against corrosive environments. In general, zinc is
not seen as very corrosion resistant and therein lies its application as a sacrificial anode.
It is often coupled to steel and because zinc is anodic to steel it will corrode, with the
steel as the cathode of the electrolytic cell. The steel is therefore protected.

1.10.1.10 Iron and steel

Iron is produced by smelting iron ore in large furnaces, called blast furnaces. The iron
produced from these furnaces is impure and it contains about 4% carbon, 2% silicon, 1%
manganese and some sulphur. In some cases the iron also contains about 2%
phosphorous. The iron is now either cast into small moulds (called iron pigs) or the hot
metal is transferred in the molten state to form sheets. The following terms needs to be
defined in relation to steel making:

(a) Pig iron: as already said this is the product from the blast furnace and it contains
iron in a relatively impure state.
(b) Acid iron: this is also pig iron, but it has a low phosphorous content.
(c) Basic iron: this is pig iron containing up to two percent phosphorous.
(d) Wrought iron: this is iron containing a certain amount of slag. It was initially an
impure form of iron, but today it is manufactured by adding slag to refined liquid
iron.
(e) Ingot iron: this is the purest type of commercial iron and is also referred to as
Swedish iron
(f) Steel: steel is an alloy containing iron and carbon.
(g) Plain carbon steel: it is a steel containing up to 1.5% carbon, not more than 0.5%
silicon and 1.5% manganese.
(h) Alloy steel: this steel contains higher amounts of silicon and manganese than the
plain carbon steel and it contains various other added elements.

There are various types of steels categorised according to their structures:

Ferrite is the name given to the body centred allotropes of iron.

Austenite is the face centred cubic variety of iron, or face centred cubic solid solutions.

Cementite is the compound FeC3 or iron carbide.

Martensite is formed when a steel is cooled very fast. It is a hard and brittle substance
and it consists of ferrite that is supersaturated with dissolved carbon.

Types of steel
The physical properties of steel can be varied with the alloying content of the steel and
the heat treatment of the steel. We are going to discuss the basic effects different
additives have on steel and the uses for the different types of steel. There are three basic
categories of steel. These categories represent the carbon content of the steel and are
shown in the table below.
 36

Steel Type Carbon Content

Mild Steel < 0.3%
Medium Carbon Steel > 0.3 % < 0.6 %
High Carbon Steel or Tool Steel > 0.6 %

The basic requirement for steel is that it should be tough with a hard surface. There are
two ways in which this can be achieved. The first is by means of heat treating the steel
and the second is by means of alloying, or adding different materials to alter the
physical properties.
The following are the main types of heat treating that can be applied to steels.

. Case carburising: this procedure involves the addition of carbon to the surface of
mild steel. This results in a mild steel with a 0.5±0.7 mm shell of high carbon steel.

. Cyaniding: in the case of cyaniding, both carbon and nitrogen are allowed to diffuse
into the surface of the steel. This is done by heating the steel components in a bath of
molten sodium cyanide and sodium carbonate at about 9508C. This results in the
formation of iron nitrides on the surface of the material.
. Nitriding is done on low alloy steel containing molybdenum and chromium. This
procedure should not be used for plain carbon steels since it will lead to the formation
of iron nitrides and this will penetrate the surface of the steel and make it brittle.
. Flame hardening and induction hardening is done by heating the surface of the
steel to a very high temperature very quickly and then cooling it fast. This results in
hardening of the surface.

Alloying
The second method that is used to alter the physical properties of steels is alloying.
Various metals can be added to steel for different applications. A summary follows
below.

. Manganese
The addition of manganese to steel has the general effect of increasing both the
strength and the hardness. It forms a carbide in order to do this. Manganese also
increases the hardness of steel. It can produce an austenitic steel when present in
sufficient quantities.
Typical steels containing manganese are Pearlitic steels (steels consisting of a mixture
of ferrite and cementite that form when austenite decomposes during cooling). These
steels contain up to 2% manganese and they have high hardness. They can be used for
the production of gears and shafts. Hadfield's steel is a tough austenitic steel that
contains 13% manganese.
. Silicon
Silicon added to ferrite strengthens it. Silicon steel contains 0.07 % of carbon and 4%
silicon. It is used for transformer cores. A steel containing 3.5% silicon and 8%
chromium is used in internal combustion engine valves because it is very resistant to
oxidation at high temperatures.
. Chromium
Addition of chromium to steel increases the strength and hardness. Chromium forms
hard, stable carbides. The hardness of the steel is increased. If the chromium content
of a steel is higher than 12 % it is called a stainless steel. Medium and high carbon
 37 CHP311-A/1

steels with 1±1.5% chromium are used for gears, axles, shafts, springs, ball bearings
and metal working rolls. Ferritic and martensitic stainless steels containing 12 and 30
% of chromium are used for crankshafts and axles that are subject to fatigue.
. Nickel
Nickel, apart from having a strengthening effect and increasing the hardness, also has
the advantage of improving the alloy's resistance against fatigue. It can also have the
effect of stabilising austenitic steel.
Steels containing 0.3±0.4 % carbon together with 5% nickel are used to manufacture
parts that need to be resistant against fatigue.
. Tungsten
Tungsten carbide is extremely hard, and when tungsten is added to steel this carbide
forms. The resulting effect is a very hard steel that is very heat resistant and does not
lose its hardness at elevated temperatures. Tungsten steels are used as tool steels for
applications that have to be operated at high speeds (such as cutting tools). It is also
used in some permanent magnet steels.
. Molybdenum
Molybdenum added to steel reduces creep at high temperatures and it also reduces the
brittleness of Ni±Cr steels. It is used in high speed tool steels to decrease creep.
. Titanium
This metal has a strong carbide forming action and it is added to some austenitic
stainless steels to stabilise the carbides.
. Aluminium
Aluminium is added to nitriding steels to restrict nitride formation to the surface
levels.
. Copper
As discussed under copper, the main function of copper addition to steel is to increase
the corrosion resistance. It is also added to cast steels to increase the fluidity, the
castability and the strength.
. Lead
Lead is insoluble in iron and it is added to low carbon steels to give free machining
properties.

1.10.2 Ceramics
There are many definitions for ceramic materials. One of the most common is that they
are hard, brittle, crystalline inorganic materials.

You should be able to name a few ceramic materials from your everyday experience. We
have ceramic materials in our homes (plates, pottery etc.). Floors are often made of
ceramic tiles, and bricks and clayware are also called ceramics. Glass and cements also
form part of ceramic materials, along with some others. The table below shows all the
main types of ceramics and some of their applications.

Ceramic Material and Applications

Whiteware (clay products)
Heavy clayware
Refractories (high temperature)
Made of porcelain, china or stoneware.
Used for tableware, wall tiles, sanitary
ware and insulators.
Used for bricks, roof tiles and pipes.
Used for furnace linings and high tempera-
ture applications.
 38

Ceramic Material and Applications

Stone (natural product) Granite, sandstone and limestone are used
for concrete and building stone.
Glass Different types of glass and glass ceramics
are used for containers and glass planes.
Abrasives (hard substances) Diamond, carborundum and corundum are
used for abrasion resistant applications such
as grinding wheels, abrasive cloth and sand
paper.
Cements The most common types are Portland
Cement and alumina and they are mainly
used for structural applications.
Engineering ceramics These are mainly oxides, carbides and
nitrides of metals, and they are used for
dies, seals, bearings, engine components,
cutting tools and filtering elements.
Electrical and magnetic ceramics These are used for electronic applications
such as the production of thermistors,
magnets and capacitors.

1.10.2.1 Structure of ceramic materials

Ceramics are crystalline materials that are bound by means of ionic bonds. Ionic bonds
occur between two substances with varying electronegativities and electron transfer
takes place so that the bond is between a positively charged atom (cation) and a
negatively charged atom (anion). Ceramics are composed of at least two elements and
because of that their crystal structures are more complex than those of metals. The two
main influences on the crystal structure of ceramic materials are the charges on the
atoms in the crystal structure and the relative sizes of these atoms. Because the total
crystal must be electrically neutral the charges on the atoms will indicate the ratio in
which the different materials will occur in the crystal. For example, calcium fluoride
(CaF2) will have two F- anions for every Ca++ cation. The sizes of the various atoms also
play a part in dictating the crystal structure. Cations are normally smaller than anions
because they give up electrons. The crystal structure will be stable if the cation touches
all the anions that surround it. Fig 19 illustrates this concept.

FIGURE 19: Optimum cation-union ratio

In our discussion of metals we have seen that a lot of the physical properties of the
metals were related to the crystal structure and to the method of manufacturing of the
metals. As a result of their ductility and flow characteristics in the liquid state, metals
can be cast easily and many metal components are often manufactured that way.
 39 CHP311-A/1

Ceramics, on the other hand, are brittle and cannot be plastically deformed. They are
also hard with high melting temperatures. Ceramic materials are often manufactured
from powders that are reacted, dried and sintered (baked) to gain a hard structure. Glass
objects are manufactured by casting or rolling hot molten glass. Glass can also be
machined at elevated temperatures. Cement or concrete is formed by means of powders
that are placed in moulds or forms and hardened by means of chemical reactions. We
will now look at the various categories of ceramics individually.

1.10..2.2 Cement
The term cement is used for the group of materials that undergoes a hardening chemical
reaction when water is added. Cement, plaster of Paris and lime are the most common
members of this group. Portland cement is the type that is used in the greatest amounts.
It is produced by grinding and mixing clay and limestone in certain proportions and then
heating it in a kiln to about 14008C. The product of this heating process is called clinker
and it is a partly fused mixture of the raw products. This fusing process is known as
calcination. The clinker is now ground to a powder and gypsum is added ± gypsum is
calcium sulphate (CaSO4.2H2O). The function of the gypsum is to control the setting of
the cement. This product is now called Portland cement. The exact physical properties of
cement will depend on the composition. Various constituents are added to cement. Two
of these are tricalcium silicate (3CaO.SiO2) and dicalcium silicate (2CaO.SiO2). The
various cement constituents undergo hydration reactions when water is added to the
cement. One typical hydration reaction is shown below:
2Ca0-SiO2 + xH2O ? 2Ca0-SiO2±xH2O

These hydration reactions take place at a very low rate and it will be days, sometimes
weeks, before the cement is completely hardened. It is important to add the optimum
amount of water in these reactions, because the addition of too little water will result in
incomplete reaction and the addition of too much water will weaken the bonds. The first
stage of this reaction will be the setting of the cement to a gel or a paste and the
crystallisation will follow later. Portland cement is termed a hydraulic cement because of
the hardening mechanism that takes place as a result of the reaction with water. The
main use for it is in concrete. Concrete is a mixture of cement, sand and small stones.
These constituents are mixed and water is added. The cement reaction then occurs and
the cement binds the other constituents together. One of the most interesting aspects of
cement is that it is very strong in compression, but the strength in tension is about one
tenth of that in compression. The tensile strength of concrete is also very low and to
overcome this disadvantage the concrete is often hardened around a steel framework.
Figure 20 illustrates two types of steel reinforcements that are used for concrete. In the
first case the upper section of the concrete beam is in compression and the lower section
is in tension, with forces being applied at the arrows. The steel reinforcement as shown
increases the tensile strength of the concrete. The second concrete beam is pre-stressed.
This is done by embedding steel wires in the concrete. These steel wires are highly
stressed. By doing this a compressive stress is embedded in the concrete. When the
concrete is under a tensile force this compressive stress has to be relieved before any
tensile stress can develop in the concrete.

1.10.2.3 Clay
Clay is very popular because it is mined in large quantities and it often needs no refining.
Secondly it is easy to form into shapes when mixed with water. This property is called
hydroplasticity. After it is formed the clay is dried and baked (fired) at a high
 40

FIGURE 20: Reinforced and pre-stressed concrete

temperature. The purpose of the baking process is to enhance the mechanical strength.
Clay is utilised as structural clays and whiteware. Structural clay applications are bricks,
tiles and sewer pipes where a certain amount of structural strength is required.

Whiteware gets it name from the fact that, once these clays have been fired at high
temperatures, they assume a white colour. This group is used in aesthetic applications
such as porcelain, pottery, tableware and sanitary fixtures.

Clay consists mainly of aluminosilicates, such as Al2O3.SiO2, and bound water. The
exact chemical composition varies and together with that the physical properties also
vary. Various impurities are found in clay, such as oxides of barium, calcium, sodium,
potassium and iron.

The most common clay structure is the kaolinite clay structure. Kaolinite clay has the
chemical formula [Al2(Si2O5)(OH)4] and it has a layered structure so that, when water is
added to the clay, the water molecules fit in between the sheets and form a thin film
around the clay particles. The particles can now move over each other with relative ease
and this accounts for the hydroplasticity.

1.10.2.4 Glass
Glasses are mainly fabricated from silica (SiO2) containing other oxides such as CaO,
Na2O, K2O, and Al2O3. They are amorphous, brittle materials that are optically
transparent and can be easily formed at elevated temperatures. From earlier on in this
chapter you might remember that we classified materials as either crystalline or
amorphous. Amorphous materials do not have a crystal structure. When cooling a glass
the liquid becomes more and more viscous as the temperature decreases. There is no
definite temperature at which the liquid starts assuming a crystal structure. The internal
structure of the glass remains a random one, such as in the case of liquids. In the
crystallisation of liquids there is a definite stage when crystallisation is taking place that
the specific volume of the liquid drops dramatically as the particles arrange themselves
into an organised crystal pattern. In glasses this rapid drop in volume is absent. Fig 21
shows how the specific volume of a glass changes upon cooling as opposed to the
specific volume of a crystalline solid.

As can be seen from fig. 21, there is a slight change in slope in the cooling curve for a
glass. The temperature at which this occurs is called the glass transition temperature.
Above this temperature the substance is known as a supercooled liquid and below that
temperature it is called a glass.
 41 CHP311-A/1

FIGURE 21: Specific volume changes for crystalline solids and glasses

We have said that silica is the main constituent of glass. Silica has a very high melting
point (higher than 17008C) and this is one of the reasons why other elements are added
to the silica and thus make it easier to form it when hot. They decrease the melting point.
The major types of commercial glasses are:

. Silica glass: this glass has a silica content of higher than 99.5 % SiO2. It has a high
chemical stability and it can be used up to 9008C. It has a very low thermal expansion
coefficient. It is manufactured in two forms, namely translucent and transparent. It has
high shock resistance.
. Soda lime silica glass contains 15% Na2O, 10% CaO and 75% SiO2. It is the most
commonly used commercial glass and is used in containers and light bulbs.
. Lead glasses have 18±32 % PbO, 5±10% Na2O and K2O and 50±70% SiO2. This
glass has a very high transparency and is used for high quality tableware. It is also
known as crystalware. Lead glass is softer than other glasses and this makes it easier
to form and to cut into decorative objects.
. Borosilicate glasses contain 60±80% silica and 10±25% B2O3. They also contain 1±
4% Al2O3 and 1±4% Na2O. These glasses have a high thermal resistively and a high
resistance to thermal shock. They are used for ovenware, industrial piping, laboratory
ware and electrical applications. They are also known as Pyrex glasses.
. Alumino glasses contain 10±60% SiO2, 20±40% Al2O3, 5±50% CaO and up to 18%
B2O3. These glasses have a high chemical resistance and a low thermal expansion.

Glass is manufactured by melting the raw materials to a temperature well above the
melting point. This ensures homogeneity in the glass. If the glass is not homogeneous
small bubbles will occur in the glass and this will affect the appearance as well as the
structure of the glass. Glass objects are formed by means of 4 main operations:

1. Pressing
2. Blowing
3. Drawing
4. Fibre forming.

1.10.2.5 Glass ceramics

Glass ceramics are substances that are manufactured by normal glass manufacturing
techniques, but are then heat treated. At elevated temperatures controlled crystallisation
takes place. The crystal structure strengthens the glasses. These materials can also retain
their strength at much higher temperatures than glasses. They have an excellent
 42

resistance to thermal shock. This heat treatment process is called devitrification. Glass
ceramics are relatively easy to manufacture. Glass ceramics are used for high
temperature and strength applications such as ovenware.

1.10.2.6 Refractories
Refractories are made up of various mineral oxides and they are put to particular use in
high temperature applications such as the manufacturing of furnaces. This means that
they must be resistant to molten metals, slags, glasses, very abrasive materials and hot
gases. There are three main categories of refractories namely:

. acid refractories
. basic refractories
. neutral refractories.

The main acid refractory is silica (SiO2). It has a very high melting point (more than
17008C) and silica based materials are used to manufacture furnaces for the
metallurgical industries. These furnaces are very resistant to attack by high
temperatures in combination with acidic conditions. Silica refractories are also used
for tiles for the roofs of furnaces in the steel and glass industries. Silica refractories can
be used for temperatures up to the melting point of silica (17008C).

Basic refractories are manufactured from CaO and MgO, both basic oxides. These are
also used for the manufacturing of metallurgical furnaces, but as acid refractories are
resistant against acids at high temperatures, so basic refractories are resistant to bases at
high temperatures. Most basic refractories are manufactured from dolomite, a rock
consisting of calcium and magnesium carbonates.

The major group of neutral refractories is made of chrome magnesite. This is a group of
materials that is made from chrome ore and calcined magnesite. These chrome
magnesites are used to make acid and basic refractories that are used in furnaces for the
production of copper, aluminium and other metals.

Fireclays are natural clays consisting of kaolinite and quartz. They are used for the
manufacturing of refractories because they can be used in temperatures up to 14008C.
They are used for linings in blast ovens, kilns for lime and cement, pottery kilns,
furnaces for aluminium melting and for gas heaters.

The last group of fireclays consists of high alumina materials. These are used in steel
making furnaces, and for crucibles that are used to melt metals.

1.10.2.7 Industrial ceramics

Recent research in the field of material science has progressed very fast in ceramics
manufacturing. Ceramics in use are the oxides, nitrides, borides and carbides of metals.
These materials are all exceptionally hard and they are very stable in high temperature
applications. They are however very brittle and this is the main disadvantage of these
materials. They are very resistant to abrasion and wear, and they are chemically very
stable and inert in most environments. They are also good insulators.

One of the latest applications of ceramics is the manufacturing of filter elements. The
ceramics are manufactured to give a porous structure and these structures are used for
filters in the water treatment industry (de-oiling of waste water), the food and
biotechnology industry recovering beer from yeast (eliminating bacteria) and the
 43 CHP311-A/1

pharmaceutical industry (obtaining very pure products). The filter elements are
increasingly replacing membrane filters because they have a long life, good resistance
to thermal shock, high pressure resistance and high chemical inertness. These ceramic
filter elements are manufactured from Al203, TiO2 and ZrO2. These filters can also be
used in gas filtration and are used for gas filtration in the manufacturing of nitric acid,
and for the gas filtration of process gases at temperatures in excess of 10008C.

Porous ceramic elements are also used for the manufacture of aerators that are used to
kill bacteria during water purification. Figure 22 shows an aerator and its operation.
Such an aerator would be used in the purification of sewage by supplying oxygen to the
solution. It is a quiet, efficient way of aerating water and the ceramics are not subject to
corrosion, which means they last a long time.

FIGURE 22: Ceramic bottom aerators for sewage treatment

1.10.2.8 Silicon nitride

Silicon nitride is useful as a ceramic because of its resistance to strong acids and to
molten aluminium. There are various types of silicon nitride ceramics. The main types as
well as their main applications and features are listed below.

Ceramic Features & Applications

Reaction bonded silicon nitride(RBSN)
Hot pressed silicon nitride (HPSN)
Sintered silicon nitride
Pressureless sintered silicon nitride
High temperature applications such as
pouring tubes for aluminium.
High density engineering applications.
High density engineering application.
High temperature applications and manu-
facture of engine parts.

1.10.2.9 Silicon carbide

Silicon carbide has been used for a long time as an abrasive because of its hardness. It
has also been used extensively as an additive to increase the hardness of other materials.
It is also used on its own. Silicon carbide (SiC) is a hard semiconducting ceramic
material. The main types of silicon carbide are listed below.
 44

Ceramic Features & Applications

Reaction bonded silicon carbide
Clay bonded silicon carbide
Hot pressed silicon carbide
Sintered silicon carbide
Recrystallised silicon carbide
Nitride bonded silicon carbide
In situ formation of silicon carbide on a
silicon carbide matrix. Used for mechani-
cal seals, bearings and engine compo-
nents.
This material contains up to 50% fireclay.
It has coarse grains and is used for
thermal shock resistant applications.
Contains 2% alumina and is used as a
densification aid and to give a fine
product with no pores.
This material contains boron and carbon
and is used as a densffication aid.
This material is less dense with large
grains and is used for furnace elements
and refractory tubes.
Silicon carbide powders are bonded in a
nitrogen atmosphere. Used for containers
and refractory tubes.

1.10.3 Plastics and Polymers

Polymers occur in two main groups, namely synthetic and natural. Natural polymers
include wood, rubber, cotton, wool, leather and silk. Some are present in biological
systems such as proteins, enzymes starches and cellulose. Synthetic polymers include
rubbers and plastics. Polymers consist of hydrocarbons that are bound together in large
quantities called macromolecules. The atoms in each molecule are bound together by
covalent bonding. These molecules normally have the form of long chains built around
strings of carbon atoms. Fig 23 shows a typical polymerisation reaction. In this case
ethylene is reacted under the correct temperature and pressure with a catalyst R that
contains an active site. This active site then moves along the polymer, causing more
ethylene molecules to polymerise. The polymer has a zigzag structure with the carbon
molecules slightly above and beneath each other. This explains the elasticity of these
substances.

The physical characteristics of a polymer will depend on the shape, molecular weight
and the structure of the molecular chains. Polymer structures can be linear, branched,
crosslinked or networked. Figure 24 show a schematic representation of the different
types.

1. Linear polymers consist of long, flexible chains. There are van der Waals bonding
forces between the different chains. Polymers with this structure are polyethylene,
polyvinyl chloride, polystyrene, polymethyl methacrylate, nylon and the
polyfluorocarbons.
2. Branched polymers are formed when side reactions occur during polymerisation.
These branches result in the chains being less densely packed and this reduces the
density of the polymer.
3. Crosslinked polymers have connections between adjacent linear chains. These
connections are by means of covalent bonds. Crosslinking can occur during the
polymerisation reaction or in a separate high temperature process that is done after
 45 CHP311-A/1

H H H H
| | | |
C=C + R ? R- C -C
| | | |
H H H H

H H H H H H H H
| | | | | | | |
C-C + C=C ? R-C -C -C -C
| | | | | | | |
H H H H H H H H

FIGURE 23: Schematic polymerisation of ethylene

FIGURE 24: Typical polymer forms

polymerisation. Rubber materials are often crosslinked and this improves the
elasticity.
4. In the case of network polymers, single units with three active covalent bonds are
bound in three dimensional networks in stead of in a chain structure.

1.10.3.1 Classification of polymers

Polymers can be classified based on their structure and physical properties. The figure
below gives the broad classifications of polymers. Biological macromolecules include
proteins, polysaccharides, resins, glues and wood.

Elastomers describe rubber like materials. Thermohardening substances are hard and
cannot be heated and formed in their final form. These monomers have two or three
active bonds and they can form two or three dimensional structures. The primary
covalent bonds bind the structure closely so that it does not soften when heated. It will
chemically decompose (burn) before it melts.
 46

Thermoplastic polymers are mainly linear chains with few or no covalent bonds between
the chains. There are, however, van der Waals bonding forces between these chains.
These are much weaker than covalent bonds. If these materials are heated they gain
enough energy to overcome the van der Waals forces and the material softens and
eventually melts. Thermoplastics can be partly crystalline at room temperature. This
happens when the chains arrange themselves in a regular structure during cooling. If the
chains are jumbled together without a set pattern the thermoplastic is said to be
amorphous. Crystalline thermoplastics are normally transparent and amorphous
thermoplastics are translucent.

Polymers

Natural Synthetic

Elastomers
(rubbers)

Biological Thermoplastic Thermosetting

macromolecules

As with metals, polymers are not this simple. Various specialised materials and
combination materials are manufactured for specific uses. These materials are
strengthened by the addition of fibres and by various thermal and chemical
techniques. The student is encouraged to keep him/herself on top of the latest
knowledge in the field of material science because the rate of development of new,
useful, interesting engineering materials is too high for these notes to be up to date, even
at the time of printing.

BIBLIOGRAPHY
Sydney H. Avner, Introduction to physical metallurgy, 2nd Edition, McGraw-Hill Book
Company, 1986.

John H. Perry, Chemical engineer's handbook, 3rd Edition, McGraw-Hill Publishing

Company, 1950.

William D. Callister Jr., Materials science and engineering, an introduction, 3rd Edition,
John Wiley & Sons, 1994.
Vernon John, Introduction to engineering materials, 3rd Edition, Macmillan Press Ltd,
1993.
J.C. Anderson, K.D. Leaver, R.D. Rawlings & J.M. Alexander, Materials science, 4th
Edition, Chapman and Hall,1990.
 47 CHP311-A/1

REVISION QUESTIONS
1. Describe, in your own words, what you understand by the term crystal.
2. What is an amorphous material?
3. What is a unit cell?
4. Define each of the following terms: (a) Co-ordination number (b) Unit cell
5. Name the three most common crystal structure types found in metals, and give
three examples of metals with each kind of crystal structure.
6. State the atomic packing factor for each of the three types of structure in (5)
7. Describe what is meant by allotropy.
8. Describe what is meant by polymorphism and name two examples of polymorphs.
9. Name two factors that determine the crystal structure of a polymorph.
10. Describe the mechanism of crystallisation in your own words.
11. Define each of the following:
(a) Nuclei
(b) Dendrites
(c) Grain boundaries.

12. Name two characteristics which influence the grain size of a material, and describe
how each of these characteristics influences the grain size.
13. Describe the formation and characteristics of a single crystal.
14. What is a polycrystalline material?
15. Make a sketch to illustrate the difference between a vacancy and a point interstitial.
16. Distinguish between a point defect and a dislocation.
17. Make a sketch to illustrate the difference between a substitutional solid solution
and an interstitial solid solution.
18. Name a metal that, when added to silver, makes it harder.
19. When impurities are added to a metal, two structures can form. Name these two
structures.
20. What are alloys?
21. Explain, in your own words, the difference between an edge and a screw
dislocation.
22. Describe the process of etching. Also state why this is beneficial in the preparation
of materials for observation with an optical microscope.
23. Name the different steps that are followed in preparing a metal for observation by
optical microscopy.
24. Name the two pieces of equipment used for electron microscopy. What is the
difference between the two?
25. There are 4 types of forces that can act on a material. Name these 4 types and make
sketches to illustrate how each type of force is applied.
26. Define each of the following concepts: (a) stress (b) strain.
27. A cylindrical sample with a radius of 2 cm is subjected to a 400 Newton tension
force along its axis. As a result of this force the sample elongates from 12 cm to
12.6 cm. Calculate the stress and the strain.
28. A shear stress is applied to a cylindrical sample along the cylindrical axis. Make a
sketch to illustrate how the shear stress could be calculated.
29. Describe the difference between the yield strength, the tensile strength and the
fracture strength in any given sample in a material fracture test.
30. In specifying materials for engineering applications, which of the above mentioned
strengths would you specify as the material strength?
31. Name one example of a brittle and one of a ductile material. Motivate your choices
by making use of the definition of brittleness and ductility. The materials you select
need not be engineering materials.
 48

32. Is the ductility of a material a constant? If not, state the factor(s) that influence it.
33. Explain how the resilience of a material can be determined from the stress-strain
curve. Also state how the units of resilience can be determined from the stress-
strain curve.
34. What is the term toughness related to?
35. Explain the difference between (a) tearing and cleavage and (b) fatigue and creep.
36. Describe each of the following: (a) tensile test, (b) hardness test, (c) fatigue test and
(d) creep test.
37. Explain what you understand when it is said that aluminium has a high ``strength
to weight ratio?''
38. Describe how aluminium metal protects itself against corrosion.
39. Name 4 applications for commercial grade aluminium.
40. What effect does the addition of manganese have on pure aluminium, such as in
the formation of the Al-Mn alloy?
41. Name the main advantage that can be gained from using an aluminium- copper-
nickel alloy.
42. Which alloy of aluminium finds its main application in the aircraft industry? Why
do you think this is so?
43. Name the metals copper is most often alloyed with.
44. You have to select copper alloys for the manufacture of heat exchanger tubing.
Suggest two different alloys you could use for this purpose, and motivate each
choice.
45. If you want to increase the strength of copper metal, which metal would you alloy
it with?
46. How would you protect copper against erosion corrosion?
47. Name the main disadvantages in the use of lead and its alloys.
48. The high density of lead makes it applicable for use as a ....................................
49. Name the two methods by which tin is applied to steel.
50. Which property of tin makes it suitable for application in the food industry?
Explain.
51. Name the metal magnesium is most often alloyed with. What effect does this metal
have on the physical properties of magnesium?
52. A suggestion is made to you to use magnesium for the manufacture of a tank that
will be used for storage of hydrofluoric acid. Do you think this is a good
suggestion? Motivate your answer.
53. Most pure metals are corrosion resistant to some acids, but not to alkalis. If you
want to use a metal that is specifically resistant to alkalis, which would it be?
54. Zinc is not very corrosion resistant, and is attacked by most materials. Explain how
this property of zinc can be used as an advantage in the corrosion protection of
materials.
55. Define each of the following terms in relation to steel making:
(a) Pig iron
(b) Acid iron
(c) Basic iron
(d) Wrought iron
(e) Ingot iron
(f) Steel
(g) Plain carbon steel.

56. Describe what you understand by the term calcination.

57. Name three advantages of the use of clay as an engineering material.
58. Name the two main categories clay is divided into.
59. Name the main constituents of clay.
 49 CHP311-A/1

60. What happens at the glass transition temperature?

61. High quality glass objects are sometimes referred to as crystal. What is this crystal
and what is it mainly used for?
62. Make a sketch to illustrate how ceramic materials can be used as aerators in sewage
treatment.
63. Make a sketch to illustrate the difference between linear, cross linked, branched
and networked polymers.
64. State the main properties and applications of each of the following polymers:
(a) Polyvinyl chloride
(b) Polyethylene
(c) Polyester
(d) Silicones.
 50

CHAPTER 2

Corrosion

OBJECTIVES
After completion of this chapter the student should be able to:
. Define the term corrosion
. Name relevant corrosion environments
. Discuss the impact corrosion has on industry and the environment
. State the different categories under which corrosion can be classified
. Discuss each of the following forms of corrosion as to the definition, the
identification and the prevention thereof:
Uniform attack
Galvanic corrosion
Crevice corrosion
Pitting
Intergranular corrosion
Selective leaching
Erosion corrosion
. Discuss the expression of the corrosion rate
. Discuss the electrochemical and thermodynamic aspects of corrosion and
electrochemical reactions
. Explain the terms polarisation and passivity
. Discuss the effect of each of the following terms on the corrosion rate:
Oxidation capacity of solution
Velocity of solution
Temperature of solution
Concentration of corrosive solution
Galvanic coupling
. Discuss the terms anodic and cathodic protection
. Discuss the prevention of corrosion with reference to specific examples

INTRODUCTION
This chapter deals with corrosion in a typical engineering environment. It discusses the
general effects that corrosion can have on the operation of a plant, and also typical
corrosion forms and the identification of these forms. Ways to prevent and combat
corrosion are also explained.

2.1 DEFINITION
Corrosion can be defined as the destruction of a material because of a chemical or
electrochemical reaction with its environment. Corrosion can be defined in relation to
 51 CHP311-A/1

metals alone, or in relation to metals and non metals. For the purpose of this course we
will stick to the broader definition that includes the non metals such as ceramics, plastics
and rubber. While we are defining things, let's say something about two other terms that
are similar in meaning and might lead to some confusion. The first such term is rust.
Rust is used in connection with the corrosion of iron and steel products. The second term
is erosion. This term is normally used in connection with the destruction of a material
because of physical causes.

2.2 CORROSIVE ENVIRONMENTS

A corrosive environment is an environment that facilitates corrosion when a particular
material is exposed to it. Most environments are corrosive to some extent, but some are
worse than others. Typical corrosive environments are:

. Moist air
. Water (salt and fresh water, as well as aqueous solutions)
. The atmosphere (in rural, urban, industrial and coastal areas)
. Steam
. Gases (ammonia, chlorine, sulphur dioxide, fuel gas)
. Mineral acids (e.g. hydrochloric, sulphuric and nitric acids)
. Organic acids (e.g. malefic acid, acetic acid, formic acid)
. Alkalis
. Soils
. Solvents

2.3 THE CONSEQUENCES OF CORROSION

Because the corrosion of materials is something with which we are confronted every
day, it is easy to imagine all the consequences of corrosion. Let's mention a few of them.

1. Replacement of corroded equipment: there is considerable cost and time

involved in the replacement of equipment that has failed because of corrosion. In
some cases this is inevitable and in some cases this can be avoided. This leads to
loss of profit.
2. Design compensations to provide for corrosion: corrosion, as defined,
deteriorates materials. If it is known that a given piece of equipment will be
subjected to corrosion it is possible to increase the wall thickness of that piece of
equipment to ensure that it lasts longer in the case of corrosion. The particular
piece of equipment would therefore be ``overdesigned'' to compensate for possible
corrosion deterioration.
3. Preventative maintenance: this requires additional labour and time, but
minimises the loss of equipment due to corrosion. Preventative maintenance
includes activities such as painting and coating of equipment and cathodic or
anodic polarisation.
4. Decommissioning of equipment: when corrosion damages equipment to the point
that the operation of that equipment becomes hazardous or the equipment fails, it
has to be taken out of operation. This might cause down time in cases where there
is no back up equipment and this can lead to considerable loss of profit.
5. Loss of efficiency: apart form causing failure of equipment, corrosion products
can decrease the efficiency of the operation by forming deposits on process
equipment. If corrosion products are deposited on heat exchange equipment the
coefficient of heat transfer and the area of heat transfer changes. Normally
 52

corrosion products are some kind of oxide that has a lower capacity for heat
transfer than the metal. This results in a reduced efficiency.
6. Loss of product: in the case of failure of equipment the product will leak out.
Often large amounts of product leak out before the leak is isolated and this product
is then lost.
7. Contamination of product: if a batch of product is contaminated by corrosion
products it might fail quality control tests. This product now has to be dumped or
recycled. In the case of dumping, the profit from the sale of the product is lost and
the cost of dumping it has to be paid. In the case of recycling the time cannot be
used for the production of new product while the old product is being recycled, and
this also results in a loss of productivity and time.
8. Environmental contamination: environmental awareness is increasingly empha-
sised in the process industries. Any discharge of unwanted substances into the
environment might exceed the allowable levels of that contaminant and result in
fines for the company. This escalates costs, reduces profit and causes bad publicity
for the company.
9. Safety: discharge of hazardous materials can lead to the loss of lives or disease
among those exposed, and the corrosion of material has to be minimised to prevent
discharge and provide the safest operation possible.
10. Appearance: Materials subject to corrosion look unsightly. You wouldn't want to
buy a car if it is corroded (rusted) because it looks bad.

