1

EN 14 104 Engineering Chemistry

(Common for all branches)
Module I
Organo Metallic Compounds Definition Classification based on the nature of Metal-Carbon
bond. Metal carbonyls 18 electron rule Mononuclear and polynuclear carbonyls (give e.gs of Fe, Co, Ni)
Bio-Inorganic chemistry Metal ions in biological system Trace and Bulk metal ions Hemoglobin
and myoglobin (elementary idea only)
Green Chemistry Goals of green chemistry Limitations Twelve principles of green chemistry
with their explanations and examples Designing a green synthesis Prevention of waste / byproducts Atom
economy (maximum incorporation of materials used in the process) Minimization of hazardous / toxic
products prevention of chemical accidents Green synthesis
Module II
Polymers Classification Types of polymerization Addition, Condensation,
Coordination polymerization and Co-polymerisation Polymerisation techniques Bulk, Solution,
Suspension and Emulsion Concept of Tg and Factors affecting Tg Crystallinity in polymers Physical and
Mechanical properties Density, Tensile, Tear, Abrasion resistance and Resilience
Lubricants Theories of friction Mechanism of lubrication Thick film, Thin film and Extreme
pressure Classification Solid, Liquid, Semisolid Properties Viscosity, Flash point, Fire point, Cloud
and Pour point, Aniline point and Corrosion stability
Fuels Classification Calorific Value Cracking and Reforming Petrol Knock and Octane
number Diesel knock and Cetane number Bio-Diesel
Module III
Single electrode potential Helmholtz double layer
Electrochemistry
Nernst equation Derivation Types of electrodes (S.H.E, Calomel, Quinhydrone, glass electrode),
pH measurements using glass electrode, Electrochemical cells, Concentration cells - salt bridge
emf measurement Poggendorfs compensation method Electrochemical series Applications
Storage cells Lead acid accumulator Alkaline cells Nickel Cadmium Fuel cells H2/O2 fuel
cell Solar cells
Module IV
Corrosion and its control Theories of corrosion Dry corrosion and Wet corrosion Galvanic
series - Corrosion of iron in acidic, neutral and basic conditions Differential aeration corrosion, Stress
corrosion Galvanic corrosion Factors influencing corrosion. Corrosion control methods Protection by
sacrificial anode Impressed current - self protecting corrosion products Pilling Bed worth rule
Coatings Organic (Paints and Polymers) Inorganic Metallic (galvanizing, tinning, electroplating,
cementation) Nonmetallic (phosphate, chromate, anodising, chemical oxide)
Water Hardness alkalinity Determination of hardness (EDTA
Softening Soda Lime and Ion exchange methods Purification of water for domestic use
Water pollution BOD, COD, DO

method)

Theory

Internal Continuous Assessment

(Maximum Marks - 50)
% of Marks
Marks
60% - Tests (minimum 2)
30
30% - Assignments (minimum 2)
15
10% - Attendance
05

Practical

Internal Continuous Assessment

(Maximum Marks - 50)
% of Marks
Marks
50% - Practical and Record
25
40% - Test
20
10% - Attendance
05

Theory University Examination Pattern (Maximum Marks - 100)

Part A: Analytical/problem solving short questions
Candidates have to answer eight questions out of ten. There shall be minimum of
two and maximum of three questions from each module with total ten questions.

Part B: Analytical/Problem solving descriptive questions
Two questions from each module with choice to answer one question

8 x 5 marks =
40 marks
4 x 15 marks =
60 marks
3

Organo Metallic Compounds

Introduction
Organometallic chemistry, the chemistry of compounds containing metal-carbon bonds,
it encompasses a wide variety of chemical compounds and their reactions, including compounds
containing both and bonds between metal atoms and carbon; many cluster compounds, containing
one or more metal-metal bonds. Aside from their intrinsically interesting nature, many organometallic
compounds form useful catalysts and consequently are of significant industrial interest.
Cr(CO)6 and [Ni(H2O)6]2+ example, are both octahedral. Both CO and H2O are donor ligands;
in addition, CO is a strong acceptor. Other ligands that can exhibit both behaviors include CN-, PPh3,
SCN-, and many organic ligands. Cyclic organic ligands containing delocalized systems can team up
with metal atoms to form sandwich compounds. A characteristic of metal atoms bonded to organic
ligands, especially CO, is that they often exhibit the capability to form covalent bonds to other metal
atoms to form cluster compounds. These clusters may contain only two or three metal atoms or as
many as several dozen; there is no limit to their size or variety. They may contain single, double,
triple, or quadruple bonds between the metal atoms and may in some cases have ligands that bridge
two or more of the metals.

The first organometallic compound to be reported was synthesized in 1827 by Zeise,

who obtained yellow needle-like crystals after refluxing a mixture of PtC14 and PtC12 in ethanol,
followed by addition of KC1. It is an ionic compound (Zeise's salt) of formula K[Pt(C2H4)Cl3]H2O.
In 1890, Mond reported the preparation of Ni(CO)4, a compound that became commercially useful for
the purification of nickel. Reactions between magnesium and alkyl halides, performed by Barbier in
1898 and 1899, and subsequently by Grignard led to the synthesis of alkyl magnesium complexes now
known as Grignard reagents. Kealy and Pauson reacted the Grignard reagent cyclo-CSH5MgBr with
FeC3, using anhydrous diethyl ether as the solvent. This reaction yield an orange solid of formula
(C5H5)2Fe, ferrocene. The structure of ferrocene consist of an iron atom sandwiched between two
parallel C5H5 rings.
4

Classification based on the nature of Metal-Carbon bond

The following five types of organometallic compounds can be distinguished depending
upon the nature of metal-carbon bond; [1] Ionic organometallic compounds [2] Organometallic compounds
containing metal-carbon sigma bond [3] Ylides [4] Organometallic compounds with multicentre bonds [5]
Organometallic compounds with pi bonded ligands.
[1] Ionic organometallic compounds: Most of the organometallic compounds of alkali metals fall in this
category. They have short life because of their high reactivity. Examples are Na+(CH2=CH-CH2)-, Na+(CH2C6H5)-, Na+(C6H5)-, Na+(C5H5)-, etc
[2] Organometallic compounds containing metal-carbon sigma bond: Metallic elements of Group II, III, IV
and V as well as transition metals form organometallic compounds in which the metal atoms are bonded to
carbon atoms by sigma bond.
OMC of Group II

OMC of Group III

OMC of Group IV

OMC of Group V

Represented as R2M

Represented as R3M

Represented as R4M

Represented as R3M

(CH3)2Hg, (CH3)2Cd,

(CH3)3Ga, (C6H5)3Ga,

(CH3)4Si, (CH3)4Ge,

(CH3)3P, (CH3)3As,

(CH3)2Zn, (CH3)2Mg,

(CH3)3In,(CH3)3Tl,

(CH3)4Sn, (CH3)4Pb,

(CH3)3Sb, (CH3)3Bi,

Organometallic compounds of transition metals: Very few examples of alkyl compounds of transition
metals are known because of their greater reactivity. But organic ligand does not contain any hydrogen will
form stable complex, e.g., [CH3-CH2-Rh(NH3)5]. The alkynyl compounds [M-CC-R] are more stable than
alkyl or aryl complexes. The reason is that alkynyl group acts as donor as well as acceptor. Similar
situation occurs in alkenyl compounds [M-CH=CR2]. Some other compounds are cyclopentadienyl
complexes containing (1-C5H5)M linkage.
[3] Ylides: These are the compounds in which the metal is doubly bonded with the carbon atom of the
ligand. Such compounds are formed by the main group elements as well as by the transition elements.
The example is Wittig reagent, Ph3P=CH2.
[4] Organometallic compounds with multicentre bonds: Organometallic compounds which are
loosely called electron-deficient and thus occur in polymeric forms fall under this category.
Examples are (Li-CH3)4, [Be(CH3)2]n, [Al(CH3)3]2, etc. These compounds are considered as intermediate
between ionic organometallic compounds of alkali metals and bonded organometallic compounds of Si, Sn,
Pb, etc. Elements which have highest tendency to form this complex are Li, Be, Mg, B and Al.
[5] Organometallic compounds with pi bonded ligands: This category includes organometallic compounds of
alkenes, alkynes and some other carbon-containing compounds having electrons in their molecular orbitals.
Overlapping of these orbitals with the vacant orbitals of the metal atom gives rise to an arrangement in which
the metal atom gets bound to all the carbon atoms over which the molecular orbital of the organic ligand is
spread. The most important compound of this category is ferrocene or (bis-cyclopentadienyl)iron, represented
as (5-C5H5)2Fe. It is known to have a sandwitch structure
5

The 18-Electron Rule or Inert Gas Rule or EAN Rule

A complex compound in which the central metal atom appears to have acquired the
configuration of an inert gas by sharing of electrons tends to be more stable, this generalization is
known as inert gas rule. The total number of electrons which the central metal atom appears to
possess in the complex including those gained by it in bonding is called Effective Atomic Number of
the central metal atom.
The effective number of electrons in the (n-1)d, ns and np orbitals of metal (valence shell) in its
complex should be equal to 10 + 2 + 6 = 18, so called 18-electron rule. The total number of electrons
gained by the metal through bonding plus the number of original electrons already present in
(n-1)d, ns and np orbitals of metal should be equal to 18 in any of the stable complexes of the metal.
There are many exceptions to the 18-electron rule, but the rule nevertheless provides some useful
guidelines to the chemistry of many organometallic complexes.
Electrons in the complex may be counted by Donor Pair Method. This method considers
ligands to donate electron pairs to the metal. To determine the total electron count, we must take into
account the charge on each ligand and determine the formal oxidation state of the metal.

Cr(C0)6: A Cr atom has 6 electrons outside its noble gas core. Each CO is considered to act as
a donor of 2 electrons. The total electron count is represented in Table 1. Cr(CO)6 is therefore
considered an 18-electron complex. It is thermally stable; for example, it can be sublimed without
decomposition. Cr(CO)5, a 16-electron species, and Cr(CO)7, a 20-electron species, on the other hand,
are much less stable and are known only as transient species.

Table 2

Table 1

(5-C5H5)Fe(CO)2Cl:

Pentahapto-C5H5

is

considered

by

this

method

as

C5 H 5 - ,

a donor of 3 electron pairs; it is a 6-electron donor. As in the first example, CO is counted

as a 2-electron donor. Chloride is considered C1-, a donor of 2 electrons. This complex is formally
an iron(II) complex. Iron(II) has 6 electrons beyond its noble gas core. This electron count
is represented in Table 2.
Carbonyl (CO) Complexes
Carbon monoxide is the most common ligand in organometallic chemistry. It serves as the only
ligand in binary carbonyls such as Ni(CO)4, W(CO)6, and Fe2(CO)9 or, more commonly,
in combination with other ligands, both organic and inorganic. CO may bond to a single metal or
6

it may serve as a bridge between two or more metals. In this section, we will consider the bonding
between metals and CO, the synthesis and some reactions of CO complexes, and examples of the
various types of CO complexes.
Two features of the molecular orbitals of CO deserve attention. First, the highest energy
occupied orbital (the HOMO) has its largest lobe on carbon. It is through this orbital, occupied by an
electron pair, that CO exerts its a-donor function, donating electron density directly toward an
appropriate metal orbital (such as an unfilled d or hybrid orbital). Carbon monoxide also has two
empty * orbitals (the lowest unoccupied, or LUMO); these also have larger lobes on carbon than on
oxygen. A metal atom having electrons in a d orbital of suitable symmetry can donate electron density
to these * orbitals. These -donor and -acceptor interactions are illustrated in Figure. The overall
effect is synergistic. CO can donate electron density via a -orbital to a metal atom; the greater the
electron density on the metal, the more effectively it can return electron density to the * orbitals of
CO. The net effect can be strong bonding between the metal and CO; however, as will be described
later, the strength of this bonding depends on several factors, including the charge on the complex and
the ligand environment of the metal.

The metal-carbon bond in metal carbonyls possess both s and p character. The MC bond is
formed by the donation of lone pair of electrons on the carbonyl carbon into a vacant orbital of the
metal. The MC bond is formed by the donation of a pair of electrons from a filled d orbital of metal
into the vacant antibonding * orbital of carbon monoxide. The metal to ligand bonding creates a
synergic effect which strengthens the bond between CO and the metal
Bridging modes of CO
Although CO is most commonly found as a terminal ligand attached to a single metal atom,
many cases are known in which CO forms bridges between two or more metals. In cases in which CO
bridges two metal atoms, both metals can contribute electron density into * orbitals of CO to weaken
the C - O bond. Ordinarily, terminal and bridging carbonyl ligands can be considered 2-electron
donors, with the donated electrons shared by the metal atoms in the bridging cases. For example, in the
complex the bridging CO is a 2-electron donor overall, with a single electron donated to each metal.
The electron count for each Re atom according to method B is
7

Bioinorganic Chemistry
Introduction
When one considers the chemistry of biological processes, the boundary between inorganic and
organic chemistry is blurred. The bulk biological elements that are essential to all life include
C, H, N, O (the four most abundant elements in biological systems) along with Na, K, Mg, Ca, P, S
and Cl. The fundamental elements that make up the building blocks of biomolecules (e.g. amino acids,
peptides, carbohydrates, proteins, lipids and nucleic acids) are C, H, N and O, with P playing its part
in, for example, ATP and DNA and S being the key to the coordinating abilities of cysteine residues in
proteins. The roles of the less abundant, but nonetheless essential, elements include osmotic control
and nerve action (Na, K and Cl), Mg2+ in chlorophyll, Mg2+ containing enzymes involved in phosphate
hydrolysis, structural functions of Ca2+ (e.g. bones, teeth, shells) and triggering actions of
Ca2+ (e.g. in muscles). The trace metals are V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo, while trace nonmetals comprise B, Si, Se, F and I.
So the chemical elements essential to life forms can be divided into the following
(i) Bulk elements: C, H, N, O, P, S (ii) Macrominerals and ions: Na, K, Mg, Ca, Cl, PO43-, SO42(iii) Trace elements: Fe, Zn, Cu (iv) Ultratrace elements comprises of (a) Non-metals: F, I, Se, Si,
As, B (b) Metals: Mn, Mo, Co, Cr, V, Ni, Cd, Sn, Pb, Li
Na+ and K+
Mg2+
Ca2+
VIV/V, MoIV/VI, WIV/VI,
MnII/III/IV, FeII/III,
NiI/II/III, CuI/II
Fe and Cu
Fe3+
Fe2+ + Fe3+
Co
Zn2+
SiIV (silicate)
PV (phosphate)
Se2FClI

Most important free intra- and extracellular cations. Regulation of the osmotic
pressure, membrane potentials, enzyme activity, signalling.
Chlorophyll; anaerobic energy metabolism (ATP > ATP).
Signalling, muscle contraction, enzyme regulation. Main inorganic part of the
endoskeletons (bones, teeth, enamel: hydroxyapatite; Ca5(PO4)3(OH)). Exoskeletons
of mussels, shells, corals, sea urchins etc: aragonite or calcite; CaCO3)
Active centres in electron-transport (redox) enzymes, oxygenases, dismutases.
Transport of oxygen
Iron-storage proteins (ferritins)
Orientation of magnetobacteria, pigeons, bees in Earths magnetic field
Synthases and isomerases (cobalamines, e.g. vitamin-B12); methylation of
inorganics
In the active centre of hydrolases, carboanhydrase, alcohol dehydrogenase,
synthases; genetic transciption (zinc fingers), stabilisation of tertiary and quartary
structures of proteins; repair enzymes
Involved in the built-up of bones. In the form of SiO2/silica-gels as support in
monocotyledonous plants (like grass) and the shells of diatoms
Constituent in hydroxi- and fluorapatite (Ca5(PO4)3(OH/F)); energy metabolism
(ATP), NADPH, activation of organic substrate; phospholipids in cell membranes;
phosphate esters (DNA, RNA,).
Selenocystein in special enzymes (e.g. glutathionperoxidase)
Fluorapatite (Ca5(PO4)3F) in dental enamel
Along with hydrogencarbonate the most important free anion.
Constituent of thyroid hormones (such as thyroxine).
9

V
Mn, Fe, Cu, Ni, Zn
Co
Mo
B
Si
Se
F
I

Accumulated by a few organisms, and has been shown to be

essential for growth in rats and chicks
Essential to all organisms
Essential to mammals and many other organisms
Essential to all organisms although green algae may be an exception
Essential to green algae and higher plants, but its role is unknown
Exoskeletons of marine diatoms composed of hydrated silica,
but its role in other biological systems is less well defined
Essential to mammals and some higher plants
Its role is not fully established but its deficiency causes dental caries
Essential to many organisms.

The average amount of iron in the human body (70 kg) is ca. 5 g; iron is thus the most abundant
transition metal in our organism. About 70% of this amount is used for oxygen transport and storage
(haemoglobin, myoglobin), almost 30% are stored in ferritins (iron storage proteins), and about 1% is bound to
the transport protein transferrin and to various iron dependent enzymes; cf. the rough classification to the right.
10

Porphyrins
One of the most important groups of compounds is the porphyrins, in which a metal ion is
surrounded by the four nitrogens of a porphine ring in a square-planar geometry and the axial sites are
available for other ligands. Different side chains, metal ions, and surrounding species result in very
different reactions and roles for these compounds.

Porphyrins are found in many metalloenzyme

Enzyme
Fe-porphyrin
Fe-porphyrin
Mg-porphyrin

Function

Cytochrome
Electron transfer
Hemoglobin & Myoglobin Dioxygen carrier
Chlorophyll
Photosynthesis

Oxygen transport
In the pulmonary alveoli, O2 is taken up by haemoglobin (Hb) and 1 L of blood can dissolve
200 ml of oxygen. Simultaneously, hydrogencarbonate is converted to carbonic acid, which in turn is
catalytically degraded into CO2 und H2O (by the zinc enzyme carbonic anhydrase):

After transport of O2 by haemoglobin in the blood stream, the oxygen is transferred to tissue
myoglobin (Mb). Mb has a higher affinity to O2 than Hb.
11

Iron Porphyrins
Hemoglobin and Myoglobin: The best known iron porphyrin compounds are hemoglobin and
myoglobin, oxygen transfer and storage agents in the blood and muscle tissue, respectively.
Each of us has nearly 1 kg of hemoglobin in our body, picking up molecular oxygen in the lungs and
delivering it to the rest of the body. Each hemoglobin molecule is made up of four globin protein
subunits, two and two . In each of these, the protein molecule partially encloses the heme group,
bonding to one of the axial positions through an imidazole nitrogen. The other axial position is vacant
or has water bound to it (the imidazole ring from histidine is too far from the iron atom to bond).
When dissolved oxygen is present, it can occupy this position, and subtle changes in the conformation
of the proteins result. As one iron binds an oxygen molecule, the molecular shape changes to make
binding of additional oxygen molecules easier. The four irons can each carry one O2, with generally
increasing equilibrium constants: In hemoglobin, the Fe(I1) is about 70 pm out of the plane of the
porphyrin nitrogens in the direction of the imidazole nitrogen bonding to the axial position. When
oxygen bond to the sixth position, the iron becomes coplanar with the porphyrin, oxygen bonds at an
angle of approximately 130, also with considerable back bonding (as nearly that of Fe(II1) - O2-).

12

As soon as some oxygen has been bound to the molecule, all four irons are readily oxygenated.
In a similar fashion, initial removal of oxygen triggers the release of the remainder and the entire load
of oxygen is delivered at the required site. This effect is also favored by pH changes caused by
increased CO2 concentration in the capillaries. As the concentration of CO2 increases, formation of
bicarbonate causes the pH to decrease and the increased acidity favors release of O2 from the
oxyhemoglobin, called the Bohr effect.

Myoglobin has only one heme group per molecule and serves as an oxygen storage molecule in
the muscles. The myoglobin molecule is similar to a single subunit of hemoglobin. Bonding between
the iron and the oxygen molecule is similar to that in hemoglobin, but the equilibrium is simpler
because only one oxygen molecule is bound: When hemoglobin releases oxygen to the muscle tissue,
myoglobin picks it up and stores it until it is needed. The Bohr effect and the cooperation of the four
hemoglobin binding sites make the transfer more complete when the oxygen concentration is low and
the carbon dioxide concentration is high; the opposite conditions in the lungs promote the transfer of
oxygen to hemoglobin and the transfer of CO2 to the gas phase in the lungs. Myoglobin binds O2 more
strongly than the first O2 of hemoglobin.

13

Green Chemistry
Introduction
Green Chemistry is the use of chemistry techniques and methodologies that reduce or eliminate
the use or generation of feedstock, products, by-products, solvents, reagents, etc., that are hazardous to
human health or the environment. Green Chemistry is an approach to the synthesis, processing and use
of chemicals that reduces risks to humans and the environment. This approaches include
new synthesis and processes as well as new tools for instructing aspiring chemists how to do
chemistry in a more environmentally benign (caring, kindly, gentle or compassionate) manner.
In order to evaluate the greenness of a particular process attention must be paid in the first
instance to issues related to safety, health and protection of the environment, due to reactants
(substrates and reagents), auxiliaries (mainly solvents) and waste. While all elements of the lifecycle
of a new chemical or process may not be environmentally benign, it is however important to improve
those stages where improvements can be made.

Definition
The term Green Chemistry is defined as -The invention, design and application of chemical
products and processes to reduce or to eliminate the use and generation of hazardous substances.
Green Chemistry is defined as environmentally benign chemical synthesis. Goal of Green Chemistry is
to create better, safer chemicals while choosing the safest, most efficient ways to synthesize them and
to reduce wastes. Green chemistry is the sustainable practice of chemical science and manufacturing
within a framework of industrial ecology in a manner that is sustainable, safe, and non-polluting,
consuming minimum amounts of energy and material resources while producing virtually no wastes.
The key notion of Green Chemistry is efficiency, including material efficiency,
energy efficiency, man-power efficiency, and property efficiency (e.g., desired function vs. toxicity).
Any wastes aside from these efficiencies are to be addressed through innovative Green Chemistry
means. Atom-economy and minimization of auxiliary chemicals, such as protecting groups and
solvents, form the pillar of material efficiency in chemical productions.

Principles of Green Chemistry

Green Chemistry aims to eliminate hazards right at the chemical design stage, then throughout
the design, production, use/reuse and disposal processes. Practitioners of Green Chemistry try hard to
invent new chemical methods that do not pollute and that minimize the consumption of energy and
natural resources. In 1998, two US chemists, Dr. Paul Anastas and Dr John Warner outlined
Twelve Principles of Green Chemistry to demonstrate how chemical production could respect human
health and the environment while also being efficient and profitable.
14

1. It is better to prevent waste than to treat or clean up waste after it is formed:

It is most appropriate to carry out a synthesis by following a pathway so that formation of waste is
minimum or absent. One type of waste product common and often avoidable is the starting material or
reagent that remains unreacted. The well known saying Prevention is better than cure should be
followed.
2. Synthetic methods should be designed to maximize the incorporation of all the materials
used in the process into the final product: A synthesis may generate significant amount of waste or by

product, such a synthesis, even though gives 100% yield, is not considered to be green synthesis.
In order to find, if a particular reaction is green, the concept of atom economy was developed by Berry
Trost of Stanford University. This considers the amount of stating materials incorporated into the
desired final product. Thus by incorporation of greater amounts of the atoms contained in the starting
materials (reactants) in to the formed products, fewer waste by products are obtained. In this way,
using the concept of atom economy along with ideas of selectivity and yield, greener more efficient
synthesis can be developed. The atom economy for a reaction can be calculated using the equation,

3. Whenever practicable synthetic methodologies should be designed to use and generate a

substance

that

poses

little

or

no

toxicity

to

human

health

and

the

environment:

Wherever practicable, synthetic methodologies should be designed to use and generate substances that
pose little or no toxicity to human health and the environment. Redesigning existing transformations to
incorporate less hazardous materials is at the heart of Green Chemistry.
4. Chemical products should be designed to preserve efficiency of function while reducing
toxicity: The designing of safer chemical is now possible since the understanding of chemical toxicity.