2.4 CORROSION CATEGORIES

Corrosion can be classified in various ways, depending what properties one uses.

1. Process conditions: corrosion can be classified into high temperature/pressure

corrosion and low temperature/pressure corrosion according to the conditions of
the process where the corrosion takes place.
2. Nature of environment: corrosion can be divided into wet or dry corrosion
according to the type of environment in which the corrosion takes place. It is easy
to see that wet corrosion would pertain to conditions where a liquid is in contact
with the corroded material and dry corrosion is when the corrosion takes place in a
dry gas without any liquid particles present. Dry corrosion often takes place at
elevated process conditions.
3. Mechanism of corrosion process: corrosion can take place by means of a
chemical or an electrochemical mechanism. In the case of chemical corrosion the
material corroded is depleted by means of a chemical reaction alone. In the case of
electrochemical corrosion a current is developed in the corrosion reaction.
4. Appearance of corroded material: there are different types of corrosion that can
be distinguished with the naked eye because they look different. Some corrosion
types appear in even layers and some form holes, etc.

For the purpose of this course the focus will be on classification according to the
appearance of the corroded material.

2.5 CORROSION FORMS

We have stated previously that corrosion can be classified according to the appearance
of the corroded surface. This section is devoted to the different types of corrosion ± how
they look, how they can be identified and how each of the types can be avoided. There
will be a complete section on the prevention of corrosion later on, so some terms are not
explained in detail.
 53 CHP311-A/1

The eight forms of corrosion that we are going to look at are the following:

. Uniform attack
. Galvanic corrosion
. Crevice corrosion
. Pitting
. Intergranular corrosion
. Selective leaching
. Erosion corrosion
. Stress corrosion cracking

2.5.1 Uniform Attack

As the name indicates, this type of corrosion attacks a surface evenly. It is the most
common type of corrosion and you have surely seen it in, for instance, a food tin that
rusts. It can occur because of a chemical or an electrochemical reaction that proceeds
evenly over an exposed surface. The exposed material is depleted in thin layers and
slowly becomes thinner until it eventually fails. Since this is the most common form of
corrosion, it is the one that causes the greatest loss of material to corrosion products in
industry. It is however not the most dangerous corrosion type, because it is easy to
estimate the rate at which it proceeds, and because it proceeds evenly, it is possible to
estimate when a piece of material is about to fail. In some of the other corrosion forms it
is hard to see the corrosion and, because it is not distributed over the surface evenly, it is
not as simple to predict the time of failure of the equipment.

Uniform corrosion attack can be prevented by each or a combination of the following

factors:
1. Selection of the proper materials
2. Coating of material with corrosion resistant layers
3. Adding inhibitors to the corrosion environment to make it less corrosive
4. Cathodic protection of the material exposed (more about cathodic protection later)

The corrosion rate will be dependent on the temperature and concentration of the
corrosive fluid. An increase in temperature will usually increase the corrosion rate, but
not always.

The corrosion rate will also be affected by other factors such as oxygen solubility, which
is in turn also temperature dependent.

The concentration is also a very complex effect. For example, the corrosion rate of steel
is unacceptable in high (above 70%) and low concentrations of certain acids, but is
acceptable at intermediate conditions.

2.5.2 Galvanic Corrosion

You are familiar with the operation of an electrolytic cell. Two metals with different
electrochemical potentials that are contacted in a corrosive solution will form an
electrochemical cell. This will result in the corrosion of the one metal (the one which is
most likely to corrode) and the protection of the other one.

The identification of galvanic corrosion is in some cases not simple. The galvanic series
is set up for metals in solutions of their ions. It is also assumed that the metals are clean.
You can easily imagine that this is not often the case in practice. In general the metals are
not clean and the solutions are not that of the particular metal ion. The concentrations of
 54

these solutions also vary considerably. This sometimes results in unpredicted behaviour.
One such an example is that of aluminium and zinc. Aluminium appears below zinc in
the galvanic series and one can therefore expect that it will be anodic with respect to
zinc. In practice it is found, however, that aluminium is normally covered with a thin
layer of aluminium oxide and that it is in fact the zinc that is anodic. As galvanic
corrosion proceeds the rate at which it proceeds also changes. Often metal oxides are
deposited on either of the metals and this shields the metal surface from the corrosive
solution. This can slow down the corrosion rate considerably. Galvanic corrosion is also
dependent on the atmosphere to which the two metals are exposed. It is a fairly well
known fact that metals corrode at a higher rate in areas close to the coast than in inland
areas. This is because the humidity is higher at the coast (there is more moisture in the
air) and because there is more salt in the air at the coast).

Galvanic corrosion is also influenced by the distance between the two metals. If the two
metals are in contact with each other, the corrosion rate will be lower the further one
moves away from the point they are actually attached. If the two metals are in contact in
a solution that has very high conductivity the distance over which they corrode will be
greater. The worst attack is, however, closest to the junction and this is often used to
identify galvanic corrosion. The ratio of the cathodic to the anodic areas also affects the
rate at which galvanic corrosion proceeds. The current density over a corrosion area is
defined as the current that flows divided by the area exposed. The current density is
therefore larger over a small area than over a large one, and this would result in a higher
corrosion rate.

If a small area of a metal is therefore anodic to a large area of cathode, the small area will
corrode with an increased corrosion rate and this might lead to undue failures of
material. The classical example here is that of a steel plate that is riveted with copper
rivets and a copper plate that is riveted with steel rivets. The two plates are both
immersed in sea water for a given period of time. The copper metal is more resistant to
sea water in this galvanic couple and it is the steel that would corrode. In the case of the
copper plate with the steel rivets the current density is much higher on the steel rivets
because of the smaller area and they corrode fast leading to failure. If these rivets were
used to keep two plates together under these conditions, they would fail, resulting in
damage.

In the case of the steel plate with the copper rivets the rivets are cathodic in relation to
the steel and they do not corrode. The steel plate is of a much larger area than the copper
rivets and the corrosion rate is so small that it is barely noticeable. Situations such as
these should be avoided and careful consideration should be given when two metals are
attached, not only because of the galvanic coupling of the two metals, but also because
of the relative areas that will be exposed.

The best way to combat galvanic corrosion is to prevent it. Each of the following
strategies can be used to prevent galvanic corrosion:

1. If two different metals have to be contacted, do it wisely and choose metals as

close together as possible in the galvanic series. If the metals chosen are far apart in
the galvanic series the potential of the galvanic cell is higher and the corrosion rate
will also be higher. Metals closer together will have a lower potential difference
and will corrode at a much lower rate.
2. Avoid a small anode and a large cathode. If materials have to be riveted, or if
handles, flanges, lids etc. of a different material have to be attached to a vessel,
make sure that the smaller parts are cathodic in relation to the larger parts.
3. Try to avoid the junction of two different materials wherever possible. If two
materials have to be contacted, try to insulate them.
 55 CHP311-A/1

4. When one or other of the materials is coated, make sure that the coating is in good
condition. A hole or a rupture in the coating will result in a junction between the
two materials and if this is done with a small anode and a large cathode it can result
in accelerated corrosion.
5. Inhibitors can be added to the environment to reduce the aggressiveness thereof.
This will reduce the corrosion rate.
6. If different metals which are far apart in the galvanic series are to be connected,
threaded joints should be avoided because a corrosive medium can be captured in
such joints and this can increase the corrosion rate.
7. If it cannot be avoided that some parts are anodic to others and that they will
corrode, the design must make provision for them to be easily replaceable.
8. Lastly, if two metals far apart in the galvanic series have to be connected a third
metal which is anodic to both these metals can be installed as a sacrificial anode.
This third material will then corrode and protect the other two.

2.5.3 Crevice Corrosion

As the name indicates, crevice corrosion is a corrosion type that occurs in small crevices
or slots. The corrosive solution enters these small areas, which are large enough to allow
for a little of the corrosive solution to enter, but small enough so that it will not flow out
again, and because the corrosive solution is trapped in these areas this gives rise to an
extremely localised form of corrosion. Any area that can cause small amounts of
corrosive fluid to be trapped is a candidate for crevice corrosion. Small holes, joints,
rivets, bolts and dirt deposits are all potential sites for crevice corrosion. Crevice
corrosion is a more destructive type of corrosion than, for instance, uniform corrosion
because it penetrates into the material and it is sometimes hard to detect. This can result
in sudden failure of a piece of equipment for no apparent reason.

Crevice corrosion can be minimised by avoiding situations that can give rise to the
formation of crevices. Welded joints would be better in this respect than riveted joints or
bolted joints. If welded or riveted joints are unavoidable the joints can be closed by
welding or soldering. Sharp corners have to be avoided so that material cannot lurk there
to form corrosion crevices.

By ensuring that equipment is kept clean one can avoid crevice corrosion, because no
deposits will be left on equipment for long periods of time. If a plant is shut down for a
prolonged period of time some equipment is out of use, all wet material should be
removed.

2.5.4 Pitting
This type of corrosion can easily be confused with crevice corrosion. It is similar in
appearance, but one must remember that pitting does not require crevices of stagnant
corrosive solution. Pits can form on a flat surface. They are sometimes far apart and
sometimes so close together that the surface has a rough appearance. These pits have
more or less the same diameter and depth. The pits penetrate into the material and
weaken the structure of the material without looking dangerous. This can result in
sudden unexpected failure of equipment. It is hard to detect pits because they are very
small in diameter. In some cases the pits are covered with corrosion product so that it is
even harder to detect them.

Pitting can be caused by a variety of circumstances; any situation that causes a localised
increase in corrosion rate may result in the formation of a pit. In an aerated medium the
oxygen concentration will be lower at the bottom of a pit, and the bottom will be anodic
 56

to the surrounding metal, causing increased corrosion and deepening of the pit. A good
surface finish will reduce this type of attack. Pitting can also occur if the composition of
the metal is not uniform e.g. due to the presence of slag inclusions in welds. The
impingement of bubbles can also cause pitting.

The reaction in a pit is autocatalytic. This means that the reaction catalyses itself and can
therefore sustain itself. This makes pitting extremely dangerous because once it has
started, it is hard to stop.

The following situations encourage pitting and should be avoided:

1. Chloride and bromide solutions, especially in the presence of oxidising metal ions
give rise to pitting. Solutions such as copper chloride and iron chloride should be
avoided.
2. Pitting is more likely to occur in the presence of oxygen. Hydroxides, chromates
and silicate salts reduce the amount of oxygen in solution and thus reduce the
amount of pitting that occurs.
3. Pitting will occur easier in relatively stagnant flow regions. If a solution is agitated
or if the flow is kept in the turbulent region the chances of pitting will be reduced.
4. Stainless steel alloys are particularly susceptible to pitting. If molybdenum is
added to these alloys the pitting corrosion is reduced.
5. If surface areas are well polished the chances of pitting are reduced. Pitting can be
avoided in the same way as crevice corrosion.

2.5.5 Intergranular Corrosion

Metals and alloys are crystalline solids. Metals are usually cast from a molten metal
solution. As the solution starts to cool down solidification starts at various crystallisation
nuclei. This means that the crystals start to grow from various points in the metal melt.
After some time all these different crystals reach each other and the metal is solidified.
The global crystal structures are not perfect, because there are mismatches at all the areas
where the crystals are joined. These areas are called grain boundaries. These grain
boundaries are subject to small intermolecular stresses and because of that they have a
slightly higher energy state than the rest of the crystal. In some cases, however these
grain boundaries are much more reactive and the corrosive medium will attack them at
an elevated rate. The corrosion then proceeds along this grain boundaries and weakens
the metal. This form of corrosion is called intergranular corrosion.

There are many reasons for the occurrence of intergranular corrosion. In the formation of
metals or alloys the impurities in the melt do not get incorporated into the crystal and are
then trapped in the grain boundaries. There are also cases where some of the components
of an alloy are present in the grain boundaries in a higher or a lower concentration. One
such an example is the case of iron-aluminium alloy where the solubility of iron in
aluminium is sometimes low and the iron is found in the grain boundaries.

Intergranular corrosion is a common form of attack on alloys but occurs rarely with pure
metals. The attack is usually caused by a differential couple being set up between
impurities existing at the grain boundary. Impurities will tend to accumulate at the grain
boundaries after heat treatment. The classic example of intergranular corrosion in
chemical plant is the weld decay of unstabilised stainless steel. This is caused by the
precipitation of chromium carbides at the grain boundaries in a zone adjacent to the
weld, where the temperature has been 500±8008C during welding. Weld decay can be
avoided by annealing after welding, if practical; or by using low carbon grades (< 0.3
per cent C); or grades stabilised by the addition of titanium or niobium. A test for the
susceptibility of stainless steels to weld decay is BS 1502.
 57 CHP311-A/1

2.5.6 Selective Leaching

Selective leaching occurs when one of the components of an alloy is removed faster than
the others and this causes the metal to lose its ductility and strength.

Dezincification is the removal of zinc from brass alloys. Brass consists of zinc and
copper and the dezincification can be seen. When the zinc is removed from zinc - copper
alloy the alloy loses its yellowish colour and turns more red. This dezincification is of
two types:

. layered type
. plug type.

The layer type tends to be more uniform than the plug type. Because the zinc is removed
from between copper areas the alloy does not lose its original dimensions. It becomes
brittle, but if the piece of equipment is very dirty or covered in some way, this type of
corrosion might go undetected.

Uniform dezincification usually occurs in brasses with a high zinc content in acid
environments. The plug type dezincification is usually apparent in brasses with a lower
zinc content in alkaline, neutral or slightly acidic solutions.

Dezincification can be prevented:

. by reducing the aggressiveness of the environment or

. by cathodic protection or
. by the choice of a more suitable alloy.

Graphitisation is a similar process where grey cast iron undergoes selective leaching and
the iron or steel is removed form the matrix. Graphite, rust and dirt stay behind and the
metal assumes the soft, brittle properties one would usually find in graphite.

2.5.7 Erosion Corrosion

Erosion corrosion occurs when contact with a corrosive liquid is combined with flow of
a corrosive fluid over the metal surface. Erosion corrosion usually occurs when the flow
is fast or very turbulent, or in the case of bends or discharges at an angle to the metal.
The metal is corroded partly because of the corrosiveness of the fluid and partly because
of friction which is caused by the fast flowing liquid. The metal dissolves and is
removed as ions. In some cases solid corrosion products form and they are removed by
the fast flowing fluid.

Erosion corrosion can be seen with the naked eye and it appears as shallow rounded
holes or grooves that indicate a flow pattern. Erosion corrosion proceeds at a very high
rate and it is normally not expected because the corrosion testing for materials is
normally done under stagnant fluid conditions.

This corrosion type affects most metals and soft metals such as copper and lead are
particularly susceptible to erosion corrosion. The following types of process equipment
are susceptible to erosion corrosion:

. Pipes (bends, elbows, tees)

. Valves
. Pumps (impellers)
. Blowers
 58

. Turbines (blades)
. Equipment subject to spray (nozzles)
. Mills

There are various factors that influence erosion corrosion. A few of these are discussed
below:

2.5.7.1 Surface protection of metals

Some metals form protective films that increase their corrosion resistance. In the case of
erosion corrosion these films are important, because if they are soft or brittle they will be
removed from the surface and this will greatly increase the corrosion rate. If the
protective films are hard and very abrasion resistant they will serve to protect the
surface. The nature of these films depends on the metal and on the nature of the
corrosive fluid.

Stainless steels are particularly susceptible to erosion corrosion in most environments.

Lead is normally used in sulphuric acid environments because of the formation of a lead
sulphate or lead oxide protective film. Under elevated temperatures and corrosive
conditions these films break down resulting in a rapid increase in corrosion rate.
Titanium is resistant to erosion corrosion because it forms a titanium dioxide film that is
very stable. It shows good resistance to sea water and chloride solutions.

2.5.7.2 Velocity of corrosive fluid

Because erosion corrosion deals with corrosion that occurs at fairly high fluid velocities,
an increase in fluid velocity would normally increase the corrosion rate ± the higher the
velocity, the higher the rate of mechanical wear. Velocities of greater than 10m.s-1 are
particularly dangerous. The amount of solids that is present in the solution also increases
the corrosion rate because it increases the amount of mechanical wear. There are
however cases where an increased velocity will decrease the rate of corrosion. One such
case is where an inhibitor is used in the corrosive fluid to combat corrosion. When the
velocity is low the corrosion will proceed because the rate to which the inhibitor is
supplied to the surface is restricted. When the velocity increases the inhibitor is supplied
to the surface faster and the corrosion rate decreases.

2.5.7.3 Turbulence
Turbulence would increase erosion corrosion because the mechanical wear would be
greater than in laminar conditions. This can be seen in many condensers or heat
exchangers where the flow in the tubes is essentially laminar, but the inlet to the tubes
has a large pipe mounting into a small one. The flow in the small section of the pipe
tends to be turbulent and the corrosion would be markedly worse in this section than in
the laminar section even though the fluid is the same.

2.5.7.4 Flow at right angles to metal surface

This phenomenon would typically occur in the case of fluid flowing around a pipe bend
or a discharge that would come in at a right angle to a tank. This form of corrosion
would also be common in steam turbines.
 59 CHP311-A/1

2.5.7.5 Galvanic effects

when two metals are in contact with each other in a corrosive fluid under high velocities
the corrosion rate can be greatly affected. One such an example is the contacting of lead
and 316-stainless steel. Under static conditions this combination of fluids shows no
noticeable corrosion because the lead is protected by a protective film. Under high
velocity conditions these films are destroyed and galvanic corrosion proceeds quite
rapidly.

2.5.7.6 Nature of metal

The various chemical and physical properties of a metal influence corrosion resistance
and erosion corrosion is no exception. The degree of chemical inertness, the hardness
and the nature of the metal would all influence the erosion corrosion rate. It is often
possible to alloy materials so that they are more erosion resistant. Other methods of
treating such as heat treatment can also be employed.
Erosion corrosion can be prevented by the following strategies:

1. The material specified must be able to withstand erosion corrosion to a satisfactory

degree.
2. Equipment design must be done to minimise erosion corrosion possibilities. We
have seen that any fluid moving at right angles to a metal will increase the amount
of erosion corrosion. This happens because a fluid impacting a metal at a right
angle does so with a greater force than a fluid flowing down a pipe, for example. In
the design of equipment this should be avoided as far as possible. A larger pipe
diameter will decrease the amount of turbulence and also the fluid velocity. When
the diameters of bends are increased the friction in them will be less. Short pieces
of tubing can be inserted in the inlet end to condensers etc. to even out the flow.
Parts like pump impellers and turbine blades can be properly aligned.
3. Adjusting the environment. There are various changes that can be made to the
environment which can combat erosion corrosion. Inhibitors can be added in
selective cases and solids can be removed from solutions by means of filtration and
settling.
4. Coatings can be applied to protect the surface of materials. Where coatings are
applied they must be maintained regularly to ensure that cracks don't occur
because this can give rise to other forms of corrosion.
5. Cathodic protection can be of some help, but it is generally not very effective.

2.5.8 Cavitation
Cavitation is a special form of erosion corrosion that is caused due to the collapse of
vapour bubbles. It is a phenomenon often found in pumps and turbines. When the
pressure in a liquid is reduced fast enough, the liquid will boil at room temperature.
When this liquid is then recompressed the bubbles collapse causing shock waves and
considerable damage to metal surfaces. Cavitation damage looks like pitting with a
rough surface. Cavitation can be reduced in much the same way as erosion corrosion.

2.5.9 Stress Corrosion Cracking

In the previous section we have looked at the simultaneous presence of corrosive fluids
and fast moving fluids. In this section we are going to consider the simultaneous
presence of a corrosive fluid and a cyclic stress. The stress under question is usually a
tensile stress. Stress corrosion cracking differs from the other types of corrosion in that
 60

the surface of the material is virtually unaffected. A crack can be seen where the material
has fractured. The presence of a corrosive environment as well as a tensile stress often
lead to the material cracking and failing at a much lower temperature than it would fail at
under any one of these factors. This type of corrosion is affected by each of the
following factors:

. Temperature
. Solution composition
. Stress
. Metal structure.

It can be prevented by the following methods:

1. Lowering the stress. This can be done by annealing the material or by adjusting the
design to relief the stress (e.g. round corners instead of sharp corners).
2. The corrosive species can be eliminated from the environment.
3. If neither of the above can be done the alloy can be substituted for a different one.
4. Cathodic protection of the exposed material.
5. Addition of inhibitors.

A subsection of stress corrosion cracking is corrosion fatigue. This usually happens in

the case of a repeated cyclic stress that is applied to the material. The material then fails
at a stress level much below the yield point. You might have seen how people break
through wires if they do not have a wire cutter. They bend the wire in opposite directions
very fast, and the wire eventually breaks. This happens because the metal is weakened
under the influence of a cyclic stress. If such a situation occurs under corrosive
conditions it is known as corrosion fatigue.

Corrosion fatigue can be distinguished from other corrosion types by the presence of a
large smooth area with a rough area in the centre of it. This shows where the material
failed. Corrosion fatigue is also defined as the reduction in the resistance to fatigue
because of a combination of cyclic stress and a corrosive environment. The frequency at
which the stress cycle occurs greatly affects the corrosion fatigue.

Corrosion fatigue can be prevented by reducing the stress on the component is or by heat
treating the component. Coatings can also in some cases reduce the amount of corrosion
fatigue.

2.6 CORROSION RATE

It is important to be able to quantify the rate at which corrosion proceeds. This corrosion
rate enables us to estimate the cost of corrosion as well as the predicted life of
equipment. Corrosion rates are also useful in comparing different substances for
corrosion applications.

There are various ways to express corrosion rates such as mass lost and mass lost per
time unit, or mass lost per area per time unit. When corrosion rates of different materials
are compared it is important that the tests done to determine these rates are done in a
way that will produce reliable data. The shape of material, the concentration of the
electrolyte, the temperature of the electrolyte, the time of exposure and the degree of
turbulence of the solutions are all factors which can influence the corrosion rate. The
conditions under which an experiment is carried out must be well documented when the
rates are recorded. The most common way in which to record the rate of corrosion is as
follows:
 61 CHP311-A/1

534W
mpy ˆ
DAT
Where:

mpy = millimetres penetration per year

W = weight loss in milligrams
D = density of specimen in g/cm3
A = area of specimen in cm2
T = exposure time in hours

2.7 THERMODYNAMICS
There are some useful thermodynamic considerations in the study of electrochemical
reactions and corrosion. Thermodynamics defines the terms of corrosion language and it
also provides a mechanism with which we can extract valuable information about
corrosion systems. It is possible, by making use of a simple calculation, to predict
whether a corrosion reaction will occur between two substances or not. This information
is very useful in the selection of materials for the construction of engineering equipment,
because it enables the engineer to make decisions regarding the best combination of
materials for engineering purposes.

It is possible that you might have encountered basic electrochemistry in your chemistry
courses. In that case the first part of the section that is to follow might be familiar to you.
Read through it as revision and make sure you can still remember it all. The section that
follows will apply basic electrochemical knowledge to corrosion principles, and then go
on to define a few corrosion phenomena related to the electrochemical reactions.

2.7.1 Calculation of Cell Potential

You should have some idea about the working of an electrochemical cell, even if it is
just from school science. Let's briefly revise your knowledge.

The old favourite for electrochemical reaction explanations is the zinc-copper

electrochemical cell. See below:

FIGURE 2.1: A zine-copper electrochemical cell

 62

The cell is made up of two metal electrodes, one made of Zn metal and the other of Cu.
Each of these metals is submerged in a solution of its ions. The concentrations of the
ions in the respective solutions are 1 mol/litre. A porous membrane is inserted between
the two solutions to prevent them from mixing. Both these metals will be in equilibrium
with their ions in solution. That means that some of the Cu++ ions will be reduced (gain
electrons) to Cu metal and some of the Cu atoms in the metal will be oxidised (lose
electrons) to Cu++ ions. The same will happen on the Zn side. The copper electrode in
copper solution is called a half cell. When the two half cells are connected the electrons
that will be released at the zinc electrode will flow through the external conductor and
will be absorbed by the copper electrode. The electrode at which the oxidation process
occurs (electrons are lost) is called the anode, and the electrode at which the reduction
reaction occurs is called the cathode.

A copper ion concentration of 1 mol/litre is considered to be the standard, so this is also

a standard half cell. If a voltmeter is installed in the circuit as indicated, it will have a
reading of approximately 1.1 volts if the positive terminal is connected to the copper and
the negative terminal is connected to the zinc. If the terminals are switched, the reading
obtained will be negative. The 1.1 volts is the potential difference that exists between the
two electrodes. Each standard half cell is allocated a cell potential according to a specific
reference. The reference electrode most commonly used is a hydrogen electrode. The
hydrogen electrode consists normally of a platinum carrier electrode that facilitates the
reaction between hydrogen gas and a one molar solution of hydrogen ions. The
potentials of all the other half cells are measured with reference to this standard
electrode. If the copper half cell is to be connected to the hydrogen electrode the reading
would be ±0.337 volts (table 2.1), and this is the half cell potential of the copper. In the
case of the zinc, the reading would be +0.763 volts. The copper electrode is +0.337 volts
and the zinc electrode is +0.763 volts because the copper reaction is reversed.

The two half cell reactions can be added and the electrons cancelled to give the complete
cell potential:

Zn = Zn++ + 2e- +0.763 V

++
Cu + 2e- = Cu +0.337 V
Cu++ + Zn = Zn++ + Cu +1.1V

Note that sometimes the electrochemical series is written for M+++e?M, in which case
the voltages changes from positive to negative and vice-versa. Also note that for
galvanic cells, the anode is negative, while for electrolytic cells the anode is positive (but
in both cases oxidation occurs at the anode). An analogy would be a rechargeable
battery. The positive terminal during discharge becomes the negative terminal when
recharging. Note also that ``conventional current'' is in the opposite direction to electron
flow.

Under standard conditions, the following equation can be used to calculate the cell
voltage for any combination of half cells.

0:059
E ˆ E0 ÿ log10 Q
n
where:

E = cell potential
E0 = standard voltage
n = number of electrons transferred in the reaction
Q = (concentration of anode product)y/(concentration of cathode product)z
 63 CHP311-A/1

TABLE 2.1 Standard oxidation potentials for corrosion reactions at 258C.

Corrosion Reaction Potential Eo/Volts vs. Hydrogen Electrode

Au?Au3++3e ±1.498
2H2O?02+4H++4e ±1.229
2+
Pt?Pt +2e ±1.200
2+
Pd?Pd +2e ±0.987
Ag?Ag++e ±0.799
2Hg?Hg22++2e ±0.788
Fe2+?Fe3++e ±0.771
4(OH)-?402+2H2O+4e ±0.401
Cu?Cu2++2e ±0.337
2+ 4+
Sn ?Sn +2e ±0.150
-
H2?2H +2e 0.000
Pb?Pb2++2e +0.126
Sn?Sn2++2e +0.136
Ni?Ni2++2e +0.250
Co?Co2++2e +0.277
Cd?Cd2++2e +0.403
2+
Fe?Fe +2e +0.440
3+
Cr?Cr +3 e +0.744
Zn?Zn2++2e +0.763
Al?A13++3 e +1.662
Mg?Mg2++2e +2.363
Na?Na++e +2.714
K?K++e +2.925

The superscripts y and z are used to express the number of moles of electrons transferred
in the reaction.

From the cell potential, we can calculate a commodity known as free energy. It is
calculated as follows:

G ˆ ÿnFE

where:

G = free energy, J/mol

n = number of electrons transferred
E = cell potential, V
F = Faraday constant, 96 489 coulomb/mol
 64

The importance of this free energy is that it indicates whether a specific electrochemical
reaction will proceed spontaneously or not.

The half cell with the most positive cell potential will be oxidised (it will act as the
anode) and the half cell with the most negative half cell potential will be reduced (it will
act as the cathode). If we look back to the zinc copper cell we see that the zinc will be
corroded. If we look at the table of half cell potentials we can deduce that all those
metals which have half cell potential values that are positive with respect to hydrogen
will be corroded in acid solutions (acid solutions have free H+ ions). The more negative
the half cell potential of a particular metal, the lower the tendency of that metal to
corrode. The metals at the top of the table are very inert.

A reaction will proceed if the spontaneous reaction indicates that a metal will corrode. In
some cases, however, the thermodynamics indicate that a spontaneous reaction will take
place and then there are other factors that come into effect that prevent the reaction.
Sometimes metals form layers of metal oxide on the surface of the metal, and the
corrosion reaction will therefore not take place, although calculations indicate that it
should. However, if the calculations show that a reaction will not take place, it is a clear
indication, because a thermodynamically impossible reaction will never take place.

Example 2.1
(a) What is the cell potential in a zinc-silver cell with a 1-molar concentration of zinc
and silver ions?
(b) What is the new cell voltage with a Zn2+ concentration of 0.1 M and an Ag
concentration of 0.01 M?

Answer
(a) Zinc is more anodic than silver (table 2.1)
Zn?Zn2++2e E0 = +0.763 V (written as anode)
2Ag++2e-?2Ag E0 = +0.799 V (written as cathode)

Summing the reactions to remove the electrons:

Zn+2Ag+?Zn2++2Ag E0 = +0.763+0.799 = +1.562 V

(b) 0:059 ‰Zn2‡ Š

E ˆ E0 ÿ log10
n ‰AgŠ2
0:059 ‰0:1Š
E ˆ 1:562 ÿ log10
2 ‰0:01Š2
ˆ 1:562 ÿ 0:0295…3†
ˆ 1:474V

We have now discussed the electrochemical and thermodynamic factors that are
important in the study of corrosion phenomena. We have also discussed the use of
thermodynamic calculations for practical applications such as the prediction of corrosion
reactions. The next section deals with the factors that influence the rate of a corrosion
reaction. We have mentioned some of these factors in our previous discussions, but here
we will discuss them in more detail. Before we take a look at all the factors that
influence the corrosion rate we have to define two concepts that are frequently used to
describe the behaviour of metal in terms of its corrosion rate. These terms are
polarisation and passivity.
 65 CHP311-A/1

2.8 POLARISATION
Polarisation is a term used to describe the retardation of an electrochemical reaction.
There are various mechanisms by which such a reaction can be retarded. Polarisation
can be divided into two main types, namely activation polarisation and concentration
polarisation. To clarify these explanations we are going to make use of the reaction
between an acidic solution and zinc metal.

Zinc is corroded according to the reaction:

Zn?Zn+++2e

And hydrogen is formed according to the reaction:

2H+ + 2e- ? H2

The reaction can be broken up into various steps. The first step is the adsorption of the
hydrogen ions onto the surface of the zinc metal. The second step is the transfer of
electrons from the zinc (which is being oxidised) to the hydrogen ions, which will be
reduced to form hydrogen atoms. In the next step the hydrogen atoms combine to form
molecules of diatomic hydrogen gas, and these diatomic molecules form bubbles of
hydrogen gas. The picture below gives a representation of these steps:

FIGURE 2.2: Reaction steps in hydrogen reduction

Now if this hydrogen formation reaction proceeds at a relatively low rate, there will be
enough hydrogen ions at the surface so that the reaction rate will not be affected. If the
reaction rate is high, however, all the hydrogen ions at the surface of the metal will be
used up and the reaction will be limited because of the fact that there are not enough
hydrogen ions to react with the zinc. The rate is therefore limited by the rate at which the
hydrogen ions diffuse to the zinc surface. The concentration of the hydrogen ions at the
surface therefore limits the reaction rate and this type of polarisation is called
concentration polarisation. If step 1 in the sequence above, namely the diffusion of ions
to the metal surface, is slower than all the other steps, it is called the rate limiting step.

The rate at which transfer can take place at the surface of the metal is now influenced
by:

. The diffusion coefficient.

. The thickness of the diffusion layer.

This type of polarisation might be less evident for zinc, because there are lots of metal
atoms available at the metal surface.
 66

In some instances the reaction rate could be limited by the electrolytic reaction itself.
This process is called activation polarisation.

It is important to understand what polarises a corrosion reaction. Polarisation is a useful

mechanism that can be employed to inhibit the corrosion rate of a substance. If we know
that the polarisation in question is concentration polarisation (because of a limited
supply of reactants at the surface of reaction) we can expect that agitation of the
electrolyte will result in an increased corrosion rate because the species (for instance, the
hydrogen ions) are supplied to the metal surface by agitation as well and not by diffusion
alone. In the case of activation polarisation the amount of agitation of the electrolyte
solution will have no effect on the corrosion rate.

2.9 PASSIVITY
Passivity is another factor that can lead to the reduction of corrosion rates. Certain
metals and alloys demonstrate peculiar behaviour under certain oxidising conditions.
Normally, one would expect that, as the concentration of the corrosive fluid increases,
the rate of corrosion would increase accordingly. This happens for most metals. In the
case of some metals, however, this does not happen. The metals under consideration
here are iron, nickel, silicon, chromium, titanium, and in some cases, zinc, cadmium, tin,
uranium and thorium. Alloys containing these metals are also included.