It is now fairly understood that a correlation exist between chemical structure (presence of functional
groups) and the existence of toxic effects. The idea is to avoid the functionality related to
the toxic effect.
5. The use auxiliary substances should be made unnecessary wherever possible and
innocuous when used: An auxiliary substance (e.g. solvents, separating agents) are used in the

manufacture, processing at every step, it is one that helps in manufacture of chemical, but does not
become an integral part of the chemical. Major problem with many solvents is their volatility that may
damage human health and the environment. The problem of solvents has been overcome by using such
solvents which do not pollute the environment. Such solvents are known as green solvents.
Examples include liquid supercritical CO2, use near-critical water at higher temperatures where water
behaves more like organic solvent, ionic liquid water, or many new ionic liquids have been developed
with a broad range of properties.

Even reactions have been conducted in solid state.

15

Microwave technology can be used in some reactions to provide the heat energy required to make the
transformation go to completion .With microwave technology, reactions can take place with less toxic
reagents and in a shorter time, with fewer side reactions, all goals of Green Chemistry. Microwave
technology has also been used to create supercritical water that behaves more like an organic solvent
and could replace more toxic solvents in carrying out organic reactions. Another Green Chemistry
approach is the use of a catalyst which facilitates transformations without the catalyst being consumed
in the reaction and without being incorporated in the final product. Therefore, use of catalyst should be
preferred whenever possible.
6. Energy requirements should be recognized for their environmental and economic impacts
and should be minimized: Energy generation, as we know has a major environmental effect.

The requirement of energy can be kept to a base minimum in certain cases by the use of a catalyst.
It is now possible that the energy to a reaction can be supplied by using microwaves, by sonication or
photo chemically.
7. A raw material or feedstock should be renewable rather than depleting, whenever
technically and economically practicable: Non reversible or depleting sources can exhaust by their

continual use. So these are not regarded as sustainable from environmental point of view. The starting
materials which are obtained agricultural or biological processes are referred to as renewable starting
materials. Substances like carbon dioxide (generated from natural sources or synthetic routes like
fermentation) and methane gas (obtained from natural sources such as marsh gas, natural gas, etc)
are available in reasonable amounts and so are considered as renewable starting material.
Methane, a constituent of biogas and natural gas can easily be converted into acetylene by partial
combustion. Acetylene is a potential source of number of chemicals such as ethyl alcohol,
acetaldehyde, vinyl acetate, etc.
8.

Unnecessary

derivatization

(blocking

group,

protection,

deportation,

temporary modification of physical/chemical processes) should be avoided whenever possible:

A commonly used technique in organic synthesis is the use of protecting or blocking group.
These groups are used to protect a sensitive moiety from the conditions of the reaction, which may
make the reaction to go in an unwanted way if it is left unprotected.
9. Catalytic reagents (as selective as possible are superior to stoichiometric reagents:

The catalyst as we know facilitates transformation without being consumed or without being
incorporated into the final product. Catalysts are selective in their action in that the degree of reaction
that takes place is controlled, e.g. mono addition v/s multiple addition. In addition to the benefits of
yield and atom economy, the catalysts are helpful in reducing consumption of energy.
Catalysts carry out thousands of transformation before being exhausted.
16

10. Chemical products should be designed so that at the end of their function they
do not persist in the environment and break down into innocuous degradation products:

It is extremely important that the products designed to be synthesized should be biodegradable.

They should not be persistent chemicals or persistent bio accumulators. It is now possible to place
functional groups in a molecule that will facilitate its biodegradation. Functional groups which are
susceptible to hydrolysis, photolysis or other cleavage have been used to ensure that products will be
biodegradable. It is also important that degradation products do not possess any toxicity and
detrimental effects to the environment.
11. Analytical methodologies need to be further developed to allow for real time,
in process monitoring and control prior to the formation of hazardous substances:

Methods and technologies should be developed so that the prevention or minimization of generation of
hazardous waste is achieved. It is necessary to have accurate and reliable reasons, monitors and other
analytical methodologies to assess the hazardous that may be present in the process stream.
These can prevent any accidents which may occur in chemical plants.
12. Substances and the form of a substance used in a chemical process should be chosen
so as to minimize the potential for chemical accidents, including releases, explosions and fires:

The occurrence of accidents in chemical industry must be avoided. It is well known that the incidents
in Bhopal (India) and Seveso (Italy) and many others have resulted in the loss of thousands of life.
It is possible sometimes to increase accidents potential inadvertently with a view to minimize the
generation of waste in order to prevent pollution. It has been found that in an attempt to recycle
solvents from a process (for economic reasons) increases the potential for a chemical accident or fire.
The principles of green chemistry and some examples of their applications to basic and applied
research are illustrated below:
Prevention of Waste: It is better to prevent waste than to treat or clean up waste after it is
formed. The ability of chemists to redesign chemical transformations to minimize the generation of
hazardous waste is an important first step in pollution prevention.
Maximize Atom Economy: Atom Economy is a concept that evaluates the efficiency of a
chemical transformation, and is calculated as a ratio of the total mass of atoms in the desired product
to the total mass of atoms in the reactants. Choosing transformations that incorporate most of the
starting materials into the product are more efficient and minimize waste. The examples are
[1] DielsAlder reaction is 100%. Atom Economy reaction as all the atoms of the reactants are
incorporated in the cycloadduct. [2] Disinfection of water by chlorination. Chlorine oxidizes the
pathogens there by killing them, but at the same time forms harmful chlorinated compounds.
17

A remedy is to use another oxidant, such as O3 or supercritical water oxidation. [3] Production of allyl
alcohol CH2=CHCH2OH. Traditional route: Alkaline hydrolysis of allyl chloride, which generates the
product and hydrochloric acid as a by-product. CH2=CH-CH2-Cl + H2O CH2=CH-CH2-OH +HCl
Greener route, to avoid chlorine: Two-step using propylene (CH2=CHCH3), acetic acid (CH3COOH)


and oxygen (O2). Step I. CH2=CH-CH3 + CH3-COOH + O2 CH2=CH-CH2-O-CO-CH3 + H2O



Step

II.

CH2=CH-CH2-O-CO-CH3

H2 O

CH2=CH-CH2-OH

CH3-COOH.

Added benefit: The acetic acid produced in the 2nd reaction can be recovered and used again for the
1st reaction, leaving no unwanted by-product.
Less Hazardous Chemical Syntheses: Synthetic methodologies should be designed to use and
generate substances that possess little or no toxicity to human health and environment.
Some toxic chemicals are replaced by safer ones for a green technology, when reagent choices exist
for a particular transformation. This principle focuses on choosing reagents that pose the least risk and
generate only benign by-products. Production of styrene (=benzene ring with CH=CH2 tail).
Traditional route: Two-step method starting with benzene, which is carcinogenic) and ethylene to
form ethylbenzene, followed by dehydrogenation to obtain styrene. Greener route: To avoid benzene,
start with xylene (cheapest source of aromatics and environmentally safer than benzene).
Another option, still under development, is to start with toluene. Phosgene, COCl2, is commonly used
as a starting material for polycarbonate. Phosgene is a highly toxic substance, and the by-products of
many of its reactions are undesirable. A superior alternative might be dimethyl carbonate
Designing Safer Chemicals for Accident Prevention: New products can be designed that are
inherently safer for the target application. Pharmaceutical products often consist of chiral molecules,
and the difference between the two forms can be a matter of life and death for example, racemic
thalidomide when administered during pregnancy, leads to horrible birth defects in many new borns.
Evidence indicates that only one of the enantiomers has the curing effect while the other isomer is the
cause of severe defects. That is why it is vital to be able to produce the two chiral forms separately.
Catalysts that can catalyse important reactions that produce only one of the two mirror image forms
are developed. Design chemicals and their forms (solid, liquid, or gas) to minimize the chemical
accidents including explosions, fires and releases to the environment, e.g., manufacture of gold atom
nano particles used diborane (highly toxic and bursts into flame near room temperature) and cancercausing benzene. Now, diborane has been replaced by environmentally benign NaBH4 which also
eliminates the use of benzene. Nanoscience and nanotechnology is another important contribution to
green chemistry. Nanotechnology provides huge savings in materials by development of microscopic
and submicroscopic electronic and mechanical devices.
18

Atom Economy

Less Hazardous Chemical Syntheses

Polycarbonate Synthesis: Phosgene Process
[phosgene is highly toxic, corrosive]

A superior alternative might be dimethyl

carbonate

Designing Safer Chemicals for Accident Prevention:

Prevention The classical way of synthesis of carbaryl involves
very toxic compounds. It is this production that led to the disaster in Bophal in India in 1984.
Classical way of synthesis

Alternative reaction routes

Designing a Green Synthesis

Using green catalyst is that its action mimics nature in respect that all natural synthesis is
enzyme catalyzed reactions. This not only helps in designing a highly stereo specific, stereo selective
and enantio - selective product but also these reactions
reactions takes place under ambient conditions.
Generally chloroform, DMC, carbon tetra chloride etc are used as a solvent in organic synthesis
which is not only costly but is very harmful for those who is handling them also. Among them carbon
carb
tetrachloride is worst solvent as it is highly environment destructive. In green chemistry an attempt has
been made to minimize or eliminate these effects by using water as a solvent. Not only this super
critical carbon dioxide which are obtained by elevating
elevating the temperature and pressure of the gas above
its critical temperature and pressure. Other super critical fluids used in green chemistry are ethane,
ethene, water, xenon etc.
A great attempt has been made to shift the usage of petroleum based products
produc which currently
forms 95% of cases as a starting material for various chemicals required in tons per year.
On this basis shifting to biomass for such a vast need is the call of an hour. Researchers are now
finding new ways of converting biomass into starting material. E.g. converting D-glucose
D
into lactic
acid using certain enzymes helps us to prepare aliphatic compounds from lactic acid.
19

On a similar basis E-coli converts D-glucose to catechol which acts as a starting material for aromatic
compounds. On the other hand isomaltulose which is widely available in biomass can be converted
into glucosylmethyl furfural which can be used for production of many heterocyclic compounds.
Besides biomass cash crops is a new hope as ethanol from sugarcane has been derived successfully
and now scientists are trying to use this bio alcohol as a source of vehicle for future.
Exhaust from Corn plant has been successfully utilized for preparing bio-degradable plastic.
In a chemical reaction the major concern is the percent yield of desired product.
If the yield in a chemical reaction is satisfactory we hardly bother about the formation of
bi-products. An attempt has been made to further maximize the yield of the desired products by
developing such reactions which are catalyzed reactions whose catalyst can be extracted and further
utilized for other reactions. These reactions are further focused to undergo addition reactions,
rearrangements or pericyclic reaction where a single product is obtained which further increases the
atom efficiency. . For reactions whose desired product is a chiral compound, it is advisory to design
such reactions which eliminates the formation of racemic mixtures. Hence these type of synthesis
should always be either highly stereo-specific or either highly stereo-selective.
Minimizing the energy requirements of industries by maximizing the efficiency of chemical
conversion and decreasing the activation energy of the reactions by using recyclable catalysts can cut
off the energy requirement of industries by half or even more. Eliminating the use of energy
consuming steps like distillation, crystallization, sublimation, ultra filtration etc. and incorporation of
microwave energy which aims to achieve a high temperature at much faster rates and also utilization
of ultrasonic energy for certain reaction can eventually solve this problem.
Besides the above mentioned pillars of green chemistry some other points that can also been
incorporated as the supports of green chemistry are as follows: (a) Use of light as a carrier of
electrons which can eventually reduce the usage of other chemical agents which act as a carrier of
electron and is obtained as waste products at the end of a redox reaction. (b) Eliminating the unnecessary use of protection- deprotection methodologies. (c) Replacement of soluble Lewis acids by
mesoporous solids containing bound sulphonates in green synthesis.(d) Utilization of milder reaction
conditions for carrying out a chemical reaction.
Green chemistry is not a solution to all environmental problems but the most fundamental
approach to preventing pollution. Green chemistry is more effective, efficient, elegant, safe and better
chemistry.

20

Polymers
The word Polymer is coined from two Greek words: poly means many and mer means unit or
part. The term polymer is defined as very large molecules having high molecular mass. These are also
referred to as macromolecules, which are formed by joining of repeating structural units on a large
scale. The repeating structural units are derived from some simple and reactive molecules known as
monomers and are linked to each other by covalent bonds. This process of formation of polymers from
respective monomers is called polymerization. The transformation of ethene to polythene and
interaction of hexamethylene diamine and adipic acid leading to the formation of Nylon 6, 6 are
examples of two different types of polymerisation reactions.

The functionality of a monomer is the number of sites it has for bonding to other monomers
under the given conditions of the polymerization reaction. Thus, a bifunctional monomer, i.e.,
monomer with functionality two, can link to two other molecules under suitable conditions.
A polyfunctional monomer is one that can react with more than two molecules under the conditions of
the polymerization reactions.
The

number

of

repeating

units

(n)

in

the

chain

so

formed

is

called

the

degree of polymerization (DP = n). Polymers with a high degree of polymerization are called
high polymers and those with low degree of polymerization are called oligopolymers
(short chain polymers or oligomers). Polymers do not exhibit strength for n < 30 and
that the optimum strength of most of the polymers is obtained at n around 600.
The useful range of n is from 200 to 2000.

21

There are several ways of classification of polymers based on some special considerations.
The following are some of the common classifications of polymers: [1] by Source [2] by Backbone of
the chain [3] by Structure [4] by Compostion [5] by Mode of Polymerization [6] by Molecular force
Classification Based on Source: [1] Natural Polymers: These polymers are found in plants
and

animals.

Examples

are

proteins,

cellulose,

starch,

resins

and

rubber.

[2] Semi-synthetic Polymers: Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate,
etc. are the usual examples of this sub category. [3] Synthetic Polymers: A variety of synthetic
polymers as plastic (polythene), synthetic fibres (nylon 6,6) and synthetic rubbers (Buna - S) are
examples of man-made polymers.
Classification Based on Backbone of the polymer chain: Organic and Inorganic Polymers:
A polymer whose backbone chain is essentially made of carbon atoms is termed as organic polymer.
The atoms attached to the side valencies of the backbone carbon atoms are, however, usually those of
hydrogen, oxygen, nitrogen, etc. The majority of synthetic polymers are organic. On the other hand,
generally chain backbone contains no carbon atom is called inorganic polymers. Glass and silicone
rubber are examples of it.
Classification Based on Structure of Polymers: [1] Linear Polymers: These polymers consist
of long and straight chains. The examples are high density polythen, PVC, etc. Linear polymers are
commonly relatively soft, often rubbery substances, and often likely to soften (or melt) on heating and
to dissolve in certain solvent. [2] Branched Polymers: These polymers contain linear chains having
some branches, e.g., low density polythene. [3] Cross-linked Polymers: These are usually formed from
bi-functional and tri-functional monomers and contain strong covalent bonds betweenvarious linear
polymer chains, e.g. vulcanized rubber, urea-formaldehyde resins, etc. Cross linked polymers are hard
and do not melt, soften or dissolve in most cases.

Linear Polymers

Branched Polymers

Cross-linked Polymers

Classification Based on Composition of Polymers: [1] Homopolymer: A polymer resulting

from the polymerization of a single monomer; a polymer consisting substantiallyof a single type of
repeating unit. [2] Copolymer: When two different types of monomers are joined in the same polymer
chain, the polymer is called a copolymer.

22

Let's imagine now two monomers (A and B) made into a copolymer in many different ways.
In an alternating copolymer, the two monomers are arranged in an alternating fashion.
In a random copolymer, the two monomers may followin any order. In a block copolymer,
all of one type of monomers are grouped together, and all of the other are grouped together.
In graft copolymer, a block copolymer can be thought of as two homopolymers joined together at the
ends: branched copolymers with one kind of monomers in their main chain and another kind of
monomers in their side chains.
Alternating
Random
Block

Graft

Copolymerization: A heteropolymer or copolymer is a polymer derived from two

(or more) monomeric species, as opposed to a homopolymer where only one monomer is used.
Copolymerization refers to methods used to chemically synthesize a copolymer. Commercially
relevant

copolymers

include

ABS

plastic,

SBR,

Nitrile

rubber,

styrene-acrylonitrile,

styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate.

Classification Based on Mode of Polymerisation: Polymers can also be classified
on the basis of mode of polymerisation into two sub groups; (a) Addition Polymers and
(b) Condensation Polymers.
Addition Polymers: The addition polymers are formed by the repeated addition of monomer
molecules possessing double or triple bonds, e.g., the formation of polythene from ethene and
polypropene from propene. However, the addition polymers formed by the polymerisation of a single
monomeric species are known as homopolymer, e.g., polythene.

The polymers made by addition polymerisation from two different monomers are termed as
copolymers, e.g., Buna-S, Buna-N, etc.

23

Condensation Polymers: The condensation polymers are formed by repeated condensation

reaction between two different bi-functional or tri-functional monomeric units. In these polymerisation
reactions, the elimination of small molecules such as water, alcohol, hydrogen chloride, etc. take
place. The examples are terylene (dacron), nylon 6, 6, nylon 6, etc. For e.g., nylon 6, 6 is formed by
the condensation of hexamethylene diamine with adipic acid.

It is also possible, with three functional groups (or two different monomers at least one of
which is tri-functional), to have long linkage sequences in two (or three) dimensions and
such polymers are distinguished as cross linked polymers.
Classification Based on Molecular Forces: The mechanical properties of polymers
are governed by intermolecular forces, e.g., van der Waals forces and hydrogen bonds,
present in the polymer. These forces also bind the polymer chains. Under this category,
the polymers are classified into the following groups on the basis of magnitude of intermolecular
forces

present

in

them.

They

are

(i)

Elastomers

(ii)

Fibers

(iii)

Liquid

resins

(iv) Plastics [(a) Thermoplastic and (b) thermosetting plastic].

Elastomers: These are rubber like solids with elastic properties. In these elastomeric
polymers, the polymer chains are held together by the weakest intermolecular forces.
These weak binding forces permit the polymer to be stretched. A few crosslinks are introduced in
between the chains, which help the polymer to retract to its original position after the force is released
as in vulcanised rubber. The examples are buna-S, buna-N, neoprene, etc.
Fibers: If drawn into long filament like material whose length is at least 100 times its diameter,
polymers are said to have been converted into fibre. Fibres are the thread forming solids which
possess high tensile strength and high modulus. These characteristics can be attributed to the strong
intermolecular forces like hydrogen bonding. These strong forces also lead to close packing of chains
and thus impart crystalline nature. Examples are polyamides (nylon 6, 6), polyesters (terylene), etc.
Liquid Resins: Polymers used as adhesives, potting compound sealants, etc. in a liquid form
are described liquid resins. Examples are epoxy adhesives and polysulphide sealants.
Plastics: A polymer is shaped into hard and tough utility articles by the application
of heat and pressure; it is used as a plastic. Typical examples are polystyrene, PVC
and polymethyl methacrylate. They are two types (a) thermoplastic and (b) thermosetting plastic.

24

Thermoplastic Polymers: Some polymers soften on heating and can be converted into any
shape that they can retain on cooling. The process of heating, reshaping and retaining the same on
cooling can be repeated several times. Such polymers, that soften on heating and stiffen on cooling,
are termed thermoplastics. These are the linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardening on cooling. These polymers possess intermolecular
forces of attraction intermediate between elastomers and fibres. Polyethylene, PVC, nylon and sealing
wax are examples of thermoplastic polymers.
Thermosetting Polymers: Some polymers, on the other hand, undergo some chemical change
on heating and convert themselves into an infusible mass. They are like the yolk of egg,
which on heating sets into a mass, and, once set, cannot be reshaped. Such polymers, that become
infusible and insoluble mass on heating, are called thermosetting polymers. These polymers are
cross linked or heavily branched molecules, which on heating undergo extensive cross linking in
moulds and again become infusible. These cannot be reused. Some common examples are bakelite,
urea-formaldelyde resins, etc.

25

Types of Polymerization
There are four types of polymerisation reactions; (a) Addition or chain growth polymerisation
(b)

Coordination

polymerisation

(c)

Condensation or

step

growth polymerisation

and

(d) Copolymerization
Addition Polymerisation: In this type of polymerisation, the molecules of the same monomer
or different monomers add together on a large scale to form a polymer. The monomers normally
employed in this type of polymerization contain a carbon-carbon double bond (unsaturated
compounds, e.g., alkenes and their derivatives) that can participate in a chain reaction.
A chain reaction consists of three stages, Initiation, Propagation and Termination.
In the Initiation step an initiator molecule is thermally decomposed or allowed to undergo a
chemical reaction to generate an "active species." This "active species," which can be
a free radical or a cation or an anion, then initiates the polymerization by adding to the monomer's
carbon-carbon double bond. The reaction occurs in such a manner that a new free radical or cation or
anion is generated. The initial monomer becomes the first repeat unit in the incipient polymer chain.
In the Propagation step, the newly generated "active species" adds to another monomer in the same
manner as in the initiation step. This procedure is repeated over and over again until the final step of
the process, termination, occurs. In the Termination step,

the growing chain terminates through

reaction with another growing chain, by reaction with another species in the polymerization mixture,
or by the spontaneous decomposition of the active site. Under certain conditions, anionic can be
carried out without the termination step to generate so-called "living" polymers.
The

following

are

several

general

characteristics

of

addition

polymerization:

[1] Once initiation occurs, the polymer chain forms very quickly [2] The concentration of active
species is very low. Hence, the polymerisation mixture consists of primarily of newly-formed polymer
and unreacted monomer [3] Since the carbon-carbon double bonds in the monomers are, in effect,
converted to two single carbon-carbon bonds in the polymer, so energy is released making the
polymerization exothermic with cooling often required.
The mechanism of addition polymerisation can be divided broadly into two main classes,
free radical polymerization and ionic polymerization, although there are some others.
Ionic polymerisation was probably the earliest type to be noted, and is divided into
cationic and anionic polymerisations.
Free radical polymerization: A variety of alkenes or dienes and their derivatives are
polymerised in the presence of a free radical generating initiator (catalyst) like benzoyl peroxide,
acetyl peroxide, tert-butyl peroxide, etc. A free radical may be defined as an intermediate compound
26

containing an odd number of electrons, but which do not carry an electric charge and are not free ions.
For example, the polymerization of ethene to polythene consists of heating or exposing to light a
mixture of ethene with a small amount of benzoyl peroxide initiator.
The first stage of the chain reaction is the initiation process; this process starts with the
addition of phenyl free radical formed by the peroxide to the ethene double bond thus generating a
new and larger free radical.

The second stage of the chain reaction is the propagation process, the radical reacts with
another molecule of ethene, and another bigger sized radical is formed. The repetition of this sequence
with new and bigger radicals carries the reaction forward and the step is chain propagating step

The final stage of the chain reaction is the termination process; the product radical formed
reacts with another radical to form the polymerised product.

Ionic Polymerisation:

The

addition

polymerization

that

takes

place

due

to

ionic intermediate is called ionic polymerization. Based on the nature of ions used for the initiation
process ionic polymerization classified into two types; (a) Cationic polymerization and
(b) Anionic polymerization
Cationic polymerization depends on the use of cationic initiators which include reagents
capable of providing positive ions or H+ ions. Typical examples are aluminium chloride with water
(AlCl3+H2O) or boron trifluoride with water (BF3+H2O). They are effective with monomers
containing

electron

releasing

groups

like

methyl

(-CH3)

or

phenyl

(-C6H5)

etc.

They include propylene(CH3CH=CH2) and the styrene (C6H5CH=CH2).

i) Chain Initiation: Decomposition of the initiator is shown as BF3 + H2O
H+ + BF3(OH). The proton (H+) adds to C C double bond of alkene to form stable carbocation.

27

ii) Chain Propagation: Carbocation add to the C C double bond of another monomer molecule to
from new carbocation.

iii) Chain Termination: Reaction is terminated by combination of carbocation with negative ion (or)
by loss of proton

Anionic polymerization depends on the use of anionic initiators which include reagents
capable of providing negative ions. Typical catalysts include sodium in liquid ammonia,
alkali

metal

alkyls,

Grignard

reagents

and

triphenylmethyl

sodium

[(C6H5)3C-Na].

They are effective with monomers containing electron withdrawing groups like nitrile (CN) or
chloride (-Cl), etc. They include acrylonitrile [CH2=C(CN)], vinyl chloride [CH2=C(Cl)],
methyl methacrylate [CH2=C(CH3)COOCH3], etc.
i) Chain Initiation: Potassium amide (K+NH2-) adds to C C double bond of alkene to form stable
carbanion.

where W is electron withdrawing group

ii) Chain Propagation: Carbanion adds to the C C double bond of another monomer molecule to
from new carbanion.

iii) Anionic polymerization has no chain termination reaction. So it is called living polymerization.
28

Coordination polymerization: It is also a subclass of addition polymerization. It usually

involve transition-metal catalysts. Here, the "active species" is a coordination complex, which initiates
the polymerization by adding to the monomers carbon-carbon double bond. The most important
catalyst for coordination polymerization is so-called Ziegler-Natta catalyst discovered to be effective
for alkene polymerization. Ziegler-Natta catalysts combine transition-metal compounds such as
chlorides of titanium with organometallic compounds [TiCl3 with Al(C2H5)3]. An important property
of these catalysts is that they yield stereoregular polymers when higher alkenes are polymerized,
e.g., polymerization of propene produces polypropene with high selectivity. Branching will not occur
through this mechanism since no radicals are involved; the active site of the growing chain is the
carbon atom directly bonded to the metal.
Zeigler-Nata catalysts: These are a special type of coordination catalysts, comprising two
components, which are generally referred to as the catalyst and the cocatalyst. The catalyst component
consists of chlorides of titanium (TiCl3 and TiCl4) and the cocatalysts are organometallic compound
such as triethyl aluminium (Al(C2H5)3).
Triethyl aluminium [Al(R)3] act as the electron acceptor whereas the electron donor is titanium
halides and the combination, therefore, readily forms coordination complexes (Fig.

1).

The complex formed, now acts as the active centre. The monomer is complexed with the metal ion of
the active centre in a way that the monomers attached towards the TiC bond (C from the
alkyl group R) in the active centre, when it forms a complex with the Ti ion(Fig. 2).

Figure. 1

Figure. 2

The bonds between R and Ti opens up producing an electron deficient Ti and

a carbanion at R (Fig. 3). The Ti ion attracts the electrons pair or the monomer and forms bond
(Fig. 4). This transition state now gives rise to the chain growth at the metal carbon bond, regenerating
the active centre (Fig. 5). Repeating the whole sequence, with the addition of second monomer
molecule, we will get the structure of the resultant chain growth as shown in Fig. 6.

Figure. 3

Figure. 4

Figure. 5

Figure. 6
29

Condensation Polymerisation: This type of polymerisation generally involves a repetitive

condensation reaction (two molecules join together, resulting loss of small molecules) between two bifunctional monomers. These polycondensation reactions may result in the loss of some simple
molecules as water, alcohol, etc., and lead to the formation of high molecular mass condensation
polymers. In these reactions, the product of each step is again a bi-functional species and the sequence
of condensation goes on. Since, each step produces a distinct functionalised species and is independent
of each other; this process is also called as step growth polymerisation. The type of end polymer
product resulting from a condensation polymerization is dependent on the number of functional end
groups of the monomer which can react.
Monomers with only one reactive group terminate a growing chain, and thus give end products
with a lower molecular weight. Linear polymers are created using monomers with two reactive end
groups and monomers with more than two end groups give three dimensional polymers
which are cross linked.
Polyester is created through ester linkages between monomers, which involve the functional
groups carboxyl and hydroxyl (an organic acid and an alcohol monomer). The formation of polyester
like terylene or dacron by the interaction of ethylene glycol and terephthalic acid is an example of this
type of polymerisation.
30

Polyamide is created through amide linkages between monomers, which involve the functional
groups carboxyl and amine (an organic acid and an amine monomer). Nylon-6 is an example which
can be manufactured by the condensation polymerisation of hexamethylenediamine with adipic acid
under high pressure and at high temperature.

This type of polymerization normally employs two difunctional monomers that are capable of
undergoing typical organic reactions. For example, a diacid can be allowed to react with a diol in the
presence of an acid catalyst to afford polyester. In this case, chain growth is initiated by the reaction of
one of the diacid's carboxyl groups with one of the diol's hydroxyl groups. The free carboxyl or
hydroxyl group of the resulting dimer can then react with an appropriate functional group in another
monomer or dimer. This process is repeated throughout the polymerization mixture until all of the
monomers are converted to low molecular weight species, such as dimers, trimers, tetramers, etc.
These molecules, which are called oligomers, can then further react with each other through their free
functional groups. Polymer chains that have moderate molecular weight can he built in this manner.

31

The following are several general characteristics of this type of polymerization:

(1) The polymer chain forms slowly, sometimes requiring several hours to several days
(2) All of the monomers are quickly converted to oligomers, thus, the concentration of growing chains
is high (3) Since most of the chemical reactions employed have relatively high energies of activation,
the polymerization mixture is usually heated to high temperatures (4) Step-reaction polymerizations
normally afford polymers with moderate molecular weights, i.e., <100,000 (5) Branching or
crosslinking does not occur unless a monomer with three or more functional groups is used.

Copolymerization: It is a polymerisation reaction in which a mixture of more than one

monomeric species is allowed to polymerize and form a copolymer. The copolymer can be made not
only by chain growth polymerisation but by step growth polymerisation also. It contains multiple units
of each monomer used in the same polymeric chain. For example, a mixture of styrene and
1, 3 butadiene can form a copolymer called styrene butadiene rubber (SBR).

32

Technology of Polymerization
Monomers may be polymerised by the following methods (1) polymerization in homogeneous
systems (2) polymerization in heterogeneous systems
Polymerization in Homogeneous systems: The homogeneous polymerization techniques
involve pure monomer or homogeneous solutions of monomer and polymer in a solvent.
These techniques can be divided into two methods: (i) the bulk and (ii) the solution polymerizations.
Bulk polymerization: Bulk polymerization is the simplest technique and produces the highestpurity polymers. Only monomer, a monomer-soluble initiator are used. This method helps easy
polymer recovery and minimum contamination of product. The viscosity of the mixture is low initially
to allow ready mixing, heat transfer, and bubble elimination. This method is used for the preparation
of polyethene, polystyrene, etc. Disadvantages: Reaction medium becomes increasingly viscous as
reaction goes to higher conversion, making stirring, heat removal and processing more difficult.
It leads to uneven polymerization and loss of monomer. Free-radical polymerizations are typically
highly exothermic. An increase temperature will increase the polymerization rate; generate heat
dissipation and a tendency to develop of localized hot spots. Near the end of polymerization, the
viscosity is very high and difficult to control the rate as the heat is trapped inside. It leads to the
autoacceleration process in which the propagation rate is very higher than that of termination rate. This
method is seldom used in commercial manufacture.
Solution polymerization: This method is used to solve the problems associated with the bulk
polymerization because the solvent is employed to lower the viscosity of the reaction, thus help in the
heat transfer and reduce autoacceleration. It requires the correct selection of the solvents. Both the
initiator and monomer be soluble in each other and that the solvent are suitable for boiling points,
regarding the solvent-removal steps. It is often used to produce copolymers. This method is used for
the preparation of polyvinyl acetate, poly (acrylic acid), and polyacrylamide.
Advantages: (i) Solvent has low viscosity, reaction mixture can be stirred (ii) Solvent acts as a
diluent and aids in removal of heat of polymerization (iii) Solvent reduces viscosity, making
processing easier (iv) Thermal control is easier than in the bulk and (v) Cheap materials for the
reactors (stainless steel or glass lined). Disadvantages: (i) Reduce monomer concentration which
results in decreasing the rate of the reaction and the degree of polymerization (ii) Mobility is reduced
and this can affect termination events, so the rate of reaction is increased (iii) Solvent may terminate
the growing polymer chain, leading to low molecular weight polymers (iv) Difficult to remove solvent
from final form, causing degradation of bulk properties (v) Clean up the product with a non solvent or
evaporation of solvent (vi) Small production per reactor volume (vii) Not suitable for dry polymers.
33

Polymerization in heterogeneous systems: Polymerization occurs in disperse phase as large

particles in water or occasionally in another non-solvent (suspension polymerisation), or dispersed as
fine particles. The last-named process is usually known as emulsion polymerisation.
Suspension (Bead or Pearl) polymerisation: Monomer, initiator (must soluble in monomer)
and polymer must be insoluble in the suspension media such as water i.e., the reaction mixture is
suspended as droplets in an inert medium. Suspension polymerization consists of an aqueous system
with monomer as a dispersed phase and results in polymer as a dispersed solid phase. This method is
used for the preparation of polystyrene, polyvinyl chloride, polyvinyl acetate, etc.
A reactor fitted with a mechanical agitator is charged with a water insoluble monomer and
initiator. Droplets of monomer (containing the initiator) are formed. As the polymerization proceeds,
the viscosity of dispersed phase increases and they become sticky. Aggregation of these sticky droplets
is prevented by the addition of a dispersing agent (protective colloid, e.g., water-soluble colloid such
as gum acacia). Near the end of polymerization, the particles are hardened, are the bead or pearl
shaped polymers recovered by filtration, and followed by washing step.
Advantages: (i) Polymerisation to high conversion (ii) Low viscosity due to the suspension
(iii) Easy heat removal due to the high heat capacity of water (iv) Excellent heat transfer because of
the

presence

of

the

solvent

(v)

Solvent

cost

and

recovery

operation

are

cheap

(vi) Polymerization yields finely divided, stable latexes and dispersions to be used directly in coatings,
paints, and adhesives. Disadvantages: (i) Contamination by the presence of suspension and other
additives low polymer purity (ii) Must separate and purify polymer, or accept contaminated product
(iii) Reactor cost may higher than the solution cost
Emulsion polymerisation: An emulsion polymerization consists of water (as the heat-transfer
agent), monomer, initiator (is soluble in water and insoluble in the monomer), a surfactant or
emulsifier (such as sodium salt of long-chain fatty acid). This method is used for the preparation of
polyvinyl acetate, polychloroprene, butadiene/styrene/acrylonitrile copolymers, etc.
A typical recipe for emulsion polymerization consists of water, monomer, fatty acid soap
(emulsifying agent), and water soluble initiator. When a small amount of soap is added to water,
the soap ionizes and the ions move around freely. The soap anion consists of a long oil-soluble portion
(R) terminated at one end by the water-soluble portion. So emulsifier molecules arrange themselves
into colloidal particles called micelles. In water containing a insoluble monomer molecule, the soap
anion molecules orient themselves at the watermonomer interfaces with the hydrophilic ends facing
the water, while the hydrophobic ends face the monomer phase. When the water-soluble initiator
undergoes thermal decomposition to form the water-soluble radicals react with monomer dissolved in
34

interior of the micelle. Emulsion polymerization takes place almost exclusively in the micelles.
As polymerization proceeds, the active micelles consume the monomers within the micelle.
Monomer depletion within the micelle is replenished first from the aqueous phase and subsequently
from the monomer droplets. The active micelles grow in size with polymer formation, to preserve their
stability;

these

growing

polymer

particles

absorb

the

soap

of

the

parent

micelles.

Advantages: (i) Overcomes many environmental problems: solvent is water (ii) If final desired
product is polymer is washed with water to remove the soap phase by coagulation

Bulk

Solution
Suspension

Suspension

Emulsion
Emulsion

Concept of Glass Transition Temperature (Tg)

The glass transition temperature (Tg) is the temperature at which the internal energy of the
chains of the polymer increases such as extends that the chains just starts leaving their lattice sites.
It is the temperature at which a hard amorphous polymer becomes soft. It is the transformation from a
rigid material to one that has rubber like characteristics and temperature has large effect on chain
flexibility. Below glass transition temperature (Tg), polymers are usually hard, brittle and glass-like in
mechanical behavior. Above glass transition (Tg), polymers are usually more soft and rubbery (elastic).
Why is that? bond rotations are freezing which means chains cant slip past each other so polymer
becomes brittle.
35

Melting of a crystalline polymer (Tm): Transforming solid with an ordered structure to a

viscous liquid with a highly random structure. It is the temperature at which the crystalline regions of
the polymer melt to become amorphous. More ordered polymers have higher Tm

In the study of polymers and their applications, it is important to understand the concept of the
glass transition temperature Tg. The glass transition is a phenomenon observed in linear amorphous
polymer. It occurs at fairly well defined temperature when the bulk material ceases to be brittle and
glassy in character and become less rigid and more rubbery. The knowledge of Tg is essential in the
selection of materials for various applications.
Many Physical properties change profoundly at the glass transition temperature, including
mechanical properties and electrical properties. All of these are dependent on the relative degree of
freedom for molecular motion within a given polymeric material and each can be used to monitor the
point at which the glass transition occur.
36

Factors affecting glass transition temperature: Any structural features or externally imposed
conditions that influence chain mobility will also affect the value of Tg. Some of these structural
factors include chain flexibility; stiffness, including steric hindrance, polarity, or interchain attractive
forces; geometric factors; copolymerization; molecular weight, branching; cross-linking; and
crystallinity. External variables are plasticization, pressure, and rate of testing.
1. Chain Flexibility: Chain flexibility is determined by the ease with which rotation occurs about
primary valence bonds. Polymers with low hindrance to internal rotation have low Tg values.
Long-chain aliphatic groups ether and ester linkages enhance chain flexibility, while rigid
groups like cyclic structures stiffen the backbone.
2. Geometric Factors: Geometric factors, such as the symmetry of the backbone and the presence of
double bonds on the main chain, affect Tg. Polymers that have symmetrical structure have lower Tg
than those with asymmetric structures. Additional groups near the backbone for the symmetrical
polymer would enhance steric hindrance and consequently raise Tg. Another geometric factor affecting
Tg is cistrans configuration. Double bonds in the cis form reduce the energy barrier for rotation of
adjacent bonds, soften the chain, and hence reduce Tg.
3. Interchain Attractive Forces: Intermolecular bonding in polymers is due to secondary attractive
forces. Consequently, it is to be expected that the presence of strong intermolecular bonds in a
polymer chain, i.e., a high value of cohesive energy density, will significantly increase Tg.
The steric effects of the groups like CH3, Cl, and CN are similar, but the polarity increases,
consequently, Tg is increased. The same effect of increased Tg when one considers going from the
intermolecular forces in poly(methyl acrylate), an ester, through the strong hydrogen bonds in
poly(acrylic acid) to primary ionic bonds in poly(zinc acrylate). Secondary bonding forces are
effective only over short molecular distances. Therefore, any structural feature that tends to increase
the distance between polymer chains decreases the cohesive energy density and hence reduces Tg.
4. Copolymerization: It is desirable to be able to control Tg, however, this is often impossible.
Polymer chemists have circumvented this problem to some extent by copolymerization.
A copolymer system may be characterized by the arrangement of the different monomers
(random, alternating, graft, or block). The increased disorder resulting from the random or
alternating distribution of monomers enhances the free volume and consequently reduces Tg.
For block or graft copolymers in which the component monomers are incompatible, phase separation
will occur. Two separate glass transition values will be observed, each corresponding to the Tg of the
homopolymer.

37

5. Molecular Weight: Since chain end segments are restricted only at one end, they have relatively
higher mobility than the internal segments, which are constrained at both ends. At a given temperature,
therefore, chain ends provide a higher free volume for molecular motion. As the number of chain ends
increases (which means a decrease in molecular weight), the available free volume increases,
and consequently there is a depression of Tg.
6. Cross-Linking and Branching: By definition, cross-linking involves the formation intermolecular
connections through chemical bonds. This process necessarily results in reduction in chain mobility.
Consequently,

Tg

increases.

For

lightly

cross-linked

systems

like

vulcanized

rubber,

Tg shows a moderate increase over the uncross-linked polymer. For highly cross-linked systems like
phenolics and epoxy resins, the glass transition is virtually infinite. This is because the molecular chain
length between cross-links becomes smaller than that required for cooperative segmental motion.
Like long and flexible side chains, branching increases the separation between chains, enhances the
free volume, and therefore decreases Tg.
7. Crystallinity: In semicrystaline polymers, the crystallites may be regarded as physical cross-links
that tend to reinforce or stiffen the structure. Viewed this way, it is easy to visualize that Tg will
increase with increasing degree of crystallinity.
8. Plasticization: Plasticity is the ability of a material to undergo plastic or permanent deformation.
Consequently, plasticization is the process of inducing plastic flow in a material. In polymers, this can
be achieved in part by the addition of low-molecular-weight organic compounds referred to as
plasticizers. Plasticizers are usually nonpolymeric, organic liquids of high boiling points. Plasticizers
are miscible with polymers and, in principle, should remain within the polymer. Addition of
plasticizers to a polymer, even in very small quantities, drastically reduces the Tg of the polymer.
Plasticizers function through a solvating action by increasing intermolecular distance, thereby
decreasing intermolecular bonding forces.

Crystallinity in polymers
Linear and branched polymers do not form crystalline solids because their long chains prevent
efficient packing in a crystal lattice. Most polymer chains have crystalline regions and amorphous
regions: Ordered crystalline regions, called crystallites, are places where sections of the polymer chain
lie in close proximity and are held together by intermolecular interactions. Ordered regions of
polyethylene, are held together by van der Waals interactions, whereas ordered regions of nylon chains
are held together by intermolecular hydrogen bonding. Amorphous regions are places where the
polymer

chains

are

randomly

arranged,

resulting

in

weak

intermolecular

interactions.

Crystalline regions impart toughness to a polymer, while amorphous regions impart flexibility.
38

The greater the Crystallinity of a polymerthat is, the larger the percentage of ordered regionsthe
harder the polymer. Branched polymers are generally more amorphous and, since branching prevents
chains from packing closely, they are softer, too.
Although it may at first seem surprising, polymers can form crystal structures (all we need is a
repeating unit, which can be based on molecular chains rather than individual atoms).
Some parts of structure align during cooling to form crystalline regions (chains align alongside each
other). Around crystallites get amorphous regions. Most real polymers contain both amorphous and
crystalline regions, called semicrystaline.
The morphology of most polymers is semi-crystalline. That is, they form mixtures of small
crystals and amorphous material and melt over a range of temperature instead of at a single melting
point. The crystalline material shows a high degree of order formed by folding and stacking of the
polymer chains. An amorphous solid is formed when the chains have little orientation throughout the
bulk polymer. The amorphous or glass-like structure shows no long range order, and the chains are
tangled as illustrated below. There are some polymers that are completely amorphous, but most are a
combination with the tangled and disordered regions (amorphous regions) surrounding the crystalline
areas called semicrystaline. Such a combination is shown in the following diagram.

Crystalline

Amorphous

Crystalline and Amorphous regions

Semicrystaline
39

In the crystallization process, it has been observed that relatively short chains organize
themselves into crystalline structures more readily than longer molecules. Therefore, the degree of
polymerization (DP) is an important factor in determining the Crystallinity of a polymer. Polymers
with a high DP have difficulty organizing into layers because they tend to become tangled.
The cooling rate also influences the amount of Crystallinity. Slow cooling provides time for
greater amounts of crystallization to occur. Fast rates, on the other hand, such as rapid quenches, yield
highly amorphous materials. Subsequent annealing (heating and holding at an appropriate temperature
below the crystalline melting point, followed by slow cooling) will produce a significant increase in
Crystallinity in most polymers, as well as relieving stresses.
Low molecular weight polymers (short chains) are generally weaker in strength. Although they
are crystalline, only weak Van der Waals forces hold the lattice together. This allows the crystalline
layers to slip past one another causing a break in the material. High DP (amorphous) polymers,
however, have greater strength because the molecules become tangled between layers. In the case of
fibers, stretching to 3 or more times their original length when in a semi-crystalline state produces
increased chain alignment, Crystallinity and strength. In most polymers, the combination of crystalline
and amorphous structures forms a material with advantageous properties of strength and stiffness.
Also influencing the polymer morphology is the size and shape of the monomers' substituent
groups. If the monomers are large and irregular, it is difficult for the polymer chains to arrange
themselves in an ordered manner, resulting in a more amorphous solid. Likewise, smaller monomers,
and monomers that have a very regular structure (e.g. rod-like) will form more crystalline polymers.
% Crystallinity depends on several factors: Rate of cooling (faster cooling less Crystallinity).
Type of polymer (simple structures more Crystallinity, Copolymers less Crystallinity).
Linear polymers more easily form crystals. Degree of Crystallinity ranges from 5 - 95% The higher % Crystallinity higher strength. When polymers are crystallized they form spherical
structures called spherulites.

Physical properties of polymers

40

Mechanical properties of polymers

(Density, Tensile, Tear, Abrasion resistance, Resilience)

41

Engineering applications of polymers are governed to a great extent by strain hardening

considerations. The designer using polymeric materials must, therefore, understand their mechanical
behaviour with respect to the maximum permissible strains to avoid failure. As for most materials, a
simple tensile stress-strain curve provides a good start towards understanding the mechanical
behaviour of a particular polymer. This curve is usually established by continuously measuring the
force developed as the sample is elongated at constant rate of extension until it breaks.
Portions of the curve in Fig.1 represent the stress-strain behaviour of any polymer and are used to
define several useful quantities.
The initial slope provides a value for Young's modulus (or the modulus of elasticity) which is a
measure of stiffness. The curve also gives yield stress, strength and elongation at break.
The area under the curve or work to break is a rough indication of the toughness of the polymeric
material. The stress at the knee in the curve (known as the yield point) is a measure of the strength of
the material and resistance to permanent deformation. The stress at the breaking point, commonly
known as ultimate strength, is a measure of the force required to fracture the material completely.

Hard and Brittle material such as an amorphous polymer far below its Tg, usually has an
initial slope indicative of very high modulus, moderate strength, a low elongation at break, and a low
area under the stress-strain curve. Polymeric materials showing hard brittle behaviour at room
temperature or below are polystyrene, poly(methyl methacrylate) and phenol-formaldehyde resins.
Hard and Strong polymers have high modulus of elasticity, high strength, and elongation at
break of approximately 5 percent. The shape of the curve often suggests that the material has broken
where a yield point might be expected. This type of curve is characteristic of thermoplastics such as
poly(vinyl chloride) formulations and polystyrene polyblends.
Hard and Tough polymers have high yield points, high modulus, high strength and large
elongations. This behaviour is shown by polymers such as fibers like rayon, dacron and nylons.
Soft and tough polymers have low yield points, low modulus, moderate strength at break,
and very high elongation ranging from 20 to 100 percent. This behaviour is shown by polymers such
as elastomers like NR, SBR, and NBR
42

Hardness: The ability of a polymer to resist scratching, abrasion, cutting, or penetration. It is measured by its ability to
absorb energy under impact loads. It is also a measure of the wearing quality of a material and it is an indication of machinability
qualities of the polymer. Toughness: It is the amount of energy a polymer can absorb before actual fracture or failure takes place.
The ability of a polymer to withstand shock and vibrations. It is related to impact strength, i.e., resistance to shock loading.
It is the ability of a polymer to withstand both plastic and elastic deformation. Stiffness: The resistance of a polymer to elastic
deformation, i.e., a polymer which suffers slight deformation under load has a high degree of stiffness.