To illustrate the effects of passivity, let's consider an experiment conducted by Faraday.

He immersed a piece of steel in a 70% nitric acid solution. Being quite a strong acid
solution, one would expect at least some visible corrosion reaction. Almost no corrosion
was observed at this concentration. However, when the steel is immersed in a nitric acid
solution of half the original strength a violent corrosion reaction occurs. The steel is
dissolved and nitrogen oxide gases are released.

If the acid in the container that held the first piece of steel is diluted there is still no
corrosion in this container until the piece of steel is scratched or the solution is stirred.
Then the corrosion reaction occurs at the same rate as in the second container. If the
concentration of the corrosive medium is increased in the first container without
scratching the steel, the corrosion rate would be small for a long while, and only at very
high acid concentrations would the corrosion rate increase again.

This behaviour of the steel is very strange. In the case of most metals, the corrosion rate
increases more or less logarithmically as the concentration of the solution increases. In
the case of the metals mentioned earlier we have an original increase in the corrosion
rate with an increased corrosive fluid concentration and then, suddenly the corrosion rate
drops to almost nothing. It was determined that the decrease in the corrosion rate is
between 1000 and 1000000 times! At high corrosive fluid concentrations this rate
increases again as the corrosive fluid concentration increases.

The only logical explanation for such a phenomenon is the fact that some kind of film
forms on the metal at medium corrosive fluid concentrations. This film is able to reduce
the corrosion rate for a whole range of corrosive fluid concentrations, but it is destroyed
at very high concentrations. This film is also not very strong, since it can be destroyed
by stirring the corrosive fluid or by scratching the metal surface.

The formation of such a film is a very useful thing, and the best part is that the metals
that seem to be subject to these films are the most common construction metals. One
must keep in mind, however that these films are not very strong. Passivity is divided into
three zones or areas according to the corrosive medium concentration and the
 67 CHP311-A/1

subsequent behaviour of the metal. In the case of low corrosive fluid concentrations
where there is an increase in corrosion rate as the concentration is increased, this region
of concentrations represents the active region. In the range where the corrosion rate is
decreased, the concentrations represent the passive region, and the region of high
concentrations of increasing corrosion rate beyond the passive region is called the
transpassive region.

2.10 FACTORS INFLUENCING THE CORROSION RATE

At this stage you should be in a position to list a few factors that will influence the
corrosion rate that we have mentioned in passing. Let's take a look at some of these
factors.

2.10.1 Oxidation Capacity of the Solution

In some cases the addition of dissolved oxygen can increase the corrosion rate of a metal
quite rapidly. Let's consider the corrosion of zinc in hydrochloric acid. We already know
that zinc has a half cell potential more than hydrogen, so zinc will be corroded in acidic
solutions. Zinc will therefore be oxidised to form zinc ions and the hydrogen ions in the
solution will be reduced to form hydrogen gas. In some cases, however, there is
dissolved oxygen in the acid. In the case of this aerated acid the following reaction can
occur between the hydrogen ions and the dissolved oxygen:

02 + 4H+ + 4e- ? 2H2O

This implies that there are two reactions that occur on the zinc surface. Both these
reactions need electrons to proceed and these electrons will be taken from the zinc
atoms. This increases the zinc corrosion rate in the case where the oxygen is also a
competitor for electrons. Oxygen in acid solutions will therefore increase the rate of
corrosion. This dissolved oxygen also plays a part in corrosion by water. Impure or
natural water sometimes contains much more dissolved oxygen than pure water, and is
as a result much more corrosive.

The strength of the oxidising solution also has an effect on the corrosion rate. We have
discussed the impact of this in our discussion on passivity. We know that for low
oxidiser strengths the metal shows an exponential increase in corrosion rate with an
increase in oxidiser strength. At some stage there will be a decrease in the corrosion rate
due to the formation of a passive film. Remember that not all substances are subject to
passivity and this is true only for the metals that are. In the case of metals that are not
subjected to passivity, the corrosion rate keeps on increasing with the strength of the
corrosive solution. In the case of iron or steel in nitric acid or sulphuric acid, the
passivity behaviour can be seen quite nicely. At very high acid concentrations the rate of
corrosion will increase when these protective passivating films are destroyed.

Fig 2.3 illustrates this graphically. The corrosion rate is plotted against the strength of
the oxidiser added. In the first region of this graph the behaviour of a metal in the active
state is shown. Remember that some metals only have an active state and will therefore
not show the second and third regions. In section 2 the region of metal passivity is
reached and the corrosion rate drops dramatically. For a certain region of oxidiser
strengths there is absolutely no increase of corrosion rate with increased oxidiser
strength. Then the transpassive region is entered (region 3) where the corrosion rate is
once again on the increase.
 68

1 2 3
Corrosion rate

Oxidiser concentration

FIGURE 2.3: Influence of oxidiser concentration on corrosion rate

We have now seen that the corrosion rate can be influenced by both the oxygen content
of the corrosive solution as well as the type of metal and its passivity behaviour. The
information that we can gather about the corrosion rate as a function of the oxygen
content or of the oxidising power of the solution is useful to the engineer in the
prediction of corrosion behaviour.

2.10.2 Velocity of the Oxidising Solution

At this stage you are able to appreciate that the influence of velocity on the corrosion
rate is not simple. In some cases the increase in the amount of turbulence can increase
the corrosion rate and in some cases it will have no affect at all. Can you remember
which cases are applicable when?

Fig 2.4 shows the most common responses to an increase in the velocity of the oxidation
fluid. In the case labelled 1, we have a metal which is under the influence of activation
polarisation. You will recall that the corrosion rate is limited in such a case by the rate of
electron transfer. In this case the amount of electrolyte supplied at the surface is
sufficient and agitation will have no influence on the reaction rate. In the section labelled
2, we have a metal that is under diffusion control. This metal will show an increased
corrosion rate as the velocity of the corrosive fluid increases, because an increased
velocity supplies more of the corrosive species (e.g. H+ ions) to the surface of the metal.
In some cases metals will undergo an active to passive transition when the velocity of
the corrosive fluid is high enough.

We have said before that passivity can occur with increased oxidiser strength and now
we say that passivity can occur with increased velocity. So which one is correct? They
both are.

Remember the effect of an increased velocity is the increased supply of active medium
at the metal surface. So to the metal it seems as if the concentration has increased
because it has more of the corrosive species at its disposal. It will therefore act as if a
concentration increase has occurred, and passivate. In the section labelled 3, we have no
initial effect on corrosion rate. This happens in the case where metals are protected by
films that form on the surface of the metal. These films are said not to be the same as the
actual passivating films because they can be seen with the naked eye. Both lead and steel
form sulphate films when immersed in sulphuric acid. This film protects the metal and it
 69 CHP311-A/1

is as a result not corroded by the acid. If these metals are exposed to very violent
turbulence, however, it is possible that these films are destroyed and that they will start
corroding. This is clearly visible from the graph where the corrosion rate only goes up at
very high velocities.

FIGURE 2.4: Velocity effects on corrosion rate

2.10.3 Temperature Effects of the System

Graph 2.5 shows the different effects that an increase in temperature can have on a
corrosion system. Any chemical reaction will proceed at an increased rate as the
temperature increases. In the graph labelled A, this effect is illustrated. An exponential
increase in corrosion rate is experienced as the temperature increases. In the section
labelled B, we see no initial effect followed by quite a rapid rise in corrosion rate at
elevated temperatures. This happens in the case of systems such as stainless steel in
nitric acid. The reaction will not start until a certain temperature is reached.

FIGURE 2.5: Temperature effects on corrosion rates

2.10.4 Concentration
We have said something about concentration under the strength of the oxidising
medium. In figure 2.6 curve A, we once again have the situation that the metal under
question forms a bulk protective film. We have already mentioned the example of lead
which forms a lead sulphate protective film in the presence of sulphuric acid. At high
acid concentrations this protective film is destroyed and the lead corrodes at an elevated
 70

rate. In curve B we have a situation typical for the corrosion of metals in acid. Initially
the metal experiences an increased corrosion rate because as the concentration of the
acid increases there are more hydrogen ions available at the surface for metal
dissolution. As the acid concentration increases the corrosion rate reaches a maximum
and then starts to decrease. This happens because, as the acid concentration increases the
amount of ionisation decreases and, along with that, the amount of free hydrogen ions.
That also explains why very strong acids are less corrosive than weaker acids.

FIGURE 2.6: Corrosion rate versus acid concentration

Many common acids such as sulphuric acid, acetic acid and hydrofluoric acid are much
less corrosive in the pure state than in a more dilute state. We have discussed quite a few
methods by which corrosion can be prevented, some under different types of corrosion
and some under general corrosion principles. You should by this stage be able to discuss
what the best ways would be to combat corrosion in a given situation. There are two
aspects of corrosion

prevention that we haven't discussed yet. They are called cathodic and anodic protection
and they were briefly mentioned under prevention of the different corrosion types.

2.11 CATHODIC PROTECTION

You are well aware of the corrosion reactions that take place between a metal and an
acidic solution. If we take the by now familiar example of zinc in hydrochloric acid, we
know that the reactions are:

Zn ? Zn ++ + 2e-
2H+ + 2e- ? H2

By looking at these reactions you can see that the metal loses electrons and this causes it
to be corroded. Cathodic protection simply involves supplying, from an external source,
electrons to the metal to be protected, making it a cathode. This forces the above
reactions into reverse, reducing the metal.

This can be done in two ways:

1. By supplying an external direct current

2. By galvanic coupling (sacrificial anode)
 71 CHP311-A/1

Figure 2.7 below shows a typical set up with an external power supply. An underground
tank needs to be protected against corrosion. A power supply is fixed to the tank so that
the negative pole runs to the tank and the positive pole is attached to an inert anode. The
tank becomes the cathode, which protects the tank from being corroded.

In the case of galvanic coupling the metal that needs to be protected is coupled with a
metal that is more anodic than itself. This implies that the anodic metal gets corroded in
order to protect the cathodic one. The anode is referred to as a sacrificial anode because
its sole purpose is to protect the cathode. Steel pipes are often protected if they are
exposed to damp soil, ground water or sea water. They are coupled to magnesium which
acts as a sacrificial anode. Those magnesium anodes are cheaper than the steel, so it is
more economical to replace the sacrificial anode every once in a while than to replace
expensive steel pipes.

FIGURE 2.7: Set-up for cathodic protection by external direct current

2.12 ANODIC PROTECTION

Anodic protection is a more complicated process than cathodic protection. In the case of
anodic protection the principle of passivity is used to protect metals from corrosion. An
external anodic current is supplied to the metal in order to keep it in the passive reaction.
The materials are then passivated and the corrosion rate reduced. This is done by means
of an instrument called a potentiostat. This potentiostat keeps the metal at a certain
potential in relation to a reference electrode. This ensures that the metal in question stays
within the passive region.

2.13 MATERIALS SELECTION FOR CORROSION RESISTANCE

The resistance of some commonly used materials to a range of chemicals is shown in
table 2.2. A wide variety of these corrosion charts is available in the literature and on the
Internet.
 72

TABLE 2.2 Chemical Resistance Chart

Resistance Material
E = Excellent PTFE = Polytetrafluoroethylene inc. Teflon1
G = Good SS = Stainless Steel (316)
F = Fair PE#1 = Conventional Polyethylene
N = Not Recommended PE#2 = Rigid Polyethylene
PP = Polypropylene
PVC = Polyvinylchloride

This information, based on experience to date, is believed to be reliable. It is intended as a guide for use at
your own discretion and risk. All indications refer to room temperature.

Chemical PTFE SS PE#1 PE#2 PP PVC

Acetaldehyde E E G G G G

Acetamide E E E E E N

Acetic Acid, 5% E E E E E E

Acetic Acid, 50% E E E E E E

Acetone E E E E E E

Aluminum Hydroxide E E E E E E

Ammonia E E E E E E

Ammonium Hydroxide E E E E E E

Ammonium Oxalate E E E E E E

N-Amyl Acetate E E G E G F

Amyl Chloride E ± N F N N

Aniline E E E E G N

Benzaldehyde E ± E E E N

Benzene E E F G G N

Benzoic Acid, Sat. E E E E E E

Benzyl Acetate E ± E E E F

Boric Acid E F E E E E

Bromine E N N F N G

Bromobenzene E ± N F N F

n-Butyl Acetate E F G E G N

sec-Butyl Alcolhol E ± E E E G

Butyric Acid E E N F N G

Calcium Hypochlorite E F E E E G
 73 CHP311-A/1

Chemical PTFE SS PE#1 PE#2 PP PVC

Carbazole E ± E E E N

Carbon Disulfide E E N N E N

Carbon Tetrachloride E G F G G G

Chlorine E G G G G E

Chloroacetic Acid E F E E E F

Chloroform E E F G G N

Chromic Acid E F E E E F

Citric Acid E E E E E G

Cresol E E N F E N

Cyclohezane E E G E G G

Decalin E ± G E G E

o-Dichlorobenzene E ± F F F G

p-Dichlorobenzene E ± F G E N

Diethyl Benzene E ± N F N N

Diethyl Ether E ± N F N F

Diethyl Ketone E ± G G G N

Diethyl Malonate E ± E E E G

Dimethyl Formamide E ± E E E F

Ether E E N F N F

Ethyl Acetate E E E E E F

Ethyl Benzene E ± F G F N

Ethyl Benzoate E ± F G G N

Ethyl Chloride, Liquid E E F G F N

Ethyl Cyanoacetate E ± E E E NF

Ethyl Lactate E ± E E E F

Ethylene Chloride E E G G G N

Ethylene Glycol E E E E E E

Ethylene Oxide E ± F G F F

Fluorine G ± F G G N

Formic Acid, 50% E F E E E G

Fromic Acid, 90±100% E N E E E F

Fuel Oil E E F G E E

Gasoline E E F G E G

Glycerine E E E E E E
 74

Chemical PTFE SS PE#1 PE#2 PP PVC

n-Heptane E E F G E F

Hexane E E N G E G

Hydrochloric Acid, 1±5% E N E E E E

Hydrochloric Acid, 35% E N E E E G

Hydrodluoric Acid, 4% E N E E E G

Hydrofluoric Acid, 48% E N E E E G

Hydrogen E ± E E E E

Hydrogen Peroxide E F E E E E

Isopropyl Acetate E ± G E G N

Isopropyl Benzene E ± F G F N

Kerosene E E F G G E

Lactic Acid, 3% E G E E E G

Lactic Acid, 85% E F E E E G

Magnesium Salts E G E E E E

Methoxyehyl Oleate E ± E E E N

Methyl Ethyl Ketone E E E E E N

Methyl Isobutyl Ketone E E G E G N

Methyl Propyl Ketone E ± G E G N

Methylene Chloride E E F G F N

Nitric Acid, 50% E G E G G G

Nitric Acid, 70% E N E G G F

Nitrobenzene E E F G F N

n-Octane E ± E E E F

Orange Oil E ± F G G F

Perchloric Acid E ± G G G G

Perchloroethylene E E N N N N

Phenol, Crystals E E G G G F

Phosphoric Acid, 1±5% E E E E E E

Phosphoric Acid, 85% E G E E E E

Potassium Hydroxide E G E E E E

Propane Gas E E N F N E

Propylnee Glycol E E E E E E

Propylene Oxide E ± E E E F

Resorcinol E ± E E E F
 75 CHP311-A/1

Chemical PTFE SS PE#1 PE#2 PP PVC

Salicylaldehyde E ± E E E F

Sulfuric Acid, 1±6% E F E E E E

Sulfuric Acid, 20% E N E E E E

Sulfuric Acid, 60% E N E E E E

Sulfuric Acid, 98% E N E E E N

Sulfur Dioxide, Liq E E N F N F

Sulfur Salts E E F G F N

Tartaric Acid E G E E E E

Tetrahydrofuran E E F G G N

Thionyl Chloride E ± N N N N

Toluene E E F G G F

Trichloreoethane E E N F N N

Trichloroethylene E E N F N N

Turpentine E E F G G G

Vinylidene Chloride E ± N F N N

Xylene E E G G F N

Zinc Salts/Stearate E G E E E E

Example 2.2
You have four chemicals ± aniline, benzene, bromine and methyl isobutyl ketone
(MIBK), and four tanks in different materials (PTFE, SS, PE#1 and PE#2) to store the
chemicals. Which chemical belongs in which tank if corrosion is to be minimised?

Answer
Aniline ± PE#1

Benzene ± SS
Bromine ± PTFE

MIBK ± PE#2

REVISION QUESTIONS
1. Define the term corrosion.
2. Typical corrosion environments include (a) gases, (b) mineral acids and (c) organic
acids. Name at least two examples of each.
3. Name three corrosion environments, other than those mentioned in question 2.
4. Name five consequences of corrosion.
5. What would you say is the main implication (or impact) of corrosion? Motivate
your answer.
 76

6 .Depending on the properties one uses, corrosion can be classified into different
categories. Name the categories one can use to classify corrosion.
7. Give a) the definition b) the identification and c) the prevention of each of the
following:
. Uniform attack
. Pitting
. Erosion corrosion
. Selective leaching
. Galvanic corrosion
. Crevice corrosion
. Intergranular corrosion.

8. What would happen to the following when they are both immersed in sea water for
a given time? (a) A copper plate riveted with steel and (b) A steel plate riveted with
copper?
9. (a) Name the four factors affecting stress corrosion cracking.
(b) How can stress corrosion cracking be prevented?

10. Name four factors that will influence the corrosion rate of a substance.
11. What is the most common way to record the corrosion rate of a substance? Define
all symbols used.
 77 CHP311-A/1

CHAPTER 3

Water and wastewater treatment

OBJECTIVES
After completion of this chapter the student should be able to:
. Describe what is meant by each of the following terms:
Water quality
Total suspended solids
Turbidity
Colour and odour as pertaining to water quality.
. Describe the dangers of the presence of nitrogen and its constituents in water.
. Describe the effects of the presence of metals in water.
. Describe the effects of the presence of organic materials in water.
. Describe the different types of micro organisms that can be found in water, as
well as the effects of unacceptable quantities of these.
. Discuss biodegradable organics and BOD.
. Discuss non-biodegradable organics.
. Explain the principle and purpose of the following unit operations used in water
treatment processes, and describe and sketch the equipment involved:
Screening
Aeration
Coagulation
Flocculation
Sedimentation
Filtration
Flotation
Chemical treatments.
. Choose an appropriate process flow sheet for treatment of a waste water type.
. Calculate dosing parameters for lime-soda water softening.
. Calculate cycle times for ion exchange processes.
. Explain general and special effluent standards set by the government.

INTRODUCTION
The remaining chapters cover aspects of environmental engineering. The environment
can be defined as our physical surroundings, and engineers and engineering
technologists are constantly in interaction with this environment. Civil engineers build
roads and dams. Mechanical engineers build heavy machinery, means of transportation,
factories and piping systems. Chemical engineers design, build and run plants that
manufacture various chemical substances. All of these processes have an effect on the
water, air and soil and are thus the concern of environmentalists. Chemical engineers
 78

have the tools to build ``clean'' processes, and to reduce pollution levels from existing
plants. This chapter describes the treatments used for water both when it is a process
input and when it is a process effluent.

3.1 WATER QUALITY

Water quality can be described by physical, chemical and biological parameters. Water is
considered below standard when certain impurities exceed predetermined concentra-
tions. Impurities enter water through the decomposition of domestic, commercial and
industrial waste, the natural decay of organic materials, the dissolution of minerals by
rain water, etc. Unacceptable physical properties in water are odours, colour, suspended
solids and high temperatures. Chemical constituents in water are classified as organic,
inorganic and gases. Table 3.1 shows some common compounds. The last category of
impurities is biological constituents. These include animals, plants, bacteria and
viruses.

3.1.1 Total Suspended Solids

Solids can appear in water in suspended and dissolved forms. This section deals with the
suspended solids and the dissolved solids are treated under the chemical constituents.
The amount of total solids in any sample of water is determined by evaporating the
water at 1048C and weighing the residue. Substances that are volatile enough to
evaporate at this temperature are not considered to be solids. The amount is expressed as
mg/litre based on the dry mass of the solids.

TABLE 3.1

Chemical constituents
Organic carbohydrates, fats, oils, grease, pestici-
des, phenols, proteins, surfactants, volatile
organic compounds
Inorganic chlorides, heavy metals, nitrogen, high or
low pH, phosphorous, sulphur
Gases hydrogen sulphide, methane, oxygen

The settleable solids content is determined by placing the liquid in a cone shaped
container (called an Imhoff cone) and allowing it to settle. The amount of solids that
settle to the bottom of the cone in one hour is known as the settleable solids. These are
expressed as ml/l and it gives an indication of the amount of sludge that can be removed
from a liquid by means of primary sedimentation.
The amount of suspended solids in water is determined by filtering the water (in glass
fibre or polycarbonate membrane filters) drying the filter cake and weighing it. The mass
(in milligrams per litre) gives the suspended solids.

The organic content of both the filterable and the non filterable solids can be determined
by firing the dried solids at 6008C for one hour. The organic fraction of the solids will be
converted to water vapour, carbon dioxide and other gases and will be driven off, and
the ash will remain behind. The ash represents the inorganic or fixed residue.
 79 CHP311-A/1

3.1.2 Turbidity
For natural water supplies and drinking water the turbidity is often reported instead of
the total solids. The turbidity of water is defined as the way in which light is scattered or
absorbed by the suspended material in water. It does not measure the suspended solids
directly. It is easy to imagine that fine solids will scatter light much more than a few
coarse particles, so it is quite possible for the turbidity of a sample to be high while the
suspended solids contend is quite low.

Turbidity causes natural water to assume a brown colour. This can affect the amount of
light that is absorbed by the water and it can affect the photosynthetic processes in water
plants. If the turbidity is too high deposits can settle out of the water. This can have an
effect on, e.g., farmland.

Turbidity is measured by a turbidity meter. This meter consists of a sample vial that is
filled with water. A light shines through this vial and the light intensity of the light
leaving the water is measured. Turbidity is measured in formazin turbidity units (FTUs)
or nephelometry turbidity units (NTUs).

3.1.3 Colour
As you all know, water is colourless but colour can be imparted to water by means of
suspended matter or dissolved solids. The colour imparted to water because of
suspended matter is called apparent colour and the colour imposed due to dissolved
solids is called true colour.

Water colour is unacceptable, not only because it gives an indication of impurities in

water but also because it looks bad. People will prefer to drink water with a slightly
lower quality and no colour than a better quality water that has a colour. Coloured water
can also have an effect on various processes such as laundry washing, dying of
materials, food production, paper making and plastic production.

Colour is measured by filtering the water and comparing the filtered samples with a set
standard that was made up to be a certain colour. The colour of water is expressed in true
colour units and one colour unit is said to be the colour of water when 1 mg/l of
chloroplatinate ions are dissolved in water. This colour test is only used for cases of
colours in natural waters. In cases of industrial waters that have other colours than
yellowish brown, different spectrophotometric tests are developed according to the
specific situation.

3.1.4 Odours
The term odour needs no explanation. Odours in waste water are often present together
with taste. There are various inorganic and organic materials that can impart odours and
tastes to water. Mineral salts, soil, decomposing organic matter and industrial wastes can
all cause tastes and odours in water. The most objectionable odour is that of hydrogen
sulphide. Table 3.2 contains some of the most common odorous compounds and their
chemical formulae.

In some cases, if it is known what produces the odour, a direct analysis can be done for
that particular substance. If odours are just measured without considering the source, the
following guidelines are used:
 80

TABLE 3.2

Odorous Compounds Chemical Formulae Odour

Amines CH3NH2, (CH3)3N Fishy
Ammonia NH3 Ammoniacal
Diamines NH2(CH2)4NH2 Decayed Flesh
NH2(CH2)5NH2

Hydrogen Sulfide H2S Decayed Cabbage

Mercaptans CH3SH, CH3(CH2)3SH Skunk
Organic Sulphides (CH3)2S, (C6H5)2S Rotten cabbage
Skatoles C9H9N Faeces

Adapted from: Wastewater Engineering ± TREATMENT,DISPOSAL REUSE, 3rd Edition, Metcalf &
Eddy, McGraw-Hill 1991

. Character: the character of an odour is quite a subjective measurement and it deals

with the connotations a person would make when smelling it.
. Detectability: this property is reported as the number of dilutions necessary to reduce
the odour so that it is just detectable.
. Hedonics: the hedonics of an odour are related to the relative pleasantness or
unpleasantness of the odour (for example, a very strong odour can smell bad or
pleasant).
. Intensity: this is fairly self explanatory and it relates to the strength of the odour.

Odours are often measured by sensory methods. A panel of subjects is presented with a
sample and then evaluates it according to set criteria. An instrument was also developed
that produces a direct reading of the H2S content of a gas to as low as 1 ppb (part per
billion).

For wastewater a threshold odour number is often detected. This is determined by

stipulating the number of times a sample must be diluted with odour free water before
the odour is only barely detectable. This threshold odour number (TON) can be
calculated as follows:
A‡B
TON =
A

where

A = ml of sample
B = ml of odour free water.

3.1.5 Temperature
The temperature of wastewater is not normally a measure of the water quality, but the
temperature plays a quite significant part in natural waters to influence the ultimate
measurable water quality. The biological species that are present in the water, as well as
the rates of the biological reactions, are influenced by the water temperature. In general
the rates of biochemical reactions double with every 10 degrees C increase in the
temperature. Cooler water tends to have more biological species present than warm
 81 CHP311-A/1

water. The amount of dissolved oxygen is less in warmer water than in cooler water. The
optimum temperature for biological activity in water is between 258C and 358C.
Common processes like aerobic digestion and nitrification stop when the water
temperature reaches 508C.

Temperature changes in water can have natural as well as industrial sources. The depth
of the water determines how much it will be affected by changes in the ambient
temperature. Shallow water will undergo a temperature change much faster than deeper
water. Often natural waters are used as heat transfer media and are pumped through a
system in order to remove process heat. This water is then released to the natural
environment (river, dam, sea) at a much higher temperature. This disturbs the ecosystem
in those areas, bacterial activity is elevated or the bacteria are killed, depending on the
exact temperature of the effluent water. The higher temperature affects the oxygen
content of the water and this has a dramatic effect on the fish, etc. The solubility of
substances in water is also affected by an increase in temperature. There is also a slight
decrease in viscosity and density of water at elevated temperatures and both these
phenomena have an influence in the micro-organisms in natural water systems.

3.1.6 Alkalinity
Alkalinity in water is due to the presence of ions that will react with H+ ions. Some of
the ions that can cause alkalinity are CO32-, HCO3-, OH-, HSiO3-, H2BO32-, H2PO4-,
HS- and NH3. Alkalinity can have numerous sources ranging from the dissolution of
organic matter to pesticides and fertilisers. Alkalinity can be increased by the presence
of algae. The formation of bicarbonate from carbonate is as follows:

CO32- + H20 . HCO3- + OH-

If algae are present in water they use the bicarbonate ion as a source of carbon and thus
shift this reaction equilibrium to the right so that the OH- ion concentration increases
dramatically. It is not uncommon for water with a high percentage of algae to have pH
values as high as 10.

Alkalinity can give water a bitter taste and the ions present can react with the water to
form salts that precipitate and foul pipes.

The alkalinity of water is determined by titrating the water with a weak acid and
determining the equivalent amount of H+ needed to neutralise the alkalinity.

3.1.7 Hardness
The hardness of water is defined as the concentration of specified multivalent cations in
water (such as Ca++ and Mg++). When the concentration of these ions in water becomes
too high they react with anions to form insoluble salts. These salts precipitate and can be
seen as scale on heat exchanger tubes and domestic and industrial kettles.

The divalent ions most commonly present in water are those of calcium and magnesium.
The amounts of these ions can be determined by titration. The most common substance
used for this purpose is called EDTA (ethylenediamine tetraacetic acid). Eriochrome
black T (EBT) is used as an indicator. When such a titration is started the solution is red,
because the EBT forms a red complex with the divalent metallic ions. The EDTA
replaces the EBT in the complex and once all the EBT ions have been replaced the
 82

solution becomes blue. Hardness is reported in mg/l as CaCO3. Concentrations above

150 mg/l as CaCO3 are considered to be hard. Softening processes are explained in
section 3.2.8.5.

3.1.8 Nitrogen
Nitrogen, together with carbon and phosphorus, are some of the main nutrients for
aquatic life forms. Nitrogen is a building block in the synthesis of protein. Therefore
nitrogen is often used to determine the treatability of wastewater by biological processes.
In some cases, if there is not sufficient nitrogen present in waste water, additional
nitrogen can be added to the waste water.

Nitrogen can be present in the form of organic nitrogen (N2), ammonia (NH3), nitrite
(NO2-), and nitrate (NO3-). Ammonia can also be present in the form of the ammonium
ion, depending on the pH of the solution.

Nitrogen is present in organic life forms in complex molecules. These molecules are
broken down to simpler forms by means of bacterial decomposition. They are broken
down to amino acids and ammonia. The ammonia is then oxidised to form nitrite and
nitrate. Animal wastes, chemical fertilisers and wastewater discharges are the main
sources of nitrogen. Tests are conducted to determine the amount of organic nitrogen,
ammonia and ammonium, nitrites and nitrides in water. The nitrite concentration in
water is usually very low, but it is a dangerous ion that is poisonous to aquatic species
and small children, and should thus be carefully controlled. Nitrites are also oxidised by
chlorine and this affects the amount of chlorine that needs to be added to the water
during dosing.

3.1.9 Metals
The presence of metal ions in water is categorised into toxic and non-toxic metals. Toxic
metals means toxic in low concentrations. Metals in wastewater originate in natural
deposits or in domestic and industrial wastes.

The most common non-toxic metal present in water is sodium. High sodium
concentrations impart a bitter taste to water and can be a health hazard. It can also be
toxic to plants. Iron and manganese are also fairly common in waste water but they do
not pose serious health problems. Both iron and manganese impart colour to water.
Some bacteria use iron and manganese as a source of food and the increased number of
bacteria in the water can cause slime, taste and odour problems.

Toxic metals that can be dissolved in water include barium, cadmium, arsenic,
chromium, lead, mercury and silver. These get concentrated in the water and are passed
on along the food chain. Areas of industrial development are at a high risk for the
concentration of toxic metals.

3.1.10 Organic Materials

It is important that people in contact with wastewater and the treatment thereof be aware
of all the biological organisms that are present in waste water. We will only take an
introductory look at some of these.
 83 CHP311-A/1

3.1.10.1 Micro-organisms
Micro organisms present in water can be categorised as:

. Bacteria
. Fungi
. Algae
. Protozoa
. Plants
. Animals
. Viruses.

. Bacteria play a significant role in the decomposition process of organic material.

This process happens in nature as well as in some biological treatment plants.
Bacteria are single celled creatures that have spheroid, rod, curved or spiral forms.
The most common one of these is Escherichia Coli or E Coli, which is found in
human faeces. Bacteria are also usually colourless. Bacteria are responsible for the
transmission of diseases such as cholera, a disease that causes severe vomiting and
diarrhoea and results in dehydration and death. Salmonella bacteria in reheated
chicken cause fever, gastrointestinal disorders and possible nerve damage. There are
various other bacteria that live in water and a decrease in the water quality can lead to
an outbreak of diarrhoea in the surrounding community.
. Fungi are multicellular organisms that obtain most of their food from organic matter.
They play an important role in the decomposition of carbon in the biosphere. Fungi
can operate under conditions of very low moisture and pH, unlike bacteria. Fungi are
aerobic and thus need oxygen to live.
. Water that is high in biological nutrients is often riddled with algae. These algae
spread through natural waters at an alarming rate, often covering the surface of the
water completely. The quality of the water is often affected, the aquatic life forms
suffer and the water can have a taste or an odour.
. Protozoa are single celled creatures without cell walls. They feed on bacteria and
other micro-organisms and they are important in biological treatment facilities and in
natural waters because they maintain a balance between the other biological species.
Protozoa also cause infections that are associated with gastrointestinal disorders.
These infections are not as violent as those caused by bacteria, but they can also reach
epidemic proportions.
. Viruses are parasites that are composed of a strand of deoxyribonucleic acid (DNA)
or ribonucleic acid (RNA) that is coated by proteins. Viruses invade other organisms
and redirect the activities of healthy cells to produce new virus cells. Eventually the
cell dies, releasing new viral particles into its surroundings. Viruses in water can
spread to epidemic proportions. Diseases such as hepatitis have been known to spread
through the water supplies. Viruses can be eliminated from water with ordinary
disinfection techniques, but in cases where treated waste water is used for drinking
water or as irrigation water, insufficient disinfecting increases the risk of viral
infections.

3.1.10.2 Biodegradable Organics

Biodegradable organics are materials such as acids, fats, proteins, alcohols, aldehydes
etc. that can be broken down to simpler materials by the natural organisms that occur in
water. These materials can cause colour, taste and odour problems, but their main effects
are the waste products that are generated by their further decomposition. These dissolved
organics can be broken down by means of oxidation (adding oxygen) or reduction
(adding hydrogen) to the waste water. Aerobic decomposition (in environments that
contain oxygen) results in acceptable, stable end products. In anaerobic decomposition
 84

the end products are unstable, but they can be oxidised to acceptable products with the
addition of oxygen. It is for this reason that the oxygen content of wastewater needs to
be sufficient to facilitate aerobic decomposition.

The amount of oxygen needed by waste water in order to decompose aerobically is

called the biochemical oxygen demand (BOD). The BOD is determined by placing a
sample (typically 300 ml) of water in a BOD sample bottle and incubating it for a set
period of time at a prescribed temperature. The bottle must be protected from sunlight
because if algae are present this might lead to the production of additional oxygen.
Typical incubation conditions are 5 days at 208C. The dissolved oxygen in the water is
measured before the incubation period. After the incubation period it is measured again
and if the oxygen content is higher than the equilibrium concentration for dissolved
oxygen (20 mg/l at 208C) then the water is diluted to determine the dissolved oxygen.
The BOD is calculated as follows:

Grams of oxygen used

BOD = ÐÐÐÐÐÐÐÐÐÐÐ
Grams of carbon oxidised

The BOD is therefore an indirect measure of the amount of the amount of organic
matter.

3.1.10.3 Non-biodegradable Organics

Non-biodegradable materials resist break down by biological organisms. These can be
woody plants that biodegrade so slowly that they can be considered non-biodegradable,
and organic material that contains unreactive ringed bonds such as benzene.

Some organisms are considered to be non-biodegradable because they are toxic to

biological organisms. Pesticides fall in this category.

Non-biodegradable organics are measured by the chemical oxygen demand (COD) test.
A strong oxidising agent is added to water in an acidic medium. Potassium dichromate is
one of the substances used for this purpose. A catalyst is added at an elevated
temperature. The organic compounds then oxidise chemically. The COD test results can
be obtained in 3 hours, which is much faster than the BOD test results.

The theoretical oxygen demand (TOD) can be calculated if the exact chemical
composition of a sample is known. This is the stoichiometric amount of oxygen needed
to decompose the organic matter in the water completely to water, carbon dioxide,
ammonia etc.

3.2 WATER TREATMENT PROCESSES

We have now discussed all the basic chemical and biological organisms that are found in
waste water and how their presence and concentrations are tested for. This section is
going to deal with some examples of different wastewater treatment processes. The
process used will depend on whether it is municipal waste or industrial waste and also
on the different contaminants that are present in the water. The required quality of the
water after purification is also important. Not all water is treated to the purity of drinking
water. In some cases water that is used for cooling water in a plant is treated to a level
acceptable for re-use as cooling water. Water might also be treated to a level acceptable
for dumping in the municipal waste water system. Section 3.3 will show the sequence of
processes used in different water treatment plants.
 85 CHP311-A/1

3.2.1 Screening
Screening is used to remove solid waste from waste water. This is done as a first step to
rid the water from unwanted substances and also as protection for the pumps, valves and
other equipment in the water purification plant. Because of this the logical place to
install these screens would be at the entry to the water treatment plant. There are
normally two types of screens that are installed. The first step is coarse screens. These
screens are made up of steel bars of around 25 mm in diameter. They are placed 100 mm
apart at an angle away from the flow of the incoming water. There can be one of these
screens alone or several in series. Typical water velocities through these screens are of
the order of 1±5 m/s. The solids collected from these screens can be removed by raking
them off the screens. The raking can be done manually or, in the cases of larger plants,
mechanically. The screens should be mounted in a straight channel with proper
ventilation. The water flow in the section just before the screen should be straight in
order to ensure proper distribution of the solids and to facilitate removal.

The fine screens are fitted directly behind the coarse screens. These screens can consist
of a woven wire cloth or a plate with holes in it. The diameter of the openings in a fine
screen is of the order of 6 mm. These screens clog very easily because they are so fine.
This means that they have to be cleaned regularly. If this cleaning is done on a batch
scale it implies that the screens needs to be removed from the water stream often and this
can increase the risk of spillage of solid wastes past the screens. For this reason these
fine screens are often continuous. They can be of a drum or disk type, or in the form of a
rotating belt. This allows the screens to operate continuously and be cleaned at the same
time. The section of the screen that is not in the water can be cleaned. Drum screens are
also sometimes called rotary screens.

Screened solids are often covered with organic matter of a very objectionable nature.
These solids have to be disposed of fast and efficiently in order to avoid the spreading of
disease and the contamination of the environment. These solids can be disposed of by
dumping them in a landfill. They can also be ground and returned to the water stream, or
they can be incinerated.

There are pictures and more information on screens in the following books:

Perry: Section 19, page 19±18 to 19-23

Coulson & Richardson - Chemical Engineering Volume 6: pages 358 to 361 or section
10.3 Coulson & Richardson - Chemical Engineering Volume 2: pages 42 to 45 or
section 1.5.4.

3.2.2 Aeration
Aeration is a process by which oxygen in the atmosphere is added to the water. There are
two main reasons for aeration. The first is the removal of unwanted gases in water
(degasijication), and the second is the addition of oxygen to the water (oxidation). The
following gases in water normally necessitate aeration:

. Hydrogen sulphide gas, which imparts taste and odour to water.

. Carbon dioxide has the effect of increasing the corrosion rate.
. Algae release volatile oils in their growth and these oils impart tastes and odour to
water.

Iron and manganese can be removed by aeration. Both these metals are soluble in
water in the +2 oxidation state. In the presence of oxidising agents or oxygen, these ions
 86

are oxidised to higher oxidation states. In the higher oxidation state (+3 or +4) they form
insoluble ionic complexes and can thus be removed form the water by physical means.
The chemical reactions of these processes are as follows:

4Fe2+ + 02 + 10H2O ? 4Fe(OH)3 + 8H+

2Mn2+ + 02 + 2H2O ? 2MnO2 + 4H+

Aeration is the establishment of equilibrium between water and a gas, namely air. This is
done by maximising the contact area between the water and the gas, because the
absorption or desorption of a gas in water is a very slow process. The water and the gas
can be contacted in two different ways. The water can be dispersed into fine droplets to
maximise the contact area with the gas, or the gas can be forced through the water (for
instance, by bubbling it through the water).

There are various types of aerators used. Fountains are piping grids set up over catch
basins. These grids have nozzles at the intersections and these nozzles spray the water
upwards. The water is then dispersed in fine droplets. As these droplets lose their kinetic
energy and start falling they are smashed against the grids and this breaks them up even
further. All this is done to increase the contact area between the droplets and air. The
contact time between the water and the air is mainly determined by the height of the
fountain, which is in turn determined by the pressure in the pipes. The size and
dispersion of the drops are determined by the nozzle design. Because there are solids in
the drops, the nozzle outlets should not be too fine, as this will result in blocking of the
nozzles.

Cascade towers are like waterfalls that drop into small catch pools. These waterfalls are
normally 0.3 to 0.5 m high and there can be as many as ten of these stacked, one above
the other. In the case of cascade towers the water falls from the one stage to the next in
thin sheets and not in droplets, as in the case of fountains.

In the case of tray towers the water is lifted and falls over a series of restrictions that
distribute the water stream. These restrictions are often trays with porous bases. These
trays can be packed with stones, ceramic balls or other kinds of porous packing. These
packed trays have large surface areas over which the water is spread in thin films. This
provides the large area needed for air-water contact. Tray towers are well suited for the
removal of iron and manganese. In these cases the towers are packed with trays filled
with coke that has been coated with a strong oxidant. This oxidant assists the
precipitation. Once the reaction has started films of the iron and manganese solids
deposit on the packing and this further encourages the reaction. All the methods
discussed above disperse the water into the air. It is also possible to disperse the air in the
water. This is often done in the case of wastewater treatment.

The water is brought into contact with air bubbles and the contact area is maximised.
The water flows through tanks (2.5±5 m in depth). Air is then blown through the tank
and contacted with the water. The air is blown through the water by means of various
mechanisms. In some cases the air is bubbled upwards from pipes or a grid situated at
the base of the tank. In other cases air diffusers are installed in the side of the tank, as
this creates currents in the tanks that enhance the contact. And in other cases the air is
forced through the water mechanically by means of fast turning impellers. The typical
bubble size for aeration is between 2 mm and 25 mm in diameter. Figure 3.1 shows a
few typical aeration system configurations.
 87 CHP311-A/1

FIGURE 3.1: Aeration configurations, for air-to-water dispersion

3.2.3 Coagulation

3.2.3.1 Theory
Most wastewater contains solids in suspension. If these solids are large enough they will
settle out under the effect of gravity. If the solids are smaller than 5Opm in diameter they
will not settle out readily. Such a suspension is called stable because the particles have
such a large surface area in relation to their weight that they will not settle out.
Substances are added to the water that destabilise these particles. They will then form
groups (flocs) that are large and heavy enough to settle out. Such a substance is called a
coagulant and the process is called coagulation.

These coagulants are mostly iron and aluminium salts and the chemistry will be
discussed in the next section. In some cases where the floc formation takes a long time
even with the addition of a coagulant, a coagulation aid is added. These coagulation aids
speed up the floc formation process by enhancing the formation of heavier flocs, and
because of this the size of the settling basin can be reduced. When the coagulant is added
to the water it has to be stirred very fast to facilitate proper mixing. Just after this step the
water has to be stirred very slowly because the floc needs time to grow and there has to
be sufficient movement in the water so that they do not settle out while still growing.
The process where the flocs are slowly stirred to allow the flocs to grow is called
flocculation.

The size of the flocs in the water depends heavily on the pH of the water. Each specific
floc has an optimum pH where its size is maximised. Most coagulants cause the pH of
water to fall. If the pH of water is not in the correct range the flocculation process does
 88

not take place efficiently. In some cases alkali is added to the water in order to maintain
the proper pH needed for coagulation. The optimum pH values for floc formation seem
to be below 6.8 and above 7.9. Between these two values the flocs are often small and
they do not settle.

3.2.3.2 Mechanism of coagulation

Colloidal (i.e. very small) particles can be classified into hydrophobic and hydrophilic
particles. Hydrophilic colloids are stable in water because they possess an attraction for
water molecules. Such particles are soap, soluble starch, detergents and blood serum.
Because these particles are attracted to water molecules these colloidal solutions are very
stable and these particles are very hard to remove from the water. The removal of these
particles requires much higher doses of coagulant than other particles. Luckily most
particles that are found in water are hydrophobic.

Hydrophobic particles are only stable in water because of their electrical charges.
Particles acquire an electrical charge through various mechanisms. In some cases there
are defects in the crystal structure that result in a slight charge, or particles can lose ions
due to abrasion. Most colloidal particles are negatively charged. These negatively
charged colloidal particles will attract positively charged ions from the surroundings.
The first layer of these positively charged particles will attach themselves to the negative
colloidal particle. They are bound there by van der Waals (interatomic) forces and they
will travel as a unit through the solution.

The next layer surrounding the particle will again be negative, but weaker than the first
layer. This layer will be dispersed if the particle moves relative to the solution. The
arrangement of layers becomes less ordered with increasing distance from the particle.

There are two forces that act between any two colloidal particles:

The first is an electrostatic force, which will be repulsive in the case of like charges.
The second is the van der Waals force which is an attractive force. If the particles are
somehow forced closer together there is a point at which the van der Waals force will
take over and they will be attracted to each other. When a coagulant is added to the water
it produces hydrolysed metal ions with a high positive charge. These serve to compress
the positive ionic layer around the colloidal particle and reduce the repulsive forces
between these particles. It is then easier for the van der Waals forces to attract the
particles to each other. If the solution is mixed very slowly the particles are brought
close together and they will thus agglomerate. As said before, the process of forming
larger flocs while under slow mixing is called flocculation. In some cases the
flocculation process is aided by the addition of coagulation aids. These aids are normally
polymeric molecules. They have a long, chain like structure and they attach themselves
to the colloids. They help in the formation of large, massive particles that will easily
settle out. Figure 3.2 show a schematic representation of the flocculation process.

3.2.3.3 Chemical action of coagulants

We will discuss the most common coagulants, as well as the reactions and specific
applications of each.

The most common of the coagulants is aluminium sulphate. It is also known as alum,
and has the chemical formula Al2(SO4)3.18H20. It can be bought in lumps, in granules,
in blocks or in liquid form. Alkalinity in water is expressed as lime (CaO), hydrated lime
Ca(OH)2 or soda ash Na2CO3. When aluminium sulphate reacts with the water it reacts
 89 CHP311-A/1

FIGURE 3.2: Attractive and repulsive forces acting on colloid in stable suspension

with this alkalinity. The substances that impart this alkalinity are present in the water
naturally, or they can be added to the water if needed. Aluminium sulphate solutions are
corrosive and must be stored in lined tanks. All these forms of alkalinity have the effect
of producing aluminium hydroxide flocs.
These flocs aid the formation of larger flocs that will settle out. The reactions by which
aluminium hydroxide is formed are as follows:
Natural Water

Al2(SO4)3 + 3Ca(HCO3)2 . 2A1(OH)3 + 3CaSO4 + 6CO2

With lime added to water
Al2(SO4)3 + 3Ca(OH)2 . 2A1(OH)3 + 3CaSO4

With soda ash added

Al2(SO4)3 + 3Na2CO3 + 3H22 . 2A1(OH)3 + 3Na2SO4 + 3CO2
 90

Iron salts are also used as coagulants. They are in general cheaper than aluminium salts
and they produce heavier flocs. They operate over a wider range of pH than aluminium
salts. The use of iron salts, however, requires the addition of lime, and the flocculation
process is difficult to control. The storage containers also need to be lined to prevent
corrosion. These salts are unpleasant to work with. They stain and are dirty. The sludge
produced by these salts is harder to dispose of effectively than that produced by
aluminium salts.

Ferrous sulphate is also known as copperas (FeSO4.7H20).The copperas contains up to

30% Fe203. Ferrous sulphate is well suited for use as a coagulant in waters that are
alkaline and contain bicarbonates. Lime or caustic soda needs to be added together with
the ferrous chloride in order to raise the pH to between 8.5 and 10. The following
reactions occur:

Ca(HCO3)2 + FeSO4 ? Fe(OH)2 + CaSO4 + 2CO2

2Fe(OH)2 + 1/202 + H2O ? 2Fe(OH)3

Ferrous sulphate cannot be used on soft domestic water because the floc formation in
this water occurs around the pH of 6, and at such a low pH the second reaction, i.e. the
formation of ferric hydroxide Fe(OH)3 does not happen. Ferrous sulphate has a tendency
to clog and can therefore not be fed as a solid because the feeding equipment will be
blocked. It is therefore added to the water as a solution.

Chlorinated copperas is formed when 8 parts of FeSO4 react with one part of chlorine.
The result is a mixture of ferric chloride and ferric sulphate. This coagulant is very
effective in cold water and in water containing manganese. The coagulation stage can
then also act as a pre-chlorination stage. The ferric hydroxide that is formed in this
reaction has a large positive charge (Fe+++ ions) and will act as a coagulating aid. The
reactions are as follows:

6FeSO4 + 3C12 ? 2Fe2(SO4)3 + 2FeC13

2FeSO4 + 3Ca(HCO3)2 + Cl2 ? 2Fe(OH)3 + 2CaSO4 + CaCl2 + 6CO2

Ferric Chloride on its own is sometimes used in cases of very high alkalinity. It is not a
pleasant salt to work with. The reactions between ferric chloride and the alkalinity in
water (in carbonate form) are as follows:

2FeC13 + 3Ca(HCO3)2 ? Fe(OH)3 + 3CaC12 + 6CO2

or
2FeC13 + 3Ca(OH)2 ? 2Fe(OH)3 + 3CaC12

Ferric sulphate is used to decolourise water at low pH, for the removal of manganese at
high pH and clarification of certain water types. It is expensive and is not very soluble in
water, and is therefore not used often. The ferric sulphate reactions are:

Fe2(SO4)3 + 3Ca(HCO3)2 ? 2Fe(OH)3 + 3CaSO4 + 6CO2

or
Fe2(SO4)3 + 3Ca(OH)2 ? 2Fe(OH)3 + 3CaSO4

3.2.3.4 Coagulant aids

As said before, certain materials are sometimes added to the water in order to facilitate
easier coagulation and settling. These substances are called coagulation aids. They have
 91 CHP311-A/1

various mechanisms of increasing the coagulation in water. Some add additional solids
to the material, some will increase the alkalinity and some are high molecular mass
branched polymers that help to form large flocs. The most commonly used coagulation
aids are:

. Weighters (such as clay or Fuller's Earth)

. Lime (increases the alkalinity)
. Sodium carbonate (increases alkalinity)
. Activated silica (reduces the amount of coagulant needed and increases the density of
the floc)
. Poly-electrolytes (synthetic, high molecular weight organic polymers)

3.2.3.5 Coagulation equipment

Coagulation is often carried out as part of the next steps in water treatment, i.e.
flocculation and settling, but in some cases the coagulation step is separate from these
processes and done in rapid mixing tanks. Square tanks are most popular for this
application and either back-mix impellers or baffles and flat blade impellers. Figure 3.3
show a schematic representation of such a tank.

The water moves under the baffle where the velocity is increased. At this point the
coagulation aid is added and the process of agglomeration happens almost instantly. The
water is then further agitated by means of the impeller and leaves the tank at the
overflow to enter the next step of the process.

FIGURE 3.3: Rapid mixing tank

3.2.4 Flocculation
We have already mentioned that, as soon as the floc has formed as a result of the
addition of the coagulation aid, these flocs must be encouraged to grow larger in order
for them to settle out effectively. This is done by stirring the water gently. The
turbulence in the water brings the flocs into contact with each other and as they collide
they agglomerate to form larger flocs. This process is called flocculation. Often it is not
necessary to have separate flocculation processes because after the addition of the
coagulation aid in a high turbulence section the water moves through a tank at a low
velocity and this is sufficient for the necessary flocculation to take place. The type of
suspended solids dictates the equipment to a large extent. In some cases, however,
specially designed flocculation chambers are designed. These usually precede relatively
 92

shallow settling basins. Figure 3.4 show such a flocculation channel. These channels
usually have velocities around 0.3 m/s and they have 12±20 changes in direction through
1808. These direction changes provide the slight turbulence needed for the flocs to come
into contact with each other. The corners of these channels are also rounded to promote
flow and prevent floc deterioration. In some cases the channel diameter increases
towards the end of the passes. This reduces the water velocity and prevents flock
breakage.

FIGURE 3.4: Flocculation channel

In some cases flocculation is also carried out in basins. These basins are equipped with
baffles extending from the floor and the roof alternatively. As the water moves between
the baffles in an upward and downward motion, it is agitated slowly and thus enhances
floc formation. Mechanical flocculators can also be used. These are equipped with low
speed paddles. The rotation speed of the paddles is of the order of 0.15±0.6 m/s. In all
these units rapid stirring is done as the water enters the flocculators and the coagulation
aid can be added at this point. This eliminates the need for a separate coagulation
section.

3.2.5 Sedimentation
In our discussion of flocculation we have said that the purpose of the flocculation pond
is to keep the flocs in suspension so that they can grow to a sufficient size before settling
out. In sedimentation or settling the purpose is now to reduce the velocity of the water
sufficiently so that the flocs can settle out and thus be separated from the water. When
the water loses its velocity it also loses its capacity to keep the flocs suspended and
settling is inevitable.

3.2.5.1 Choosing a settling basin

There are two considerations to take into account when choosing a settling basin,
namely the efficiency and the ease of sludge removal. A settling basin with a high
efficiency is of little use if a lot of time has to be invested in cleaning it properly. In some
cases it is not possible to scale these basins up, so a basin that might be ideal in a small
plant might be totally unsuitable in a larger plant. The ease of construction of these
basins also plays a part, as well as the space requirements. Shallow basins take up a large
space and if the space is not available another alternative must be considered, even
though it will be less efficient. In some cases the nature of the sludge and the
environment can also play roles. If the sludge contains lots of odorous materials or
heavy metals that can be poisonous to, for example, bird life, the basins have to be
covered in order to protect the environment. In such cases smaller basins are preferred.
 93 CHP311-A/1

3.2.5.2 Types of settling basins

Horizontal flow settling basin

The most common type of settling basin used is the horizontal flow settling basin. In
these basins the water has a very low horizontal velocity. It enters the basin at one end
and leaves at the other. Figure 3.5 shows a typical horizontal settling basin.

FIGURE 3.5: Horizontal flow sedimentation basin

These settling basins can, in some cases, be combined with flocculators in one unit. In
such cases the flocculation will take place in a sector before the main settling basin.
Screens can also be installed at the inlet of the settling basin. The purpose of these
screens is to distribute the water evenly so that the settling is more efficient. Sometimes
a smaller screen is also fitted just before the outlet. These settlers are normally in the
shape of a large open square box that is filled with water to the top. It is 3±4 meters deep
and there may be baffles fitted to the settler to prevent short circuiting and bypassing of
the sludge. These settlers are easy to design, build and operate and the fact that they are
so big has a very stabilising effect on the operation, because any fluctuations in the water
quality is buffered out in these large settling basins.

The basins are very economical and are often used in very large water treatment works.
They can handle large capacities, and water with a very high percentage of deposits.
There is enough room for the deposits to settle at the base of the column and it is
relatively easy to clean. Horizontal settlers are cheap to build and operate and, as said
before, relatively easy to clean. In some cases it is advisable to install scrapers at the
base of the settlers. In some cases the settlers can also be drained and cleaned manually,
usually with high pressure water jets.

The main disadvantage of these settlers is the fact that they are sometimes prone to
streaming. This happens when there are certain areas in the settler that have a higher
velocity than other areas. The effect of streaming is a loss in efficiency and floc in the
overflow. A loss in efficiency has also been detected in cases where flocculation has not
been done in separate units before settling. Another factor that can sometimes be a
disadvantage is the size of these basins. If they are very large they take up a lot of
ground space. These settling basins are usually quite reliable and have a high efficiency
compared to similar equipment.

In general long, narrow basins perform better than square basins. Typical velocities in
the basin are less than 0.2 m/s. Care must also be taken that the velocity is kept low in
 94

the inlet pipes. If the velocity in the inlet pipes is more than 0.6 m/s the floc runs the risk
of being broken, thus destroying all the work done in the flocculation units. It is also
advisable that the inlet of the basin should be at least as wide as the basin itself in order
to facilitate proper distribution of the sludge.

If the floc is well developed the vertical settling velocity of the floc is about 3 m.h-l. In
moderately dirty water a typical retention time in these basins will be of the order of 3
hours, but it can be as high as 6±9 hours if the water is particularly dirty. In some cases
pre-settling basins are also required.

Radial settling ±
overflow at perimeter of
tank

!
!
!

FIGURE 3.6: Radial flow settling tank

There are various deviations from this simplest square horizontal flow settling basin.
Multi-storey basins have more than one basin stacked on top of each other. These basins
operate in parallel. Radial flow basins are also used. These basins are round and the
waste water enters them in the centre and then flows outwards. The velocity in such a
system is not uniform because the cross section of flow is not uniform. The slowest
velocity occurs near the edge of the basin and this allows for the last floc to settle out
(see fig. 3.6). Plate and tube settlers have also been designed. These settlers are equipped
with plates or tubes against which the sludge settles.

Upward flow settling basin

There are various types of upward flow settling basins, but the basic principle of
operation in all of them is the same. The water enters these basins at the bottom, or close
to the bottom of the basin. It then flows upward towards the top of the vessel. In doing
this the water flows through a layer of previously deposited sludge. This sludge then has
the effect of assisting in the settling of the flock, because it traps the solid particles. The
water rising above this sludge blanket is therefore clear. The clear water overflows at the
top of the basin. Upward flow settling basins are also often equipped with flocculators so
that the flocculation and the settling takes place in the same apparatus.

One of the simplest types of upward flow settling basins is the circular upward flow
basin. This apparatus consists of a circular tank that can have a diameter from 9m to
30m. These tanks can handle capacities up to 45 000 m3.day-1. The typical rate of
upward flow of the water is 2m.hour-1. The basin is a combination of two tanks. A
smaller, inner tank in the centre of the tank is where flocculation takes place. From the
base of this tank the water escapes into the larger tank where the settling will take place.
The water will move upwards radially to the collection troughs at the periphery of the
tank. The water flows along these collection troughs to the clear water outlet. The sludge
 95 CHP311-A/1

sinks to the bottom of the tank. The bottom of the tank is equipped with a scraper. The
scraper scrapes the sludge towards a drain in the middle of the tank. The sludge can be
sucked from the drain or left to fall out under the influence of gravity, whichever method
is preferred. These tanks have the capacity to handle water with large silt loads. Figure
3.7 shows a schematic representation of such a basin.

FIGURE 3.7: A circular upward. flow settling basin

Spiral Flow Basins

Spiral flow basins differ from the two types already discussed because the waste water is
admitted into the basin tangentially to the round tank. The water is admitted to the
bottom of the tank and follows an upward spiral path. During this spiralling the sludge
settles to the bottom of the tank and the clear water can be taken off from the top. The
spiral flow pattern has led to greatly reduced retention times in some cases.

More information as well as diagrams can be found in the following books.

Perry: section 18±59 to 18±73

In Chemical Engineering Volume 2, pages 29±39

3.2.6 Filtration
Filtration can happen before or after settling in a water treatment plant. It normally
happens after the settling process. There are two main types of filtration and each will be
discussed in some detail. The first type of filtration is non biological filtration, or
physical filtration. This is the filtering process that you are most familiar with. It is a
purely physical process that removes small particles and remaining floc from the water.
The second filtering process, biological filtration, is a combination of filtration and
biological treatment. It is more often used for sewage water than in the purification of,
for instance, river water. The biological filtration process also serves to aerate the water.

3.2.6.1 Non biological filtration

This process mainly consists of passing the water through a bed of sand or a similarly
suitable medium at a low speed. The remaining suspended matter is then removed by
 96

trapping it in the filter medium. After some time the filter is washed to remove the
trapped material and the process can start afresh. We are going to take a look at the
operation of the following types of non biological filters:

. Rapid gravity sand filters

. Pressure filters
. Multi-layer filters
. Slow sand filters

3.2.6.1.1 Rapid gravity sand filters

Rapid gravity sand filters are the most commonly used type of filter. They are normally
used together with coagulation in plants, and follow settling ponds or basins. The filters
are normally square concrete basins. The filter medium, as said before, is sand. A layer
of sand with thickness between 0.54 and 0.75 m is supported by a gravel layer about 45
cm thick. In some cases the sand is supported by plates with holes drilled into the plate.
The sand grains have a fairly uniform size somewhere between 0.4 mm and 1.2 mm in
diameter. The gravel particles are normally between 2 mm and 60 mm in size. The total
bed thickness should _ normally be about 1 metre. Underneath the filter bed a drain
system is installed to remove the water from the filter. The drain system should also
include facilities to wash the filter bed and to aerate the filter bed if necessary. The filter
is washed by forcing wash water upwards through the filter bed. By doing this the
particles that were removed from the waste water and are now trapped in the filter bed
are lifted. This process is called backwashing. After the particles have been loosened
they are removed from the top of the sand. In some cases the water overflows over the
top of the filter, or in some cases the dirt is removed from the top of the tank by means of
pressurised water jets. This process can be done manually or automatically. The wash
water can be recycled to an earlier stage in the process (e.g. before the settling ponds) or
it can just be discarded.

It is important that filters be installed absolutely level in order to prevent uneven filtering
and disturbances to the filter bed. The water is passed through the filter at a rate of
between 4 and 10 m.h-l. Most filters are washed about once in 24 hours. In peak times or
after heavy rains or some other upheaval that affects the water quality, the washing can
be done more often. Most plants have sets of filters and these filters are washed
alternately so that the operation does not have to stop to allow for the washing. While a
particular filter is being washed, the water is just re-routed through the other filters. The
washing can be done by water alone, or the crust that forms on the filter medium can
first be broken up by air, and then washed by water. In the case of gravity filters it can be
seen with the naked eye when the filter needs to be washed. Signs to look out for include
cracks forming in the filter bed or the filter bed pulling away from the sides of the filter.
This happens because the particles that cling to the filter medium reduce the spaces
between them and cause them to stick together. This leads to a reduction in area and
cracking.

In some cases the pressure drop over the filter bed is also used as an indication of the
appropriate time for the filter to be washed. As the dirt causes the holes in the sand to fill
up and the sand grains to cling together the pressure drop over the bed increases and this
is used as an indication that the filter needs to be washed. The fact that the condition of
the filter bed can be seen with the naked eye is one of the great advantages of these open
types of filters.

The amount of wash water that is used to clean the filter must be carefully optimised.
About 1.5 % of the daily throughput of the filter is often used.
 97 CHP311-A/1

3.2.6.1.2 Pressure filters

Pressure filters are similar to gravity filters with respect to filter bed characteristics,
washing, etc. The main difference between pressure filters and gravity filters is the fact
that in the case of gravity filters the filters are open and the filtration process takes place
at atmospheric pressure. In the case of pressure filters the filters are enclosed units and
the filtering takes place at elevated pressures. This speeds up the filtering process and
allows smaller filters to be used. This is an attractive option where space is a limitation.
Figures 7.12±7.14 on pages 310 to 312 in Chemical Engineering Volume 2 show typical
pressure filters. These filters are normally around 2-4 m in diameter and they can be
installed horizontally or vertically. The horizontal units are normally not longer than 15
m. The water enters the filter near the top and the filtrate is removed through a drain at
the base of the filter.

3.2.6.1.3 Multi-layer filters

In the normal operation of filtering the gravel layer lies beneath the filtering sand. If the
filter is washed the sand and the gravel is upset because of the upward moving water.
Once the backwashing process is over, the sand and the stone settle to the bottom of the
filter again. The heavier particles will always settle first so the gravel is always below
the sand. The water now enters the filter from the top, so the fine sand is reached before
the coarse gravel. This has the effect that all the particles are filtered out immediately. If
the coarse layer was on top the water would filter gradually, with the larger particles
being trapped first and the finer particles being trapped only once the coarser particles
have been removed and the finer sand is reached. This implies that the sand filters are
being used inefficiently because the gravel does not get into contact with the water to get
an opportunity to remove the coarse particles.
This problem can be solved in two ways. The water can be fed into the bottom of the
filter. This way the gravel will be in contact with the waste water to remove the larger
particles first before it comes into contact with the sand. The sand is available only for
the removal of the smaller particles. This increases the capacity of the filter because
more of the available filtering medium is now utilised. Water with a higher degree of
turbidity (more solids) can also be filtered because the effective area available for
filtration is now larger.
The second method is using filter mediums of different densities. Coarse granules of a
lower density than the sand will be used. These granules will settle slower than the sand
because they are lighter. Substances such as pumice stone or anthracite can be used.
These coarse particles are now on top of the bed and as the water moves down it comes
into contact with these particles first. The larger impurities are now effectively removed
and the smaller impurities are taken out in the sand layer beneath.

3.2.6.1.4 Slow sand filters

Slow sand filters operate on much the same principle as rapid sand filters, but the sand is
usually much less defined in terms of the particle size and size distribution. The sand is
also finer. Because of the finer sand both the filtering process and the cleaning process
take more time, therefore the term slow sand filter. The filter is made up of various
layers. The first 1.2 to 1.8 m is made up of fine sand that usually has a diameter of
between 0.2 and 0.4 mm. The next 0.7 to 0.9 m is fine gravel with diameter of 5±10 mm.
Beneath this fine gravel there is medium gravel with diameter of 10±25 mm and at the
base of the filter there is coarse gravel with diameter 25±80 mm. These filters are quite
large and as a result take up a lot of space. There have to be at least 3 filters on any
particular plant, because one is usually off line to be cleaned.
 98

3.2.6.2 Biological filtration

Biological filtration is a process where waste organisms in the water are contacted with
microbial growths that are supported on media on the filter. The waste organisms serve
as food for the microbial growths and are thus depleted, leaving the water cleaned. The
supporting media for these microbial growths are stones, small rocks, bricks or synthetic
media. The biological filters or towers are up to 6m high.
Let's take a look at the mechanism of the biological process. The waste water (usually
after settling) is pumped to the top of the filter and sprinkled over the supporting media.
Initially there is a growth period where biological slimes grow on the surface of the
rocks. These slimes are a combination of bacteria, protozoa and fungi. The exact
combination of these species differs according to various factors and in some cases two
filters standing right next to each other have different combinations of these species. In
some cases other species like fly larvae, sludge worms and rotifers are also found on the
support structure. Warm weather and sunlight promote the growth of these species and it
is therefore advisable that they be open to the atmosphere.
Covers are only needed in areas where the temperature drops very low and the cold can
destroy the active species. Once the support media have been covered with microbial
species the waste water that flows through the structure is contacted with the slime layer.
The organic matter and the dissolved oxygen are removed from the water and depleted
by these species as food. The waste products excreted are harmless (such as carbon
dioxide) and this is released into the water. The oxygen in the water is continuously
replaced because the water is in contact with the surrounding air. Although the layer of
biological matter is very thin, the lower section of this layer is usually depleted of
oxygen and can thus be called an anaerobic layer. Figure 3.8 show a schematic
representation of this process.

FIGURE 3.8: Biological process in a filter bed

As in the case of sand filters the top section of these biological filters is also more
efficient than the lower section. This is because the growth of organisms is more
abundant in the top third to half of the filter due to the ample food supply. The bottom
section of the tower or filter therefore has a lowered efficiency. Sometimes these
microbial organisms come free from the support media and it is wise to follow the
biological filtration section with a final clarifier. In some cases the bed can become
overloaded. This happens when the flow rate is too low and the growth of microbial
organisms is too high. The holes between the support media are then blocked by the
microbial growths and puddles of water are trapped on top of the filter. This reduces the
filter efficiency and can lead to odours developing.
 99 CHP311-A/1

We are going to discuss two main types of biological filtration units, namely the
trickling filter and the rectangular biological contactor. If the operation of these pieces of
equipment is clear to you then others will be easy to understand once you are confronted
with them.

3.2.6.2.1 Trickling filters

A trickling filter is normally a round concrete structure filled with stones. The stones are
75 to 125 mm in diameter and the depth of the bed ranges from 1.5 to 2.1 metres. The
smaller the stones, the greater the surface area available for exchange, but the greater the
risk of clogging of the filter bed, so the selection of the correct size of filtration support
is an optimising decision. As the size of the stones increases deeper beds can be
tolerated. It is not, however, sensible to increase the bed depth to a point where all the
stones are not effective in removing waste from the water. The water is pumped up to the
centre of the filter and distributed evenly over the stones by means of a rotary distributor.
These distributors have holes at the side of a pipe extending over the length of the filter.
As the water is released through the holes, the distributor is propelled forward by action
reaction forces and turns to distribute the water evenly over the top of the filter. The filter
media or stones are supported by various types of supports such as concrete slabs or
bricks. Underneath the support a system of drains removes the water. The filter is also
open at the bottom to allow for air passage over the filter support media. In most cases
there is some type of recirculation system in place. Water from the bottom of the filter is
recirculated through the filter during times where the water flow is low. It is important
that the support structure never dries out because this will destroy the microbial growths
and then the whole microbial system has to be grown from scratch. It is also possible to
operate more than one trickling filter in series. In such cases there is often an
intermediate settling tank that helps to remove some of the microbial matter that leaves
with the water. Figure 3.9 show a side view of a typical trickling filter and figure 3.10
shows a flow sheet for a typical two stage trickling filter plant.