[1] Density: Mass per unit volume (at defined temperature). Relative Density is the mass of the
polymer with the mass of equal volume of a specific (reference) substance most often water.
Density is frequently measured as a quality control parameter. A specimen, with smooth surfaces
from crevices and dust, is weighed in air (W1) and then in freshly boiled water (W2),
then 
 =

  




[2] Tensile Strength: The strength of a polymer is its capacity to withstand destruction under
the action of loads. It determines the ability of a polymer to withstand stress without failure.
Tensile strength or ultimate strength is the stress corresponding to the maximum load reached before
rupturing the polymer, Tensile strength or Stress =

!
 "#$ % &'
(
 ) *++ +
!$,

[3] Abrasion Resistance: It is defined as the ability of a polymer to withstand mechanical action
(such as rubbing, scrapping, or erosion) that tends progressively to remove material from its surface.
Abrasion is closely related to frictional force, load and true area of contact. An increase in any one of
the three results in greater abrasion or wear. Abrasion process also creates oxidation on the surface
from the build up of localized high temperatures.
[4] Resilience: It is the capacity of a polymer to absorb energy elastically. When a body is loaded,
it changes its dimension, and on the removal of the load it regains its original dimensions.
In fact, the polymer behaves perfectly like a spring. So long as it remains loaded, it has stored energy
in itself. On removal of the load, the energy stored is given off exactly as in a spring when the load is
removed. Resilience gives capacity of the polymer to bear shocks and vibrations.
[5] Wear and Tear: It occurs when a steady rate of increase in the use of polymers in bearing
applications and in situations where there is sliding contact e.g. gears, piston rings, seals, cams, etc.
Wear and tear is characterized by fine particles of polymer being removed from the surface or
the polymer becomes overheated to the extent where large troughs of melted polymer are removed.
The wear and tear of polymers is extremely complex subjects which depend markedly on the nature of
the application and the properties of the material. Hence it is characterized by adhesion and
deformation which results in frictional forces that are not proportional to load but rather to speed.
The mechanism of wear and tear is complex; the relative rates may change depending on specific
circumstance.
43

Lubricants
In all types of machines, the surfaces of moving or sliding or rolling parts rub against each
other. Due to the mutual rubbing of one part against another, a resistance is offered to their movement.
This resistance is known as friction. It causes a lot of wear and tear of surfaces of moving parts.
Any substance introduced between two moving/sliding surfaces with a view to reduce the friction
(or frictional resistance) between them, is known as a lubricants. The main purpose of a lubricant is
to keep the moving/sliding surfaces apart, so that friction and consequent destruction of material is
minimized. The process of reducing friction between moving/sliding surfaces, by the introduction of
lubricants in between them, is called lubrication.
Function of Lubricants: (1) It reduces wear and tear of the surfaces by avoiding direct metal
to metal contact between the rubbing surfaces, i.e. by introducing lubricants between the two surfaces
(2)

It reduces expansion of metal due to frictional heat and destruction of material

(3) It acts as coolant of metal due to heat transfer media (4) It provides smooth relative motion
(5) It reduces maintenance cost (6) It also reduces power loss in internal combustion engines
Theories of Friction: (1) Welding theory: All metal surfaces, regardless how much finely
finished

they

are,

appear

as

series

of

peaks

(or

asperites)

and

valleys.

So when two solid surfaces are pressed one over the other, only the peaks of the two surfaces come in
real contact. Under the action of a load, the local pressure at the peaks becomes sufficiently great to
cause

deformation

of

the

peaks

to

create

weld

junctions

between

them.

(2) Mechanical Interlocking: When one surface moves over another, the peaks and valleys present
on the surface undergo interlocking; restrict the movement of one surface over the other.
This accounts for static friction. (3) Molecular Attraction: Atoms of one material are plucked out of
the attractive range of their counterparts on the mating surface, lead to the friction.
(4) Electrostatic Attraction: When stick-slip phenomenon takes place between rubbing metal surfaces,
a net flow of electrons takes place producing clusters of charges of opposite polarity at the interface.
These charges are responsible for holding the surfaces together by electrostatic attraction.
Mechanism
with
or

the

help

hydrodynamic

of
of

Lubrication:
the

following

lubrication)

(b)

The

phenomenon

of

mechanism;

(a)

Thin

lubrication

Film

lubrication

Thick-Film

can

lubrication

(Boundary

be

explained

(Fluid-Film

lubrication)

and

(c) Extreme Pressure lubrication

44

(a) Thick-Film lubrication: In this, moving/sliding surfaces are separated from each other by
a thick film of fluid (at least 1000 A thick), so that direct surface to surface contact and welding of
welding of junctions rarely occurs. The lubricant film covers/fills the irregularities of moving/sliding
surfaces and forms a thick layer between them, so that there is no direct contact between the material
surfaces. This consequently reduces friction.

The lubricant chosen should have the minimum viscosity (to reduce the internal resistance
between the particles of the lubricant) under working conditions and at the same time,
it should remain in place and separate the surfaces.
Hydrocarbon oils (mineral oils which are lower molecular weight hydrocarbons with about
12 to 50 carbon atoms) are considered to be satisfactory lubricants for thick-film lubrication.
In order to maintain the viscosity of the oil in all seasons of year, ordinary hydrocarbon lubricants are
blended with selected long chain polymers.
(b) Thin Film lubrication: This type of lubrication is preferred where a continuous film of
lubricant cannot persist. In such cases, the clearance space between the moving/sliding surfaces is
lubricated by such a material which can get adsorbed on both the metallic surfaces by either physical
or chemical forces. This adsorbed film helps to keep the metal surfaces away from each other at least
up to the height of the peaks present on the surface.

45

Vegetable and animal oils and their soaps can be used in this type of lubrication because they
can get either physically adsorbed or chemically react in to the metal surface to form a thin film of
metallic soap which can act as lubricant. Although these oils have good oiliness, they suffer from the
disadvantage that they will break down at high temperatures. On the other hand, mineral oils are
thermally stable and the addition of vegetable/animal oils to mineral oils, their oiliness can also be
brought up. Graphite and molybdenum disulphide are also suitable for thin-film lubrication.
(c) Extreme Pressure lubrication: When the moving/sliding surfaces are under very high
pressure and speed, a high local temperature is attained under such conditions, liquid lubricants fail to
stick and may decompose and even vaporize. To meet these extreme pressure conditions, special
additives are added to minerals oils. These are called extreme pressure additives. These additives form
more durable films (capable of withstanding very high loads and high temperatures) on metal surfaces.
Important additives are organic compounds having active radicals or groups such as chlorine
(as in chlorinated esters), sulphur (as in sulphurized oils) or phosphorus (as in tricresyl phosphate).
These compounds react with metallic surfaces, at existing high temperatures, to form metallic
chlorides, sulphides or phosphides.
Classification of Lubricants: Lubricants are classified on the basis of their physical state,
as follows; (a) Liquid lubricants or Lubricating Oils, (b) Semi-solid lubricants or Greases and
(c) Solid lubricants.
(a) Liquid lubricants or Lubricating oils: Lubricating oils also known as liquid lubricants.
The characteristics of good lubricating oils are: (1) high boiling point (2) low freezing point
(3) adequate viscosity for proper functioning in service (4) high resistance to oxidation and heat
(5) non-corrosive properties and (6) stability to decomposition at the operating temperatures.
Lubricating oils are classified into three categories; (i) Animal and Vegetables oils,
(ii) Mineral or Petroleum oils and (iii) blended oils.
(i) Animal and Vegetables oils: Animal oils are extracted from the crude fat and vegetables oils
such as cotton seed oil and caster oils. These oils possess good oiliness and hence they can stick on
metal surfaces effectively even under elevated temperatures and heavy loads. But they suffer from the
disadvantages that they are costly, undergo easy oxidation to give gummy products and hydrolyze
easily on contact with moist air or water. Hence they are only rarely used these days for lubrication.
But they are still used as blending agents in petroleum based lubricants to get improved oiliness.
(ii) Mineral or Petroleum oils: These are basically lower molecular weight hydrocarbons with
about 12 to 50 carbon atoms. As they are cheap, available in abundance and stable, hence they are
widely used. But the oiliness of mineral oils is less, so the addition of higher molecular weight
compounds like oleic acid and stearic acid increases the oiliness of mineral oil.
46

(iii) Blended oils: No single oil possesses all the properties required for a good lubricant and
hence

addition

of

proper

additives

is

essential

to

make

them

perform

well.

Such additives added lubricating oils are called blended oils. Examples: The addition of higher
molecular weight compounds like oleic acid, stearic acid, palmetic acid, etc or vegetables oil like
coconut oil, castor oil, etc increases the oiliness of mineral oil.
(b) Semi-solid Lubricants or Grease: A semi-solid lubricant obtained by combining
lubricating oil with thickening agents is termed as grease. Lubricating oil is the principal component
and it can be either petroleum oil or a synthetic hydrocarbon of low to high viscosity. The thickeners
consist primarily of special soaps of Li, Na, Ca, Ba, Al, etc. Non-soap thickeners include carbon black,
silica gel, polyureas and other synthetic polymers, clays, etc. Grease can support much heavier load at
lower speed. Internal resistance of grease is much higher than that of lubricating oils; therefore it is
better to use oil instead of grease. Compared to lubricating oils, grease cannot effectively dissipate
heat from the bearings, so work at relatively lower temperature.
(c) Solid lubricants: They are preferred where (1) the operating conditions are such that a
lubricating

film

cannot

be

secured

by

the

use

of

lubricating

oils

or

grease

(2) contamination (by the entry of dust particles) of lubricating oils or grease is unacceptable
(3) the operating temperature or load is too high, even for grease to remain in position and
(4) combustible lubricants must be avoided. They are used either in the dry powder form or with
binders

to

make

them

stick

firmly

to

the

metal

surfaces

while

in

use.

They are available as dispersions in non-volatile carriers like soaps, fats, waxes, etc
and as soft metal films.
The

most

common

solid

lubricants

are

graphite,

molybdenum

disulphide,

tungsten disulphide and zinc oxide. They can withstand temperature upto 650 C and
can be applied in continuously operating situations. They are also used as additives to mineral oils and
greases

in

order

to

increase

the

load

carrying

capacity

of

the

lubricant.

Other solid lubricants in use are soapstone (talc) and mica.

Graphite: It is the most widely used of all the solid lubricants and can be used either in the
powdered form or in suspension. It is soapy to touch; non-inflammable and stable upto a temperature
of 375 C. Graphite has a flat plate like structure and the layers of graphite sheets are arranged one
above the other and held together by weak van der Waals forces. These parallel layers which can
easily slide one over other make graphite an effective lubricant. Also the layer of graphite has a
tendency to absorb oil and to be wetted of it.

47

Molybdenum Disulphide: It has a sandwich-like structure with a layer of molybdenum atoms

in between two layers of sulphur atoms. Poor interlaminar attraction helps these layers to slide over
one another easily. It is stable upto a temperature of 400 C.
Properties

of

Lubricants:

(1)

Viscosity

(2)

Flash

Point

and

Fire

Point

(3) Cloud Point and Pour Point (4) Aniline Point and (5) Corrosion Stability
(1) Viscosity: It is the property of liquid by virtue of which it offers resistance to its own flow
(the resistance to flow of liquid is known as viscosity). The unit of viscosity is poise. It is the most
important single property of any lubricating oil, because it is the main determinant of the operating
characteristics of the lubricant. If the viscosity of the oil is too low, a liquid oil film cannot be
maintained between two moving/sliding surfaces. On the other hand, if the viscosity of the oil is too
high, excessive friction will result. Effect of temperature on viscosity: Viscosity of liquids decreases
with increasing temperature and, consequently, the lubricating oil becomes thinner as the operating
temperature increases. Hence, viscosity of good lubricating oil should not change much with change in
temperature, so that it can be used continuously, under varying conditions of temperature.
The rate at which the viscosity of lubricating oil changes with temperature is measured by
an arbitrary scale, known as Viscosity Index (V. I). If the viscosity of lubricating oil falls rapidly
as the temperature is raised, it has a low viscosity index. On the other hand, if the viscosity of
lubricating oil is only slightly affected on raising the temperature, its viscosity index is high.
(2) Flash Point and Fire Point: Flash point is the lowest temperature at which the lubricant oil
gives off enough vapours that ignite for a moment, when a tiny flame is brought near it;
while Fire point is the lowest temperature at which the vapours of the lubricant oil burn continuously
for at least five seconds, when a tiny flame is brought near it. In most cases, the fire points are
5 C to 40 C higher than the flash points. The flash and fire do not have any bearing with lubricating
property of the oil, but these are important when oil is exposed to high temperature service.
A good lubricant should have flash point at least above the temperature at which it is to be used.
This safeguard against risk of fire during the use of lubricant.
(3)

Cloud Point and Pour Point:

When the lubricant oil is cooled slowly,

the temperature at which it becomes cloudy or hazy in appearance, is called its cloud point;
while the temperature at which the lubricant oil cease to flow or pour, is called its pour point.
Cloud

and

pour

points

indicate

the

suitability

of

lubricant

oil

in

cold

conditions.

Lubricant oil used in a machine working at low temperatures should possess low pour point;
otherwise solidification of lubricant oil will cause jamming of machine. It has been found that
presence of waxes in the lubricant oil raise pour point.
48

(4) Aniline Point: Aniline point of the lubricant oil is defined as the minimum equilibrium
solution temperature for equal volumes of aniline and lubricant oil samples. It gives an indication of
the possible deterioration of the lubricant oil in contact with rubber sealing; packing, etc.
Aromatic hydrocarbons have a tendency to dissolve natural rubber and certain types of synthetic
rubbers. Consequently, low aromatic content in the lubricant oil is desirable. A higher aniline point
means a higher percentage of paraffinic hydrocarbons and hence, a lower percentage of aromatic
hydrocarbons. Aniline point is determined by mixing mechanically equal volumes of the lubricant oil
samples and aniline in a test tube. The mixture is heated, till homogenous solution is obtained.
Then, the tube is allowed to cool at a controlled rate. The temperature at which the two phases
(the lubricant oil and aniline) separate out is recorded at the aniline point.
(5) Corrosion Stability: Corrosion stability of the lubricant oil is estimated by carrying out
corrosion test. A polished copper strip is placed in the lubricant oil for a specified time at a particular
temperature. After the stipulated time, the strip is taken out and examined for corrosion effects.
If the copper strip has tarnished, it shows that the lubricant oil contains any chemically active
substances which cause the corrosion of the copper strip. A good lubricant oil should not effect the
copper strip. To retard corrosion effects of the lubricant oil, certain inhibitors are added to them.
Commonly used inhibitors are organic compounds containing P, As, Cr, Bi or Pb.
Essential requirements or characteristics of a good lubricant are as follows:
[1] It should have a high viscosity index [2] It should have flash and fire points higher than the
operating temperature of the machine [3] It should have high oiliness [4] The cloud and pour points of
a good lubricant should always be lower than the operating temperature of the machine
[5] The volatility of the lubricating oil should be low [6] It should deposit least amount of carbon
during use [7] It should have higher aniline point [8] It should possess a higher resistance towards
oxidation and corrosion [9] It should have good detergent quality

Syllabus
Lubricants Theories of friction Mechanism of lubrication (thick film,
thin film and extreme pressure) Classification (solid, liquid and semisolid)
Properties (viscosity,

flash point and fire point, cloud and pour point, aniline point,

and corrosion stability)

49

Fuels

CLASSIFICATION OF FUEL
Fuels are classified as follows: [1] Primary fuels which occur in nature, e.g. coal, petroleum
and natural gas [2] Secondary fuels which are derived from the primary fuels, e.g. coke, gasoline and
coal gas. Both primary and secondary fuels may be further classified based upon their physical state as
(a) solid fuels, (b) liquid fuels and (c) gaseous fuels

CHARACTERISTICS OF A GOOD FUEL

The following are the characteristics of a good fuel: [1] A good fuel should be cheap and
readily available [2] It should have a high calorific value [3] A good fuel should have a moderate
ignition temperature. If the ignition temperature is low, the fuel can catch fire easily and the risk of fire
hazards is high. If the ignition temperature is very high, it is very difficult to ignite the fuel.
Ignition temperature is defined as the minimum temperature at which the substance ignites and bums
without further addition of external heat [4] The moisture content of the fuel should be very low
because the moisture content reduces the calorific value [5] A good fuel should have low noncombustible matter content or ash content because the ash content reduces the calorific value or
heating value of the fuel. The disposal of ash is also a big problem and it increases the cost of
operation [6] The products of combustion should not pollute the atmosphere. Gases like CO, SO2 and
H2S are some of the harmful gases [7] Combustion should be easily controllable, i.e. combustion of
the fuel should start easily or stop when required [8] It should not undergo spontaneous combustion
[9] It should be safe, convenient and economical for storage and transport.
50

ADVANTAGES AND DISADVANTAGES OF SOLID, LIQUID AND GASEOUS FUELS

Solid Fuels: The following are the advantages of solid fuels: [1] Solid fuels occur widely and
they are cheap [2] They can be handled and transported very easily [3] No complex mechanism is
required for their burning [4] They can be stored conveniently without any problem like explosion
[5] They have a moderate ignition temperature.
The disadvantages of solid fuels are as follows: [1] Solid fuels form a lot of ash during burning
and disposal of ash is very difficult [2] A lot of labour is required to transport solid fuels
[3] The burning process of solid fuels is not as clear as that of liquid and gaseous fuels
[4] A large space is required for storage of solid fuels and sometimes they may undergo spontaneous
ignition. [5] Since a lot of air is necessary for complete combustion of solid fuels, the thermal
efficiency is not so high.
Liquid Fuels: The advantages of liquid fuels are as follows: [1] Liquid fuels occupy less storage
space than solid fuels [2] As compared to solid fuels; they have a high calorific value
[3] They can be easily transported through pipes. 4. Liquid fuels do not yield any ash or residue during
burning [5] The burning process of liquid fuels is clear [6] The combustion is uniform and very easily
controllable [7] For complete combustion of liquid fuels, less air is required than that of the solid fuels
and hence their thermal efficiency is high [8] They can be used in IC engines, boilers and gas turbines
[9] They do not undergo spontaneous combustion.
The disadvantages of liquid fuels are as follows: [1] When the liquid fuels undergo incomplete
combustion, they give unpleasant odour [2] In comparison with solid fuels they are costly
[3] Risk of fire hazards is more in the case of inflammable and volatile liquid fuels. Thus, they should
be stored and transported more carefully [4] Some amount of liquid fuels may escape due to
evaporation during storage [5] Special type of burners and sprayers are required for effective
combustion.
Gaseous Fuels: The following are the advantages of gaseous fuels: [1] Gaseous fuels on
burning do not produce any ash or smoke [2] They can be very easily transported to any place as they
can flow through the pipes [3] They have a high calorific value and produce high temperature
[4] Burning of fuels can be controlled and the nature of flame can be easily made oxidizing or
reducing [5] Gaseous fuels can be produced by the poorest quality of solid fuels [6] Gaseous fuels can
be used in IC engines, boilers and gas turbines [7] Compared to solid and liquid fuels, they have a high
thermal efficiency.
The following are the disadvantages of gaseous fuels: [1] Since gases occupy a large volume,
they require large storage tank s[2] Gaseous fuels are highly inflammable and the Possibility of fire
hazards is very high
51

CALORIFIC VALUE
The efficiency of a fuel is judged by its calorific value. The calorific value of a fuel is defined
as the total amount of heat liberated by the complete combustion of a unit mass of the fuel.
The quantity of heat can be measured by the unit, Calorie. The calorie is defined as the amount
of heat required to raise the temperature of I gram of water through 1C

(l5-16C).

The calorific values of solid and liquid fuels are expressed in cal/g. The calorific values of gaseous
fuels are expressed in cal/m3.
Gross calorific value and Net calorific value: When a fuel containing hydrogen is burnt,
the hydrogen present in the fuel undergoes combustion and is converted into steam. As the products of
combustion are cooled to room temperature, the steam gets condensed into water and latent
heat is evolved. Thus, the latent heat of condensation of steam is also included in the calorific
value determination which is called higher calorific value or gross calorific value (GCV).
GCV is defined as the heat liberated when a unit quantity of the fuel is completely burnt and the
products of combustion are cooled to room temperature.
In actual combustion practice, the products of combustion are not cooled to room temperature
and are allowed to escape into the atmosphere with the result that only a lesser amount of heat is
available. The amount of heat so available is called lower or net calorific value (NCV).
The net calorific value is defined as the net heat produced when a unit quantity of the fuel is
completely burnt and the products of combustion are allowed to escape.
Net calorific value = gross calorific value - latent heat of condensation of water vapour
produced = GCV - mass of hydrogen per unit weight of the fuel burnt x 9 x latent heat of condensation
of water vapour

52

53

54

Fixed Bed Catalytic Cracking

Moving Bed Catalytic Cracking

Reforming is a process used to improve the anti-knock characteristics of a gasoline by bringing

about structural modifications in the components of gasoline either thermally or in the presence of
catalyst. The main reactions in the reforming process are as follows: [1] Dehydrogenation
[2] Hydrocracking [3] Isomerization

Dehydrogenation

Hydrocracking

Isomerization
55

Knocking
Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.
In a petrol engine, a mixture of gasoline vapour and air (l: 17) is used as a fuel. The air and gasoline
vapours are compressed and ignited by an electric spark. The chemical reaction taking place is the
oxidation of hydrocarbons. The products of the oxidation reaction drive the piston down the cylinder.
If the combustion proceeds in a regular way, there is no problem of knocking. But in certain
circumstances, the oxidation is sudden and the mixture detonates and produces an explosive sound
called engine knock which results in the loss of power. Knocking not only results in a decreased power
output but can also cause mechanical damage by overheating of the cylinder parts.
A good gasoline should resist knocking. It was recognized that chemical structures of the fuel
hydrocarbons largely determine their knocking tendency. The tendency to knock decreases in the
following order: straight chain paraffins > branched chain paraffins > cyclo-paraffins > olefins >
aromatics.
Edgar introduced the octane number to express the knocking chracteristics of a combustion
engine fuel. It has been found that n-heptane knocks very badly and hence its antiknock value is
arbitrarily given as zero. On the other hand, isooctane gives very little knocking and so its anti-knock
value has been given as 100. Thus, the octane number is defined as the percentage of isooctane in the
n-heptane-isooctane blend which has the same knocking characteristics as the gasoline sample, under
the same set of conditions. Since isooctane has good anti-knock properties, it is clear that greater the
octane number, greater is the resistance to knocking.
Chemical structure and knocking: The knocking tendency decreases with increase in
compactness of the molecules, double bonds and cyclic structure. With normal paraffins, the antiknock
properties decrease with the increase in length of the hydrocarbon chain. Thus, the octane numbers of
n-butane,

n-pentane,

n-hexane

and

n-heptane

are

90,

60,

29

and

respectively.

Branched chain paraffins have higher anti-knock properties than their normal isomers.
Olefins have higher anti-knock properties than the corresponding paraffins. Aromatic hydrocarbons
such as benzene and toluene have high octane numbers.
Leaded Petrol
The anti-knock properties of a gasoline can be improved by the addition of suitable additives.
Tetraethyl lead (TEL) is added to petrol and is called leaded petrol. This addition process is called
doping. This addition was first proposed by Thomas Midgley. TEL reduces the knocking tendency of
hydrocarbons. Knocking is a free radical mechanism leading to a chain reaction which results in an
explosion. If the chains are terminated before their growth, knocking will cease. TEL decomposes
thermally to form ethyl free radicals which combine with the growing free radicals of the knocking
56

process and thus stop the chain growth. When this leaded petrol is used as a fuel, lead and lead oxide
vapours formed may contaminate the atmosphere. To avoid this, ethylene dibromide is added along
with TEL. This ethylene dibromide reacts with Pb and PbO to give PbBr2 which will escape into the
atmosphere.