FIGURE 3.9: A typical trickling filter

 100

Sludge return and recirculation during priods of low flow

!
! !

Influent ! Effluent
Primary Filter Inter Filter Final

!
!

!
!

!
mediate

!
! ! ! !
Waste
Sludge First Stage Recirculation Second Stage Recirculation

FIGURE 3.10: A typical trickling filter plant

3.2.6.2.2 Rectangular biological towers

Apart from natural packing such as stone and bricks there are various types of synthetic
packing available on the market for use in trickling filters. Synthetic packing can be
manufactured to have a very high surface area to volume ratio with a high void fraction
(empty space). This is the ideal configuration for a lot of slime growth together with a lot
of space for dissolved oxygen to come into contact with the slime. These synthetic
packings are also lighter than stone and that has the advantage that the supports can be
lighter and thus cheaper. The packing can also be manufactured to have a uniform size
and this enhances the distribution of water through the filter. One of the most popular
materials for the manufacturing of synthetic packing materials is polyvinyl chloride
(PVC). The PVC can be manufactured in the form of plates (sheets) or random packing.
This packing is normally applied in square towers. The tower operates in exactly the
same way as the round trickling filters we have discussed in the previous section, except
for the fact that it is now in the shape of a rectangular tank. The water is still distributed
to the top of these filters through sprayers or nozzles and runs down the packing to
effluent channels at the base that remove the water from the filter.

3.2.7 Flotation
Flotation is a process used in both sewage and waste water treatment. It can be used as a
separate step, or it can be combined with one of the other steps in the purification
process. Flotation will typically happen just before the settling out of floc, or combined
with the settling process. In a typical flotation cell, air is bubbled upward through the
cell. A distribution system in the base of the cell assures that the bubbles are evenly
distributed and are of comparable size. As the bubbles flow upwards through the cell the
finer floc adheres to the bubbles and moves upward to the top of the tank. Once the layer
of bubbles and floc at the top of the tank reaches a sufficient amount it is removed. This
removal process can either be a continuous process where the bubbles overflow once
they have reached a certain level, or it can be a batch process where the bubbles and floc
are washed off the top of the tank every few hours. Flotation is most suitable for the
removal of fine particles, and in the case where larger floc is also present the flotation
process is often combined in some way with sedimentation.

There is some cost involved in the equipment for compressing the air and entraining the
bubbles in the water, but normally the added purification of the water validates this cost.
 101 CHP311-A/1

3.2.8 Chemical Treatment

Chemical treatment is done in various stages of the process. Chemicals are added to the
process in order to remove unwanted substances such as bacteria and other organisms.
The chemical processes that we are going to discuss are:

. Chlorination
. Fluoridation
. Removal of iron and manganese
. Precipitation softening

3.2.8.1 Chemical feeding equipment

Before we take a look at the various chemical processes and how they are applied it is of
value to take a look at how chemicals are fed into the process. Some chemicals are fed to
the water treatment process in liquid form and some are fed in solid form. Some
chemicals have to be stored in liquid form because of their highly corrosive nature.
Some are stored in solid form, but because they have a low solubility in water they are
dissolved before they are fed to the water in order to facilitate better mixing and
distribution.

Chemical feeders are mechanical devices used to deposit chemicals in the water. If the
chemical that has to be added is in solution form, such as ferric chloride, the solution can
be pumped into the water by means of a small positive displacement pump. The rate at
which the chemical is fed can be controlled by the rate at which the solution is pumped
into the water. In the case of a solid chemical that has to be dissolved the dry chemical
can be mixed with a little water first, and this solution can then be fed into a tank. The
mixing can be done in a small tank with a stirrer, or in a screw type mixing device. Solid
materials can also be fed into the water by means of a screw feeding device.

3.2.8.2 Chlorination
Chlorine is usually added to water for disinfection purposes. The chlorine is stored in
liquid form in cylinders. It is added to the water in the gas form, and this addition is done
by means of a device called a chlorinator. In some cases an evaporator is added between
the tank and the chlorinator in order to prevent rapid cooling of the gas as it leaves the
cylinder. The cylinders are kept in banks containing more than one so that there are back
up supplies in the case of blockage. When a cylinder is empty the chlorine can
immediately be supplied to the water from one of the back up cylinders without
interruption in the process. Chlorine is a yellow-greenish coloured gas. It is heavier than
air and when it leaks from the cylinders it will stay close to the ground. It is therefore
important that the area in which the chlorine containers are stored be very well
ventilated. If the ventilation is poor and there is a gas leak the chlorine will stay close to
the ground and a person coming into that area will be exposed to the chlorine. That
person could die from suffocation, because the heavy chlorine gas has replaced the
lighter air. Exposure to lesser amounts of chlorine can cause serious lung injuries or
respiratory irritation.

In some cases chlorine is also added to water as hypochlorites. This is the case in
commercial swimming pool disinfectants. The salts most often used are calcium
hypochlorite Ca(OCI)2 and sodium hypochlorite NaOCI.

Chlorine is added to drinking water in order to kill the bacteria and other micro-
organisms that cause diseases in humans. When chlorine gas is contacted with water the
following reaction occurs:
 102

Cl2 + H20 . HOC1 + H+ + Cl-

The hypochlorous acid (HOC1) ionises to form the hypochlorite ion according to the
reaction below:
HOC1 . H+ + OCI-

Below a pH of 7 the hypochlorous acid is mainly ionised, and above a pH of 8 it is

mainly in the HOC1- form.
When hypochlorites are added to the water the hypochlorite ion is produced in one step
e.g.
Ca(OCl)2 + 1120 . Ca++ + 2 OCl- + H2O

The free available chlorine present in the water is the combination of the hypochlorous
acid and the hypochlorite ions.
The hypochlorous acid reacts with the bacterial or viral structure and kills the cells. The
efficiency of this reaction is dependent on the temperature, pH and time of contact.
Chlorine has the added advantage that it can be used to remove iron and manganese
from water because it is such a strong oxidising agent. Hydrogen sulphide, a substance
known for its foul smell, can be removed from ground water by chlorine according to
the following reaction:

H2S + 4C12 + 4H2O . H2SO4 + 8HC1

Chlorine also leaves a residue in the water that protects it against future contamination.
Therefore water is often dosed with chlorine gas before transporting it through pipelines
in order to avoid downstream contamination.

3.2.8.3 Fluoridation
Fluoride (the fluoride ion) in water has two effects. It can cause the mottling of teeth if it
is present in excessive quantities. Apart from looking unpleasant this can also harm the
teeth. Too little fluoride has the effect of increased cavities reported. It is therefore
important that water has the optimum amount of fluoride present in order to ensure the
optimum dental health of its users. For this reason fluoride containing substances are
sometimes added to the water. There are three main substances added to the water that
produce this effect, namely sodium fluoride, sodium silicofluoride and fluorosilicic acid.
Sodium fluoride is the substance most often used.
The optimum concentration of the fluoride ion in water is between 0.6 and 1.2 mg/l. It is
important to add the fluoride at a point in the process where all the water that has to be
treated passes. If it is at all possible the fluorine should be added to the water after the
filtration step in the process. This is done because the water is very clean at that stage
and very little fluoride will be lost due to side reactions with other substances that might
be in the water.
Both the raw water and the treated water are tested for fluoride and the fluoride
standards have to adhere to the set standards for drinking water.
We have already said that an excess of fluoride causes the mottling of teeth of the people
who drink the water. This mottling is a permanent grey and brown discoloration of the
enamel of the teeth. In some cases, especially in the case of children, the enamel is
mottled so badly that pits develop in the enamel and the teeth are damaged. In cases
where the fluoride content of the water is too high the water is defluoridated by
 103 CHP311-A/1

percolating it through a bed of activated alumina or bone char. The fluorides in the water
are removed and the bed, which becomes saturated with fluoride ions, is regenerated
from time to time.

3.2.8.4 Removal of iron and manganese

Divalent iron and manganese (Fe++ and Mn++) are often present in water. These ions are
invisible and soluble in water and cannot be detected with the naked eye. However,
when these ions are exposed to air they are oxidised to Fe+++ and Mn++++ Both these
ions are insoluble and they serve to discolour the water. The reduced form of iron also
enhances bacterial growth under certain circumstances. In some cases chemicals are
added to the water to prevent this oxidation reaction from taking place, but the best way
to get rid of these ions is to remove them completely.

The ions are removed by oxidising them and removing the precipitated oxides in filters.
If there are only ferrous ions in the water and no manganese, the water can be aerated in
order to remove the iron. The ferrous ions oxidise quite easily according to the following
reaction:

Fe++ + 02 ? FeOx; (insoluble ferric oxides)

Manganese does not oxidise this easily and in waters that contain both iron and
manganese ions free chlorine is added to the water together with aeration. This serves to
oxidise the iron and manganese to the insoluble metal oxide form according to:

Free Chlorine
Fe++ + Mn++ +Oxygen iiiiiiiiK FeOx; + MnO2;

In some cases potassium permanganate is also used. The residue of the insoluble metal
oxides is now filtered out.

A specific removal process, the Manganese Zeolite Process is used as a combined

process to remove both these ions. Water containing the soluble iron and manganese
ions is aerated and dosed with a solution of potassium permanganate. The potassium
permanganate aids in the oxidation process and insoluble oxides form. Then the solution
is fed through a unit containing anthracite and a layer of manganese treated greensand.
This is a zeolite (molecular sieve) that removes the excess soluble iron and manganese
ions (Fe++ and Mn++) from the solution. After some time the bed is regenerated by
backwashing the filter and regenerating the zeolite with potassium permanganate. Figure
3.11 show a typical flow sheet of such a system.

FIGURE 3.11: Manganese Zeolite Process

 104

As will be seen in the next section, if the water is deemed hard and is subjected to
precipitation softening, the iron and manganese ions in the water are also removed by
means of the precipitation softening process.

3.2.8.5 Precipitation softening

When discussing the chemical characteristics of waste water we have said that hardness
in water is due to the presence of calcium and magnesium ions. This hardness is
objectionable for domestic use because it causes scale formation in water and it also
reacts with household detergents, soap and washing powders. Precipitation softening is a
process that uses lime (CaO, which forms Ca(OH)2 in water) and soda ash (Na2CO3) to
remove the calcium and magnesium from the water. Lime is also beneficial in removing
turbidity from water, killing bacteria and removing iron and manganese. After the water
has been treated with lime, carbon dioxide can be added to the water to restore the pH.
Lime has a low solubility in water and it is usually added as a slurry.

Lime-soda softening cannot remove all hardness due to the solubility of CaCO3 and
Mg(OH)2, incomplete mixing and slow reactions. The practical minimum calcium
hardness is about 30 mg/1 as CaCO3, and the minimum magnesium hardness is about 10
mg/1 as CaCO3. In practice it is difficult to wash off soap if the water is too soft, and a
final hardness of about 75±120 mg/l is the usual target for domestic water supplies.
In order to speed up the reaction, an excess of Ca(OH)2 equivalent to 20 mg/l CaCO3 is
normally added. Magnesium in excess of 40 mg/l causes scaling, but is expensive to
remove, so only amounts in excess of 40 mg/l (as CaCO3) are removed. For magnesium
removals of less than 20 mg/l as CaCO3, the excess of lime mentioned earlier gives good
results. For magnesium removals of between 20 and 40 mg/1 as CaCO3, an excess of
lime must be added which is equal to the magnesium to be removed. For magnesium
removals greater than 40 mg/l as CaCO3, lime must be added equal to the magnesium
concentration in excess of 40 mg/l.

The chemical additions (as CaCO3) to soften water may be summarised as follows:

Step Chemical addition Reason

Carbonate hardness
1 Lime = CO2 Destroy H2CO3
2 Lime = HCO3- Raise pH; convert HCO3- to CO32-
3 Lime = Mg2+ to be removed Raise pH; precipitate Mg(OH)2
4 Lime = required excess Drive reaction to completion
Non-carbonate hardness
1 Soda = non-carbonate hardness to be Provide CO32-
removed

These steps are diagrammed in the flow chart overleaf:

 105 CHP311-A/1

Add Lime=CO2

!
Add Lime=HCO3-

No Mg2+ > 40 Yes Add Lime

= (Mg2+-40)

!
mg/l?

Yes (Mg2+-40) No (Mg2+-40)

!
<20? > 40?

No Yes

! ! ! !
Add Lime=20 mg/l Add Lime Add Lime=40 mg/l
= (Mg2+

!
!
!

Yes NCH No
present?

!
!
Add Soda=NCH Stop
!

present

FIGURE 3.12: Flow diagram for solving softening problems.

 106

Example 3.1
Given the following water, determine the amount (mg/1) of 90 percent purity CaO and
97% purity Na2CO3 that must be purchased to treat the water to a final hardness of:
(a) 85 mg/l
(b) 120 mg/l

Atom/Ion mg/1 as CaCO3

CO2 21
HCO3 209
Ca2+ 183
Mg2+ 97

Answer
(a) First find the total hardness (TH), carbonate hardness (CH) and non-carbonate
hardness (NCH):
TH =Ca2+ +Mg2+ = 183 + 97 = 280 mg/l
CH = HCO3- = 209 mg/l
NCH = TH - CH = 71 mg/1
Use Fig. 3.12 to find the lime dose as CaCO3, assuming that 40 mg/1 Mg2+ is left
in the water: Ca(OH)2 = 21 + 209 + (97 ± 40) + 40 = 327 mg/l as CaCO3
Since 1 mol of CaO produces 1 mol of Ca(OH)2, 327 mg/l as CaCO3 is equivalent
to:
 
56mg CaO
327 mg/I CaCO3 = 183 mg/I as pure CaO
100mg CaCO3
But, more CaO must be added as it is only 90% pure, i.e.
183
= 203 mg/I as CaO
0:9
The amount of NCH that can be left in solution is equal to the target hardness (85
mg/l) minus the CH left behind due to solubility, poor mixing, etc. (40 mg/1) = 45
mg/l. Therefore the NCH to be removed = the initial NCH (71 mg/l) - the NCH
which can be left (45 mg/l) = 26 mg/l as CaCO3.
The equivalent amount of Na2CO3 is obtained by multiplying by the ratio of the
atomic weights as before and adjusting for 97% purity:
  
106 1
Na2CO3 = 26 = 28 mg / lIasNa2CO3
100 0; 97

(b) If the target hardness is 120 mg/l, then the allowable final NCH is 120±40=80 mg/
l, which is greater than the initial NCH of 71 so no soda ash is necessary. The final
hardness would be about 40 mg/1 (carbonate solubility) plus 71 mg/1 non-
carbonate hardness =111 mg/l.

3.2.8.6 Ion exchange softening

Ion exchange involves the reversible interchange of ions between a solid and a liquid
phase with no change in the structure of the solid. Water containing hardness is passed
 107 CHP311-A/1

through a column containing the ion exchange material. The hardness in the water
exchanges with ions from this material ± usually sodium:

Ca(HCO3)2 + 2 NaR . CaR2 + 2 NaHCO3

where R represents the solid ion exchange material. Here one calcium ion is replaced by
two sodium ions without changing the alkalinity. It removes essentially 100% of the
hardness until the exchange capacity of the ion exchange material is reached (no NaR
left). At this point there is breakthrough of Cat+ ions, the column must be taken offline,
and the ion exchange material must be regenerated by reversing the above reaction. In
the above case sodium chloride could be used.

CaR2 + 2 NaCl . 2 NaR + CaCl2

The CaCl2 is a waste stream that will have to be disposed of. Ion exchange materials can
be naturally occurring clays (zeolites) or synthetically made resins (more expensive, but
higher capacity). Large industrial units are in use, but small domestic units are more
common.

Example 3.2
A home water softener has 0.1 m3 of ion exchange resin with a capacity of 57 kg/m3.
The occupants use 2000 1/day of water containing 280 mg/1 of hardness as CaCO3. If
they want to soften the water to 85 mg/l as CaCO3, what percentage of water should
bypass the unit, and when will the unit need to be regenerated?

Answer
Since virtually 100% of the hardness is removed, a portion of the water bypasses the
column:

desired hardness
% bypass = ÐÐÐÐÐÐÐÐ 6 100
initial hardness
85
=  100
280
= 30%

Therefore 70% of the water is treated, so:

Loading rate = (0.7)(280 mg/l)(2000 I/ day) = 392000 mg / day

…57kg=m3 †…0:1m3 †
Breakthrough time = = 14.5 days
…392000mg=day†…10ÿ6 kg=mg†

3.3 TYPICAL WATER TREATMENT OPERATIONS

What follows is a series of typical water treatment plant designs. These plants can treat
various types of water, from river water and dam water to sewage water and water from
industrial sites. The water is treated to different degrees of purity. In some cases the
water is treated to drinking quality and in some cases it is treated to be dumped in rivers.
 108

3.3.1 Wastewater Treatment: Example 1

The first example is used for a plant that treats water from a catchment area (dam or
river) and from the discharge of a sewage plant. The water has to be purified to drinking
purity. Figure 3.15 show a typical flow sheet of such a process.

Water enters the plant from the dams, rivers and sewage works that feed the plant. The
water flows in open channels made of concrete. The measuring of flow in these open
channels is done by weirs or a set-up called a Parshall flume. A Parshall flume is a
section in the channel that is deeper and narrower than the channel itself. Just before the
water runs through this section the level in the channel is measured and this
measurement is related to the flow rate of the liquid. A weir is a plate that is inserted in
the channel at 908 to the direction of flow. The top of this plate is often cut away to form
a v ± notch. The plate will restrict the flow of the water and the water will flow over the
top of the plate. The height of the water as it flows over the top of the plate gives an
indication of the flow rate. Figure 3.13 shows a schematic representation of a Parshall
flume and figure 3.14 shows the operation of a weir.

The first step of the purification process is the screening section. The screening is done
in two rotating disc screens. These screens remove all the large algae growths from the
water, together with any other large organic and non-organic matter that might be
present. The speed of rotation of the screen can be varied and the solids are discharged
on a continuous basis. The solids are dumped to be dried and once dried are incinerated.

FIGURE 3.13: Schematic representation of a Parshall flume

FIGURE 3.14: A weir with a 908 V notch used to measure the flow in a channel
 109
CHP311-A/1
FIGURE 3.15: Process flow sheet for example 1
 110

After the screens the water is fed to a mixing point where chlorine gas is added. The
chlorine gas is stored in cylinders in the liquid form in an enclosed, well ventilated area.
The chlorine is added to the water by means of a chlorinator. The purpose of chlorine
addition is to kill bacteria that cannot be removed in the sedimentation and filtration
processes that follow. In cases where the water contains a lot of suspended solids,
activated carbon can also be added to the water. These suspended (and sometimes
dissolved) materials impart colour and odour to the water. Activated carbon has a high
surface area and is very porous and adsorbs these colorants and odorous materials in the
water. The carbon is later removed in the sedimentation process.

From the chemicals dosing point the water moves through the flocculation channels.
These are cement channels about 1 m deep and the water moves through them slowly to
give the flocs time to grow to a sufficient size before they are left to settle out. Then the
water stream is split to pass through an old and a new section of the plant. The new
section contains a covered combined flotation and sedimentation section. It consists of a
round tank with air jets at the base. The finer flocs adhere to the air bubbles that are
distributed evenly through the tank and the bubbles and the finer flocs move to the top of
the tank and collect on the surface of the water. The heavy flocs settle to the bottom of
this tank and are sucked out by a pump and scraper system. The bubbles and lighter floc
flow over the edge of the tank to a waste system. The clear water is taken off about 15
cm below the surface to the tank through pipes with holes drilled into them. In the other
flotation and sedimentation section the two processes are done separately.

The flotation cells are square tanks with air jets that bubble pressurised air through the
tanks. The light particles and the bubbles flow over the side of the tank to a drain system
and the heavy particles flow over a weir to a sedimentation tank. The water velocities in
the sedimentation and flotation tanks are virtually zero (because of the large area of
flow) and this allows for the floc to lose its momentum and settle to the bottom of the
tank. The water then passes through a battery of sand filters. These filters are about two
metres thick with perforated plates at the base. The filters are equipped with floats that
indicate the time at which the filter needs to be washed. When the filter bed is dirty the
pores are clogged with particles. This reduces the rate of filtration. When the rate of
filtration is decreased the hol up of water in the filters increases and thus the level on top
of the filter beds also increases. When these filters reach a certain maximum level the
float activates a shut off system and the filters are shut off and backwashed
automatically.

From the filters the water is fed through another chlorination unit. This post-chlorination
is done to boost the chlorine content of the water and to protect it from bacteria that
might be in the storage or distribution facilities.

3.3.2 The Activated Sludge Process: Example 2

A flow sheet for the activated sludge process is shown in figure 3.16. The first step in
this process, as in the previous example, is screening. In some cases the water is pumped
to stabilising dams. This is done to increase the homogeneity of the water and also to
ensure a constant feed to the plant. If the plant is fed from municipal areas there will be
peak time supply of water that is higher than the off times (for example, people use more
water early in the morning and evening). The dams can therefore act as buffers for this
uneven water supply. The screening can be done in one or in two stages, depending on
the characteristics of the solids in the water. The first stage will be coarse screening and
the second stage will be screening to remove finer particles. The screenings are dried
and incinerated. After the screen the water moves through a grit removal chamber.
 111 CHP311-A/1

! !
Stabilising dams
Solids Sludge

Inflow Grit Primary

Screening

!
!
Removal Settlement

Chlorine Effluent
Sludge Settling
Contacting
!

!
! !
Reactor Tank
Chamber

CL
! NaOCl
!

FIGURE 3.16: Activated Sludge Process

The next step in the process is degritting. There is often grit (small stones, gravel etc.)
present in the sludge. It is advisable to remove these particles before the biological
sludge is treated because these particles are hard and they can cause considerable
damage to pumps, scrapers, filter belts etc. These particles can also settle out in pipes
and the pipes then have to be opened at a later stage in order to remove the grit. The
removal of grit early in the process is therefore preferable.

Grit is normally removed in an apparatus known as a cyclone degritter. The water is fed
tangentially into a cyclone with a cylindrical shape. The centrifugal force of the water
will cause the heavier grit particles to move to the outside of the cylindrical chamber.
They will settle to the bottom of this apparatus and drop out. The water will leave
through the top.

The next step is settling or sedimentation. For the activated sludge process settling or
sedimentation can be carried out in two main types of tanks, namely square tanks or
circular sedimentation tanks. The circular tanks are most often used because they are
easier to clean and the sludge does not accumulate in the corners of the tank. These
circular settling tanks can have diameters ranging from 3 to 60 metres, depending on the
output of the tanks. The water can be fed into the centre of the tanks or at the perimeter
of the tank. The sludge is removed from the base of the tank by means of scrapers.
Rectangular tanks are up to 90 m long and 24 m wide. In both these tank types the
sludge collectors at the base of the tank must be strong and robust in order to cope with
heavy sludge loads.

The piece of equipment that makes the activated sludge process unique is the sludge
reactor. Sludge reactors can be of two main types, namely constant volume stirred tank
reactors (CSTR's) and plug-flow reactors (PFR's), or any combination of the two types.
In the case of a CSTR one assumes that the whole reaction mixture is completely
homogeneous and the reaction takes place through the entire reaction volume
simultaneously. The conditions in the reactor are the same as the condition in the
outflow. In the case of a plug flow reactor, one assumes that the liquid flows through the
reactor in discs or plugs. The reaction proceeds along the length of the reactor as the
 112

liquid proceeds through it. Each cell or disc is perfectly mixed, but there is no mixing
between the discs or plugs, so that each disc is isolated from its neighbouring cells.
Figure 3.17 show schematic representations of the flow patterns in the two reactor types.

FIGURE 3.17: Typical CSTR and PFR flow patterns

The activated sludge reactor has the ability to produce an activated mass of micro-
organisms. These micro-organisms can stabilise the waste aerobically. This means that
the waste water is contacted with these micro-organisms in the presence of oxygen and
the harmful biological substances in the waste water are digested into products such as
CO2, H2O and NH3. The aerobic bacterial culture in the reactor is kept in suspension and
the organic waste is introduced (fed) into the reactor. The sludge is converted to the end
products. A portion of the discharge of the reactor is recycled back to the reactor so that
the aerobic bacteria that facilitate the reaction are continuously present in the reactor.
Sludge reactors are also equipped with aeration equipment that is used to supply oxygen
to the reactor.

The sludge reactor is followed by a second settling tank. This settling tank removes all
the small particles still present in the water. At this point all the harmful biological
substances, such as viruses and bacteria, should have been removed from the water.

Before the water leaves the plant it is disinfected with chlorine or sodium hypochlorite.
Depending on the amount of sludge removed from the water, a sludge processing and
disposal plant can be operated in series with the purification plant. Sludge still contains
lots of toxic substances and it is important to dispose of it properly after is has been
removed from the water to prevent it from contaminating the environment again. A
typical flow chart for a sludge treatment plant is shown in figure 3.19. As can be seen
from the flow chart there are 9 main categories of operations that can be carried out on
the sludge. It is not necessary in all cases to perform all the operations on the sludge. For
example the preliminary operations can be left out in cases where the sludge is uniform.
In cases where there is relatively little sludge, the conditioning step can also be left out.

3.3.3 Example 3: Sludge Treatment by Trickling Filters

A similar procedure as the one described for the activated sludge process can be used
with the sludge reactor replaced by trickling filters. A process flow sheet for such a
system is shown in figure 3.18.
 113 CHP311-A/1

! !
Stabilising dams
Solids Sludge

Inflow Grit Primary

Screening

!
!
Removal Settlement

Trickling Sludge Settling Effluent

!

!
! !
Filters Reactor Tank

CL
! NaOCl
!

FIGURE 3.18: Sludge Treatment by Trickling Filters

Trickling filters are classified according to the organic loading rate, ranging from low
rate to super-high rate. In some cases of high load two of these filters are used in series.
The table below indicates the different types of trickling filters in use, the loading of
these filters in gallons per square foot per minute and typical depths of filter bed. It also
lists the recirculation ratio, which is the volume of liquid recycled per volume of product
liquid. Recirculation of filter liquid through the filter reduces pond forming, it increases
the filter capacity and it reduces the occurrence of odours and filter flies.

Typical Design parameters for Trickling Filters

Item Low Rate Intermediate High Rate Super Roughing Two

Rate HIgh Stage
Rate
Filter Medium Rock, Slag Rock, Slag Rock Plastic Plastic, Rock
Redwood Plastic
Hydraulid 0.02±0.06 0.06±0.16 0.16±0.64 0.2±1.2 0.8±3.2 0.16±0.64
Loading
Depth of Bed 6±8 ft 6±8 ft 3±6 ft 10±40 ft 15±40 ft 6±8 ft
Recirculation 0 0±1 1±2 1±2 1±4 0.5±2
Ration

Adapted from: Waste water Engineering, 3ra Ed, Metcalf & Eddy, McGraw-Hill Inc,1991

3.3.4 Example 4: Multimedia Filtration with Flotation

This process was designed to treat large amounts of water from a dam and river
catchment area in a small area plant. The main operation on this plant uses filtration cells
that combine filtration through dual media with flotation. Water enters the plant by
means of open canals. It passes through a screen system that removes most of the large
algae and bigger particles. The water is then pre-chlorinated and ferric chloride added as
 Thickening Stabilisation
. Rotary drum . Chlorine
Thickening oxidation
Conditioning
Preliminary Operations . Gravity . Lime stabilisation Disinfection
Sludge . Chemical
. Sludge Grinding Thickening . Heat treatment . Pasteurisation
conditioning
!

!
from . Sludge Blending . Flotation . Anaerobic . Long term
treat- . Elutriation
. Sludge Storage Thickening Digestion storage
. Heat treatment
ment . Sludge Degritting . Centrifugation . Aerobic
process . Gravity belt Digestion
thickening . Composting

114
Thermal reduction
. Multiple heart
Dewatering Drying incineration Ultimate disposal
. Vacumm filter . Multple effect . fluidised bed . Landfill
. Pressure filter evaporator incineration . Land application
. Horizontal belt filter . Flash drying . Flash combustion
!

!
. Reclamation
. Centrifuge . Spray drying . Flash combustion . Reuse
. Drying bed . Rotary drying . Co-incineration
. Multple hearth with solid waste
drying . Vertical deep well
reactor
. Wet air oxidation

FIGURE 3.19: General sludge treatment flow

Adapted from: Waste water Engineering, 3ra Ed, Metcalf & Eddy, McGraw-Hill Inc,1991
 115 CHP311-A/1

a flocculent. Then it is fed through the filtration units. These units are filter beds made
up of sand and anthracite. As said before, anthracite is less dense than sand.

When the filter bed is fluidised, the sand will settle faster than the anthracite and the
anthracite will form the top layer of the filter bed. The anthracite particles are larger than
the sand particles and they will remove some of the larger impurities. The sand will
remove smaller particles that settle out. These filters are also equipped with air jets that
send pressurised air bubbles through the water. The floc adheres to these bubbles and is
carried to the top of the water surface. The bubbles are washed from the top of the unit
by pressurised water that flows across the top of the unit from left to right, skimming the
bubbles from the surface and washing them over the edge. The water that leaves these
units is post-chlorinated and distributed.
Note that the flocculation and settling sections as discussed in example 1 are not present.
The combined filtration flotation process is effective enough to remove the small floc
without the settling section. This saves a lot of space, since the settling area in any
normal plant takes up a large area.

3.4 THE WATER ACT

Any country has to have legislation that protects its water resources. In South Africa the
legislation is contained in the Water Act 54 of 1956 as Amended. The act contains
information regarding the use, ownership and treatment of water. The water rights of
both the government and private owners are spelled out. As you might be aware it is
deemed a criminal offence to pollute water and the details of polluting water are spelled
out (what is considered pollution and what is not). The law also states who has the right
to amend the law and by which procedure it has to be done.
The section of the law that is most important to us as chemical engineers and chemical
technologists is the Annexure containing the General and Special Effluent Standards.
This section was added to the act in 1984 and contains the requirements for the
purification of waste water or effluent or the use of water for industrial purposes.
Appendix A contains these standards.
 116

APPENDIX A

General and special effluent standards

GOVERNMENT GAZETTE 18 MAY 1984 NO 9225

REGULATION NO. 991 18 MAY 1984

REQUIREMENTS FOR THE-PURIFICATION OF WASTE WATER OR

EFFLUENT
By virtue of the powers vested in me by section 2I(1)(a) of the Water Act. 1956 (Act 54
of 1956) I, Sarel Antoine Strydom Hayward, in my capacity as Minister of Environment
Affairs and Fisheries, hereby prescribe the following requirements for the purification of
waste water or effluent produced by or resulting from the use of water for industrial
purposes.

SPECIAL STANDARD
Quality standards for waste water or effluent arising in the catchment area draining water
to any river specified in Schedule I or a tributary, thereof at any place between the source
thereof and the point mentioned in the Schedule, in so far as such catchment area is
situated within the territory, of He Republic of Soul Africa.

1.1 Colour, odour or taste:

The waste water or effluent shall not contain any substance in a concentration capable of
producing any colour odour or taste.

1.2 pH:
Shall be between 5.5 and 7.5.

1.3 Dissolved oxygen:

Shall be at least 75 per cent saturation

1.4 Typical (faecal) coli:

The waste water or effluent shall contain no typical (faecal) coli per 100 millilitres.
 117 CHP311-A/1

1.5 Temperature:
Shall be a maximum of 258C.

1.6 Chemical oxygen demand:

Not to exceed 30 milligrams per litre after applying the chloride correction

1.7 Oxygen absorbed:

The oxygen absorbed from acid N/80 potassium permanganate in 4 hours at 278C shall
not exceed 5 milligrams per litre.

1.8 Conductivity:
1.8.1 Not to be increased by more that 15 per cent above that of the intake water
1.8.2 The conductivity of any water, waste water or effluent seeping or draining from
any area referred to in section 2 1(6) of the aforementioned Water Act shall not
exceed 250

milli-Siemens per metre (determined at 258C).

1.9 Suspended solids:

Not to exceed 10 milligrams per litre.

1.10 Sodium content:

Not to be increased by more than 50 milligrams per litre above that of the intake water.

1.11 Soap, oil or grease:

None.

1.12 Other constituents:

1.12.1 Constituents
.............................................................................................. Maximum concentration in
........................................................................................................... milligrams per litre
Residual chlorine (as CP) ................................................................... Nil
Free and saline ammonia (as N) ......................................................... 1.0
Nitrates (as N) ...................................................................................... 1.5
Arsenic (as As) .................................................................................... 0,1
Boron (as B) ........................................................................................ 0.5
Total chromium (as Cu) ....................................................................... 0.05
Copper (as Cu) ..................................................................................... 0.02
Phenolic compounds (as phenol) ......................................................... 0,01
 118

Lead (as Pb) ......................................................................................... 0.1

Soluble ortho phosphate (as P) ........................................................... 1,0
Iron (as Fe) .......................................................................................... 0.3
Manganese (as Mn) ............................................................................. 0,1
Cyanides (as Cn) ................................................................................. 0,5
Sulphides (as S) ................................................................................... 0,05
Fluoride (as F) ..................................................................................... 1,0
Zinc (as Zn) ......................................................................................... 0,3
Cadmium (as Cd) ................................................................................. 0,05
Mercury (as Hg) .................................................................................. 0.02
Selenium (as So) .................................................................................. 0,05

1.12.2 The waste water or effluent shall contain no other constituents in concentrations
which are poisonous or injurious to trout or other fish or other forms of aquatic
life.