Improving the octane number of a fuel: The octane number of a fuel may be improved by the
following: [1] The addition of anti-knock compounds like TEL [2] Low octane petrol is blended with
high octane compounds like alcohol, e.g. straight run petrol is mixed with reformed petrol,
benzol and alcohol [3] Reforming.
Diesel Oil
Diesel oil is a fraction obtained between 2S0-320C and is a mixture of C15H32 and C18H38
hydrocarbons, Its calorific value is about 11000 kcal/kg. It is used as a diesel engine fuel.
Diesel knock: In a diesel engine, air is first drawn into the cylinder and compressed,
this compression is accompanied by a rise in temperature to about 500C. Near the completion of the
compression stroke, oil is sprayed into the heated air; Droplets of the oil in the atomized form get
vaporized and ignited. This raises temperature as well as pressure, the piston is pushed by the
expanding gases and this constitutes a power stroke.
The combustion of a fuel in a diesel engine is not instantaneous and the interval between the
start of fuel injection and its ignition is called ignition delay and is an important quality of the diesel
fuel. This delay is due to the time taken for the vaporization of individual droplets and rising of the
vapour to its ignition temperature. Long ignition delays lead to accumulation of more vapours in the
engine and when ignited an explosion results as the combined effect of increased temperature and
pressure. This is responsible for diesel knock. In order to avoid diesel knock, the ignition delay period
should be as short as possible. The cetane number decreases in the following order: straight chain
paraffins > cycloparaffins > olefins > brandied paraffins > aromatics
The diesel fuels are graded by means of cetane rating. Cetane, i.e. n-hexadecane
[CH3(CH2)14CH3] having a very short ignition delay is given the value of 100 in the rating scale.
-methylnaphthalene

having

longer

ignition

delay

represents

zero

of

the

scale,

The percentage of cetane in the cetane--methylnaphthalene mixture which has the same ignition
delay as the fuel under test is the cetane number of the fuel. High cetane number fuels eliminate diesel
knock. The cetane number of a diesel fuel may be increased by the addition of ethyl nitrite,
amyl nitrite, etc.
57

58

Biodiesel
There has been an increase in efforts to reduce the reliance on petroleum fuel for energy
generation. Among the alternative fuel, biodiesel has received much attention for diesel engines due to
their advantages as the renewable, domestically produced energy resources and they are
environmentally friendly (biodegradable spills, reduction of unburned hydrocarbon, CO and
particulate matter). Biodiesel can be produced from animal or vegetable oils via base catalyzed transesterification process. The term biodiesel refers to mixtures of alkyl esters of long chain fatty acids.
The reaction scheme for the production of biodiesel is as follows:
(1) Trans-esterification: Vegetable oils (Triacylglycerols are triesters) on reaction with methanol
(renewable resource and does not raise toxicity) in the presence of catalyst like NaOH or KOH,
produce glycerol and methyl ester of fatty acid (Biodiesel).
Vegetable Oil + Methanol + Catalyst Biodiesel + Glycerol

where R = CH3-(CH2)16- , hence composition of biodiesel is CH3-(CH2)16-COOCH3

Biodiesel contains no petroleum; it can be blended at any level with petroleum or diesel.
A 100% biodiesel fuel is referred as B100. Biodiesel blends are referred as BXX, where XX indicates
the amount of biodiesel in the blend (For example, B20 blend is 20% by volume biodiesel and
80% by volume petrol.
Biodiesel has higher cetane number; this oil reduces the emission of CO2 by 78%, CO by 44%,
sulphate by 100%, polycyclic aromatic hydrocarbon by75-85% and particulate matter. Vegetable oil
is produced from soybean and tallow (USA), rapeseed (Europe), Jatropa curcas and Karanja (India).

Syllabus
Fuels Classification Calorific Value Cracking and Reforming Petrol Knock and Octane
number Diesel Knock and Cetane number Bio-Diesel

59

Electrochemistry
What are half reactions?
Let us consider the reaction 2Na + Cl2 2Na+ + 2Cl. It occurs by the transfer of electrons
from Na to Cl. Na loses an electron and is said to be oxidized to Na+ ion. At the same time,
Cl gains an electron and is reduced to Cl ion. Such a reaction which is brought about by loss of
electrons

(oxidation)

and

gain

of

electrons

(reduction)

simultaneously

is

called

an

Oxidation-Reduction reaction or Redox reaction in brief. It may be noted that in the overall redox
reaction no free electrons are generated.
The redox reaction can be considered as made up of two reactions. For example, the redox
reaction 2Na + Cl2 Na+ + 2Cl is composed of two half-reactions: 2Na 2Na+ + 2e (oxidation)
and Cl2 + 2e 2Cl (reduction)
Each of the two reactions shows just its oxidation or just the reduction portion of the overall
redox reaction. Being half components of the redox reaction, these reactions are called Half-reactions.
The first half-reaction that proceeds by oxidation is often referred to as the Oxidation half-reaction.
The second half-reaction that occurs by reduction, is referred to as the Reduction half-reaction.
When the two half-reactions are added together, the sum is the net redox reaction.
Electrochemical cells
A device for producing an electrical current from a chemical reaction (redox reaction) is called
an electrochemical cell. How a Redox reaction can produce an electrical current? When a bar of zinc
is dipped in a solution of copper sulphate, copper metal is deposited on the bar (See Figure 1).
The net reaction is Zn + Cu2+ Zn2+ + Cu. This is a redox reaction and the two half-reactions are:

Zn Zn2+ + 2e and Cu2+ + 2e Cu

In this change, Zn is oxidized to give Zn2+ ions and Cu2+ ions are reduced to Cu atoms.
The electrons released in the first half-reaction are used up by the second half-reaction.
Both the half reactions occur on the zinc bar itself and there is no net charge.
Now, let the two half-reactions occur in separate compartments which are connected by a wire
(See Fig. 2) The electrons produced in the left compartment flow through the wire to the other
compartment. However the current will flow for an instant and then stop. The current stops flowing
because of the charge build up in the two compartments. The electrons leave the left compartment and
it would become positively charged. The right compartment receives electrons and becomes negatively
charged. Both these factors oppose the flow of electrons (electrical current) which eventually stops.
60

Fig. 2: Separate half-reactions cause flow of electrons

(Current) in the wire connecting them
This problem can be solved very simply. The solutions in the two compartments may be
connected, say, by a salt bridge. The salt bridge is a U-tube filled with an electrolyte such as NaCl,
KCl, or K2SO4. It provides a passage to ions from one compartment to the other compartment without
extensive mixing of the two solutions. With this ion flow, the circuit is complete and electrons pass
freely through the wire to keep the net charge zero in the two compartments.

Cell diagram or Representation of a Cell

A cell diagram is an abbreviated symbolic depiction of an electrochemical cell. For this
purpose, we will consider that a cell consists of two half-cells. Each half-cell is again made of a metal
electrode contact with metal ions in solution.
(1) A single vertical line

(|) represents a phase boundary between metal electrode and ion solution

(electrolyte). Thus the two half-cells in a voltaic cell are indicated as

61

It may be noted that the metal electrode in anode half-cell is on the left, while in cathode
half-cell it is on the right of the metal ion.
(2) A double vertical line

(||) represents the salt bridge, porous partition or any other means of

permitting ion flow while preventing the electrolyte from mixing.

(3) Anode half-cell is written on the left and cathode half-cell on the right.
(4) In the complete cell diagram, the two half-cells are separated by a double vertical line
(salt bridge) in between. The zinc-copper cell can now be written as

(5) The symbol for an inert electrode, like the platinum electrode is often enclosed in a bracket.

(6) The value of emf of a cell is written on the right of the cell diagram. Thus a zinc-copper cell has
emf 1.1V and is represented as

Voltaic Cells
A Voltaic cell, also known as a galvanic cell is one in which electrical current is generated by a
spontaneous redox reaction. A simple voltaic cell is shown in Fig. 3. Here the spontaneous reaction of
zinc metal with an aqueous solution of copper sulphate is used. Zn + Cu2+ Zn2+ + Cu
A bar of zinc metal (anode) is placed in zinc sulphate solution in the left container. A bar of
copper (cathode) is immersed in copper sulphate solution in the right container. The zinc and copper
electrodes are joined by a copper wire. A salt bridge containing potassium sulphate solution
interconnects

the

solutions

in

the

anode

compartment

and

The oxidation half-reaction occurs in the anode compartment.

the
Zn

cathode

compartment.
Zn2+

2e

The reduction half-reaction takes place in the cathode compartment. Cu2+ + 2e Cu

Fig. 3: A simple voltaic (galvanic) cell

62

When the cell is set up, electrons flow from zinc electrode through the wire to the copper
cathode. As a result, zinc dissolves in the anode solution to form Zn2+ ions. The Cu2+ ions in the
cathode half-cell pick up electrons and are converted to Cu atoms on the cathode. At the same time,
SO42 ions from the cathode half-cell migrate to the anode half-cell through the salt bridge.
Likewise, Zn2+ ions from the anode half-cell move into the cathode half-cell. This flow of ions from
one half-cell to the other completes the electrical circuit which ensures continuous supply of current.
The cell will operate till either the zinc metal or copper ion is completely used up.
Daniel Cell
It is a typical voltaic cell. It was named after the British chemist John Daniel. It is a simple zinc
copper cell like the one described above. In this cell the salt-bridge has been replaced by a porous pot.
Daniel cell resembles the above voltaic cell in all details except that Zn2+ ions and SO42 ions flow to
the cathode and the anode respectively through the porous pot instead of through the salt-bridge.
Inspite of this difference, the cell diagram remains the same.

Cell reaction
The flow of electrons from one electrode to the other in an electrochemical cell is caused by the
half-reactions taking place in the anode and cathode compartments. The net chemical change obtained
by adding the two half-reactions is called the cell reaction. Thus, for a simple voltaic cell described
above, we have (a) Half-reactions: Zn(s) Zn2+ (aq) + 2e and Cu2+ (aq) + 2e Cu(s)
(b) Cell reaction by adding up the half-reactions: Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)

63

Cell potential or emf

In a Zn-Cu voltaic cell, electrons are released at the anode and it becomes negatively charged.
The negative electrode pushes electrons through the external circuit by electrical repulsions.
The copper electrode gets positive charge due to the discharge of Cu2+ ions on it. Thus electrons from
the outer circuit are attracted into this electrode. The flow of current through the circuit is determined
by the push, of electrons at the anode and attraction of electrons at the cathode.
These two forces constitute the driving force or electrical pressure that sends electrons through the
circuit. This driving force is called the electromotive force (abbreviated emf) or cell potential.
The emf of cell potential is measured in units of volts (V) and is also referred to as cell voltage.
Calculating the emf of a cell
The emf of a cell can be calculated from the half-cell potentials of the two cells
(anode and cathode) by using the following formula,

/0122 = /0345671 /39671 = /: /;

where ER and EL are the reduction potentials of the right-hand and left-hand electrodes respectively.
It may be noted that absolute values of these reduction potentials cannot be determined. These are
found by connecting the half-cell with a standard hydrogen electrode whose reduction potential has
been arbitrarily fixed as zero.
Measurement of emf of a cell [Poggendorfs compensation method]
The emf of an unknown cell can be measured with the help of a potentiometer (Fig. 4).
It consists of a wire AB which is about one metre long. The two ends of this wire are connected to a
working battery W. A standard cell C1 (i.e., a cell of known emf) is connected to the end A.
At the other end, the cell C1 is connected to a galvanometer through a key K1. The galvanometer is
then joined to a sliding contact that moves on the wire AB. The cell C2 whose emf is to be measured is
similarly connected to the key K2, the galvanometer and then the sliding contact. By using the key K1,
the cell C1 is put into the circuit and the contact is moved to and fro along AB. When no current flows
through the galvanometer, the point of contact X1 is recorded. Then by using the key K2, the cell C2 is
put into the circuit and the procedure is repeated to find the corresponding point X2. The emf of the
cell C2 is calculated by using the following equation:

Fig. 4: Measuring the emf of a cell with a potentiometer

64

Potential differences at interfaces

The transition region between two phases consists of a region of charge unbalance known as the
electric double layer [Helmholtz double layer]. As its name implies, this consists of an inner
monomolecular layer of adsorbed water molecules and ions, and an outer diffuse region that
compensates for any local charge unbalance that gradually merges into the completely random
arrangement of the bulk solution. In the case of a metal immersed in pure water, the electron fluid
within the metal causes the polar water molecules to adsorb to the surface and orient themselves so as
to create two thin planes of positive and negative charge. If the water contains dissolved ions,
some of the larger (and more polarizable) anions will loosely bond (chemisorb) to the metal, creating a
negative inner layer which is compensated by an excess of cations in the outer layer.
Electrochemistry is the study of reactions in which charged particles (ions or electrons) cross
the interface between two phases of matter, typically a metallic phase (the electrode) and a conductive
solution, or electrolyte. A process of this kind can always be represented as a chemical reaction and
is known generally as an electrode process. Electrode processes take place within the double layer and
produce a slight unbalance in the electric charges of the electrode and the solution.
Single electrode potential
An electrochemical cell consists of two half-cells. With an open-circuit, the metal electrode
in each half-cell transfers its ions into solution. Thus an individual electrode develops a potential
with respect to the solution. The potential of a single electrode in a half-cell is called the
Single electrode potential. Thus in a Daniel cell in which the electrodes are not connected externally,
the anode Zn/Zn2+ develops a negative charge and the cathode Cu/Cu2+, a positive charge.
The amount of the charge produced on individual electrode determines its single electrode potential.
The single electrode potential of a half-cell depends on: (a) concentration of ions in solution;
(b) tendency to form ions; and (c) temperature.
Standard emf of a cell [E]
The emf generated by an electrochemical cell is given by the symbol E. It can be measured with
the help of a potentiometer. The value of emf varies with the concentration of the reactants
and products in the cell solutions and the temperature of the cell. When the emf of a cell is determined
under standard conditions, it is called the standard emf. The standard conditions are (a) 1 M solutions
of reactants and products; and (b) temperature of 25C. Thus standard emf may be defined as:
the emf of a cell with 1 M solutions of reactants and products in solution measured at 25C.
Standard emf of a cell is represented by the symbol E. With gases 1 atm pressure is a standard
condition instead of concentration. For a simple Zn-Cu voltaic cell, the standard emf, E, is 1.10 V.
This means that the emf of the cell operated with [Cu2+] and [Zn2+] both at 1 M and 25C is 1.10 V.
65

Determination of emf of a half-cell

By a single electrode potential, we also mean the emf of an isolated half-cell or its half-reaction.
The emf of a cell that is made of two half-cells can be determined by connecting them to a voltmeter.
However, there is no way of measuring the emf of a single half-cell directly. A convenient procedure
to do so is to combine the given half-cell with another standard half-cell. The emf of the newly
constructed cell, E, is determined with a voltmeter. The emf of the unknown half-cell,
E can then be calculated from the expression, /<13=>?17 = /: /;
If the standard half-cell acts as anode, the equation becomes, /: = /<13=>?17
On the other hand, if standard half-cell is cathode, the equation takes the form, /; = /<13=>?17
The standard hydrogen half-cell or Standard Hydrogen Electrode (SHE) is selected for
coupling with the unknown half-cell. It consists of a platinum electrode immersed in a 1 M solution of
H+ ions maintained at 25C. Hydrogen gas at one atmosphere enters the glass hood and bubbles over
the platinum electrode. The hydrogen gas at the platinum electrode passes into solution,
forming H+ ions and electrons. H2 2H+ + 2e

Fig. 6: SHE

Fig. 7: The Zn electrode coupled with H electrode

The emf of the standard hydrogen electrode is arbitrarily assigned the value of zero volts.
So, SHE can be used as a standard for other electrodes. The half-cell, whose potential is desired, is
combined with the hydrogen electrode and the emf of the complete cell determined with a voltmeter.
@
@
@
The emf of the cell is /0122
= /:AB54
/;1C4

For example, it is desired to determine the emf of the zinc electrode, Zn | Zn2+. It is connected
with the SHE as shown in Fig. 7. The complete electrochemical cell may be represented as:

66

@
@
@
The emf of the cell is /0122
= /:@ /;@ = /DE/
/F9/F9
HI = @ @. KL = @. KL M

Similarly, the emf of the copper electrode, Cu2+ | Cu can be determined by pairing it with the
SHE when the electrochemical cell can be represented as:

The emf of this cell has been determined to be 0.34 V which is the emf of the copper half-cell.
@
@
@
/0122
= /:@ /;@ = /N>/N>
HI /DE/ = @. OP @ = @. OP M

The two situations are shown in Fig. 8

Fig. 8: SHE can act both as cathode and anode when joined with another half-cell
When it is placed on the right-hand side of the Zinc electrode, the hydrogen electrode reaction
is 2H+ + 2e H2. The electrons flow to the SHE and it acts as the cathode. When the SHE is

placed on the left hand side, the electrode reaction is H2 2H+ + 2e. The electrons flow to the
copper electrode and the hydrogen electrode as the anode. Evidently, the SHE can act both as anode
and cathode and, therefore can be used to determine the emf of any other half-cell electrode.
IUPAC convention places the SHE on the left-hand side: The electrons flow from left-toright and the given half-cell electrode gains electrons (reduction). The observed emf of the combined

electrochemical cell is then the emf of the half-cell on the right-hand. Such emf values of half-cells,
or half reactions, are known as the Standard reduction potentials or Standard potentials.

67

Electrochemical Series
The standard electrode potentials (reduction) of a number of electrodes are given in Table.
These values are said to be on the hydrogen scale since in these determinations, the potential of the
standard hydrogen electrode used as the reference electrode has been taken as zero. When the various
electrodes are arranged in the order of their increasing values of standard reduction potentials on the
hydrogen scale, then this arrangement is called electrochemical series.
Applications of Electrochemical Series or Electrode Potentials: The following are the
applications of electrochemical series:
[1]The standard emf of a cell can be calculated if the standard electrode potential values are
@
@
@
known. /0122
= /:AB54
/;1C4

[2] The relative tendencies of metals to go into solution can be noted by the help of electrochemical
series. Metals on the top are more easily ionized into solution.
[3] The metal with negative reduction potential will displace hydrogen from an acid solution:
Zn + H2SO4 ZnSO4 + H2

EZn0 = -0.76 volt

The metal with positive reduction potential will not displace hydrogen from an acid solution.
Ag + H2SO4 no reaction EAg0 = +0.80 volt
[4] Metals which lie higher in the series can displace from the solution those elements which lie below
them in the series. Thus, zinc can displace copper from the solution.
[5] The anodic or more active metals in the series are more prone to corrosion. The cathodic or more
noble metals are less prone to corrosion. The galvanic series is used for this purpose.
Galvanic Series: the galvanic series is used to provide sufficient information in predicting the
corrosion behaviour in a particular set of environmental conditions. Oxidation potential measurements
of various metals and alloys have been made using the standard calomel electrode as the reference
electrode and immersing the metals and alloys in sea water. These are arranged in decreasing order of
activity and this series is known as the galvanic series. The galvanic series gives more practical
information on the relative corrosion tendencies of the metals and alloys. The speed and severity of
corrosion depends upon the difference in potential between the anodic and cathodic metals in contact.

68

Using Electrochemical Series or Electrode Potentials: In Table the standard reduction

potentials (E) are arranged in the order of increasing potentials. The relative position of electrodes
(M/M+) in the table can be used to predict the reducing or oxidising ability of an electrode.
The electrodes that are relatively positive indicate that reduction reaction involving addition of
electrons, M+ + e M is possible. In case of relatively negative potential involving loss of

electrons, M M+ + e is indicated. It also follows that the system with higher electrode potential

will be reduced by the system with lower electrode potential.

Predicting the Oxidising or Reducing Ability: (1) The more positive the value of E, the
better the oxidising ability (the greater the tendency to be reduced) of the ion or compound, on moving
upward in the Table. (2) The more negative the value of E the better the reducing ability of the ions,
elements or compounds on moving downward in the Table. (3) Under standard conditions, any
substance in this Table will spontaneously oxidise any other substance lower than it in the Table.
Predicting cell emf: The standard emf, E, of a cell is the standard reduction potential of righthand electrode (cathode) minus the standard reduction potential of the left-hand electrode (anode).
R
R
R
E!

= ES$TU
E&
)
= Cathode Potential Anode Potential

Let us predict the emf of the cell

R
R
R
by using the E values from the Table E!

= ES$TU
E&
)
= 0.80 ^ 0.763b = 1.563V

Predicting Feasibility of Reaction: The feasibility of a redox reaction can be predicted with
the help of the electrochemical series. The net emf of the reaction, Ecell can be calculated from the eqn

Predicting whether a metal will displace another metal from its salt solution or not:
The metals lying higher up in the series are strong oxidising agents and their ions are readily reduced
to the metal itself. In general we can say that a metal lower down the electrochemical series can
precipitate the one higher up in the series.
Predicting whether a metal will displace hydrogen from a dilute acid solution: Any metal
lying below hydrogen is a stronger reducing agent than hydrogen and will convert H+ to H2.
This explains why Zn lying below hydrogen reacts with dil H2SO4 to liberate H2, while Cu lying above
hydrogen does not react.

69

The Nernst Equation

We know experimentally that the potential of a single electrode or half-cell varies with the
concentration of ions in the cell. In 1889 Walter Nernst derived a mathematical relationship which
enable us to calculate the half-cell potential, E, from the standard electrode potential, E, and the
temperature of the cell. This relation known as the Nernst equation can be stated as
/ = /@

H. O@O :f
26B h
9g

Where E = standard electrode potential, R = gas constant, T = Kelvin temperature,

n = number of electrons transferred in the half-reaction, F = Faraday of electricity and
K = equilibrium constant for the half-cell reaction as in equilibrium law
Derivation: Consider a reversible cell, e.g. Daniel cell. The overall cell reaction occurring in the
cell is represented by the equation F9 + N>Hj F9Hj + N>. In general, for a reversible cell the
equation is k + l N + m. The electrical energy of a reversible cell can be measured by the free

energy decrease (-G) of the reaction taking place in the cell. In the cell, if the reaction involves the
transfer of n number of electrons, then n Faradays of electricity will flow. If E is the emf of the cell,
then the total electrical energy produced in the cell is -G = nFE where -G = decrease in free energy.
At standard conditions, -G0 = nFE0 where -Go = standard free energy change.
Standard free energy change is the change in free energy when the concentration of reactants
and products are unity. EJ is the standard emf of the cell in which the reactants and products are kept
at 1 molar concentration at 25C, G and G0 are related as G = G0 + RT ln K where K is the
equilibrium constant of the reaction defined as the ratio of the concentration of the products to the
concentration of the reactants.

Divide the above equation by nF

At 25C, T = 298 K, R = 8.314 11K/mol, F = 96500 coulombs. Therefore,

This is known as the Nernst equation. This equation may be used to calculate the emf of cells
when concentration of reactants and products of the cell reactions are known.
70

Applications of the Nernst Equation

[1] Calculation of Half-cell potential: For an oxidation half-cell reaction when the metal
electrode M gives Mn+ ion, M Mn+ + ne-. The Nernst equation takes the form
/ = /@

no9j p
H. O@O :f
26B
n op
9g

The concentration of solid metal [M] is equal to zero. Therefore, the Nernst equation can be written as
/ = /@

H. O@O :f
26Bno9j p
9g

Substituting the values of R, F and T at 25C, the quantity 2.303 RT/F comes to be 0.0591.
Thus

the

Nernst

equation

can

be

written

in

its

simplified

form

as

@. @qrs
26Bno9j p
9
This is the equation for a half-cell in which oxidation occurs. In case it is a reduction reaction,
/ = /@

the sign of E will have to be reversed.