SPECIAL STANDARD FOR PHOSPHATE:

Waste water or effluent arising in the catchment area within which water is drained to
any river specified in Schedule II or a tributary thereof at any place between the source
thereof and the point mentioned in the schedule, in so far as such catchment area is
situated within the territory of the Republic of South Africa shall not contain soluble
orthophosphate (as P) in a higher concentration than 1,0 milligram per litre.

3. GENERAL STANDARD:
Quality standards for waste water or effluent arising in any area other than an area in
which the SPECIAL STANDARD is applicable, as described in paragraph 1.

3.1 Colour, odour or taste:

The waste water or effluent shall not contain any substance in a concentration capable of
producing any colour, odour or taste.

3.2 pH:
Shall be between 5.5 and 9,5.

3.3 Dissolved oxygen;

Shall be at least 75 per cent saturation.

3.4 Typical (faecal) coli:

The waste water or effluent shall not contain any typical (faecal) coli per 100 millilitres.

3.5 Temperature:
Shall be a maximum of 358C.
 119 CHP311-A/1

3.6 Chemical oxygen demand:

Not to exceed 75 milligrams per litre after applying the chloride correction.

3.7 Oxygen absorbed:

The oxygen absorbed from acid N/80 potassium permanganate in 4 hours at 278C shall
not exceed I0 milligrams per litre.

3.8 Conductivity:
3.8.1 Not to be increased by more than 75 milli-Siemens per metre (determined at
258C) above that of the intake water.

3.8.2 The conductivity of any water, waste water or effluent seeping or draining from
any area referred to in section 21(6) of the aforementioned Water Act shall not
exceed 250 milli-Siemens per metre (determined at 258C).

3.9 Suspended solids:

Not to exceed 25 milligrams per lire.

3.10 Sodium content:

Not to be increased by more than 90 milligrams per litre above that of the intake water.

3.11 Soap, oil or grease:

Not to exceed 2,5 milligrams per litre.

Other constituents:
3.12.1 Constituents:
.............................................................................................. Maximum concentration in
........................................................................................................... milligrams per litre
Residual chlorine (as CP) .......................................................................... 0,1
Free and saline ammonia (as N) ............................................................. 10,0
Arsenic (as As) .......................................................................................... 0,5
Boron (as B) .............................................................................................. 1,0
Hexavalent chromium (as Cr) ................................................................... 0,05
Total chromium (as Cr) ............................................................................. 0.5
Copper (as Cu) ........................................................................................... 1,0
Phenolic compounds (as phenol) ............................................................... 0,1
Lead (as Pb) ............................................................................................... 0,1
Cyanides (as Cn) ....................................................................................... 0,5
Sulphides (as S) ......................................................................................... 1,0
Fluoride (as F) ........................................................................................... 1.0
Zinc (as Zn) ............................................................................................... 5,0
Manganese (as Mn) ................................................................................... 0.4
Cadmium (as Cd) ....................................................................................... 0,05
 120

Mercury, (as Hg) ...................................................................................... 0,02

Selenium (as Se) ...................................................................................... 0,05

3.12.2 The sum of the concentrations of the following metals shall not exceed I mg/l:
Cadmium (as Cd), chromium (as Cr), copper (as Cu), mercury (as Hg) and lead
(as Pb).

3.12.3 The waste water or effluent shall contain no other constituents in concentrations
which are poisonous or injurious to humans, animals, fish other than trout, or
other forms of aquatic life, or which are deleterious to agricultural use.

4. METHODS OF TESTING:
All tests shall be carried out in accordance with methods prescribed by and obtainable
from the South African Bureau of Standards. Referred to m in the Standards Act. No. 30
of 1982. as listed in Schedule III.

NOTE (a) Further information and elucidation may be obtained from the Director
General: Environment Affairs. Private Bag X313. Pretoria. 000I.
(b) Governrnent Notices R. 553 of 5 April 1962, R. 969 of 22 June 1962 and R.
I567 of 1 August 1980 are hereby withdrawn.

SCHEDULE 1

CATCHMENT AREAS WITHIN THE TERRITORY OF THE REPUBLIC OF

SOUTH AFRICA IN WHICH WASTE WATER OR EFFLUENT MUST BE
PURIFIED TO COMPLY WITH THE SPECIAL STANDARD
........................................................................................................... Division or district
1 Hour Bay River to tidal water .............................................. Cape
2. Eerste River to tidal water .................................................... Stellenbosch
3 .Lourens River to tidal water ................................................ Stellenbosch
4. Steenbras River to tidal water ............................................... Caledon
5. Berg and Dwars Rivers to their confluence ......................... Stellenbosch
6. Little Berg River to Vogelvlei weir ...................................... Tulbagh
7. Elands and Sonderend Rivers to their confluence ............... Caledon
8. Witte River to confluence with Breede River ...................... Paarl, Wellington,
................................................................................................. Worcester, Tulbagh
9. Dwars River to Ceres divisional boundary, .......................... Ceres
10. Olifants River to the Ceres divisional boundary .................. Ceres
11. Helsloot and Smalblaar (or Molenaars) Rivers
to their. confluence with Breede River ................................. Pearl and Worcester
12. Hex River to its confluence with Breede River ................... Ceres and Worcester
13. Van Stadens River to tidal water .......................................... Port Elizabeth
14. Buffalo River from the Ciskei border to where it
enters the King William's Town municipal area .................. King William's Town
15 . Swart Kei and Klipplaat Rivers to their confluence .......... Tarka, Queenstown
................................................................................................. and Cathcart
16. Bongola River to Bongola Dam ........................................... Queenstown
17. Kubusie River to the Stutterheim municipal boundary ........ Stutterheim
18. angkloof and Kraal Rivers to their confluence .................... Barkly East
19. ittle Tsomo River to the Transkei border ............................. St Marks
 121 CHP311-A/1

20. uka River to the Elliot district boundary .............................. Elliot

21. sitsa and Inxu Rivers to their confluence ............................. Maclear,
................................................................................................. Mount Fletcher,
Tsomo .................................................................................... and Qumbu
22. Mvenyane and Umzimvubu Rivers to the Transkei
border ..................................................................................... Matatiele.
................................................................................................. Mount Currie and
................................................................................................. Mount Ayliff
23. Umzimhlara River to the Transkei border ............................ Mount Currie
24. Ingwangwana River to its confluence with Umzimkulu
River ...................................................................................... Umzimkulu, Mount
................................................................................................. Curtie, Polcta and
................................................................................................. Underb erg
25. Umzimkutu and Polela Rivers to their confluence .............. Underberg and Polela
26. Elands River to the Pietermaritzburg-Bulwer main road ..... Impendle
27. Umtamvuma and Weza Rivers to their confluence .............. Bizana and Alfred
28. Umkomaas and Isinga Rivers to their confluence ............... Impcndlc. Polela and
................................................................................................. Underberg
29. Lurane River to its confluence with the Umkomaans
River ...................................................................................... Polela
30. Sitnundjwana Spruit to its confluence with the
Umkomaas river ...................................................................... Impendle
31. Inudwini River to the Polela district boundary .................... Polela
32. Inkonza River to the bridge on the Donnybrook-Creighton
Road ....................................................................................... Polela and Ixopo
33. Umlaas to the bridge on District Road 334 on the farm
Maybole ................................................................................. Richmond Division or
district
35. Mooi River to the road bridge at Rosetta ............................ Estcourt and Lions
River
36. Little Moot and Hlatikula Rivers to their confluence .......... Estcourt
37. Bushmans River to Wagendrift Dam .................................... Estcourt
38. Little Tugela River and Sterkspruit to their confluence ....... Estcourt
39. M'Lambonjwa and Mhlawazeni Rivers to their
confluence .............................................................................. Bergville
40. Mnweni and Sandhlwana Rivers to their confluence ........... Bergville
41. Tugcla River to its confluence with the Kombe Spruit ....... Bergville
42. Inyamvubu (or Mnyamvubu) River to Craigie Bum
Dam ....................................................................................... Umvoti
43. Umvoti River to the bridge on the Seven Oaks-Rietvlei
road ........................................................................................ Umvoti
44. Yarrow River to its confluence with the Karkloof
River ...................................................................................... Lions River
45. Incandu and Ncibidwane rivers to their confluence ............. Newcastle
46. Ingogo River to its confluence with the Harte River ........... Newcastle
47. Slang River and the Wakkerstroom to their confluence ...... Utrecht and
............................................................................................... Wakkerstroom
49. Elands and Swartkops Rivers to their confluence ................ Belfast and Carolina
50. All tributaries of the Komati River between Nooitgedacht
Dam and its confluence with and including Zevenfontein
Spruit ..................................................................................... Belfast and Carolina
51. Seekoeispruit to its confluence with Buffelskloofspruit ....... Carolina
 122

52. Crocodile River and Buffelskloofspruit to their confluence .. Belfast and

............................................................................................... Lydenburg
53. All tributaries of the Steclpoort River down to its con-
fluence with and including the Dwars River ........................ Lydenburg, Belfast,
............................................................................................... Middelburg,
............................................................................................... Groblersdal
54. Potspruit to its confluence with the Waterval River ............ Lydenburg
55. Dorps River (or Spekboom River) to its confluence
with the Marambanspruit ...................................................... Lydenburg
56. Ohrigstad River to the Ohrigstad Dam ................................. Lydenburg
57. Klein-Spekboom River to its confluence with the
Spekboom .............................................................................. River Lydenburg
58. Blyde River to the Pilgrim's Rest municipal boundary ....... Pilgrim's Rest
59. Sable River to the Sabie municipal boundary ...................... Pilgrim's Rest
60. Nels River to the Pilgrim's Rest district boundary .............. Pilgrim's Rest
61. Houtbosloop River to the Lydenburg distriict boundary ..... Lydenburg, and
............................................................................................... Pilgrim's
............................................................................................... Rest
62. Blinkwaterspruit to Longmere Dam ..................................... Nelspruit
63. All streams flowing into Ebenezer Dam on the Great
Letaba River .......................................................................... Pietersburg and
............................................................................................... Letaba
64. Dokolewa River to its confluence with the Politzi River .... Pietersburg and
............................................................................................... Lctaba
65. Ramadiepa River to the Merensky Dam on the farm
Wesffalia 223. Letaba ............................................................ Letaba
66. Pienaars River and tributaries up to Bophuthatswana
boundary ................................................................................ Pretoria, Cullinan and
............................................................................................... Warmbad

SCHEDULE H
CATCHMENT AREAS WITHIN THE TERRITORY OF THE REPUBLIC OF
SOUTH AFRICA IN WHICH WASTE WATER OR EFFLUENT MUST BE
PURIFIED TO CONTAIN NO SOLUBLE ORTHO PHOSPHATE (AS P) IN A
HIGHER CONCENTRATION THAN 1,0 MILLIGRAM PER LITRE
(i) Vaal River upstream and inclusive of the Bloemhof Dam;
(ii) Pienaars and Crocodile Rivers upstream of their confluence;
(iii) Great Olifants River upstream and inclusive of the Loskop Dam;
(iv) Umgeni River upsteam of the influence of tidal water
(v) Umlaas River upstream of its point of discharge into the sea
(vi) Buffels River upstream and inclusive of the Bridie Drift Dam
(vii) Berg River upstream of the influence of tidal water
 123 CHP311-A/1

BIBLIOGRAPHY
Basic Water Treatment for Application World Wide, 2nd Edition, George Smethurst,
Open University Press, 1988.

Environmental Engineering, Peavy, Rowe, & Tchobanoglous, McGraw-Hill Internatio-

nal Editions, 1985.

Pollution Engineering Practice Handbook, Chermishof & Young, Ann Arbor Science
Publishers Inc., (Butterworth), 1981.

Water and Wastewater Technology, 2nd Edition, Mark J. Hammer, Prentice-Hall, 1986.

Introduction to Environmental Engineering, 2nd Edition, Davis & Cornwell, McGraw-

Hill, 1991.

REVISION QUESTIONS
1. Name 5 sources of contamination in water.
2. Describe in your own words what you understand by the concept of ``turbidity''.
3. What is the difference between true and apparent colour?
4. Explain what is meant by the following sentence. ``Odours are often measured by
sensory methods.''
5. Name 3 physical properties of water that are affected by the water quality.
6. Describe how the presence of algae in water affects the alkalinity.
7. Explain the mechanism of scale formation on heat exchanger tubes.
8. Briefly explain the effects each of the following micro organisms can have on
people when they are present in water:
8.1 Bacteria
8.2 Fungi
8.3 Protozoa
8.4 Viruses

9. Explain what is meant by the ``biochemical oxygen demand'' of waste water.

10. Name 3 types of non-biodegradable organic materials.
11. Describe equipment that can be used to remove coarse and medium sized solid
materials from water.
12. Briefly explain the difference between degasification and oxidation.
13. Discuss and describe the operation of 3 types of aerators that make use of the
method of dispersing water into air.
14. Describe the difference between the processes of coagulation and flocculation.
15. Name the two forces at work in the destabilisation of colloidal suspensions. State
which of the forces is repulsive and which is attractive.
16. Explain fully the chemical action of aluminium sulphate (alum) as a coagulant for
waste water.
17. Name 2 limitations in the use of ferrous sulphate as a coagulant in domestic water.
18. How is chlorinated copperas formed?
19. Name 3 mechanisms by which coagulant aids facilitate coagulation and settling of
floc in wastewater.
20. Name 5 coagulant aids as well as each one's specific mechanism.
21. Describe with the use of a sketch how a flocculation tunnel works.
22. Would it be possible to skip the flocculation stage in water treatment and go
straight from the coagulation phase to the sedimentation phase? Give reasons for
your answer.
 124

23. List, in point form, the factors one needs to consider when choosing a settling
basin.
24. Describe the operation of an upward flow settling basin.
25. Explain the process of back-washing as is applied to the rapid gravity sand filter.
26. Describe the main difference between pressure filters and gravity filters.
27. Explain how a multi layer filter improves on the operation of a regular sand filter.
28. Why is it normally advisable that biological filters be open to the atmosphere?
29. What does ``anaerobic'' mean?
30. How can one increase the contact area in a trickling filter?
31. (a) Is it possible to use more than one biological filter in series? Why is this done?
(b) Make a sketch of a typical plant that contains more than one biological filter.
32. What material(s) is the packing for biological filters made of?
33. Is the process of flotation better suited for the removal of fine or coarse particles
from flocculated waste water?
34. Name 4 chemical treatment processes that can be performed on waste water.
35. Why is chlorine added to water?
36. Briefly describe how fluoride is removed from water.
37. State two negative effects that the presence of iron can have in water.
38. Describe how the Manganese Zeolite Process works.
39. Describe how one can dispose of algae after it has been removed from waste water.
40. In some water treatment processes, carbon is added to the water. Why is this done?
 125 CHP311-A/1

CHAPTER 4

Air pollution

OBJECTIVES
After completion of this chapter the student should be able to:
. Define air pollution.
. Name the harmful effects of air pollution.
. Discuss those effects in detail.
. Name and discuss the sources of air pollution.
. Convert pollutant concentrations from mass to volume basis and vice-versa.
. Calculate emission rates of pollutants.
. Discuss natural purification processes.
. Name and discuss different meteorological phenomena.
. Describe how dispersion models are used to predict the spread of pollution.
. Calculate plume rise using Briggs' equations.
. Discuss and name methods that can be used to purify air.

INTRODUCTION
In the previous chapter we have discussed the issue of water treatment quite extensively.
Treatment of effluent water is, of course, part of the developing subject of environmental
engineering. This chapter deals with another branch of environmental engineering - air
pollution.

4.1 AIR POLLUTION

4.1.1 Definition
As with most concepts it is hard to formulate a proper scientific definition for air
pollution. Let's try by saying it is the presence of substances in the air around us
(ambient air) in such quantities that they can damage the human, animal, plant or
physical environment.

Air pollution can have acute or chronic (prolonged) effects. Areas where air pollution is
high are known for a higher occurrence of certain diseases, of which sinusitis, throat and
chest infection and asthma are only a few. These areas are also more subject to acid rain
(see next section) and this will lead to the gradual destruction of buildings, farmland, etc.
There are also numerous examples of large scale incidents resulting in many deaths
which are a direct result of air pollution. One of these was the London smog disaster that
occurred between 5 and 9 December 1952. Smoke and fog got trapped close to the
ground by colder, denser upper air layers. The air quality deteriorated rapidly and more
 126

than 4000 people died. Old people and people with respiratory diseases were the first
ones to die. Thousands more people became ill. This incident shocked the British
government enough that they passed the Clean Air Act in 1956.

4.1.2 Environmental Impact of Air Pollution

The harmful effects of air pollution on the environment can be divided into the
following 5 categories:

1. Acid rain
2. Smog
3. Hazardous substances in air
4. Ozone depletion of the stratosphere
5. Greenhouse effect.

4.1.2.1 Acid rain

Oxides of sulphur and nitrogen are carried to the ground by three main mechanisms. In
some cases these particles, together with other organic and inorganic compounds, are
carried to the ground in the gaseous form, or as small solid particles. This is called dry
deposition. In other cases these oxides react with water vapour and sunlight and are
converted to strong acids (HNO3 and H2SO4). These acid droplets can be carried to the
earth as snow, raindrops, fog or dew. This process is called wet deposition. Sometimes
sulphur and nitrogen compounds attach themselves to aerosol particles which are
deposited on crops and vegetation. This is called occult deposition. Sulphur and
nitrogen oxides also combine with ammonia, hydrocarbons, chlorines and ozone to form
various harmful substances.

Acid rain or acid deposition can have various negative effects on the environment. The
acidity of the environment with which these acids come into contact will increase. In
some environments a lot of these acid particles can be deposited before the acidity will
be raised significantly. These environments are naturally buffered against an increase in
acidity. In areas that are poorly buffered, the acidity of the soil, surface and ground water
increase dramatically with acid deposition.

If ground water, rivers and lakes experience a significant increase in acidity, the aquatic
life (fish, shellfish and plants, etc.) as well as the birds and animals drinking the water,
will be adversely affected. An increase in acidity can also have an effect on crops and
forests. In highly industrialised countries acid rain causes considerable damage to
buildings and monuments. Acid rain does not always occur close to the source of
pollution. The stacks deposit these nitrogen and sulphur compounds high in the air and
they can be carried many kilometres in air currents. In some cases, pollution that was
generated in one country can cause acid rain in an adjacent country. If these strong acids
land in the water distribution system, heavy metals such as lead, which are toxic to
humans and animals, can be leached out of pipes and storage tanks, and taken in with
drinking water.

4.1.2.2 Smog
The consumption of solid fuels such as wood and coal leads to the emission of small
particles into the atmosphere, which we see as smoke. These particles mix with the water
vapour in the air to form a dense mass called smog. Smog reduces visibility greatly and
 127 CHP311-A/1

also irritates the human respiratory system and eyes. In petrochemical processes the
substances emitted by the process react to form secondary pollutants. These secondary
pollutants are often heavy enough to create a type of smog called brown haze.

4.1.2.3 Hazardous substances in air

In some cases substances that can have a detrimental effect on human health are released
into the air. There can be various sources of these substances such as industrial plants,
mining operations and emissions from automobile engines. Some of these substances
include volatile lead, organics such as benzene, maleic acid and other organic acids,
polycyclic aromatic compounds and heavy metals such as arsenic and mercury. All these
substances are harmful to human health. Mercury causes neurological disorders;
benzene is carcinogenic and so are the heavy metals.

4.1.2.4 Ozone depletion in the stratosphere

The atmosphere is divided into different layers, each with a different function. The layer
of air between 10 km to 50 km from the earth is called the stratosphere. The stratosphere
contains ozone (03) which has the function of screening harmful ultraviolet rays from
the sun. The emission of chlorofluorocarbons (CFC's) into the atmosphere together with
nitrous oxides, is responsible for the depletion of the ozone layer. Various industrial
processes using chlorine, fluorine and CFC's are responsible for these emissions. The
main purpose of CFC's are as heat transfer fluids in fridges, air conditioners and cooling
plants. They are also used in aerosols. Legislation has reduced the use of CFO's greatly
in the past decade in an attempt to reduce the depletion of the ozone layer. UV radiation
from the sun is responsible for, amongst other things, skin cancer in humans.

4.1.2.5 Greenhouse effect

Various gases such as CO2, methane, water vapour, nitrous oxide, CFC's and others are
transparent to short wave radiation but trap radiation with longer wavelengths. The high
energy radiation reaching the earth is short wave, and thus penetrates through these
gases in the atmosphere. Once the energy has been reduced by contact with the earth, the
outgoing radiation has longer wavelengths. The long wave radiation is trapped in the
atmosphere by the gases mentioned above and absorbed by them. The energy is thus not
dissipated but is trapped on the surface of the earth. The lower atmosphere is now
warming. The effects of this can be seen in altered regional and global climates. This in
turn affects agricultural growing patterns. There is also an increase in desertification
(desert formation) and an increase in melting of global ice, resulting in the rise of sea
levels. It has been proved that 75% of the CO2 formed is due to the burning of fossil
fuels and that CO2 is the largest contributor to the greenhouse effect.

4.1.3 Sources of Pollution

There are various natural sources that emit contaminants into the air. These include
smoke and dust particles from forest fires, hydrogen sulphide and methane from
decomposing organic matter, volcanic eruptions, natural gas emissions and various
others. These contaminants, however, are present in concentrations low enough that they
can be dispersed by natural means. Excessive emissions of harmful substances into the
atmosphere have various sources other than the natural ones mentioned.
 128

Mobile transportation, such as motor vehicles, ships, aircraft and trains, is the largest
source of air pollutants. These sources emit various dangerous substances into the
atmosphere, of which the bulk is CO (carbon monoxide). Carbon monoxide results from
the incomplete combustion of fossil fuel. Nitrogen oxides and various hydrocarbons also
form significant parts of emissions from fossil fuels. There has been widespread concern
about heavy metals, such as lead, that are emitted into the atmosphere. These metals
have been released into the atmosphere due to exhaust gas emissions.

The next contributor is fuel combustion from stationary sources. This includes
industrial and residential power and heat generation. South Africa is a particular culprit
in this respect because almost all our power plants use coal as an energy source, and
there are large areas in which people use coal, paraffin, and wood as their energy source.
Stationary sources of combustion accounted for 80% of the sulphur oxides and 51% of
the nitrogen oxides released into the atmosphere in 1980. Apart from these, there are
also emissions of dust and carbon monoxide from these sources.

Industrial processes include the chemical and metallurgical industries, pulp and paper
industries, petroleum refineries and various others. The main type of emission from the
petrochemical side is hydrocarbons, such as hexane, benzene, ethylene, butane,
butadiene, alcohols and CFC's. Industries also emit minor amounts of sulphur dioxide,
dust and carbon monoxide. Particular industries have special emissions that stem from
specialised processes.

Before we look at each pollution type in more detail, let's look at some of the terms used
to define or classify pollutants.

. Primary pollutants: these are substances that exist in the atmosphere in the form in
which they were emitted. Examples are NOX, SOX, CO etc.
. Secondary pollutants: sometimes the primary pollutants undergo chemical reactions
to form other substances. These are called secondary pollutants, because they were
not emitted into the atmosphere directly but were formed from other substances.
These include ozone (O3), sulphuric acid, nitric acid and peroxyacetyl nitrate (PAN).
Secondary pollutants can be formed by reaction with water, oxygen or sunlight
(photochemical reactions).
. Organic compounds: you should have sufficient chemistry knowledge to be able to
identify organic compounds on your own. They are compounds containing carbon
and hydrogen and elements such as oxygen, nitrogen, phosphorous and sulphur.
Organic compounds frequently counted as air pollutants are aldehydes and ketones,
carboxylic acids, alcohols, ethers, esters, amines and organic sulphur compounds.
. Inorganic materials: common inorganic air pollutants are carbon monoxide, carbon
dioxide, carbonates, sulphur oxides, nitrogen oxides, ozone, hydrogen fluoride and
hydrochloric acid.
. Particulate pollutants: these are substances large enough, when the conditions are
suitable, to settle out of the atmosphere and fall to the ground. They include dust,
fumes, smoke, fly ash, mist and spray.
. Gaseous pollutants: these are substances in the gaseous state that will not settle out
unless condensed.

Let us now consider the occurrence and detection of some of these substances in more
detail.
 129 CHP311-A/1

4.1.4 Particulate Pollutants

The size of these particulate pollutants is measured in cËm (10-6m). Typical particle sizes
are between 0.01 and 1000 m. Table 4.1 shows different particulate solids and the size
ranges in which they occur.

One of the most important properties of particulate solids is their settling characteristics.
These substances are divided into suspended particles that will not fall to the ground
(settle) in favourable conditions, and settleable particles that will settle out. There are
two factors that determine whether a particle will settle out or not. The one is the density
of the particle and the other is the size. Particles larger than 20m are usually classified
as settleable and those smaller are suspended, with an area of overlap between 10±
201m.
TABLE 4.1

Particulate solid Size Range

Dust 1.0±10000m
Fly Ash 1.0±1000m
Spray 10±1000m
Mists 0.06±10m
Smoke 0.5±1.0m
Fumes 0.03±0.3m

4.1.4.1 Measurement of settleable particulates

Suspended particulates are determined in a device called a high volume sampler. In
essence this is a filter through which air is blown or sucked. The filter is made out of
glass fibre material. A flow meter measures the air flow in 1/min at the beginning and at
the end of the trial run. A run normally takes 24 hours to complete. The amount
deposited on a filter gives a reading for the total suspended particulates for the sampling
period. The filter can also be used to determine the identity of some of these particles.
Benzene, soluble organics, metals, fluorides, radio active materials and materials such as
sulphate, nitrate and ammonium can be detected. A device called a cascade impactor can
separate the particles into various sizes so that the particle size distribution of these
substances can be determined.

4.1.4.2 Measurement of opacity

Air pollution reduces the visibility of the atmosphere. This is because the light gets
scattered by the presence of particulate matter in the atmosphere. The density of the
particulate matter, the shape and the surface characteristics contribute to the reduction of
visibility. The property measured to quantify the visibility or the reduction thereof is
called the opacity. Opacity is the reduction of the emission of light or the destruction of
the view of an object in the background. Opacity is usually determined with the naked
eye. A trained observer looks at a pollution plume and compares it with either black or
white plumes that have standard values of opacity attached to them.

4.1.4.3 Lead
Special analyses done for lead in air are worth mentioning because of the extreme health
hazards posed by lead. Lead can be in the form of elemental lead, lead oxides, lead
 130

sulphides, lead sulphates and organic lead compounds.* Lead can enter the human body
through inhalation and indigestion. Lead analyses can be done by atomic absorption on
large numbers of samples.

4.1.4.4 Hydrocarbons
Hydrocarbons are present in the atmosphere due to natural emissions, and the following
human related sources:

. Fuel combustion in stationary heating

. Transportation
. Industrial processes
. Solid waste disposal.

Of all the aliphatic hydrocarbons the alkenes are by far the most dangerous group. They
are highly reactive because they are unsaturated (contain double bonds) and are
therefore subject to reaction in the atmosphere. In the presence of sunlight alkenes react
with nitrogen dioxide to form various secondary pollutants, of which peroxyacetyl
nitrate (PAN) and ozone (03) are only two. Damage to certain plants (such as tomato and
pepper plants) has been reported at ethylene exposure of more than 0.01 ppm.

The aromatic hydrocarbons present in the atmosphere are more numerous and slightly
more dangerous than the aliphatic ones. Because the aromatic hydrocarbons all contain a
benzene ring which is a very stable structure, they are not as reactive as the alkenes. The
main health risk posed by aromatic hydrocarbons is the fact that some of them are
carcinogenic. For that reason it is important to keep the levels of these substances as low
as possible.

Hydrocarbons can be analysed by gas chromatography and by flame ionisation

techniques. Both these techniques are expensive and sophisticated and therefore these
analyses are not generally available.

4.1.4.5 Carbon monoxide

Carbon monoxide does not react with substances in the atmosphere. It is relatively inert.
The harmful effects are seen when it is absorbed into the human body. Carbon monoxide
has an extremely high affinity for haemoglobin, a substance found in blood. The
function of haemoglobin is to absorb and carry oxygen. The carbon monoxide reacts
with the haemoglobin to form carboxyhaemoglobin. Each molecule of CO that reacts
with the haemoglobin reduces the blood's ability to absorb and carry oxygen. This is
because the haemoglobin would much rather react with the CO than with oxygen and
this means that even low concentrations of CO will affect humans. Table 4.2 show the
increasing effects in human beings with increased CO absorption. The concentration of
CO in the air is important, as well as the duration of the exposure.

Carbon monoxide can be monitored on a continuous or an intermittent basis. There are

various sampling methods and typical techniques for the analyses done in determining
carbon monoxide include gas chromatography, catalytic conversion and flame ionisation
detection.
 131 CHP311-A/1

TABLE 4.2

% CO EFFECTS
<1 No effects
1±2 Lowered performance
2±5 Central nervous system affected; distorted
time perception; visual distortions;
reduced brightness discrimination
5±10 Cardiac & Pulmonary (lung) functional
changes
10±80 Headaches; fatigue; drowsiness; coma;
respiratory failure; death

Adapted from: Environmental Engineering, Peavy, et al, McGraw-Hi11,1985

4.1.4.6 Sulphur oxides

Sulphur oxides (denoted SOx) are some of the most widely present air pollutants. There
are six main types of sulphur oxides, namely SO, S02, S03, SO4, S203 and S2O7. The
most widely known of these is sulphur dioxide (SO2). Sulphur dioxide is a colourless,
non-flammable and non explosive gas. It is twice as heavy as air, but can be carried very
far in the atmosphere before settling out. It is very reactive with water. If S02 reacts with
water it forms a weak acid called sulphurous acid. Sulphurous acid reacts with organic
dyes. Apart from providing a means for detecting S02, this reaction can cause damage to
clothes, upholstery etc. Sulphur trioxide reacts with water to form droplets of sulphuric
acid. The reactions are as follows:

S02 + H2O ? H2SO3 (Sulphurous acid)

S03 + H2O ? H2SO4 (Sulphuric acid)

Sulphur compounds tend to cause respiratory irritation when inhaled by humans.

Chronic exposure to these compounds leads to the development of bronchitis and
emphysema. The longer the exposure period, the worse or more acute are the effects
experienced. In dusty conditions people are more affected by S02 than in clear weather,
because in dusty conditions there is more strain on the respiratory system. Table 4.3
shows the effects of SO2 exposure on humans.
SO2 can also have adverse effects on vegetation. Vegetation can either be damaged by
short, high concentration exposure, or by exposure to lower concentrations over longer
periods of time. Some of the effects of exposure are dead or brownish red or bleached
white areas on the leaves. Certain plants such as cotton and soy beans are particularly
sensitive to SO2 exposure, while others are more resistant.

If sulphuric acid droplets formed by the reaction of sulphur trioxide with water come
into contact with buildings they react with the calcium carbonate that forms part of most
building materials according to:
CaCO3 + H2SO4 ? CaSO4 + CO2 + H20

Calcium sulphate is soluble in water. This calcium sulphate is now washed away and the
surfaces of the buildings are left looking pitted and discoloured. The sulphuric acid
droplets can also cause the weakening and disintegration of textiles such as cotton, linen,
rayon, nylon and even leather. Paper in contact with these droplets becomes yellow and
brittle and many metals are subject to corrosion when in contact with SO2 and SO3 in
 132

TABLE 4.3

Concentration Exposure Time Effects

(ppm)
0±0.6 Ð No effects
0.15±0.25 1±4 days Cardio. respiratory response
1,0±2,0 3±10 min. Cardio respiratory respopse
1,0±5,0 Ð Uncori;fortable breathing
5 1 hour Choking & increasing lung resistance
to air flow
10 1 hour Impaired breathing, nose bleeding
20 Ð Severe respiratory imitation, digesti-
ve tract and eyes also irritated
400±500 Ð Extremely dangerous, even for short
periods of exposure

Adapted from: Environmental Engineering, Peavy et al, McGraw-Hill, 1985.

wet conditions. The corrosion rates of metals exposed to these gases have been reported
to be 1,5 to 5 times higher than those in cleaner areas. There are various ways used to
detect and analyse for sulphur oxides. Sampling can be done on a continuous or on an
intermittent basis. Analyses can be done by means of spectroscopic, ultraviolet or
infrared analyses, or by means of ultraviolet absorption.

4.1.4.7 Nitrogen oxides

As in the case of sulphur, nitrogen also forms six oxides (NO, NO2, N2O, N2O3, N2O4
and N2O5), of which only 2 (NO and NO2) are of great significance in air pollution.
Nitrogen dioxide (NO2) is heavier than air and will react with water to form either
nitrous acid or nitric oxide according to the following two reactions:

2NO2 + H2O ? HNO2 + HNO3

3NO2 + H2O ? 2HNO3 + NO

Both nitric acid (HNO3) and nitrous acid (HNO2) will fall to the earth as acid rain. Nitric
oxide (NO) released into the atmosphere is oxidised to nitrogen dioxide very rapidly.
Apart from forming acid rain, nitrogen dioxide can also cause irritation to the respiratory
system. People and animals exposed to NO2 levels higher than 3.5 ppm have shown a
reduced resistance to respiratory infections. Nitrogen oxides are also instrumental in the
formation of photochemical smog.
In the analysis for nitric oxide, NO has to be converted to NO2. The nitrogen dioxide is
analysed in various ways, amongst others ultraviolet spectroscopy, electrical transducers
and infrared spectroscopy.

4.1.4.8 Photochemical oxidants

There are various substances that add to the oxidising ability of the oxygen in air. These
include atomic oxygen (0), peroxyacetyl nitrate (PAN) and hydrogen peroxide.
 133 CHP311-A/1

These substances have negative effects on people, plants and animals. In people and
animals respiratory irritations such as coughing, shortness of breath, tightness of the
chest and throat infections are detected, as well as eye irritations and headaches. Plants
show cell changes, as well as spots on the leaves and leaf discoloration. Ozone is a very
strong oxidant that can affect polymers such as paints, rubber and other elasotmers,
textile fibres and dyes.