[2] Calculation of Cell potential: The Nernst equation is applicable to cell potentials as well. Thus,
@. @qrs
26B h
9
K is the equilibrium constant of the redox cell reaction.
@

/0122 = /0122

[3] Calculation of Equilibrium constant for the cell reaction: The Nernst equation for a cell is
@
/0122 = /0122

@. @qrs
26B h
9

At equilibrium, the cell reaction is balanced and the potential is zero. The Nernst equation becomes
@=

@
/0122

@
@. @qrs
9/0122

26B h , 51901 26B h =

9
@. @qrs

Concentration Cells
A concentration cell is an electrochemical cell which produces electrical energy by the transfer
of material from a system of higher concentration to a system of lower concentration. The difference
in concentration may be due to the difference in concentration of the electrodes or electrolytes. Based
on this, concentration cells are divided into two categories; (i) Electrode Concentration Cells and
(ii) Electrolyte Concentration Cells
Electrode Concentration Cells
In electrode concentration cells, two electrodes of the same metal with different concentrations
are dipped in the same solution of the electrolyte, e.g. amalgam concentration cells. Amalgam
electrodes are produced by mixing various proportions of any metal and mercury. Depending on the
amount of metal taken during the preparation of amalgam, the concentration of electrodes will vary.
71

Electrolyte Concentration Cells

Cell potentials depend on concentration of the electrolyte. Thus a cell can be constructed by
pairing two half-cells in which identical electrodes are dipping in solution of different concentrations
of the same electrolyte. Such a cell called Electrolyte concentration cell. It may be described as:
a cell in which emf arises as a result of different concentrations of the same electrolyte in the
component half-cells.
The electrode dipped in the solution of lower concentration is an anode and the electrode
dipped in solution of higher concentration is a cathode. The overall reaction involves the transfer
of material from higher concentration to lower concentration. The two solutions are connected
together by a salt bridge. A typical concentration cell is shown in Figure. It consists of two silver
electrodes, one immersed in 0.1 M silver nitrate solution and the other in 1 M solution of the same
electrolyte. The two solutions are in contact through a membrane (or a salt bridge). When the
electrodes are connected by a wire, it is found experimentally that electrons flow from the electrode in
more dilute (0.1M) solution to that in the more concentrated (1 M) solution.
Explanation: The concentration of Ag+ ions in the left compartment is lower (0.1M) and in the
right compartment it is higher (1M). There is a natural tendency to equalize the concentration of
Ag+ ions in the two compartments. This can be done if the electrons are transferred from the
left compartment to the right compartment. This electron transfer will produce Ag+ ions in
the right compartment by the half-cell reactions: Ag

Ag+ + e- (Left compartment) and

Ag+ + e- Ag (Right compartment)

Fig. 9: A typical Electrolyte Concentration Cells

Emf of Concentration Cell

Suppose the concentrations in the two half-cells are C1 and C2 at 25C, C2 being greater than
C1. Then emf, E, of the concentration cell will be given by the difference between the two electrode
potentials. In terms of Nernst equation
/ = u/o +

@. @qrs
@. @qrs
@. @qrs
NH
26B NH v u/o +
26B Ns v =
26B
9
9
9
Ns

EM is the standard electrode potential of the metal M and n is the valence of the ions in contact with it.
72

Types of Electrodes (S.H.E, Calomel, Quinhydrone, glass electrode)

[1] Gas electrode {Pt/H2, H+}: It contains an inert electrode like platinum dipped in a solution
containing

ions

(H+

ions)

to

which

the

gas

(H2

gas)

is

bubbled

continuously.

The electrode is represented as Pt (s)/H2 (P = x atm), H+ (aq). The electrode reaction can be written as
@
2H+ (aq) + 2e- H2 (g). The electrode potential is /w4/EH /EI = /w4/E
I
H /E

:f
9g

xy

NEH

zNEI {

Example is Standard Hydrogen Electrode (SHE). It consists of a platinum electrode immersed

in a 1 M solution of H+ ions maintained at 25C. Hydrogen gas at one atmosphere enters the glass
hood and bubbles over the platinum electrode.

[2] Metal-metal insoluble salt electrode {M (s) /MX (s)/X- (aq)}: It consists of a pure metal
[M (s)] coated by a layer of its sparingly soluble salt [MX (s)] and kept immersed in a solution
containing a common anion [X- (aq)]. It is represented as M (s) /MX (s)/X- (aq). The electrode reaction
can be written as MX (s) + ne- M (s) + X- (aq). Electrode potential is
@
}
/o/o|/|} = /o/o|/|

:f No . N|}
xy
No|
9g

Example is Calomel electrode: The standard calomel electrode, SCE, consists of a wide glasstube with a narrow side-tube. It is set up as illustrated in Fig. 10. A platinum wire is dipping into
liquid mercury covered with solid mercurous chloride (Hg2Cl2, calomel). The tube is filled with a 1 M
solution of KCl (or saturated KCl solution). The side-tube containing KCl solution provides the salt
bridge which connects the electrode to any other electrode. The calomel electrode is represented as
The half-cell reaction is Hg2Cl2 + 2e- 2Hg + 2Cl-

Calomel electrode

Fig. 10: The calomel electrode coupled with zinc electrode

73

[3] Quinhydrone Electrode: It is a widely used secondary standard electrode.

It involves the redox reaction between quinine (Q) and hydroquinone (QH2), represented in Figure 1.
The

hydroquinone

solution

of

half-cell

quinhydrone

consists
at

of

definite

platinum
H+

ion

strip

immersed

concentration

in

(buffered

saturated
solution).

Quinhydrone is a molecular compound which gives equimolar amounts of quinone and hydroquinone
in solution represented in Figure 2. The potential developed is measured against a hydrogen electrode
or calomel electrode. The emf with respect to a standard hydrogen electrode is 0.2875 V at 25C.
The electrode system may be represented in Figure 3

Figure 1

Figure 2

Figure 3

[4] Glass electrode: It consists of a glass tube having a thin-walled bulb at the lower end.
The bulb contains a 1M HCl solution. Sealed into the glass-tube is a silver wire coated with silver
chloride at its lower end. The lower end of this silver wire dips into the hydrochloric acid, forming
silver-silver chloride electrode. The glass electrode may be represented as
When placed in a solution, the potential of the glass electrode depends on the H+ ion
concentration of the solution. The potential develops across the glass membrane as a result of a
concentration difference of H+ ions on the two sides of the membrane. This happens much in the same
way as the emf of a concentration cell develops. A commonly used secondary standard electrode is
the so-called glass electrode. Its emf is determined by coupling with a standard calomel electrode
(SCE). The glass electrode provides one of the easiest methods for measuring the pH of a given
solution.

A simple type of glass electrode is shown Fig. 11.

Fig. 11: Glass electrode

74

The pH of solutions
A knowledge of the concentration of hydrogen ions (more specifically hydronium ions) is of the
greatest importance in chemistry. Hydrogen ion concentrations are typically quite small numbers.
Therefore, chemists report the hydrogen ion concentration of a solution in terms of pH. It is defined as
the negative of the base-10 logarithm (log) of the H+ concentration. Mathematically it may be
expressed as pH = log [H+] where [H+] is the concentration of hydrogen ions in moles per litre.
Alternative and more useful forms of pH definition are:

The pH concept is very convenient for expressing hydrogen ion concentration.

It was introduced by Sorensen in 1909. It is now used as a general way of expressing other quantities
also, for example,
pH Scale: In order to express the hydrogen ion concentration or acidity of a solution, a pH
scale was evolved. The pH is defined as

The hydrogen ion concentration of different acidic solutions were determined experimentally.
These were converted to pH values using the above relations. Then these pH values were computed on
a scale taking water as the reference substance. The scale on which pH values are computed is called
the pH scale.
Thus the H+ ion and OH ion concentrations in pure water are both 107 mol l 1 at 25C and it
is said to be neutral. In acidic solution, however, the concentration of H+ ions must be greater than
107 mol l1. Similarly in a basic solution, the concentration of OH ions must be greater than
107 mol l1. Thus we can state:

Expressing the [H+] in terms of pH for the different solutions cited above, we get what we call
the pH scale. On this scale the values range from 0 to 14. Since pH is defined as log [H+] and the
hydrogen ion concentration of water is 10 7, the pH of water is 7. All solutions having pH less than 7
are acidic and those with pH greater than 7 are basic. pH decreases with the increase of [H+].
The lower the pH, higher is the [H+] or acidity.
In any aqueous solution, the product of [H+] and [OH] is always equal to Kw. This is so
irrespective of the solute and relative concentrations of H+ and OH ions. However, the value of Kw
depends on temperature. At 25C it is 1.0 10 14. Thus,
75

Determination of pH of a solution using glass electrode: A half-cell is set up with the test
solution as electrolyte. The emf of the cell depends on the concentration of H+ ions or pH of the
solution. The emf of the half-cell is determined by coupling it with another standard half-cell and
measuring the emf of the complete cell. The commonly used standard electrode is the glass electrode.
A glass electrode is immersed in the solution of unknown pH. It is coupled with a standard calomel
electrode (SCE) as shown in Figure. The emf of the complete cell can be determined experimentally.

Glass electrode

A glass electrode coupled with standard

calomel electrode for determining pH

Calomel electrode

Calculations: The potential of the glass electrode, EG, at 25C is given by equation

The value of the potential of calomel electrode is known while Ecell can be found
experimentally. Therefore, we can find pH of a given solution if EG is known. It can be determined by
using a solution of known pH in the cell and measuring Ecell. This value of EG is constant for a
particular glass electrode and can be used for any subsequent determinations of pH of unknown
solutions with the help of equation. The potential of the cell, Ecell, cannot be measured using ordinary
potentiometer or voltmeter as the resistance of the glass membrane is very high and the current small.
Therefore, an electronic voltmeter is required which reads pH directly.
Merits and demerits of Glass electrode: A glass electrode is universally used because
[1] It is simple to operate. [2] It is not easily poisoned. [3] Its activity is not affected by strong
oxidising and reducing agents. [4] Since EG depends on a particular glass electrode used, it is not a
universal constant and also changes with time. Hence a glass electrode only compares pH values while
the hydrogen electrode measures pH absolutely.
76

Batteries
Introduction
Batteries are considered as storehouses for electrical energy on demand. An electrochemical
power source or battery is a device which converts the chemical energy derived from a chemical
reaction into electrical energy.
The chemical reaction involved in a battery is a redox reaction and some of these reactions are
reversible. The reverse reaction can be brought out by supplying energy, i.e. by applying the current to
the system from an external source. This process is called charging of the battery. Such batteries in
which the cell reactions can be reversed by passing direct electric current in opposite direction are
called secondary batteries. Lead-acid accumulators, nicad battery, etc. are secondary batteries.
Batteries that cannot be charged in this manner, because the cell reactions are irreversible, are called
primary batteries. Primary batteries are the most common batteries available today because they are
cheap and simple to use. Carbon-zinc dry cells, alkaline batteries, mercury batteries, lithium batteries,
etc. are examples for primary batteries. Table shows the differences between primary and secondary
batteries. In the following sections we will discuss in detail primary and secondary batteries.

Primary Batteries
Lechlanche Cell or Zinc-Carbon Dry Cell: The zinc-carbon cell uses a zinc anode, a
manganese dioxide cathode and an electrolyte of ammonium chloride dissolved in water. Powdered
carbon is mixed with manganese dioxide to improve conductivity and retain moisture.
In the dry cell which is a modified Lechlanche cell consists of a zinc anode shaped as a
container for the electrolyte and a graphite rod as a cathode surrounded by MnO2 and a paste of NH4CI
and ZnCl2 as an electrolyte. The dry cell is so called since there is no fluid phase presents (Figure 1).
The voltage of the cell is about 1.5 volt. It is commonly used in flash lights and radios.
77

Chemistry: As the cell is discharged zinc is oxidized and manganese dioxide is reduced:

Figure 1: Interior section of a dry cell

Drawbacks

of

dry

cells:

The

following

are

the

drawbacks

of

dry

cells:

[1] Dry cells do not have an indefinite life period. Since the electrolyte medium is acidic,
zinc metal dissolves slowly there by reducing the life time even if it is not in use.
[2] When current is rapidly drawn from the cell, due to the building up of products on the electrodes
there is a drop in voltage.
Alkaline

Battery:

An alkaline battery is an improved form of the dry cell.

In this cell, the electrolyte is a concentrated solution of potassium hydroxide (35-52%).

As the electrolyte in this cell is an alkali, it is called alkaline battery. The cathode is made from a
mixture of manganese dioxide and carbon. The anode mix consists of alkaline electrolyte, zinc powder
and small quantity of gelling agent (starch) to immobilize the electrolyte and suspend the zinc powder.
The alkaline cell derives power from the oxidation of zinc anode and the reduction of MnO2 cathode.

78

The emf of the cell is 1.5 volt. The advantages of this battery over a dry battery are as follows:
[1] As potassium hydroxide is used as an electrolyte, zinc does not readily dissolve.
[2] Since there is no corrosion of zinc, the life of alkaline battery will be longer.
[3] Its output capacity is high.

Secondary Batteries or Storage Batteries or Accumulators

Lead-acid Accumulator or Acid Battery: A storage cell is one which can operate both as a
voltaic cell and as an electrolytic cell. When it acts as a voltaic cell it supplies electrical energy. On
recharging it acts as an electrolytic cell.
An acid battery consists of a negative electrode of porous lead (lead sponge) as the anode and a
positive electrode of lead dioxide as the cathode. A number of such electrode pairs are immersed in an
aqueous solution of 20% sulphuric acid (specific gravity: 1.15 at 25C) which is the electrolyte
(Figure 2).

Figure 2: Lead-acid storage cell

Discharging: The electrode reactions that occur during the discharge of the cell, i.e. when
current is drawn from the cell are as follows:
Anode

Cathode

The overall cell reaction is as follows:

The PbSO4 formed gets precipitated on the cathode and in the solution.
79

Charging: When both anode and cathode become covered with PbSO4, the cell stops its
functioning. Recharging is done by applying a voltage across the electrodes that is slightly higher than
the voltage that the battery can deliver. The net reaction during discharging is as follows:

During the discharge process the consumption of sulphuric acid is replaced by an equivalent
quantity of water and the sulphuric acid concentration decreases. On charging the reverse reaction
takes place. During the reverse reaction water is consumed and sulphuric acid is regenerated. Hence
the original strength of acid is restored. Since both of these changes are associated with variations in
the specific gravity of the acid, the extent of charge or discharge of the cell at any time can be
determined by testing the specific gravity of the acid.
Uses: The following are the uses of lead-acid storage cells: [1] Lead-acid storage cells are used
in automobiles, hospitals, telephone exchanges, etc. [2] As it is rechargeable it is used in UPS
(uninterrupted power supply) a power system which maintains current flow without even a momentary
break in the event of current failure.
Maintenance: If the lead-acid batteries are properly maintained in the following ways,
they can function for long periods: [1] Avoid over discharging of the battery. [2] Maintain the
electrolyte at the proper level by adding water (whenever required). [3] Keep the battery clean.
[4] Avoid overheating of the battery.
Nickel-Cadmium Battery or Nicad Battery: A nickel-cadmium battery is a type of alkaline
storage battery. This battery consists of a cadmium anode, nickel oxyhydroxide cathode and an
alkaline electrolyte (potassium hydroxide).
During discharge cadmium metal oxidizes to cadmium hydroxide at the anode:

By accepting the electrons, nickel oxyhydroxide [NiO(OH)] is reduced to nickel hydroxide [Ni(OH)2]
at the cathode:

The overall cell reaction is:

The emf of the cell is 1.3 volt. This is a rechargeable battery. When the discharged battery is
connected to an external voltage source, the cell reaction is reversed.

80

Advantages: Nickel--cadmium cells are characterized by long life, relatively high rates of
discharge and charge and ability to operate at low temperatures.
Uses: Nicad cells are used in calculators, electrical shavers, etc. The good low
temperature performance has lead to wide use of nickel-cadmium batteries in aircraft and space
satellite power systems.

Fuel cells
A fuel cell is an electrochemical cell in which the chemical energy of the fuel-oxidant system is
directly converted into electrical energy. It is an energy conversion device or electricity generator.
A fuel cell operates like a galvanic cell with the exception that the reactants are supplied from
outside. It is an example for a primary cell. This is capable of supplying current as long as it is
provided with the supply of reactants.
Hydrogen-Oxygen Fuel Cell: A fundamental and important example of a fuel cell is the
hydrogen/oxygen cell. Like an electrochemical cell, the fuel cell is also having two electrodes and an
electrolyte. The two electrodes are made up of porous graphite admixed with nickel powder.
The electrolyte used is potassium hydroxide solution maintained at 200C and 20-40 atmospheres.
Hydrogen and oxygen gases are bubbled through the anode and cathode compartments respectively.
Hydrogen is oxidized at the anode whereas the oxygen gets reduced at the cathode (Figure 3).

Figure 3: Hydrogen-oxygen fuel cell

81

The cell reaction is the same as combustion of hydrogen in air or oxygen. Generally a large
number of these cells are stacked together in series to make a battery called fuel cell battery
or fuel battery.
In the fuel cells, gaseous fuels used are hydrogen, alkanes and co. Among the liquid fuels
methanol, ethanol, etc. are very important. Oxygen, air, hydrogen peroxide, etc. are some of the
oxidants used.
Advantages

of

fuel

cells:

The

following

are

the

advantages

of

fuel

cells:

[1] The energy conversion efficiency is very high (75-83%). [2] They are used as power sources in
spacecrafts. [3] The product of a hydrogen-oxygen fuel cell is pure water which can be used for
drinking purpose. [4] Noise and thermal pollution are very low. [5] The maintenance cost is very low.
[6] It saves fossil fuels.
Limitations: The following are the limitations of fuel cells: [1] The cost of power from a fuel
cell is high as result of the cost of electrodes and pure hydrogen gas. [2] As the fuels used are gases,
they have to be stored in big tanks under high pressures

Solar Cells or Photovoltaic Cells

Photovoltaic

cells

convert

solar

energy

directly

into

electrical

energy.

Description of solar cells: The conventional solar cells made up of p-type doped semiconductor
(i.e., silicon doped with boron) and n-type doped semiconductor (i.e., silicon doped with phosphorus)
is shown in Figure 4

Figure 4: Solar cell

82

The surface layer is made up of n-type semiconductor and it is extremely thin (~ 0.2 m) so
that sun light can penetrate through it. The bottom layer is made up of p-type semiconductor. The
electrodes made of Ti-Ag solder are attached to both the sides to provide electrical contact. The
electrode on the top surface is in the form of a metal grid with fingers which permit sun light to pass
through. On the back side, the electrode completely covers the surface. An anti-reflection coating of
silicon oxide having a thickness of 0.1 m is also put on the top surface.
Working: When p-type and n-type semiconductors are placed together, electrons from
n-type side diffuse across p-n junction to combine with holes present in p-type semiconductor side.
As a result positive ions (on n-type side) and negative ions (on p-type side) are created near
the junction to certain thickness. The separation of charges produces an electric field across
p-n junction which is about 0.6-0.7 volt. This potential at p-n junction prevents the charges moving
across it further.
When light strikes on the p-n junction, electron-hole pair is produced. As the potential barrier
resists the flow of charge carriers across it, they flow through the conductor/load connected externally
to produce electric current. Since the emf of a single solar cell is about 0.6 V, they are arranged into
larger groupings called arrays in solar panels.
Applications: The following are the application of solar cells: [1] Solar cells are used to
provide power supply for space satellites. [2] They are used for the distillation of water to get pure
drinking water. [3] Solar cells provide thermal energy for solar cookers, solar furnaces, etc.
[4] They provide electricity for street lighting in remote areas, and to run water pumps and radios in
desert areas. [5] Solar cells provide electric power to light houses.

Chemical sensors
A chemical sensor is a transducer which provides direct information about the chemical
composition of its environment. It can warn occupants of potentially toxic agents in air. It consists of a
physical transducer and a chemically selective layer.
Actually, it contains an array of tiny micro-hot-plates in conjunction with thin metalized films
such as tin, titanium, or zinc oxides. Both the hot plates and sensing films are incorporated into an
integrated circuit device. Sensitive films create a sensitive surface for detecting ambient chemicals.
If a specific chemical of interest is present, the resistance of the device changes. It produces a type of
signature for a specific chemical that can be matched up against a library of chemical signatures to
identify both the type and concentration of the gas in the ambient air. Metal-oxide semiconductors
(MOS) structures are of particular interest for chemical sensors.
83

Corrosion
Introduction
Metals and alloys are used as construction and fabrication materials in engineering. If the metal
or alloy structure is not properly maintained, they deteriorate slowly by the action of atmospheric
gases, moisture and other chemicals. This phenomenon of metals and alloys to undergo destruction by
the act of environment is known as corrosion.
Corrosion is defined as the gradual eating away or deterioration of a metal by chemical or
electrochemical reactions with its environment.
Due to corrosion the useful properties of a metal such as malleability, ductility and electrical
conductivity are lost. The most familiar example of corrosion is rusting of iron when exposed to
atmospheric conditions. During this, a layer of reddish scale and powder of oxide (Fe3O4) is formed
and the iron becomes weak. Another example is the formation of green film or basic carbonate
[CuCO3 + Cu(OH)2] on the surface of copper when exposed to moist air containing CO2.
It has been roughly assessed that the amount of iron wasted due to corrosion is one fourth of
world production. The direct loss due to corrosion in India amounts to Rs. 200 crore/annum while the
money spent annually in controlling corrosion is of the order of Rs. 50 crore. It is better to control
rather than to prevent corrosion, since it is impossible to eliminate corrosion.
Cause of Corrosion
In nature, most metals are found in a chemically combined state known as an ore. All the metals
except gold, platinum and silver exist in nature in the form of their oxides, carbonates, sulphides,
sulphates, etc. These combined forms of the metals represent their thermodynamically stable state (low
energy state). The metals are extracted from these ores after supplying a large amount of energy.
Metals in the uncombined condition have a higher energy and are in an unstable state. It is their natural
tendency to go back to the low energy state, i.e., combined state by recombining with the elements
present in the environment. This is the main reason for corrosion.
Effects of corrosion: The following are the effects of corrosion: [1] Lost production during a
shut down [2] Replacement of corroded equipment [3] High maintenance costs such as repainting
[4] Loss of efficiency [5] Contamination of the product.
Theories of Corrosion:
[2]

Electrochemical

theory

[1] Direct chemical attack or Chemical or Dry corrosion

or

Wet

corrosion

[3]

Differential

aeration

or

Concentration cell corrosion

84

Theories of Corrosion
[1] Direct Chemical Attack or Chemical or Dry Corrosion
Whenever corrosion takes place by direct chemical attack by gases like' oxygen, nitrogen and
halogens, a solid film of the corrosion product is formed on the surface of the metal which protects the
metal from further corrosion. If a soluble or volatile corrosion product is formed, then the metal is
exposed to further attack. For example, chlorine and iodine attack silver generating a protective film of
silver halide on the surface. On the other hand, stannic chloride formed on tin is volatile and so
corrosion is not prevented.
Oxidation corrosion is brought about by direct action of oxygen at low or high temperatures on
metals in the absence of moisture. Alkali metals (Li, Na, K, etc.) and alkaline earth metals
(Mg, Ca, Sn, etc.) are readily oxidized at low temperatures. At high temperatures, almost all metals
except Ag, Au and Pt are oxidized. Alkali and alkaline earth metals on oxidation produce oxide
deposits of smaller volume. This results in the formation of a porous layer through which oxygen can
diffuse to bring about further attack of the metal. On the other hand, aluminium, tungsten and
molybdenum form oxide layers of greater volume than the metal from which they were produced.
These non-porous, continuous and coherent oxide films prevent the diffusion of oxygen and hence the
rate of further attack decreases with increase in the thickness of the oxide film.
The protective or non-protective nature of the oxide film is determined by a rule known as the
Pilling-Bedworth rule. The ratio of the volume of the oxide formed to the volume of the metal
consumed is called the Pilling-Bedworth rule. According to it, if the volume of the oxide layer is
greater than the volume of the metal, the oxide layer is protective and non-porous. On the other hand,
if the volume of the oxide layer formed is less than the volume of the metal, the oxide layer is nonprotective and porous.
[2] Electrochemical Theory or Wet Corrosion
According to the electrochemical theory, the corrosion of a metal in aqueous solution may be a
two-step process, one involving oxidation and another reduction. It is known that two metals having
different electrode potentials form a galvanic cell when they are immersed in a conducting solution.
The emf of the cell is given by the difference between the electrode potentials. When the electrodes are
joined by a wire, electrons flow from the anode to the cathode. The oxidation reaction occurs at the
anode, i.e. at the anode the metal atoms lose their electrons to the environment and pass into the
solution in the form of positive ions. Fe

Fe2+ + 2e-. Thus, there is a tendency at the anode to

destroy the metal by dissolving it as ions. Hence corrosion always occurs at anodic areas. The
electrons released at the anode are conducted to the cathode and are responsible for various cathodic
reactions such as electroplating (deposition of metals), hydrogen evolution and oxygen absorption:
85

(i) Electroplating: The metal ions at the cathode collect the electrons and deposit on the cathode
surface. Cu2+ + 2e- Cu
(ii) Liberation of hydrogen: In an acid solution, (in the absence of oxygen) hydrogen ions
accept electrons and hydrogen gas is formed. 2H+ + 2e- H2
In a neutral or alkaline medium, (in the absence of oxygen) hydrogen gas is liberated with the
formation of OH- ions. 2H2O + 2e- H2 + 2OH(iii) Oxygen absorption: In the presence of dissolved oxygen and in an acid medium, oxygen
absorption reaction takes place. 4H+ + O2 + 4e- 2H2O
In the presence of dissolved oxygen and in a neutral or weakly alkaline medium, OH- ions are
formed. 2H2O + O2 + 4e- 4OH- Thus it is clear that the essential requirements of electrochemical
corrosion are as follows: (a) Formation of anodic and cathodic areas. (b) Electrical contact between the
cathodic and anodic parts to enable the conduction of electrons. (c) An electrolyte through which the
ions can diffuse or migrate. This is usually provided by moisture.
[3] Differential Aeration or Concentration Cell Corrosion
Anodic and cathodic areas may be generated even in a perfectly homogeneous and pure metal
due to different amounts of oxygen reaching different parts of the metal which form oxygen
concentration cells. In such circumstances, those areas which are exposed to greater amount of air
become cathodic while the areas which are little exposed or not exposed to air become anodic and
suffer corrosion. Figure shows the part of a metal surface covered with dirt which is less accessible to
air than the rest of the metal.