In monitoring and analysing for these gases, their oxidising ability is employed as a
testing mechanism. A solution of potassium iodide that is buffered with phosphates will
be oxidised to potassium hydroxide and free iodine. The iodine that is released can be
used to determine the oxidising power of the substance tested, or the concentration of
oxidants present. With ozone, the reaction is as follows:

03 +2KI+H2O ? 02+2KOH+I2

There are also other measurement methods available for these oxidants, such as gas
chromatography and infrared spectroscopy.

Example 4.1
A one cubic metre sample of air was found to contain 80 g of SO2. The temperature
and pressure were 258C and 103.193 kPa when the sample was taken. What was the SO2
concentration in ppm (mol wt SO2 = 64.06)?

Answer
For gas samples ppm is a volume-to-volume ratio, unlike water samples, which use
mass-tomass ratios. The conversion is based on the fact that one mol of an ideal gas
occupies 22.414 litres at 08C and 101.325 kPa. Thus we can calculate the actual volume
of pollutant Vp per volume of air Va.
  
298K 101:325kPa
Vp = (mols pollutant)(22.4141/mol)
278K 103:193kPa
    
80  10ÿ6 298K 101:325kPa
= …22:424† = 3.00610-5litres
64:06g 273K 103:193kPa

Vp 3:00  10ÿ5 l…106 †

ppm SO2 =  106 ˆ = 0.0300 ppm SO2.
Va 1m3 …10001=m3 †

Example 4.2
A coal is burned at a rate of 1 kg/s. If the coal analysis measures 3% sulphur, what is the
annual rate of emission of SO2?

Answer
Because the combustion process is not 100% efficient, a ``rule of thumb'' is that 5% of
the sulphur in the fuel ends up in the ash. A sulphur balance gives:

Sin = Sash + SS02

Sin = 1 kg/s 6 0.030 6 86400 s/day 6 365 day/year = 9.46 6 105 kg/year
SS02 = Sin ± Sash = 9.46 6 105 ± (0.05)(9.46 6 105) = 8.99 6 105 kg/year
 134

Since the atomic weight of sulphur is 32 and the molecular weight of SO2 is 64, SO2
emitted = 64/32(8.99 6 105) =1.80 6 106 kg/year.

4.2 NATURAL PURIFICATION PROCESSES

In some cases unwanted emissions can be dispersed by natural processes. The converse
is also true. Often the conditions in a certain area are such that they promote dangerous
situations with high concentrations of unwanted substances in the air. The properties in
the atmosphere that will determine the dispersion (or not) are called meteorological
properties. These properties also determine local and global weather patterns. There are
four main meteorological phenomena namely heat, pressure, wind and moisture. It is
important for an environmental engineer to understand these meteorological phenomena
and the influence these can have on pollution occurrences. We are going to discuss each
of these in a little more detail so that the natural means by which the air is purified can
become clear.

Before we start discussing these phenomena individually, let's first describe how the
movement of these take place on a global, regional and local scale. There are various
factors that describe the movement of air in the atmosphere. The movement of air has an
influence on the occurrence of the meteorological phenomena. The different factors that
influence the movement of air in the atmosphere determine the scale on which the
movement takes place. Air movements on the macro scale are determined by global
movement of air over the planet, and are mainly dictated by air movement due to
temperature changes. The sun warms the air around the equator more than the air at the
poles (because of the angle at which the sun's rays hit each area respectively). This
causes the warmer air, which has a lower density, to rise over the equator. Cooler air
from the poles moves in to take its place. This causes two main circulation patterns to
form over the globe; one in the northern and one in the southern hemisphere.

The second factor that influences the movement of air over the globe is the movement
of the earth. The rotation of the earth has the effect of deflecting the air to the right in
the northern hemisphere and to the left in the southern hemisphere. These deflections,
together with the two temperature cells described before, divide the global air movement
into three cells for each hemisphere. The effect that the rotation of the earth has on the
global air movement is called the Coriolis force. The Coriolis force and the temperature
cells combined are responsible for the formation of global high and low pressure areas,
cold and hot fronts, hurricanes and storms.

The third factor that influences global patterns on a macro scale is sea and land masses.
Land masses (such as continents) are better conductors of heat than water masses. Land
masses will therefore warm under the sun during the day and cool during the night.
Water masses will take longer to absorb heat and become warmer, but because the heat
can penetrate deeper into water than into land masses, they will take longer to lose this
heat and cool off. All this will lead to temperature gradients existing between the air over
the land masses and the air over the water masses, and this will cause smaller convection
cells.

Air movement on an intermediate scale is determined by changes in the geographical

configuration on a smaller scale (of the order of 100 km). Air movement on this scale is
influenced by oceans, mountain ranges, urban development and forests. Land and sea
breezes can be attributed to these geographical phenomena, as well as smaller high and
low pressure fronts and hot areas developing over urbanised areas.
 135 CHP311-A/1

In the 10 km range the air movement patterns can be affected by stacks and heated areas
in factories, or turbulence caused by high buildings. Let us now discuss the different
meteorological phenomena separately.

4.2.1 Heat
without becoming too theoretical, let's consider the effect that heat can have on the
amount and presence of unwanted substances in the atmosphere. The density of air (and
other gases) changes as temperature changes. As we have said before, air of a lower
density tends to rise when surrounded with air at a higher density. As this air rises it
cools. At the point where the temperature and the density of this air is the same as that of
the surrounding air the air pocket will stop rising and stabilise in the surroundings.
Normally, gases emitted from stacks, exhaust pipes of cars and fires are hotter than the
surroundings, and thus lighter. The gases will rise and exchange heat with the
surrounding air until the temperature is roughly the same as that of the ambient air. Then
the gases will stabilise in the atmosphere. There are, however, cases where the
temperature of the air increases with increasing altitude. This phenomenon is called
inversion.

There are two main types of inversion that occur under different circumstances. The first
type is called radiation inversion. This usually happens at the end of the day when the
earth cools down faster than the air above it. This inversion is normally not more than a
few hundred metres above the earth. The second type, called subsidence inversion,
occurs in a high pressure air system. In an area of high pressure, hot air is sometimes
forced downwards and this can also cause temperature inversions.

4.2.2 Pressure
The presence of air results in the presence of air pressure. We report average air pressure
as the atmospheric pressure. There are also various changes in air pressure on a smaller
scale, resulting in slightly lower and slightly higher pressures in some places. These
pressure changes can occur because of different ground structures, mountains, forests,
radiation, temperature changes and wind energy. These high and low pressure systems
are responsible for many weather changes. Let's see what effects a high pressure system
and a low pressure system respectively have on the atmospheric conditions.

The high pressure systems in the air are of a fairly uniform quality. The temperature,
pressure and humidity vary little for large areas. Weather changes, if any, take place
gradually. In such systems pollutants that are released into the atmosphere will not be
dispersed, but they will build up in the areas where they are released.

In a low pressure system one is likely to find cloudy skies, erratic winds and fluctuating
areas of pressure. These low pressure systems are associated with turbulence and
instability and pollutants will be dispersed and diluted into the ambient area.

4.2.3 Wind
Wind, being moving air, arises from factors such as temperature changes, density
changes and topographical and other structural phenomena such as mountains, valleys,
high buildings and streets in between them.

Wind is responsible for the dispersion and transport of pollutants. The rate at which air
pollutants will spread or disperse depends on the presence and speed of the wind.
 136

4.2.4 Moisture
The moisture present in the atmosphere has quite a significant effect on the air quality.
Water vapour scatters or absorbs radiation energy from the sun and determines how
much energy leaves and reaches the earth. If water precipitates in the atmosphere and
falls to earth as rain, it can clean the air because it removes harmful substances. The
disadvantage is that these substances are now carried to the earth, sometimes, as in the
case of acid rain, in a more harmful form than originally emitted.

4.2.5 Dispersion Modelling

A dispersion model is a mathematical description of the natural purification processes
that have been described. It is used to predict concentrations of a pollutant at specific
locations and times. One such model was developed by Briggs to estimate the rise of
bent-over buoyant plumes and is illustrated in fig. 4.1. This is just the first step in
modelling pollutant dispersal ± such problems are typically solved on powerful
computers.
LOGIC DIAGRAM FOR USING BRIGGS' EQUATIONS TO CALCULATE
BUOYANT PLUME RISE
START

!
No Yes
Is F  55?

! !
0.625
Xf = 49 (F) Xf = 119 (F)0.40

!
No Yes
Is stability E or F?
!
Yes 1/2
Is 1.84 us  Xf ?

No ! ! Yes Yes !

Is x < xf ? Is x < 1.84 us1/2 ?

! ! ! !
1/3 2/3 -1 1/3 2/3 -1

h = 1.6 (F) (xf) (u)
h = 1.6 (F) (x) (u)
h = 2.4 (F/us)1/3

h = plume rise, m
F = buoyancy factor, m4/sec3
x = downwind distance form source, m
xf = downwind distance from source to point of maximum plume rise, m
u = windspeed at actual stack height, m/sec
s = stability parameter, sec-2
 137 CHP311-A/1

Fig. 4.1.

In the above equations:

 
2
T
T
F = gvd and s ˆ g z
Ta
4Ts
d = stack diameter, m

v = stack gas exit velocity, m/s

T ˆ Ts ÿ Ta , where Ts = stack gas temperature and Ta Ta is ambient temperature,

K
T
The temperature gradient gives a measure of atmospheric stability. Atmospheric
z
stability can be classified from A (least stable) to F (most stable) depending on wind
T
speed, solar radiation and cloud cover. As a default approximation, = 0.020 (class E)
z
and 0.035 (class F).

Example 4.3
Estimate the rise of a plume under unstable (class F) conditions from a 4 m diameter
stack at a distance of 1 km downwind. The ambient temperature and wind speed are
258C and 2 m/s, the temperature and exit velocity of the stack gas are 1508C and 20 m/s
respectively.

Answer
 
125
f ˆ …9:81†…20†…42 † ˆ 329m4 =s3
…4†…298†
xf ˆ 49…329†0:625 ˆ 1834m
 
0:035
2 ˆ 9:81 ˆ 1:15  10ÿ3 sÿ2
298

1 1
1.84 u sÿ2 = (1.84)(2)(1.15 6 10-3)ÿ2 =108

According to the log is diagram

 13  13
F 329

h ˆ 2:4 ˆ 2:4 ˆ 126m
us …2†…1:15  10ÿ3 †

4.3 SYSTEMS FOR AIR POLLUTION CONTROL

We have seen in the previous section that the atmosphere has a limited capacity to get rid
of unwanted substances. They can be removed by falling to the ground, being dispersed
by the wind, being diluted by mixing with clean air and raining out with the moisture in
the atmosphere. These mechanisms are, however, not enough to deal with the vast
amounts of unwanted substances that are emitted into the atmosphere on a daily basis.
Ways have to be found to rid the atmosphere of these substances in order to avoid and
minimise air pollution incidents and the subsequent deterioration of the quality of life
due to a deteriorating air quality.
 138

The best solution is, of course, to ensure that as few pollutants as possible escape into
the atmosphere in the first place. This can be done by cleaning emissions from pollution
sources before they are emitted into the atmosphere. Often, especially in the case of
emissions from industry, certain changes can be made to the design of the process and
this can reduce the formation and emission of harmful substances. Filters containing a
platinum catalyst have been fitted to automobile exhaust systems to eliminate the
emission of some harmful substances.

Even with measures being taken to reduce the amount of emissions to the atmosphere
there will still be some pollutants present. Cleaning systems may not be effective, or
accidents can cause occasional high emission levels. Underdeveloped areas will still use
fossil fuel as an energy source for quite a few years. Therefore, an attempt should also be
made to clean the atmosphere to rid it of unwelcome contaminants.

4.3.1 Dilution
Dilution is the only effective way to disperse harmful substances once they have been
emitted into the atmosphere. This is done by building high stacks and releasing the
substances very high (> 150m) into the atmosphere. By doing this the harmful
substances are diluted to tolerable concentrations. Because they are carried so high into
the air they will be moved a considerable distance before they fall to the ground.

It is not hard to see that diluting harmful substances does not eliminate them. They are
just reduced to tolerable quantities and spread over a wider area. One of the problems
arising from this is that neighbouring countries can be polluted.

The method of dilution should only be used in extreme cases. Substances emitted into
the atmosphere must eventually come down and putting all the harmful substances into
the air will only prolong the harmful effects.

4.4 CONTROL DEVICES FOR GASEOUS AND PARTICULATE CONTAMI-

NANTS
The following section is going to discuss all the unit operations that can be used by
industries to reduce the amounts of gaseous and particulate pollutants released into the
atmosphere. The removal of any substance makes use of some appropriate physical
property of that substance. It is rarely possible to remove gaseous and particulate
contaminants at the same time. Figure 4.2 shows an overview of all the purification
processes we are going to discuss.

4.4.1 Gravitational Settling

Settling of dust particles in a gas stream is done by the same principles as the settling of
solid particles in a liquid stream, such as discussed in the water treatment module. The
essence of this procedure is that the velocity of the air has to be reduced to a point where
the turbulence in the air is too low to support suspended particles and the particles will
then settle out. There are two main types of settling chamber that are used for gases, the
plain gravitational settling chamber and the baffled gravitational chamber. Figure 4.3
show the plain gravity settling chamber. These chambers are nothing more than enlarged
sections in a pipe. The dirty gas enters the chamber at the one end and as the air stream
reaches the larger area the linear velocity is reduced to maintain the same mass flow rate.
The dust particles settle out to the base of this enlargement and are collected in conical
 139 CHP311-A/1

Air Pollution

Particulate Gaseous
Substances Contaminants

Cleaning Operations Cleaning Operations

. Gravitational . Adsorption
Settling . Absorption
. Centrifiugal . Condensation
Collection . Combustion
. Filtering
. Electrostatic
Precipitation

FIGURE 4.2: Air pollutant purification processes

sections, called dust hoppers. The gas leaving the enlargement is free of most of the
solid particles. It is very important that the air velocity in these chambers is fairly low, of
the order of 0.5 to 2 m/s.

FIGURE 4.3: Gravity settling chamber

In figure 4.4 you can see a baffled gravity settling chamber. These chambers operate on
the same principle as the plain gravitational settling chamber, but they are equipped with
horizontal baffles. These baffles are normally spaced about 2.5 cm apart. They shorten
the distance the dust particles have to fall in order to settle and thus make it easier for
them to settle. These chambers are normally more efficient than the plain chambers.
 140

FIGURE 4.4: Baffled gravity settling chamber

The advantage of settling chambers is that they are simple to design, commission and
operate. The main disadvantage of these chambers, however, is the fact that they take up
a lot of space. In order to reduce the air velocity sufficiently they have to be made very
large. The efficiency of these chambers is also often much lower than estimated. In
theory these chambers should be able to remove particles as small as 5 microns, but 50
microns is the realistic cut off point.

4.4.2 Centrifugal Collectors

In the case of centrifugal collectors, centrifugal force is used to remove particles from an
air stream instead of the force of gravity. The benefit of these systems is the fact that
centrifugal force is able to remove particles much smaller than those that can be
removed by gravity, and they therefore have higher efficiencies.

A front and a top view of a cyclone are shown in Coulson and Richardson, Volume II on
page 347. On page 348 you will find a photograph of a cyclone separator. The dirty air is
fed into the top of the cylindrical section tangentially. The gas has momentum and
continues to spin around the walls of the cyclone. Because the dust particles have a
higher density than the gas, they are flung to the sides of the cyclone. They slide down
the walls of the cylindrical section into the hopper. The clean air forms a spiral and
leaves the cyclone at the top. The efficiency of the cyclone depends on the size of the
centrifugal force. This centrifugal force can be increased by increasing the radius of the
cyclone. Cyclones are effective in removing particles down to 5 microns. It is sometimes
necessary to use more than one cyclone in series. Cyclones, as in the case of gravity
chambers, are simple to use and maintain and they can handle large throughputs. They
can also operate at elevated temperatures (up to 10008C).

Dynamic precipitators are the second type of centrifugal collectors. They are small units
that are equipped with rotating blades that induce the centrifugal force. The centrifugal
force of these precipitators is normally about seven times higher than the centrifugal
force of a cyclone that can handle the same capacity of gas. These units are effective in
many industries but they cannot be used in cases where the gases are wet, or contain
fibres, or contain acid drops which are corrosive.
 141 CHP311-A/1

4.4.3 Wet collectors

Wet collectors are machines that contact dirty air with water droplets in some
configuration. The water then washes the dust particles from the air stream. There are
various types of wet collectors; some are better suited to the removal of gaseous
pollutants and will be discussed later. The types best suited for the removal of particulate
solids are the spray tower, the wet cyclone scrubber, and the venturi scrubber. All
three of these devices produce dirty water as a by product. This water has to be cleaned
before it is disposed of. In the cost calculations, the cost of cleaning the waste water also
has to be incorporated.

FIGURE 4.5: Schematic representation of a spray tower

Figure 4.5 show a representation of a spray tower. Spray towers are cheap and they can
handle very large capacities. The gas enters the tower at the base and moves upwards.
As the gas moves upwards in the tower it comes into contact with water droplets from
spray nozzles installed at regular heights in the tower. The clean gas leaves the tower at
the top and the dirty water drains from the bottom. These spray towers can remove
particles as small as 10 microns.

In wet cyclone scrubbers the air is fed to the bottom of the scrubber tangentially to
generate a centrifugal force. Nozzles situated inside the scrubber dispersed fine water
droplets under high pressure into the chamber. These water droplets remove the dust
particles from the air stream and fling them against the sides of the scrubber. The dust
mixed with the water flows down the sides of the scrubber and drains at the base, while
the cleaned air stream leaves at the top of the scrubber. Particles as small as 5 microns
can be removed. The efficiency of the tower depends on the liquid flow rate, the dust
particle size and the water droplet size. For particles of the order of 100 microns, almost
a hundred percent efficiency can be achieved.

For small particles in the range of 0.5 to 5 micron, the most effective means of removal
is the venturi scrubber. These scrubbers are often used in cleaning smoke. The gas
enters this scrubber in the venturi, a section that first increases and then decreases the gas
velocity.
 142

There the fast moving gas stream is contacted with very small (atomised) water droplets
that are emitted from a spray nozzle. The dust and smoke particles are absorbed into the
water. As the water reaches the section of larger diameter the flow velocity decreases
and the water droplets settle out. The gas now flows through a liquid entrainment
separator, a cylindrical section that facilitates disengagement (separation) between the
last of the water droplets and the gas. The cleaned gas leave the top of the scrubber and
the water is discharged at the base for recycling and dumping. These venturi scrubbers
have a high efficiency, but also a high cost. A schematic representation of a venturi
scrubber is shown in figure 8.21 in Chemical Engineering, Volume 2.

4.4.4 Filters
Fabric filters or bag filters are one of the most efficient and popular methods used to
remove particulate substances from air streams. These filters were initially used by the
mining industry, but are widely employed in pollution control by numerous industries.
Air filters can vary in size from quite small (the size of a small room) to huge (the size of
a building). The filters contain bags that can be tubular or envelope shaped, and these
bags can range from 1.8 m to 9 m in length. The filter cloth is made up of woven or
felted material. It is important that the material should be resistant against heat, that it
should be relatively resistant against chemicals, and that it should be strong.

Fabric filters include all types of bag filters in which the filter medium is in the form of
woven or felted textile fabric which may be arranged as a tube or supported on a suitable
framework. This type of filter is capable of removing particles of a size down to 1 cËm or
less by the use of glass fibre paper or pads. In normal fabric filters, particles smaller than
the apertures in the fabric will be trapped by impingement on the fine ``hairs'' which
often span the apertures, the main strands of the material may have a diameter of 500
m, spaced 100±200 m apart. The individual textile fibres with a diameter of 5±10 m
criss-cross the aperture and form effective impingement targets capable of removing
particles of size down to 1 m.

In the course of operation, filtration efficiency will be low until a loose ``floc'' builds up
on the fabric surface and it is this which provides the effective filter for the removal of
fine particles. The cloth will require cleaning from time to time to avoid excessive build-
up of solids which gives rise to a high pressure drop. The velocity at which the gases
pass through the filter must be kept low, typically 0.005 to 0.03 m/s, in order to avoid
compaction of the floc and consequently high pressure drops, or to avoid local
breakdown of the filter bed which would allow large particles to bypass the filter.

There are three main types of bag filter. The simplest, which is shown in Fig 8.11 in
Chemical Engineering Volume 2, consists of a number of elements assembled together
in a ``bag-house''. This is the cheapest type of unit and operates with a velocity of about
0.01m/s across the bag surface.

A more sophisticated and robust version incorporates some form of automatic bag-
shaking mechanism which may be operated by mechanical, vibratory or air-pulsed
methods. A heavier fabric allows higher face velocities, up to 0.02m/s, to be used and
permits operation under more difficult conditions than the simpler bag type can handle.

The third type of bag filter is the reverse-jet, illustrated in Figs. 8.12 and 8.13 in
Chemical Engineering, Volume 2. With face velocities of about 0.05m/s and with the
capability of dealing with high dust concentrations at high efficiencies, this type of filter
can deal with difficult mixtures in an economic and compact unit. Use of the blow ring
enables the cake to be dislodged in a cleaning cycle which takes only a few seconds.
 143 CHP311-A/1

Natural fibres such as cotton and wool, and some artificial fibres that are manufactured
to have certain properties, are normally used for the manufacturing of filter cloths. As
the dust and gas pass through this material the dust gets trapped. As with all filtering
operations, the initial filtering is done by the cloth alone. Then as soon as there is some
dust that is deposited on the cloth the dust itself also helps to filter out the next layer of
dust. This process increases the efficiency of the filter greatly, because now particles are
removed from the air stream that are much smaller than the openings in the filter cloth.
Filtering can remove particles as small as 0.1 microns from an air stream.

Filters can also operate over a large amount of dust concentrations, from as low as
0.0001 grams per cubic meter to as high as 1000 grams per cubic meter. Envelope gas
filters are placed next to each other. The gas stream passes over these filters and the dust
is collected on the outside of the envelopes. The clean air penetrates to the inside of the
envelope and leaves the system. These filters are cleaned by shaking them so that the
dust falls off, or by passing air through them in the opposite direction. The dust falls to
the ground or the floor of the chamber and is collected there.

In the case of tubular filters, the filter bags are placed in a chamber with the closed ends
up and the open ends facing the floor. The gas enters the filter at the bottom and passes
upwards through the filter bags. Dust collects in the filter bags and the clean air leaves
the chamber somewhere near the top. These bags have to be cleaned at regular intervals
to prevent the pressure drop rising too high and the efficiency of the filtering operation
from decreasing. The cleaning can be done on a batch scale, where the entire filter
chamber is taken off-line and all the bags are cleaned out by shaking or by reverse air
flow, or the cleaning can be done while the filters are still on line. This is done in two
ways. In the first case some of the bags are taken off line and cleaned while the rest are
still in operation and in the second case one filter bag is cleaned at a time on a
continuous basis. It is preferable to clean these bags on a continuous basis rather than
batchwise, because the smoothness of operation is less affected this way. Figure 4.6
show a tubular filter baghouse.

FIGURE 4.6: A tubular filter baghouse

4.4.5 Electrostatic Precipitators

Figure 4.7 illustrates the principle of operation of an electrostatic precipitator. The air
stream containing the dust particles passes through the first stage, which is an ioniser.
The air stream is passed through a high voltage direct current ionised air section. The air
particles are ionised (positively charged) and they adhere to the dust particles. Then the
 144

air stream passes over a section of collector plates. These plates have alternative charges,
and each plate is grounded to relay any charge that might be imparted to it. The positive
particles are attracted to the negative plates electrostatically and as they reach the plates
the charge is neutralised. The particles now need to be removed from the plates. They
can flow off to the bottom under the influence of gravity, or they can be scraped from the
surfaces of the collector plates. Electrostatic precipitators generally require a lot of
space. They can handle large volumes of gas, up to 1000 m3/s and have low
maintenance requirements. Figure 8.14 in Chemical Engineering Volume 2, shows a
sketch of an electrostatic precipitator.

Electrostatic precipitators are capable of collecting very fine particles, < 2 m, at high
efficiencies. However, their capital and operating costs are high, and electrostatic
precipitation should only be considered in place of alternative processes, such as
filtration, where the gases are hot or corrosive. Electrostatic precipitators are used
extensively in the metallurgical, cement and electrical power industries. Their main
application is probably in the removal of the fine fly ash formed in the combustion of
pulverised coal by power-station boilers.

FIGURE 4.7: The electrostatic precipitation process

4.4.6 Adsorption
Adsorption is a process by which gas molecules adhere themselves to the surface of an
adsorbent material. It is mainly used for the removal of gaseous particles. An adsorbent
material is usually a porous solid material that will have a high surface to volume ratio.
The most common adsorbent is activated carbon. Activated carbon is manufactured by
burning wood, fruit pits or coconut shells and treating them with steam afterwards. The
steam removes part of the surface and a substance is left that is very porous, so it has a
high surface area and is therefore suitable for adsorption. Activated carbon is used
extensively in odour elimination, gas purification and solvent recovery from gas
streams. When using activated carbon it is important to make sure that the temperature
does not go too high. If this is the case the carbon might be oxidised to form CO and
CO2, substances one ideally wants to remove, not emit into the atmosphere. Other
adsorbents are alumina (aluminium oxide), bauxite, bone char, Fuller's Earth, magnesia
and molecular sieves. Each of these devices is suitable for the removal of specific
substances.
 145 CHP311-A/1

There are two main mechanisms by which adsorption takes place. The first one is
physical adsorption. In the case of physical adsorption gases adhere to the surface of the
adsorbent at temperatures above the condensation temperature. They are attracted to the
surface of the adsorbent by van der Waals forces. The conditions such as temperature
and pressure have an influence on the amount of gas adsorbed on the surface of the
adsorbent, so the gas can also be desorbed quite easily by just changing the temperature
and the pressure. It is quite possible that more than one layer of gas can be adsorbed to
the surface of the adsorbent before desorption needs to take place.

In the case of chemical adsorption, the gas molecule forms a chemical bond with the
adsorbent material. This process is much slower than physical adsorption because a
chemical reaction takes place. Because a molecule of the adsorbent material needs to be
replaced for every gas molecule that adsorbs to the adsorbent chemically, only one layer
of gas molecules can be adsorbed in the case of chemical adsorption. It is also not
possible to regenerate the adsorbent. The amount of gas that is adsorbed in the chemical
adsorption process also depends on temperature and pressure.

There are various types of adsorption equipment, but only three main categories. The
categories are divided according to the characteristics of the bed of adsorbent material.
They are:

. Fixed bed adsorbers

. Moving bed adsorbers
. Fluidised bed adsorbers

A typical fixed bed adsorber is shown in figure 4.8. These adsorbers can be horizontal or
vertical shells that contain trays filled with the adsorbent material. Provision has to be
made for steam lines in these adsorbers, in order to clean them.
!
Steam out (cleaning)

Dirty gas in Clean gas out

!

!
Trays
!

containing
! adsorbent
Steam cleaning line material

FIGURE 4.8: A horizontal fixed bed adsorber

In the case of moving bed adsorbers the air moves over a layer of adsorbent material that
is placed in an annular section in a revolving drum. The dirty air enters at the base of this
annular section and passes through the revolving bed of adsorbent into the inside section
of the drum. The cleaned air is then discharged from the inside of the drum. These
adsorbers sometimes have provision for cleaning and filtering of the air. The side section
of the annulus is equipped with a steam inlet line, while the inside is equipped with a
steam outlet line for the cleaning or regeneration of the adsorbent material. Figure 4.9
shows a side view of such a moving bed adsorber.
 146

Rotating bed of

!
Steam in adsorbent

!
Steam out

!
Air out

!
! !

Air in

!
!
!
FIGURE 4.9: A moving bed adsorber

In the case of fluidised beds, the adsorption tower is filled with the adsorbent material up
to a certain level. Then, once the gas is fed through, the gas flow rate is regulated such
that the bed of adsorbent material is fluidised. This means that the particles are lifted
from each other in the gas stream so that they do not touch each other. This improves the
contact area between the adsorbent material and the gas greatly. Figure 4.10 Show a
fluidised bed in the unfluidised and fluidised states. The gas velocity must not be so high
as to blow the adsorbent through the outlet.

These fluidised beds can be regenerated by passing steam or heated air through the bed.

FIGURE 4.10: Fluidised adsorption tower

4.4.7 Absorption
In the case of absorption the gas is contacted with a liquid and the liquid removes or
treats the harmful substances in the gas stream. As in the case of adsorbents there are
also chemical and physical absorbents, one which takes part in a chemical reaction with
the liquid and the other not. In physical absorption, the gas is taken up in the water by a
simple solution process and in chemical absorption the gas takes part in a chemical
reaction with the solvent. The amount of gas that will react with or dissolve in a certain
solution depends on the following factors:
 147 CHP311-A/1

. The properties of the gas and the liquid such as the polarity, etc.
. The pressure of the gas in contact with the solution
. The temperature of the system
. The degree of mixing or contact, which is related to the turbulence of the system.

There are various solvents used for the removal of different gases. Water is often used,
as well as ethanol, benzene and acetone. Care should be taken when using acetone and
benzene; these materials are highly flammable. Benzene can also be a health hazard.
Gases that are often removed by means of the above solvents are nitrogen oxides and
carbon dioxide. Other solvents used in the removal of, amongst others, CO2 gas, are
solutions of sodium, ammonia, calcium and magnesium in water. Solutions of calcium
are also used to remove combinations of nitrogen and sodium oxides. Some of the
lighter hydrocarbons such as acetic acid, chloroform, formic acid, amines and ketones
are also removed by absorption. The absorption apparatus needs to distribute the solvent
in such a way that the maximum contact area exists between the liquid and the gas. The
removal rate of gas is related to the rate of diffusion of the gas into the liquid.

Absorption is carried out in absorption towers, and there are three main design types of
absorption towers, namely:

. Spray towers
. Packed towers
. Plate towers.

Spray towers are well suited to large volume gas streams with low concentrations of
contaminants. The pressure drop over spray towers is relatively low. The absorption
efficiency in spray towers is determined by the amount of turbulence in the tower and by
the droplet size. Small droplets can be produced by high pressure nozzles. The increased
efficiency obtained by the decreased droplet size must be weighed against the increased
cost of producing high pressure droplets. Spray towers tends to have a lower efficiency
than the other absorber types, but they are cheaper to install and to operate.

Plate towers contain perforated plates at even spacings along the tower. Depending on
the height and the diameter of the tower, the plates are spaced 0.3m to 0.9 m apart. The
solvent enters at the top of the tower and flows over the plates. The plates have the
function of distributing the solvent evenly. The solvent falls from one plate to the next
one in a downward movement. The dirty gas enters the tower at the base and moves
upward through perforations in the plates. In doing so the gas bubbles through the liquid
that is held up on the plates. As the gas moves up through the plates, more and more of
the unwanted substances are removed from the gas stream and are absorbed into the
liquid stream. These towers can also be used to remove particulate solids from effluent
gases.

In the case of packed towers, manufactured packing types are often used. These
packing materials have been manufactured to provide a large contact area between the
liquid and the gas. These packing materials should also be light and strong. Typical
packing materials can be seen in figure 11.37 in Chemical Engineering, Volume 6, on
page 544. Figure 4.11 shows the flow arrangement of a packed column. The solvent
enters at the top and is sprayed onto the packing to facilitate even distribution and a large
contact area between the liquid and the gas. The gas moves upwards countercurrently
and the absorption takes place in the packed section.
 148

4.4.7.1 Types of packing

The principal requirements of a packing are that it should:

. Provide a large surface area: a high interfacial area between the gas and liquid.
. Have an open structure: low resistance to gas flow.
. Promote uniform liquid distribution on the packing surface.
. Promote uniform vapour gas flow across the column cross-section.

Many diverse types and shapes of packing have been developed to satisfy these
requirements. They can be divided into two broad classes:

1. Packings with a regular geometry, such as stacked rings, grids and proprietary
structured packings.
2. Random packings such as rings, saddles and proprietary shapes which are dumped
into the column and take up a random arrangement.

Grids have an open structure and are used for high gas rates, where low pressure drop is
essential; for example, in cooling towers. Random packings and structured packing
elements are more commonly used in the process industries.

4.4.7.2 Choice of plates or packing

The choice between a plate or packed column for a particular application can only be
made with complete assurance by costing each design. However, this will not always be
worthwhile, or necessary, and the choice can usually be made on the basis of experience
by considering the main advantages and disadvantages of each type, which are listed
below:

1. Plate columns can be designed to handle a wider range of liquid and gas flow-rates.
2. Packed columns are not suitable for very low liquid rates.
3. The efficiency of a plate can be predicted with more certainty than the equivalent
term for packing (HETP or HTU).
4. Plate columns can be designed with more assurance than packed columns. There is
always some doubt that good liquid distribution can be maintained throughout a
packed column under all operating conditions, particularly in large columns.
5. It is easier to make provision for cooling in a plate column; coils can be installed
on the plates.
6. It is easier to make provision for the withdrawal of side-streams from plate
columns.
7. If the liquid causes fouling or contains solids, it is easier to make provision for
cleaning in a plate column. With small-diameter columns it may be cheaper to use
packing and replace the packing when it becomes fouled.
8. For corrosive liquids a packed column will usually be cheaper than the equivalent
plate column.
9. The liquid hold-up is appreciably lower in a packed column than a plate column.
This can be important when the inventory of toxic or flammable liquids needs to be
kept as small as possible for safety reasons.
10. Packed columns are more suitable for handling foaming systems.
11. The pressure drop per equilibrium stage (HETP) can be lower for packing than
plates, and packing should be considered for vacuum columns.
12. Packing should always be considered for small diameter columns, say less than
0.6m, where plates would be difficult to install, and expensive.
 149 CHP311-A/1

4.4.8 Condensation
Unwanted components can be removed from a gas stream by condensation. This can be
done by reducing the temperature of the gas stream or by increasing the pressure. Since
it is expensive to increase the pressure, the temperature reduction route is normally
followed. The temperature of the gas mixture is decreased until the vapour pressure of
the unwanted gas is less than its partial pressure. The two main condenser types are
contact condensers and surface condensers.

Surface condensers operate according to the same principles as shell and tube heat
exchangers. The cooling medium flows in the tubes and the gas runs through the shell.
The contaminant gas is adsorbed onto the outside surface of the tubes and then runs
down to the bottom of the shell where it is drained.

In the case of a contact condenser there is contact between the dirty gas and the cooling
medium. The gas flows upward in a spray tower type apparatus and is contacted with the
cooling medium that is sprayed downwards from the top. The unwanted components in
the gas condense and fall to the bottom of the condenser where they are drained.

FIGURE 4.11: Packed absorption tower for air pollution control

4.4.9 Combustion
Up to this point we have discussed combustion only as a culprit in producing harmful
substances that are released into the atmosphere. Combustion can, however, also be
employed as a mechanism to rid air of unwanted substances. This is a process
specifically applied to remove hydrocarbons from effluent gas streams. If hydrocarbons
are combusted, they form carbon dioxide and water vapour, and although carbon dioxide
in excess quantities is also an unwelcome pollutant, it is less harmful than more complex
hydrocarbons. In combusting gases, care should be taken to ensure that proper
combustion takes place. Incomplete combustion will lead to the emission of harmful
substances into the atmosphere and defeat the purpose of the combustion process.

The complete combustion of gases is dependent upon a sufficient supply of oxygen to

the combustion chamber.

Other factors important to the combustion process are turbulence and temperature. The
temperature of the reaction must be high enough to ensure that sufficient heat is present
for proper combustion. An adequate amount of turbulence is needed to ensure that
proper mixing takes place between the oxygen (or air) and the gas to be combusted.
 150

There are three different types of combustion equipment, namely:

. direct flame combustion equipment

. thermal combustion equipment
. catalytic combustion equipment.

Direct flame combustion takes place in chambers where the effluent gases themselves
are ignited and burned to form CO2 and water vapour. Depending on the nature of the
gases, a little fuel and air is sometimes added. In cases where there is enough oxygen in
the air stream there is no need for the addition of air. Petrochemical industries often
make use of this method of cleaning the effluent gas. The effluent gas is exhausted into
the air and ignited at the top of stacks (high chimneys).
In the case of thermal combustion the effluent gas is not ignited itself, but is combusted
in the hot air exhaust stream of a gas burner. The temperature of the gas stream is usually
lower than in the case of direct flame combustion and in some cases the gas is pre-
heated. If the concentration of the gas is low, fuel can once again be added to ensure
proper combustion. The combustion temperatures in these systems are in the region of
10008C.
In the case of catalytic combustion the dirty gas, air and fuel are fed into a combustion
chamber and ignited. A catalyst is placed inside the combustion chamber. The function
of the catalyst is to increase the combustion rate. The catalyst itself does not undergo any
reaction. Most common air pollutants can be removed by means of catalytic combustion.
Problems experienced with this combustion process are the poisoning of the catalyst
(substances adsorbed by the catalyst that cannot be removed and that inhibit the function
of the catalyst) and the inability of these systems to handle large capacities.

BIBLIOGRAPHY
Environmental Engineering, Peavy, H.S., Rowe, D.R., & Tchobanoglous, G., McGraw-
Hill International, 1985.
Pollution Engineering Practice Handbook, Cheremisinoff, P.N., Young, R.A., Ann
Arbor Science, 1981.
Coulson & Richardson's Chemical Engineering, Volume II, Pergamon Press, 1985.

Introduction to Environmental Engineering, 2nd Edition, Davis & Cornwell, McGraw-

Hill, 1991.
 151 CHP311-A/1

REVISION QUESTIONS
1. List five of the harmful consequences of air pollution.
2. Explain how acid rain is formed.
3. Name six hazardous substances in air pollution.
4. At what distance from earth is the so-called ``ozone layer''?
5. Which gas is the main contributor to the ``greenhouse effect''?
6. Explain the difference between primary and secondary pollutants.
7. List three natural and three man-made sources of pollution.
8. Explain how you would measure the concentration of particulates in air.
9. Above what concentration is carbon monoxide considered dangerous?
10. Above what concentration does sulphur dioxide cause breathing discomfort?
11. How many oxides can nitrogen form?
12. Name three factors that affect global air movements.
13. Discuss the relative stability of low and high pressure systems.
14. List four unit operations used to control gaseous pollution.
15. List four unit operations used to control particulate pollution.
1.6. Describe the principle of operation of electrostatic precipitators.
17. Distinguish between absorption and adsorption processes for pollution control.
18. What is the advantage of catalytic combustion over thermal combustion
equipment.
 152

CHAPTER 5

Solid waste management

OBJECTIVES
After completion of this chapter the student should be able to:
. Classify solid waste.
. Discuss each category of solid waste.
. Name and discuss the treatment of the main categories of solid waste.
. Calculate the heating capacity of solid waste from its ultimate composition.
. Calculate leakage rates from punctured landfill liners.
. Discuss environmental management.

INTRODUCTION
The last aspect of environmental engineering that we will consider is solid waste
management. This chapter will also cover environmental management ± the
development of an environmental policy in a company, the procedure of doing an
environmental impact study and how to perform an environmental assessment.

5.1 SOLID WASTE

We can classify solid wastes as seen in the diagram below. Since we are concerned with
pollution and the control thereof, we are not going to concern ourselves with natural
wastes but go straight to discussing synthetic wastes.

Solid waste

Natural waste Synthetic waste

High bulk solid Toxic waste

waste

Under high bulk solid waste we group all those materials which are not harmful to the
environment, but are present in such large amounts that disposing of them poses a
problem in itself. These materials can be produced by the mining industry,
petrochemical industries and power stations making use of fossil fuels. Ash is such a
 153 CHP311-A/1

material, which is harmless to the environment, but has to be disposed of in enormous

quantities. These materials are placed on the land, and the land then becomes useless for
other purposes. Ecosystems existing on the land are destroyed (that is, all the plants,
animals etc. that live there) and the land is also unsuitable for the development of
housing or industries. Land made useless by the dumping of waste is called derelict land.

This problem has escalated to proportions too large to be ignored. The only reasonable
solution to this problem is to find ways to re-establish an ecosystem on the land where
the waste has been dumped. This requires introducing nutrients into the waste so that it
will be able to sustain plant and animal life.

Toxic wastes are all the solid waste products that can harm the environment in any way.
If these waste materials are simply dumped they can have various detrimental effects to
the environment such as:

. They can be blown into the air and cause air pollution or be inhaled by humans
. They can be taken up into the groundwater and have negative effects on humans and
plants
. They can decompose into more dangerous substances
. In some cases, spontaneous combustion can occur.

We are going to discuss various ways to minimise the harmful effects of solid wastes.
Before we discuss the various operations one can perform on solid wastes, let us
determine a general strategy for their disposal. It is the responsibility of each company,
and therefore each employee in the company, to minimise damage to the environment as
far as possible. Therefore the material dumped by any company must be as friendly to
the environment as possible. It is not somebody else's problem; it is the problem of each
person in charge of industrial operations or the disposal of materials. There are various
operations that can be performed on waste in order to treat it and remove some of the
harmful materials before it is dumped. The main categories in which solid wastes are
treated are:

. Volume reduction
. Incineration
. Landfilling
. Solid waste recovery
. The disposal of radioactive wastes.

5.1.1 Volume Reduction

Volume reduction is a process carried out on waste types such as municipal waste and
paper that is thrown away in bulk. There are three main types of operations used for the
volume reduction of solid wastes, namely:

. shredding
. pulverising
. compacting.

Solid waste normally has a low bulk density because it is made up of various objects of
all shapes and sizes. Shredding the waste reduces the volume, and it also homogenises
the waste to make it easier to handle. There are various pieces of equipment on the
market that can be used to shred waste. These pieces of equipment can handle various
sizes of waste of various characteristics (e.g. hardness, moisture content and toughness).
Two of these apparati are shown below. The first one, called a Dodge crusher, crushes
materials by means of an impacting force. The crusher has two crushing surfaces; one is
 154

stationary while the other one moves in and out. The material to be crushed is fed at the
top, at the section of largest movement. Therefore the material that can be fed to this
type of crusher can be fairly large. The crushed and reduced material falls out of the base
of the crusher. See Chemical Engineering Volume 2, Figure 2.4 on page 45 for a sketch
of a Dodge crusher.
The second type of crusher is the hammer mill. Hammer mills consist of metal casings,
normally cylindrical in shape. These casings are lined with abrasion resistant materials.
In the centre is a rotating disc connected to the driving mechanism. This disc or cylinder
contains various hammers. The hammers are made from hardened steel or other
materials with high impact strength. The hammers are pivoted at the connections with
the cylinders. The pivots allow the hammers to swing against the material and not break
when the material to be crushed is large or contains large particles. The inside cylinder
rotates. The feed to the hammer mill is introduced at the top, and it is crushed against the
sides of the mill under the impact force of the hammers. The bottom of the mill contains
sections of perforated plate. The perforations can be of various sizes. When the material
is small enough to fall through these perforations it leaves the mill.
Pulverisation is a method widely used to reduce the volume of waste paper.
Pulverisation operations run the risk of producing a lot of dust, so the procedure is
normally carried out wet. Pulverisation is the reduction of material to pieces smaller than
a centimetre. The material is shredded by metal blades that moves very fast, and is then
forced through a wire mesh. This reduces the pieces to quite a small size. These
pulverisation machines can reduce large capacities of paper, but they are in general not
suitable for harder materials such as metal or glass. Although harder materials can be
crushed, the pieces flying at high speed are extremely dangerous.
Compacting is a method of volume reduction that is primarily used for municipal
wastes. Compactors are large machines that run on electricity and they can be used
effectively for all types of waste, except rubbery materials which are hard to compact. It
is also hard, and sometimes almost impossible, to compact materials with high moisture
contents. Compacting can reduce the volume of waste by as much as 10 to 1, but with an
increase in density. It is, however, much easier to transport compacted waste than loose
waste, because it is easier to handle compacted slabs. There are various types of
compactors on the market. Most types compact the loose materials into bags and seal the
bags so that the waste can be handled in separate units. Compactors used for the
compacting of, for instance, cool drink cans for recycling, compact the material into
blocks, without the need for plastic covering.

FIGURE 5.1: A hammer mill

 155 CHP311-A/1

5.1.2 Incineration
Incineration is one of the most effective ways of treating solid waste. Incinerating
(burning) solid waste can be clean, cheap and efficient if the incineration procedure is
properly designed and managed. One should keep in mind that incineration is burning
and we have seen in the section on air pollution what harmful effects can come from
burning. In cases where these incinerators are not controlled properly, smoke, odours,
fumes and ash can result from the burning process. Then air pollution is increased in
order to reduce solid waste, and air pollution is harder to control than solid waste.

When designing an incinerator one should make sure that it is as effective as possible
with the minimum amount of emissions into the atmosphere. One of the most important
quantities to consider is the amount of air fed to the incinerator. If the oxygen
requirements are not met the combustion will be incomplete and smoke and harmful
gases will be emitted into the atmosphere. The general procedure is to calculate the
amount of air (oxygen) needed for complete combustion and multiply this value with a
factor of between 2 and 6 in order to make sure enough air is present. A typical
incinerator will have two combustion chambers, a primary combustion chamber and a
mixing chamber. In the primary chamber the waste is combusted to a gas, but the gas
contains various incomplete combustion products. The gas then passes into the mixing
chamber where complete combustion will take place. Provision must be made for a gain
in volume from the solid stage to the gas stage. Typical values of volume gain are of the
order of 6% in the primary chamber and 300% in the mixing chamber. Just before the
outlet of the incinerator there should be a third chamber, a settling chamber. Here the
gases disengage from all the solid particles that might still be present. Some materials
are more likely to form smoke than others. The greater the tendency of the material to
form smoke, the longer the retention time inside the incinerator should be. In many cases
it might be necessary to clean the waste gas from the incinerator by means of scrubbing
or by means of an afterburner.

An area where incineration is becoming increasingly popular is in the treatment of

biological sludge. Large amounts of concentrated sludge from water treatment plants
have to be disposed of. Some of this sludge can be recycled (see next section), but in
some cases the composition is such that incineration seems to be the best option.
Incineration of concentrated sludge is more expensive than dumping it and the method
of sludge disposal should be weighed carefully. In most cases fuel is also required for
incineration equipment, which increases the costs.

Let's take a brief look at each of the most common types of sludge incineration
equipment.

Multiple hearth furnaces are cylindrical units consisting of various layers. The sludge
is scraped form the one layer to the next by arms. This is done to expose new areas of
the sludge to the hot gases. These furnaces are multifunctional because they heat, dry
and incinerate the sludge. Fuel often needs to be added to these furnaces in order to
supply the energy needed for the combustion process. These furnaces have very low heat
efficiencies because a lot of heat is lost during the heating and drying operations, and as
a result of that they have high operating costs.
Flash drying and incineration units are complicated systems that operate at reduced
pressure, designed for combined drying and incineration. They are complicated and, as a
result, expensive and not very popular.

The cyclone reactor is used for the incineration of small capacities of sludge. It consists
of a small cylindrical chamber. Hot air enters the chamber at a tangent to the reactor
wall, and swirls around the chamber. The sludge is introduced at the centre of the
 156

reactor. It is sprayed radially outwards and makes contact with the hot air stream. It is
incinerated before it has time to reach the walls of the reactor. The ash leaves the reactor
with the air stream and is scrubbed from the air.

Rotary kilns are complete sludge treatment units. The kiln is rotary oven, mounted at a
downward slope towards the outlet. The heat is supplied to the oven by a burner and
sludge and combustion air is fed into the oven. The combustion process takes place at a
controlled rate and is normally fast enough so that the sludge does not get time to stick
to the oven walls. The ash moves along the floor of the kiln and is collected at the outlet.
Any gases or incomplete combustion products are combusted to completion in the
afterburner. The exhaust gases and ash are then fed through a scrubber. The last of the
fly ash is removed in the scrubber and the air and combustion products are exhausted
through a chimney. These units are relatively effective with low maintenance costs.

The fluidised bed incinerator has high heat efficiency and no moving parts in the
reactor, which reduces the risk of failure. The reactor is shaped like an upright cylinder.
A plate at the bottom prevents the bed of sand of falling out of the reactor. The plate is
equipped with holes to let air through. The bed is made of silica sand. The sand is heated
and fluidised by air that is blown through the bed by a burner. The sludge is introduced
into the bed and incinerated by contact with the hot sand. The ashes leave the reactor
with the exhaust gas. The heat efficiency of this reactor is high because the heat is
trapped in the sand and conserved that way. The ash is removed from the exhaust gas by
scrubbing the exhaust gas stream.

In the wet oxidation process the sludge is oxidised in the presence of steam. The
pressure and the temperature in the combustion chamber control the efficiency of the
combustion process. The solids are separated from the condensed steam by settling,
filtering or any other suitable procedure.

Example 5.1
Combustion characteristics can be measured in the laboratory. A potential cost-saving
measure is to estimate heat value from the ultimate composition. ' Use the Chang
equation to predict the heating value of food waste containing 45.4% C, 6.9% H, 0.32%
S, 32.3% 0, 0.74% Cl and 3.3% N.

Answer
HHV = 15410 C + 32350 H ± 11500 S ± 20010 O ± 16200 Cl ± 12050 N

where HHV is the higher heating value in Btu/lb and C = %C/100, etc.

HH = 15410(0.454) + 32350(0.069) ±11500(0.0032) ± 20010(0.323) ± 16200(0.0074)

± 12050(0.033)

= 2211 Btu/lb 6 2.326 (kJ/kg)/(Btu/lb)

= 5132 kJ/kg (dry basis)

5.1.3 Landfilling
If suitable land is available, landfilling can be a very economical option. Landfill design
is important because improperly designed landfill can cause water and air pollution.
 157 CHP311-A/1

One of the most important factors to consider when choosing an area for landfill is the
volume of land that is available. The volume of available land is connected to the
available area and also to factors such as the topography of the land. The location of the
site chosen for the landfill is also important. An ideal location for a landfill would be
relatively close to the area where the waste is generated. This reduces the cost of
transportation, and no intermediate storage is needed for the wastes.

It is good practice to cover the landfill with a layer of sand or soil at the end of each day.
The soil provides nutrients between the layers of waste. This makes it possible for the
land to be used afterwards. The soil also provides drainage for water. At least 15 cm of
soil needs to be added at a time. In selecting an area for a natural landfill it is important
to determine the distribution of natural water. It is important that the landfill should not
be dug to the same depth as the water table, because the waste material will contaminate
the natural water system. It is therefore important to make a careful study of the land in
order to make sure streams and springs can be protected from the waste material. It is
good practice to have some distance between the landfill and residential areas, because
people often object to living next to a landfill.

There are various methods of landfilling. The area method involves spreading the waste
over the surface of the selected land. The waste is then compacted and covered with a
layer of soil. This method can be used to fill up depressions in the land. The trench
method of landfilling is used where the natural water is not close to the surface. Trenches
are dug in the ground and the waste is placed inside the trenches. The soil that is
removed from the ground in digging the trenches is used to cover the waste. In the slope
method the waste is spread out against an existing slope, covered with soil and
compacted.

Problems are experienced with landfilling because it is not possible to compact the waste
dumped on the land completely. When the waste decomposes later, voids cause the
landfill to become uneven and unsafe. If the waste is pulverised or compacted prior to
landfilling, this problem can be eliminated.

Example 5.2
Landfills are often lined with special materials called geomembranes to prevent leakage
into the groundwater system. However, defects in the liner can occur in manufacture and
during installation. Bernoulli's equation for flow through an orifice does not account for
impeded flow to the defect or puncture. Estimate the rate of leakage from a 4000 m2
geomembrane with a 0.1 cm2 puncture. The hydraulic head is 0.3 m.

Answer
Giroud et al developed the following equation where Q is the leakage rate (m3/s), A and
a are the areas of the membrane and puncture (m2), and h is the liquid head (m):
Q p
ˆ 0:6a 2gh
A p
Q ˆ …4000†…0:6†…0:1=104 † 2…9:81†…0:3†
ˆ 2:42  10ÿ5 m3 =s or 1:46 l=min

5.1.4 Solid waste recovery

Up to this stage we have only considered ways to destroy or dump unwanted solid
waste. There are, however, various substances normally thrown away that can be re-
 158

used. The re-use of garbage leads to interesting debate. It is more expensive to build a
plant for the re-use of, say metals, than to bury the scrap metals in a landfill, so from an
immediate cost perspective, re-use might not seem a wise option. But the picture is
bigger than this. If one reuses a material the burden on the natural resources is smaller,
and the amount of garbage that has to be dumped in the long run is much less. With
awareness of the environment, pollution control and other environmental issues
increasing on all levels of society, waste recycling is an increasingly popular field of
research, and more and more waste recycling plants are being built.

Before any type of recycling can be done, it is important to separate or sort waste
according to different categories. Sensible categories for recycling would be paper,
metal, glass and other materials, such as organic material and plastic materials. The
processes for manufacturing various products from materials that have been recovered
from waste are beyond the scope of this course. We are just going to discuss the various
methods of separating waste materials and processing them to manageable forms for
reselling. We are going to consider three types of recycling operations, namely those for
paper, metal and rubber.

Most industrial waste contains high percentages of paper. This can be in the form of
paper packaging, paper board or ordinary paper. Before paper can be sold to recycling
companies, it must be sorted from the rest of the waste. The ideal situation would be to
obtain the paper separately, and not mixed with the rest of the waste. This can be done
by encouraging people to collect all waste paper separately from the rest of the waste
they put out for collection. If this cannot be done the waste paper must be separated from
the rest of the waste materials manually. There are two main operations carried out on
waste paper before it can be sold. One is called baling and the other is packing the bales
of material in large containers which makes it suitable for transport. A baling system is
shown in figure 5.2. It is in effect a combined shredding and baling system. The
separated paper materials are fed into the shredder via a hopper. The shredded pieces of
paper leave the shredder and are conveyed to the next step through an air handling
system. The shredded paper pieces then move to a cyclone separator. Here they are
removed from the air stream by means of centrifugal action. The paper moves to the
outside of the cyclone and falls out of the base under the influence of gravity. The air
leaves through the top. The base of the cyclone feeds the paper shreds into the baler
feeder chamber. In the baler the paper pieces are compacted to a high density. The bales
are held together by plastic, wire or steel straps.

FIGURE 5.2: A typical baler plant

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The next separation example we are going to consider as part of the waste recycling
process is that of removing scrap steel from waste materials. There are various uses for
scrap steel, but it has to be separated from other waste. This procedure is also used in the
recovery of steel or metals from motor vehicles. In some countries the amount of motor
vehicles deserted is so large that the most feasible way to deal with them is either to
compact them, or grind them up and recover the steel. When the process is designed
correctly, the separation of steel from other waste materials is fairly easy. The magnetic
property of steel is utilised in this separation procedure. In some cases the steel needs to
be ground up in order to separate it from other materials (such as in the case of motor
vehicle recovery) but this is not necessary if the steel is present in separable form. This
separation method can also be used to separate iron cans from aluminium cans.

The magnetic separation drum is shown in figure 5.3. The drum itself is not magnetised.
A fixed magnetic element is installed inside a certain section of the drum. This results in
the section of the drum over the magnet being magnetic. Steel and non magnetic
material is fed to the drum, and the non magnetic material falls from the drum
immediately. It is important to say at this stage that the feed rate should not be too high,
because this will result in some of the non magnetic material being trapped between the
magnetic material. The magnetic material is now carried around as the drum rotates.
When it reaches the section where the magnet inside the drum is no longer there, it drops
off onto a conveyor belt.

FIGURE 5.3: Magnetic separation drum

The next type of waste recovery was designed specifically for rubber materials. In our
discussion on landfilling we have said that rubbery materials are not suited for
landfilling operations because it is hard or impossible to compact them. They also have
such a low rate of biodegradation that they take a long time to decompose. It is not
feasible to incinerate used rubber materials because these materials produce a lot of soot
and smoke when burned. This will lead to air pollution. Scrap rubber, and more
specifically scrap tyres can be very problematic in terms of disposal.

Research has come up with a distillation procedure that will enable one to recover at
least some of the rubber material. It is a process similar to distillation and various
fractions of reusable product can be recovered. The scrap rubber is ground and placed in
a heated furnace. The temperature is high enough to oxidise the rubber materials to
carbon. At this temperature the volatile oils present in the rubber are evaporated and
passed on to a series of condensers where the heavy oil fractions are recovered. Any
particulate matter present in the light oil vapours is removed, and then these vapours are
 160

sent through a caustic and then an acidic scrubber to remove acidic and basic impurities.
The light oils can now be condensed and used as fuels. The process is not selective
enough that pure materials can be recovered, but the waste is greatly reduced and the
products obtained can be put to good use.

About 45% of the tires are left behind in the furnace as solid residue. This residue
contains mainly carbon. It has various uses, such as packing for filters, ingredients in
concrete and solid fuels.

5.1.5 Radioactive waste disposal

The use of radioactive materials is not new to the chemical industry or industry in
general. Nuclear power stations are known to be much cleaner than power stations that
make use of fossil fuel. Nuclear power stations that make use of radioactive fuel do not
emit any harmful substances into the atmosphere under normal operations. The concern
of those opposed to the use of radioactive energy sources is the risk of accidental
radioactive emissions into the atmosphere. A debate on the benefits of the use of
radioactive fuel is beyond the scope of this course. Let us concern ourselves with the
disposal of radioactive waste. Radioactivity is also used in the medical field, in research
and in defence. Radioactive waste can be defined as any waste material that has an
unacceptable level of radioactivity. This can be used containers, used radioactive fuel
cells, clothing or equipment that was used in the operation of plants handling radio
active materials and discarded or broken equipment.

Radioactive waste is classified into low level, intermediate level and high level wastes.
The levels depend on the radioactivity of the waste materials and the radioactivity will in
turn affect the disposal procedure of the waste. Low level waste is protective clothing
worn by exposed people, wrapping materials of equipment and old damaged and broken
equipment. The radiation levels in these materials are low enough that they can be stored
in containers on the site of operation without any special precautions. People handling
these materials should wear protective clothing, but other than that no special
precautions are needed. Intermediate level radioactive waste is a thousand times more
radio active than low level wastes. This is process equipment such as metal fuel cans that
contained fuel for nuclear reactors, reactor parts, ion exchange resins, filter elements and
cloths and various other equipment in direct contact with radioactive emissions. The
intermediate level waste needs more stringent storage and dumping requirements. These
materials have to be shielded during transportation and storage. This shielding is done
by packing it into concrete or steel containers.

There are two options for radioactive wastes. The first option is to place it in containers
and store it on the site of operations. This option is suitable for low level waste, and only
in cases where there is not much waste material produced. If the amount of waste
material is very large, or in the case of intermediate level waste, the safest option is to
store the waste underground. It is important to remember that, even in the case of low
level waste, it is hundreds of years (sometimes thousands) before these material will be
safe. Storage underground will ensure that the material is not released into the
atmosphere and can cause no harm. The storage procedure is not as simple as it might
sound. These are various factors that need to be considered. The material must be stored
in a stable place where the earth will not be disturbed by earthquakes. The storage must
also be in areas where there is little or no movement of groundwater. This protects the
containers and reduces the risk of leakage and release into the groundwater. The
evaluation and selection of a suitable site for a radioactive dump is often the task of a
group of experienced geologists and scientists.
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FIGURE 5.4: Typical dump sites for radioactive waste disposal

 162

The following types of geographical areas will be suitable for a radioactive dump site:

(a) Hard rocks in areas that are not very mountainous. These areas do not normally
have a lot of underground water movement and are relatively stable.
(b) Small islands far from any coasts are suitable because these islands have their own
under ground water distribution system that does not mix with that of the main
land. In the case of leakage into the groundwater the damage will be contained to
that island.
(c) Seaward dipping and offshore sediments are also known for very slow
groundwater movement, and the groundwater will move into the sea and not in
an inland direction.
(d) Inland basins are basins with deep sedimentary rocks, and the groundwater will
have the tendency to move towards the centre of these basins. In cases of
contamination the groundwater will be confined and not spread.
(e) Rocks covered by sedimentary layers are also very stable because the groundwater
tends to move inside the sedimentary layers and not in the rocks.

Figure 5.4 shows schematic representations of the various land types for radioactive
waste dumps. The radioactive material is encased in steel or concrete containers and
stored in underground bunkers built from concrete, in order to minimise the risk of
leakage.

5.2 ENVIRONMENTAL MANAGEMENT

We have now discussed the various types of pollutants, the sources of these pollutants
and the impact that these pollutants can have on humans and animals, and on the
environment in general. The last section of this chapter is devoted to the subject of
environmental management. Typically, an industrial organisation will consist of various
processes interacting with each other. All these processes have the potential for emitting
dangerous substances into the environment and thus contributing to the pollution
problem. There is legislation in many countries (including South Africa) that prohibits
industries from exceeding certain maximum emission standards, and heavy fines are
payable in cases where these standards are not met. Therefore it is extremely important
that a company manages the environmental side of its operations well. Many companies
have done environmental audits on their production processes. These audits are studies
that show which substances are emitted, and in what quantities. They are a valuable first
step, but this is still far from a complete environmental management program. The ISO
(International Organisation for Standardisation) has set up guidelines for the structure
and implementation of an environmental management policy on an international,
national and company scale. The Department of Environmental Affairs has also set up
guidelines for the development of an environmental management policy or program,
which is in accordance with ISO standards. The Environmental Management System
Model is shown in figure 5.5 below.

This model suggests an iterative procedure (starting with environmental policy and
finishing with management review) that will be improved with each iteration. Let's take
a brief look at each of the main sections:

5.2.1 Policy
A policy document is a document drawn up to state the approach and intent of a
company towards a specific issue. This policy must be available to all in the organisation
 163 CHP311-A/1

FIGURE 5.5

as well as to the public. An environmental management policy will typically contain a

company's commitment to comply with government environmental legislation (and/or
standards it has set itself). It will also usually contain the company's commitment to the
protection of the environment in general and/or the particular area where the company
operates. The policy should also contain the framework by which these standards are
drawn up and evaluated.

5.2.2 Planning
In the planning stage of the environmental management system, the company must
identify all the possible effects its operations can have on the environment as a whole.
 164

Then these effects must be investigated to identify those that can have a significant
Impact.

The legal requirements and emission standards must be obtained. These standards
change continuously, so a mechanism must be put in place for the company to obtain
updated standards on a regular basis. There must be a person in the company who is
responsible for the updating of environmental policy, and for the distribution of this
throughout the company.

The company must also identify the objectives and targets that it wants to meet and
maintain with regards to environmental standards. These targets must be documented
and reviewed regularly. The targets set here are different from the objectives set in the
environmental policy, because the objectives are of a general nature and the targets are
more specific.

The precise structure of the environmental management programme must also be

planned. This includes the people responsible for the establishments of the program, all
the parties that will be involved in implementing the program, the structure by which it
has to be implemented, and the specific people who will be responsible for the
implementation and evaluation of the program.

5.2.3 Implementation & Operation

In this stage all the procedures set out in the planning stage have to be implemented in
accordance with the planned structures. The roles of various people have to be clearly
defined and documented. The people concerned should then be informed and briefed as
to their responsibilities. Management has the responsibility to provide the resources for
the implementation of the system in terms of funds, labour and time.

The organisation must also identify training needs that are required for the successful
implementation and administration of this program. Once the training needs have been
identified the structure to provide this training must be put in place. Management has the
responsibility to provide time, funds and training facilitators.

A structure must also be implemented by which the communication procedures can be

documented and controlled. Proper communication is necessary to keep all parties
informed and motivated. Included in the communication procedure can be regularly
scheduled meetings with relevant parties, the circulation of relevant documentation such
as updates on the legislation, published articles on related topics, minutes of meetings
held, etc.

The environmental management system has to be documented. This implies that the
procedure by which this system operates must be written up. This seems to be redundant
with a system that functions properly, but it often happens that various key figures leave
within a short period of time. They take their knowledge with them when they leave, and
if the procedures were not documented before, the people taking over their
responsibilities often have to develop their own procedures from the start. This wastes
lots of valuable time in reinventing the wheel.

Apart from developing the proper documentation, it is also important that document
control is carried out. Document control implies that the documents are filed and stored
in a place where they can be located easily, that the documentation is reviewed
periodically to ensue it is still applicable, that relevant documents and information are
available on the sites where they are needed, and that all documents stored for legal or
other purposes are properly marked and filed according to a logical system.
 165 CHP311-A/1

Operational control procedures must also be implemented. This is done to ensure that
the environmental management program is operating properly on all its levels. It can
include evaluation sessions, feedback meetings, written reports and audits. Operating
criteria must also be properly spelled out to ensure that all parties involved are sure
about their specific responsibilities and tasks.

Procedures to deal with accidents must also be drawn up and implemented. This ensures
that all relevant parties are aware of the procedures to be followed in the case of an
emergency or an accident, and that they can act in the best way to minimise the damage
done. It is also important to have a system in place by which accidents are properly
documented. This will provide information on the effectiveness of the environmental
management program, and can be used to prevent further incidents.

5.2.4 Checking and Corrective Action

As said before, it is important that the implementation and the effectiveness of the
program be checked or evaluated regularly. In evaluating the implementation of the
program one would check if the procedures as they stand are followed properly, and in
evaluating the system one would look at the total system and evaluate whether the
system meets the set objectives, or whether it needs to be improved. In this process the
input of all the parties that operate within the system can be of valuable use, because
people working with certain procedures on a day to day basis can often best evaluate
them and suggest useful improvements. Regular audits of the environmental
management system should be carried out. The whole system will then be evaluated
at once and possible changes suggested and implemented.

5.2.5 Management Review

The top level of evaluating the environmental system of a company is the review of the
system by management. This review can include evaluation of the suitability and
applicability of the policy, down to the operations of the system and the auditing
procedure. It is management who will be confronted with losses suffered due to heavy
fines payable for standards not met. The ultimate responsibility of the implementation
and control of an environmental policy lies with them.

5.3 ENVIRONMENTAL LEGISLATION

In the previous module the Water Act was discussed. The legislation concerning
environmental protection and conservation is the Environmental Conservation Act of
1989, and the Atmospheric Pollution Prevention Act of 1965. These acts contain all
the legislation concerning the dumping of solid waste, air emissions, and standards that
have to be adhered to when dumping materials.

BIBLIOGRAPHY
Environmental Engineering, Peavy, H.S., Rowe, D.R., & Tchobanoglous, G., McGraw-
Hill International, 1985.

Pollution Engineering Practice Handbook, Cheremisinoff, P.N., Young, R.A., Ann

Arbor Science, 1981.

Environmental Management in SA, Fuggle, R.F. & Rabe, M.A., Juta & Co. Ltd, 1992.
 166

The Treatment and Handling of Wastes, Bradshaw, A.D. et al, Chapman & Hall, 1992.

Environmental Management Systems ± Specifications with Guidance for Use, ISO,

1995.

Coulson & Richardson's Chemical Engineering, Volume II, Pergamon Press, 1985.

REVISION QUESTIONS
1. List five main categories for treatment of solid wastes.
2. Describe three ways in which the volume of solid wastes can be reduced.
3. Explain the function and operation of a cyclone reactor.
4. Discuss three criteria for selecting a landfill.
5. Draw simple flow sheets for the recycling of the following materials. a) rubber, b)
metal and c) wood.
6. Give one example of a) high level, b) intermediate level and c) low level
radioactive waste.
7. Explain the difference between targets and objectives in an Environmental
Management System.