Hence, the area covered with dirt becomes anodic and suffers corrosion. The anodic
reaction is Fe Fe2+ + 2eThe most common reactions taking place at the cathode are

which is further oxidized to Fe(OH)3. Since the anodic area is small and the cathodic area is large,
corrosion is more concentrated at the anode. Thus, a small hole is formed on the surface of the metal.
This type of intense local corrosion is called pitting. Figure shows a wire fence in which the areas
where the wires cross are less accessible to air than the rest of the fence and hence corrosion takes
place at the wire crossings which are anodic.
86

In a similar way, iron corrodes under drops of water or salt solution. Areas covered by droplets,
having less access of oxygen become anodic with respect to the other areas which are freely exposed
to air. Differential aeration corrosion occurs when one part of metal is exposed to a different air
concentration from the other part. This causes a difference in potential between differently aerated
areas. It is experimentally found that poor oxygenated parts are anodic. Consequently, differential
aeration of a metal causes a flow of current.

Factors influencing corrosion: The rate and extent of corrosion depend mainly on
(a) the nature of the metal and (b) the nature of the environment.
Nature of the Metal
[I] Position in the galvanic series: The extent of corrosion depends upon the position of the
metal in the galvanic series. Greater the oxidation potential, the greater is the rate of corrosion.
When two metals are in electrical contact, the metal higher up in the galvanic series becomes anodic
and suffers corrosion. Further, the rate and severity of corrosion depend upon the difference in their
positions in the galvanic series. The greater is the difference, the faster is the corrosion
of anodic metal.
87

[2] Relative areas of the anode and cathode: The rate of corrosion is more when the area of the
cathode is larger. When the cathodic area is larger, the demand for electrons will be more,
and this results in increased rate of dissolution of metals at anodic regions.
[3] Purity of the metal: The impurities present in a metal create heterogeneity and thus galvanic
cells are set up with distinct anodic and cathodic areas in the metal. The higher the percentage of
impurity present in a metal, the faster is the rate of corrosion of the anodic metal. For instance,
impurities such as Pb and Fe in zinc lead to till formation of tiny electrochemical cells at the exposed
part of the impurity and the corrosion of zinc around the impurity takes place due to local action.
It is evident that the corrosion resistance of a metal may be improved by increasing impurity.
[4] Physical state of the metal: Metal components subjected to unevenly distributed stresses are
easily corroded. Even in a pure metal, the areas under stress tend to be anodic and suffer corrosion.
Caustic embrittlement takes place in stressed parts such as bends, joints and rivets in boilers.
[5] Nature of the oxide film: Metals such as Mg, Ca and Ba form oxides whose volume is less
than the volume of the metal. Hence, the oxide film formed will be porous, through which oxygen can
diffuse and bring about further corrosion. On the other hand, metals like AI, Cr and Ni form oxides
whose volume is greater than that of the metal and the nonporous oxide film so formed will protect the
metal from further corrosion.
[6] Solubilities of the products of corrosion: Solubility of the corrosion product formed is an
important factor in corrosion. If the corrosion product is soluble in the corroding medium, the
corrosion of the metal will proceed faster. On the other hand, if the corrosion product is insoluble, then
the protective film formed tends to suppress corrosion.
Nature of the Environment
[1] Temperature: The rate of chemical reactions and the rate of diffusion of ions increase with
temperature. Hence, corrosion increases with temperature. A passive metal may become active at a
higher temperature.
[2] Humidity: Atmospheric corrosion of iron is slow in dry air but increases rapidly in the
presence of moisture. This is due to the fact that moisture acts as the solvent for the oxygen in the air
to furnish the electrolyte essential for setting up a corrosion cell. Rusting of iron increases when the
relative humidity of air reaches from 60 to 80%.

[3] Effect of pH: The possibility of corrosion with respect to pH of the solution and the
electrode potential of the metal can be correlated with the help of a Pourbaix diagram.
The Pourbaix diagram for iron in water is shown in Figure.
88

The

diagram

shows

clearly

the

zones

In the diagram x is a point where pH is 7

of

corrosion,

immunity

and

passivity.

and the electrode potential is -0.4 V.

It is present in the corrosion zone. This shows that iron rusts in water under those conditions.
This is noticed to be true in actual practice also.
From figure, it is seen that the rate of corrosion can be altered by shifting the point x into
immunity or passivity regions. The iron would be immune to corrosion if the potential is changed to
about -0.8 V and this can be achieved by applying external current. On the other hand, the corrosion
rate of iron can also be reduced by moving into the passivity region by applying positive potential. The
diagram clearly indicates that the corrosion rate can also be reduced by increasing the pH of the
solution by the addition of alkali without disturbing the potential.
[4] Nature of the electrolyte: The nature of the electrolyte also influences the rate of corrosion.
If the electrolyte consists of silicate ions, they form insoluble silicates and prevent further corrosion.
On the other hand, if chloride ions are present, they destroy the protective film and the surface is
exposed for further corrosion. If the conductance of electrolyte is more, the corrosion current is easily
conducted and hence the rate of corrosion is increased.
[5]
The
where

rate

Concentration
of

oxygen

corrosion

of

oxygen

increases

concentration

is

and
with
lesser

formation
increasing
becomes

of

oxygen

supply
anodic

of

concentration
oxygen.

and

suffers

The

cells:
region

corrosion.

Corrosion often takes place under metal washers where oxygen cannot diffuse readily.
Similarly, buried pipelines and cables passing from one type of soil to another suffer corrosion due to
differential aeration, e.g. lead pipeline passing through clay and then through sand. Lead pipeline
passing through clay get corroded because it is less aerated than sand.
89

Types

of

Corrosion:

The following are the different types of corrosion:

[1] Galvanic corrosion: Galvanic corrosion is a type of electrochemical corrosion in which two
different types of metals in contact are jointly exposed to corrosive atmosphere. Here the metal with
more negative electrode potential will become the anode and goes into solution or corrode, e.g. (a)
zinc and copper metals and (b) steel pipe connected to copper plumbing. This corrosion can be
minimized by (a) avoiding galvanic couples and (b) providing an insulating material between the two
metals.
[2] Stress corrosion cracking: Corrosion of metals is also influenced by some physical
differences like internal stresses in the metals. Such differences result during manufacture, fabrication
and heat treatment. Metal components are subjected to unevenly distributed stresses during their
manufacturing process. The electrode potential thus varies from one point to another. Areas under
great stress act as the anode while areas not under stress act as the cathode. Various treatments of
metals and alloys such as cold working or quenching, bending and pressing introduce uneven stress
and lead to stress corrosion. Corrosion takes place so as to minimize the stress. Most of the time it
ends in breaking of the components into pieces. Corrosion of head and point portions of a nail
indicates that they have been acting as anode to the middle portion. Actually the head and the point
portions were put under stress during their manufacture. In the case of iron-wire hammered at the
middle, corrosion takes place at the hammered part and results in breaking of the wire into two pieces.
Caustic embrittlement takes place in stressed parts such as bends, joints and rivets in boilers.

Corrosion

Control:

Corrosion

can

be

controlled

by

the

following

ways:

[1] By selection of the material: Selection of the right type of the material is the main factor for
corrosion control. Thus, noble metals are used for surgical instruments and ornaments as they are most
immune to corrosion. [2] By using pure metals: Pure metals have higher corrosion resistance. Even
minute amount of impurities may lead to severe corrosion, e.g. 0.02% iron in aluminium decreases its
corrosion resistance. [3] By alloying: Both corrosion resistance and strength of many metals can be
improved by alloying, e.g. stainless steels containing chromium produce a coherent oxide film which
protects the steel from further attack. [4] By annealing: Heat treatment like annealing helps to reduce
internal stresses and reduces corrosion. [5] By eliminating galvanic action: If two metals have to be in
contact, they should be so selected that their oxidation potentials are as near as possible. Further, the
area of the cathode metal should be smaller than that of the anode, e.g. copper nuts and bolts on large
steel plate. The corrosion can also be reduced by inserting an insulating material between the two
metals. [6] By cathodic protection: The principle involved in cathodic protection is to force the metal
behave like a cathode. Since there will not be any anodic area on the metal, corrosion does not occur.
90

There are two types of cathodic protection. (a) Sacrificial anodic protection. (b) Impressed current
cathodic protection.
(a) Sacrificial anodic protection: In this technique, a more active metal is connected to the
metal structure to be protected so that all the corrosion is concentrated at the more active metal and
thus saving the metal structure from corrosion. This method is used for the protection of sea going
vessels such as ships and boats. Sheets of zinc or magnesium are hung around the hull of the ship. Zinc
and magnesium being anodic to iron get corroded. Since they are sacrificed in the process of saving
iron (anode) they are called sacrificial anodes. The corroded sacrificial anode is replaced by a fresh
one, when consumed completely. Important applications of sacrificial anodic protection are as follows:
[i] Protection from soil corrosion of underground cables and pipelines (Figure a). [ii] Magnesium
sheets are inserted into domestic water boilers to prevent the formation of rust water (Figure b).

Sacrificial anodic protection

Figure a
Figure b
(b) Impressed current cathodic protection: In this method, an impressed current is applied in
an opposite direction to nullify the corrosion current and converting the corroding metal from anode to
cathode. This can be accomplished by applying sufficient amount of direct current from a battery to an
anode buried in the soil and connected to the corroding metal structure which is to be protected.
The anode is in a backfill (composed of gypsum) so as to increase the electrical contact with the soil.
Since in this method current from an external source is impressed on the system, this is called
impressed current method.

91

[8]

By

modifying

modifying

the

environment.

the

environment:
The

environment

The
can

corrosion
be

rate

modified

can
by

be
the

reduced

by

following:

(a) Deaeration: The presence of increased amounts of oxygen is harmful since it increases the
corrosion rate. Deaeration aims at the removal of dissolved oxygen. Dissolved oxygen can be removed
by deaeration or by adding some chemical substances like Na2SO3 (b) Dehumidification: In this
method, moisture from air is removed by lowering the relative humidity of surrounding air. This can
be achieved by adding silica gel which can adsorb moisture preferentially on its surface.
(c) Inhibitors: In this method, some chemical substances known as inhibitors are added to the
corrosive environment in small quantities. These inhibitors substantially reduce the rate of corrosion.
(i) Anodic inhibitors: Anodic inhibitors include alkalis, molybdates, phosphates. chromates, etc.
When these inhibitors are added, they react with the ions of the anode and produce insoluble
precipitates. The so formed precipitate is adsorbed on the anode metal forming a protective film
thereby reducing corrosion. (ii) Cathodic inhibitors: In an electrochemical corrosion, the cathodic
reactions are of two types depending on the environment. In acidic solution, the cathodic reaction is
2H+ + 2e- H2. In acidic solution; the corrosion can be controlled by slowing down the diffusion of
H+ ions through the cathode. This can be done by adding organic inhibitor like amines and pyridine.
They adsorb over the cathodic metal surface and act a protective layer. In neutral solution,
the cathodic reaction is H2O + 1/2O2 + 2e- 2OH- The formation of OH- ions is only due to the
presence of oxygen. By elimination the oxygen from the medium, the corrosion rate can be reduced.
Oxygen can be removed by adding some reducing agents (Na2SO3) or by deaeration.
(iii) Vapour phase inhibitors: Vapour phase inhibitors (VPIs) are organic inhibitor which readily
sublime and form a protective layer on the metal surface, e.g., dicyclohexylammoniumnitrite. They are
used in the protection of machinery, sophisticated equipment, etc. which are sent by ships. The
condensed inhibitor can be easily wiped off from the metal surface.
[9] By Passivation: Passivation is a phenomenon of converting an active surface of a metal into
passive i.e. more corrosion resistant by forming a thin, non-porous and highly protective film over the
surface. When the metals like aluminium and tin are exposed to the atmosphere or to the oxidizing
environment, their surfaces rapidly get converted into oxides. The non-porous nature of these oxide
layers prevents further corrosion. In other words, the metals are passivated. Similarly, metals which
are susceptible to corrosion are made passive by alloying with one or more metals which are passive or
resist corrosion. For example, iron is rendered passive by alloying it with any of the transition metals
such as chromium, nickel and molybdenum.
[10] By applying protective coating: The surface of engineering material can be protected from
corrosion by covering it by a protective coating. This coating may be of organic or inorganic material.
92

Protective Coatings
Introduction
Protective coatings are used to protect the metals from corrosion. The main types of protective
coatings are classified as follows.

The protective coatings must be chemically inert to the environment and also sufficiently thick.
Besides protection from corrosive conditions, such coatings can also give decorative appearance to the
base metals. To be more effective, these coatings should adhere well to the surface.
Pretreatment of the surface or preparation of materials for coating: The outermost surface of
the base metal (which is to be protected) usually contains impurities like rust, scale and grease.
These substances, if present at the time of coating, will give porous and discontinuous coatings.
In order to get a uniform, smooth and coherent protective coating, these substances are removed by the
following methods.
Degreasing: Oil and grease may be removed by cleaning with organic solvents such as
chloroform, toluene and acetone. Immersion in hot alkaline solutions is the most commonly used
cleaning technique. For example, sodium carbonate and sodium hydroxide are used for this purpose.
Removal of Oxide Scales or Descaling: Removal of the oxide scales and corrosion products
(rust) from the surface is called descaling. In this process, the base metal is dipped inside the acid
solution at higher temperatures. The acid penetrates through cracks and pores of the scales and then
their dissolution takes place. Acids like sulphuric acid, hydrochloric acid and nitric acid are used under
dilute conditions.
Mechanical Cleaning: Oxide scales, rust and corrosion products are also removed by abrasion
such as grinding, wire brushing and polishing.
Electrochemical Method: The electrochemical method is used to remove oxide scales which are
not removed by other methods. The base metal is made either anode or cathode with an electrolyte
(acid or base). At the anode the oxide scale is dissolved in the electrolyte and leaves the base metal,
whereas at the cathode the metal oxides are reduced to metal.
93

Metallic Coatings
Surface coatings made up of metals are known as metallic coatings. These coatings separate the
base metal from the corrosive environment and also function as an effective barrier for the protection
of base metals. Metallic coatings are mostly applied on iron and steel because they are cheap and
commonly used. Metallic coatings are usually imparted by the following methods.
Hot Dipping: In the process of hot dipping, the metal to be coated is dipped in the molten bath
of the coating metal and the thickness of the coating is adjusted by squeezing out the excess of the
coating metal with rollers. Such hot dip coatings are generally non-uniform. The common examples of
hot dip coatings are galvanizing and tinning.
[1] Galvanizing: The process of coating a layer of zinc on steel is called galvanizing.
The steel article is first pickled with dilute sulphuric acid to remove traces of rust, dust, etc, at 6090C for about 15-20 minutes. Then this metal is dipped in a molten zinc bath maintained at 430C.
The surface of the bath is covered with ammonium chloride flux to prevent oxide formation on the
surface of molten zinc. The coated base metal is then passed through rollers to correct the thickness of
the film. It is used to protect roofing sheets, wires, pipes, tanks, nails, screws, etc.
[2] Tinning: The coating of tin on iron is called tin plating or tinning. In tinning, the base is
first pickled with dilute sulphuric acid to remove surface impurities. Then it is passed through molten
tin covered with zinc chloride flux. The tin coated article is passed through a series of rollers
immersed in a palm oil bath to remove the excess tin. Tin-coated utensils are used for storing
foodstuffs, oils, etc. Galvanizing is preferred to tinning because tin is cathodic to iron, whereas zinc is
anodic to iron. So, if the protective layer of the tin coating has any cracks, iron will corrode. If the
protective layer of the zinc coating has any cracks, iron being cathodic does not get corroded. The
corrosion products fill up the cracks, thus preventing corrosion.
Cementation: In cementation, the base metal is heated with the coating metal in the form of
fine powder in order to promote the diffusion of the coating metal into the base metal.
The coatings obtained are of uniform thickness. The base metal is generally steel and the coating
metals used is zinc, chromium and aluminium. When the coating metal is zinc, the process is called
sherardizing. When the coating metal is chromium, the process is called chromizing. When the coating
metal is aluminium, the process is called calorizing.
[1] Sherardizing: Cementation with zinc powder is called sherardizing. The base metal is
heated with zinc dust in a metal drum maintained at a temperature of 350-370C. The drum is closed
tightly and rotated with constant heating for two to three hours. During this process zinc gets diffused
into iron forming an alloy of Fe-Zn on the surface. Sherardized coatings are used for protecting small
steel parts such as nuts and bolts against atmospheric corrosion.
94

[2] Chromizing: The base metal is heated with a powdered mixture of 55 per cent chromium
and 45 per cent alumina at a temperature of 1300-1400C for about 3-4 hours in a closed drum.
The purpose of using alumina is to prevent the coalescing of chromium particles. The outermost
surface of the base metal is converted into a chrome alloy which protects the metal against corrosion.
This method is used to protect gas turbine blades. [3] Calorizing: Here the base metal is heated with a
powdered mixture of aluminium and alumina in a drum at a temperature of 840-930C for 4-6 hours.
Electroplating or Electrodeposition: Electroplating is a process in which metals are deposited
or plated on base metals from solutions containing metallic ions by means of electrolysis.
The objectives of electroplating are as follows: (1) To obtain improved resistance to corrosion and
chemical attack (2) To get better appearance (3) To get increased hardness (4) To change the surface
properties of metals and non-metals. In the electroplating process, the freshly cleaned base metal
which is to receive the coat is made the cathode in a suitable electrolyte bath containing (a) a solution
of the salt of the metal 10 be electrodeposited, (b) buffer solution to control the pH, and (c) additional
reagents to enhance conductivity and to aid the formation of smooth, dense and coherent coating.
The concentration of the salt solution is maintained by the addition of the metal salt at regular intervals
or by the use of continuously dissolving anode of the metal. The plating is usually done at a high
current density. The nature of the deposit depends upon the current density, pH and the concentration
of the bath. A typical electroplating process is shown in Figure.

Organic Coatings: Organic coatings are inert organic barriers applied to the surface of
base metals for corrosion resistance and decoration. Paints, varnish, lacquers and enamels are the main
organic coatings. Paints: Paint is a viscous suspension of finely divided solid pigment in a fluid
medium which on drying yields an impermeable film having considerable hiding power.
When paint is applied to a metal surface, the thinner evaporates, while the drying oil slowly oxidizes
forming a dry pigmented film. Requirements of a good paint: A good paint should essentially have
the following: [1] A good paint should fonn a good impervious and uniform film on the metal surface.
[2] It should have a high hiding (covering) power. [3] The film should not crack on drying.
[4] A good paint should adhere well to the surface. [5] It should spread on the metal surface easily.
[6] It should give a glossy film. [7] It should be corrosion resistant. [8] A good paint should give a
stable and decent colour on the metal surface.
95

Constituents of paint and their functions: The important constituents of paint are as follows:
(1) Pigments (2) Vehicle or drying oils or medium (3) Thinners (4) Driers (5) Fillers or extenders
(6) Plasticizers (7) Anti-skinning agents
(1) Pigments: A pigment is a solid and colour-producing substance in the paint.
(2) Vehicle or drying oils or medium: The liquid portion of the paint in which the pigment is
dispersed is called a medium or vehicle. This is the film forming constituent of the paint. Vehicles are
high molecular weight fatty acids present in animal and vegetable oils, e.g. linseed oil, dehydrated
castor oil, soyabean oil and fish oil. (3) Thinners: Thinners are added to paints to reduce the
consistency or viscosity of the paints so that they can be easily applied to the metal surface. Thinners
are volatile in nature and evaporate easily after application of the paint, e.g. turpentine and petroleum
spirit (4) Driers: Driers are used to accelerate or catalyze the drying of the oil film by oxidation,
polymerization and condensation, e.g. naphthenates, borates and tungstales of lead, cobalt and
manganese. (5) Fillers or extenders: Fillers are used to reduce the cost and increase the durability of
the paint, e.g. talc, china clay, calcium sulphate and calcium carbonate. (6) Plasticizers: Plasticizers
are chemicals added to paints to give elasticity to the film and to prevent cracking of the film, e.g.
triphenyl phosphate and tricresyl phosphate. (7) Anti-skinning agents: They are chemicals added to
the paint to prevent skinning of the paint, e.g. polyhydroxy phenols.
Mechanism of drying oils: Drying oils are the film forming constituent of the paint.
These are fatty oils which are extracted from plants or animals. The fatty oils are tri-esters of glycerol.
The oil film after it has been applied to the protected surface absorbs oxygen from air at the double
bonds forming peroxides which isomerizes, polymerize and condense to form a tough and highly cross
linked macromolecular film.
Failure of paint: Paint may fail due to several reasons: (1) Chalking: Chalking is the gradual
powdering of paint. It is caused by continuous destructive oxidation of the oil after the original drying
of paint. (2) Erosion: It is very quick chalking. (3) Flaking: Flaking is caused due to poor adherence
of a paint film to the surface because of the presence of grease on the surface. (4) Checking: It is a
very fine type of surface cracking. (5) Alligatoring: The centre portion of the film remains attached to
the surface, whereas the portion around the centre peels off.
The failure of paint can be prevented by the following ways: (1) Carefully preparing the
surface before application of paint. (2) Applying a suitable primer coat. (3) Applying the paint evenly.
(4) Allowing each paint coat to dry sufficiently before the next coat is applied.

96

Water and Its Treatment

Rain water is almost pure (may contain some dissolved gases from the atmosphere).
Being a good solvent, when it flows on the surface of the earth, it dissolves many salts. Presence of
calcium and magnesium salts in the form of bicarbonate, chloride and sulphate [Cations are Ca2+ ion
and Mg2+ ion and Anions are HCO3- ion, Cl- ion, and SO42- ion] in water makes water hard.
Hard water does not give ready and permanent lather with soap. Water free from soluble salts of
calcium and magnesium is called Soft water. It gives lather with soap easily.
Hardness of Water: Hardness was originally defined as the soap consuming capacity of a
water sample. Soap is the sodium salt of higher fatty acids, e.g. sodium stearate. The sodium salt is
soluble in water, but the corresponding calcium and magnesium ions are insoluble in water.
When soap is added to soft water, it dissolves and lathers readily.
On adding soap solution to a sample of hard water which contains calcium or magnesium ions,
soap is precipitated as insoluble salts which prevent the formation of lather. This reaction causes the
loss of soap. No lather is obtained until all the ions are removed. So, large amount of soap is consumed
unnecessarily before lather is formed.
2C17H35COONa (sodium stearate) + CaCl2 (C17H35COO)2Ca [ppt of calcium stearate] + 2NaCI
The hardness of water is of two types: (i) Temporary Hardness, and (ii) Permanent Hardness.
Temporary Hardness is due to the presence of magnesium and calcium bicarbonates
[Ca(HCO3)2 and Mg(HCO3)2]. It is also called carbonate hardness (CH). It can be removed by
Boiling. During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2
is changed to insoluble CaCO3. These insoluble precipitates can be removed by filtration.
Filtrate thus obtained will be soft water.

$,T

$,T

Mg^HCO b Mg^OHb + 2CO and Ca^HCO b CaCO + CO + H O

Permanent Hardness is due to the presence of soluble salts of magnesium and calcium in the
form of chlorides and sulphates in water (CaCl2, CaSO4, MgCl2 and MgSO4). Permanent hardness is
not removed by boiling. It is also called non-carbonate hardness (NCH).
Total

Hardness:

Temporary

hardness

and

permanent

hardness

constitute

the

total hardness which is also expressed as the sum of the concentration of calcium and magnesium ions.
Total Hardness = Temporary Hardness + Permanent Hardness or = [Ca2+] + [Mg2+]
Units of hardness: The following are the common units used in hardness measurements.
[1] Parts per million (ppm): It is defined as the number of parts by weight of CaCO3 present in million parts by weight of water. 1 ppm = 1 part of CaCO3
equivalent hardness in 106 parts of water, so 1 ppm =

  ) U',
++

R + ) 


. Both temporary and permanent hardness is expressed in ppm as CaCO3. The choice of CaCO3

because is due to the fact that it is the most insoluble salt in water.
[2] Milligram per litre: It is defined as the number of milligrams of CaCO3 present in one litre of water.1 mg/l = 1 mg of CaCO3 equivalent hardness in one
litre of water Since weight of 1 litre of water = 1 kg = 1000 g = 1000 x 1000 mg = 106 mg so 1 mg/l = 1 mg of CaCO3 per 106 mg of water = 1 part of CaCO3 per
106 parts of water = 1 ppm. Thus, mathematically both units are equal.

97

Determination

of

Total

Hardness

of

Water

by

Complexometric

Titration

[EDTA Method]: Eriochrome Black-T [EBT] is the indicator used in the determination of hardness
by complexometric titration with EDTA. Here, Eriochrome Black-T is a complex organic compound
[sodium-1-(1-hydroxy 2-naphthylato)-6-nitro-2-naphthol-4-sulphonate] and EDTA is a hexadentate
ligand [disodium salt of ethylenediamine tetraacetic acid].
NaOOCH 2C

HO

OH

CH2 COOH
N

SO 3Na

H2
C

H2
C

HOOCH 2C

CH2 COONa

EDTA
[Disodium salt of ethylenediamine
tetraacetic acid]

NO 2

Eriochrome Black-T [EBT]

Principle: Estimation of hardness by EDTA method is based on the principle that EDTA forms
metal complexes with hardness producing metal ions in water. These complexes are stable when the
pH is maintained between 8 and 10 and also the indicator becomes effective only at this pH range.
In order to maintain the pH, buffer solution (NH4Cl and NH4OH mixture) is added. The completion of
the complexation reaction is indicated by Eriochrome Black-T indicator. When this indicator is added
to the sample water it forms indicator-metal complexes of wine red colour.
Ca2+/ Mg2+ + EBT [Ca2+/ Mg2+ EBT]
from hard water
Now

when

this

wine

Wine red coloured unstable complex

red-coloured

solution

is

titrated

against

EDTA

solution,

EBT in the unstable complex is replaced by EDTA to form a stable metal-EDTA complex and
liberates the free Eriochrome Black-T. At this point, the colour of the solution changes from wine red
to original blue colour which showing the end point of the titration.
[Ca2+/ Mg2+ EBT] + EDTA
Wine red coloured
unstable complex

[Ca2+/ Mg2+ EDTA]

Stable metal-EDTA complex

(Colourless)

free EBT
Blue colour

The temporary hardness is removed by boiling and after the removal of precipitate by filtration;
the permanent hardness in the filtrate is determined by titration with EDTA as before.
Therefore, total hardness - permanent hardness - temporary hardness
Experimental procedure: A known volume of the sample of hard water (V ml) is treated with
about 10 ml of a buffer solution and 5 drops of Eriochrome Black-T indicator. This solution is then
titrated against the standard EDTA reagent (standardized such that 1 ml of the reagent corresponds to
1 mg of CaCO3). The end point is the colour change from wine red to blue.
98

A known volume (V ml) of sample water is taken in a beaker and boiled for 15 minutes.
After cooling the mixture, it is filtered and thoroughly washed. The filtrate is collected and made up to
a known volume (V ml). This solution is titrated against EDTA as before. The volume of EDTA
consumed is V2 ml. Then,

Hence, (Total hardness) - (Permanent hardness) gives the temporary hardness.

Calculation steps
1 ml of Standard hard water

1 mg CaCO3

V1 ml of EDTA solution

20 ml of Standard hard water

20 mg CaCO3

20
mg CaCO
V

..mg CaCO3

1 ml of EDTA solution,

20 ml of given water sample

V2 ml of EDTA solution
V

=
1 ml of given water sample

1000 ml of given water sample

=
=
=

Total Hardness of given water sample

V
V

20
mg CaCO
V

20
1
mg CaCO
V
20

20
1
mg CaCO
1000
V
20

V 20

1000 mg CaCO
V 20
V
1000 mg CaCO
V

V
1000 ppm = . ppm
V
99

Problem: 0.5 g of CaCO3 was dissolved in dil. HCl and diluted to 500 ml. 50 ml of this
solution required 48 ml of EDTA solution for titration. 50 ml of a hard water sample required
15 ml of the same EDTA solution for titration. Calculate the total hardness of water.
500 ml of CaCl2 solution = 0.5 g of CaCO3
= 0.5 x 1000 mg of CaCO3
= 500 mg of CaCO3 hence 1 ml of CaCl2 solution = 1 mg of CaCO3
Standardization of EDTA
1 ml of CaCl2 solution = 1 mg of CaCO3
50 ml of CaCl2 solution = 50 mg of CaCO3
48 ml of EDTA solution = 50 mg of CaCO3
R
1 ml of EDT A solution = 1 = 1.04 mg of CaCO3

Total hardness
1 ml of EDTA solution = 1.04 mg of CaCO3
15 ml of EDTA solution = 1.04 X 15 = 15.6 mg of CaCO3
This amount of hardness is present in 50 ml of the water sample.
.
So total hardness present in one litre =
1000 = 312 ppm of CaCO3 equivalent
R

100

101

102

103

104

Alkalinity: The alkalinity of water is due to the presence of a wide variety of salts of weak
acids such as carbonates, bicarbonates, phosphates, etc., and also due to the presence of weak and
strong bases (due to contamination with industrial wastes). The major portion of alkalinity in natural
water is caused by the presence of bicarbonates that are formed when water containing free carbon
dioxide percolates through soils containing calcium carbonate and magnesium carbonate.
CaCO3 + CO2 + H2O Ca(HCO3)2
The alkalinity of natural water may be taken as an indication of the concentration of hydroxides,
carbonates and bicarbonates.
Caustic Embrittlement: It is the phenomenon during which the boiler material becomes brittle
due to the accumulation of caustic substances. It is a very dangerous form of stress corrosion occurring
in mild steel boiler metals exposed to alkaline solution at high temperatures, resulting in the failure of
the metal. Stressed parts like bends, joints and rivets are severely affected. Boiler water usually
contains a small proportion of Na2CO3. In high pressure boilers, this breaks up to give NaOH and
makes the boiler water more alkaline: Na2CO3 + H2O 2NaOH + CO2
This very dilute alkaline boiler water flows into the minute hair cracks and crevices by capillary
action. There the water evaporates and the concentration of caustic soda increases progressively.
The concentrated alkali dissolves iron as sodium ferroate in crevices, cracks, etc. where the metal is
stressed. This causes brittlement of boiler parts particularly stressed parts like: bends, joints and rivets
causing even failure of the boiler. Highly alkaline water may lead to caustic embrittlement.
Caustic embrittlement can be avoided (a) by using sodium phosphate as softening reagent instead of
Na2CO3 and (b) by adding tannin or lignin to boiler water which blocks the hair cracks.
Dissolved Oxygen (D.O): Oxygen is poorly soluble in water. The solubility of oxygen of air in
fresh water varies from 7.5 - 14.5 mg/Lit. Dissolved oxygen is needed for living organism
to maintain their biological process. It is an important factor in corrosion. Dissolved oxygen in water is
mainly responsible for the corrosion of a boiler. The dissolved oxygen in water attacks the boiler
material at high temperatures.
2Fe + 2H2O + O2 2Fe(OH)2
4Fe(OH)2 + O2 + 2H2O 2[Fe2O33H2O] (rust)
Determination of Dissolved Oxygen present in a given Water Sample by Iodometric Method
(Winklers Method): The principle involved in the determination of dissolved oxygen is to bring about
the oxidation of potassium iodide (KI) to iodine (I2) with the dissolved oxygen present in the water
sample after adding MnSO4, KOH and KI, the basic manganic oxide formed act as an oxygen carrier
to enable the dissolved oxygen in the molecular form to take part in the reaction.
105

MnSO + 2KOH Mn^OHb + K  SO

2Mn^OHb + O 2MnO^OHb Basic manganic oxide which on acidification gives
MnO^OHb + H SO MnSO + 2H O + nOp
2KI + H SO + nOp K  SO + H O + I
The liberated iodine (I2) is titrated against standard sodium thiosulphate (Na2S2O3) solution using
starch as indicator nStarch + I Blue coloured complexp.
I + 2Na S O Na S O + 2NaI
Procedure: Take 100 ml of given water sample into a conical flask, and titrate slowly against
N/50 standard sodium thiosulphate solution (taken in the burette). When the colour of the solution is
very light yellowish add about 2 ml of freshly prepared starch solution, so the colour of the solution
turned into blue. Continue the titration till the disappearance of blue colour of the solution and note
down the volume of the titrant used. The titration is repeated until a concordant volume is obtained.
Normality of standard Na2S2O3 solution, N1

1
= 0.02N
50

Volume of standard Na2S2O3 solution, V1

ml

Volume of given water sample, V2

.....ml

Normality of given water sample, N2 can be calculated from the normality formula,
i.e., N1 x V1 = N2 x V2
Normality of given water sample, N2

Amount of Dissolved Oxygen

Amount of Dissolved Oxygen in ppm

N V
V

..N

N Eq. wt of Oxygen = N 8 g/Lit

g/Lit

. . 1000 mg/Lit

..ppm

Removal of Dissolved O2: Dissolved oxygen can be removed from water by chemical
and mechanical means. Sodium sulphite (Na2SO3), hydrazine (N2H4), etc. are some of the chemicals
used for removing oxygen.
2Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2 + 2H2O
Hydrazine is found to be an ideal compound for removing dissolved oxygen since the products are
water and inert N2 gas. It removes oxygen without increasing the concentration of dissolved salts.
106

Impurities in water: The impurities present in water may be broadly classified as follows.
[1] Dissolved impurities: The dissolved impurities are mainly the carbonates, bicarbonates, chlorides
and sulphates of calcium, magnesium, iron, sodium and potassium. The presence of these salts imparts
hardness to water. The dissolved impurities also include dissolved gases like oxygen
and carbon dioxide.
[2]

Suspended

impurities:

The

following

are

the

types

of

suspended

impurities:

(a) Inorganic: Clay and sand (b) Organic: Oil globules, vegetable and animal matter.
The above suspended impurities impart turbidity, colour and odour to water.
[3] Colloidal impurities: They are finely-divided silica and clay, organic waste products,
complex protein amino acids, etc.
[4] Microorganisms: They are algae, fungi and bacteria.
Potable Water (water for domestic supply): Municipalities have to supply potable water,
i.e., It is a water of sufficiently high quality that it can be consumed or used without risk of immediate
or long term harm. The following are characteristics of potable water
[1] It should be sparking clear, soft, pleasant in taste, perfectly cool and odourless
[2] Its turbidity should not exceed 10 ppm [3] Its alkanity should not be high (pH = 8.0)
[4] Its dissolved solids should be less than 500 ppm [5] It should be free from objectionable minerals
such as lead, arsenic, chromium and manganese salts and also free from objectionable dissolved gases
like hydrogen sulphide [6] It should be free from disease producing micro-organisms.
Drinking water comes from two major sources: (a) Surface water such as lakes, rivers, and
reservoirs, but it requires both filtration and disinfection in order to use as drinking water.
(b) Ground water, which is pumped from wells, it is considered to be the purest source of water.
Rivers, lakes and wells are the most common sources of water used by municipalities.
The actual treatment methods depend directly on the impurities present. For removing various types of
impurities the following treatment processes are employed.

107

Treatment Processes for Removal of Impurities

Screening: It is the process of removing floating materials like wood pieces and leaves from
water. Raw water is allowed to pass through a screen having a large number of holes which removes
the small and large floating matter.
Sedimentation: It is the process of removing suspended impurities by allowing the water to
stand undisturbed for 2-6 hours in big tanks. Due to force of gravity, most of the suspended particles
settled down at the bottom and they are removed. Sedimentation removes only 70-75% of the
suspended matter.
Coagulation: Finely-divided silica, clay, etc. do not settle down easily and hence cannot be
removed by sedimentation. Most of these are in colloidal form and are negatively charged and hence
do not coalesce because of mutual repulsion. Such impurities are removed by coagulation method.
Here, certain chemicals like alum and Al2(SO4)3 are added to water. When Al2(SO4)3 is added to water,
it hydrolyzes to form a gelatinous precipitate of Al(OH)3 The gelatinous precipitate of Al(OH)3 entraps
finely divided and colloidal impurities, settles to the bottom and can be removed easily.
Filtration: For removing bacteria, colour, taste, odour, fine suspended particles, etc. and to
produce clear water, filtration is used. In this process, water is passed through beds of fine sand, coarse
sand and other granular material. The porous material used is the filtering medium and the equipment
used for filtration is known as filter, e.g. slow sand filter.
A typical slow sand filter is shown in Figure 1.5. It consists of a tank containing thick beds of
fine sand (at the top), coarse sand, fine gravel and coarse gravel (at the bottom).
When the water passes through the filtering medium, it flows through the various beds slowly due to
gravity. The rate of filtration slowly decreases due to the blockage of impurities in the pores of the
sand bed. When the rate of flow becomes very slow, filtration is stopped and the bed is cleaned by
scraping of a smaller layer of the sand bed (top layer) and replacing it with the clean sand.
Bacterias are partly removed by this filtration process.

108

Sterilization: The complete removal of harmful bacteria is known as sterilization.

The following sterilizers are generally used for sterilizing water.
[1] Sterilization by chlorine or bleaching powder: Chlorine is the most common sterilizing
agent in water treatment. Chlorine may be added in the form of bleaching powder or directly as a gas
or in the form of concentrated solution in water.
When bleaching powder is added to water, HOCI which acts as a powerful germicide is
produced. It is believed that HOCI reacts with bacteria and inactivate the enzymes present in the cells
of bacteria. These enzymes are responsible for the metabolic activities of microorganisms.
Since these enzymes are inactivated, microorganisms become dead.
CaOCl2 + H2O Ca(OH)2 + Cl2; Cl2 + H2O HCI + HOCI; HOCI + Bacteria Bacteria are killed
[2] Sterilization by ultraviolet radiations: Ultraviolet radiations emanating from electric mercury
vapour lamp is capable of sterilizing water. This process is particularly useful for sterilizing swimming
pool water. This process is highly expensive.
[3] Sterilization by ozone: Ozone is a powerful disinfectant and is readily absorbed by water.
Ozone is highly unstable and decomposes to give nascent oxygen which is capable of destroying the
bacteria. O3 O2 + [O]. This process is relatively expensive.
Break point chlorination
In break point chlorination a sufficient amount of chlorine is added to oxidize (a) organic matter,
(b) reducing substances (Fe2+, H2S, etc.) and (c) free ammonia in raw water leaving behind mainly free chlorine
which destroys pathogenic bacteria. When chlorine is added to water, initially it reacts with ammonia and there
will formation of chloramines (See equations). Thus the amount of combined residual chlorine (chloramines)
increases with increasing dosage. Then the oxidation of chloramines and other impurities start and there is a
fall in combined chlorine content. Thus combined residual chlorine decreases to a minimum at which oxidation
of chloramines and other organic compounds complete. This minimum is the breaking point of chlorine (Fig)

The reason for such behaviour is due to the fact that some organic compounds which defy oxidation at
lower chlorine concentration get oxidized when the break point chlorine concentration is reached.
Since, it is these organic compounds which are generally responsible for bad taste and odour in water, it is clear
that break point chlorination eliminates bad taste and odour. Further chlorination increases the free residual
chlorine (CI2, HOCI, OCI-). Hence, it use chlorine as a good disinfectant, the chlorine dosage has to be given
more than the break point.
109

110

111

Module IV - Water
No

Questions

Marks

Mention the chemical species causing alkanity in water?

What is the hardness of water? How is it expressed?

Distinguish between Hard water and Soft water.

What is break point chlorination?
Why buffer is added during titration of hard water against EDTA solution?
Write the structure of EDTA and EBT
0.30 g of CaCO3 was dissolved in HCl and the solution made on to one litre
with distilled water. 100 ml of this solution required 30 ml of EDTA solution
on titration. 100 ml of hard water sample required 55 ml of EDTA solution on
titration. After boiling 100 ml of this water, cooling, filtering and then titration
required 10 ml of EDTA solution. Calculate the temporary and permanent
hardness of water
20 ml of std hard water (containing 15 g CaCO3/litre) required 25 ml of EDTA
solution for end point 100 ml of water sample required 18 ml of EDTA
solution while the same water after boiling required 12 ml EDTA solution.
Calculate total hardness of water

6
7

How is water softened by lime soda process?

With a neat diagram, discuss the demineralization of water

using ion exchange method
Enumerate the various stages involved in the purification of water for
domestic use

7
8

7
8
8

10 What are the important sources of water pollution?

With relevant chemical equations, outline the estimation of dissolved
11
oxygen

12 Among BOD and COD, which is greater? Why?

13 Distinguish between BOD and COD, How it can be determined?

Write a note on experimental determination of BOD of a polluted water
14
sample

Module I Bioinorganic Chemistry

No

Questions

Marks

What is the importance of bulk and trace metal ions in biological systems

What roles of iron and copper play in biology?

Give elementary idea about haemoglobin and myoglobin

112

Module II - Polymer
No

Questions

Marks

What are the classifications of polymers?

Give one example for addition and condensation polymers

How would you classify polymers based on source and applications?

Differentiate between thermoplastic

Give two examples of each type

Discuss the various types of polymerization with suitable examples

Distinguish between polymerization by addition and condensation

processes

Discuss the mechanism of addition polymerization

Explain free radical, cationic and anionic mechanism of polymerization

Discuss the mechanism of coordination [or Ziegler-Natta] polymerization

Briefly explain the techniques of polymerization

10

What is glass transition temperature? Discuss the factors affecting Tg.

What is its significance?

11 Write notes about crystallinity in polymers and the factors affecting it

and

thermosetting

plastic.

Module II - Lubricants
No

Questions

Marks

What are lubricants? Discuss the classification of lubricants with examples

Explain the classification of liquid lubricants

What are lubricating oils? Give their properties and uses

Write a note on grease as a lubricant

Write a note on the term solid lubricants

Draw and explain the structure of graphite and molybdenum disulphide.

How are they used as lubricants?

Outline the mechanism of lubrication

Discuss in detail the properties of lubricants highlighting their importance

How do viscosity and viscosity index influence the selection of lubricants for
a particular purpose?

10

Write short notes on: (i) Solid lubricants (ii) Flash and Fire point
(iii) Aniline point (iv) Cloud and Pour point

10

113

University Questions
Module II - Fuels
No

Questions

Marks

Distinguish between Gross (or higher) and Net (or lower) calorific value of fuel

What is cracking and what for it used? What are the types of cracking?

Write informative notes on Reforming

How does knocking occur in I.C engines? How can it be prevented?

10

What is meant by knocking in a petrol engine and what is it due to?

What is octane number of petrol? How is petrol knocking related to chemical

structure of the constituents of petrol and how can it be reduced?
How do you explain knocking in a diesel engine? How can it be controlled?
What is cetane number?
Establish the relationship between knocking in I.C engines and molecular
structure of the constituents in petrol and diesel fuels

Differentiate Octane number and Cetane number

10 Write informative notes on Biodiesel

7
7
7
8
5

Module I Green Chemistry

1

What is green chemistry? How is it important?

What are the goals of green chemistry and its limitations?

Explain the twelve principles of green chemistry with examples

10

Discuss any four principles of green chemistry

Write short notes on atom economy

What are the steps involved in minimization of hazardous/toxic products?

Write notes on any two of the synthetic methods used in green chemistry

10

Discuss the designing of green synthesis

Module I Organometallic Compounds

1

What are organometallic compounds? How are they classified

Write a note on structure and bonding in organometallic compounds

Discuss the 18-electron rule with any two examples

4
5

What are pi-acceptor ligands?

Discuss in details the nature of bonding involved in metal carbonyls
What are metal carbonyls?
Discuss mononuclear and polynuclear carbonyls with examples

Write short note on carbonyls of iron and nickel

8
8
7

114

Module III - Electrochemistry

No

Questions

Marks

Define oxidation potential and reduction potential

Explain single electrode potential. Derive the expression for it

What is standard electrode potential? Give its importance

What is reference electrode? Give examples

What is a hydrogen electrode?

Write a descriptive account on different types of electrodes

How will you determine pH of a solution using glass electrode?

Describe an experiment to determine the electrode potential of an electrode

What is an electrochemical cell?

How EMF is measured by using hydrogen electrode and glass electrode?
How is EMF of an electrochemical cell determined through Poggendorfs
10
compensation method?
9

8
5

11 What is electrochemical series? What are its applications?

12 Derive the Nernst equation for electrode potential

13 What is the effect of electrolyte concentration on electrode potential

14 Differentiate between electrochemical cell and concentration cell

5
5

15 Derive the expression for EMF in concentration cells

Module III Storage Cells

No

Questions

Marks

Write the redox reactions taking place in the lead acid accumulators

Describe the construction of lead-acid battery with the reactions

Describe the construction and functioning of lead acid accumulators and

Nickel-Cadmium cells

10

Write a descriptive account on Fuel cells and Nickel-Cadmium cell

Define fuel cell. Explain the construction and working of H2-O2 fuel cells

Write a descriptive account on Fuel cells and Solar cells

Discuss the usage of solar cells

115

Module IV Corrosion
No

Questions

Marks

How is corrosion caused? What are the conditions of dry corrosion?

Outline the different types of corrosion

Describe the various factors influencing the corrosion

What is direct corrosion?

Explain the mechanism of dry corrosion.

Explain the role of oxide film in dry corrosion and classify them
Explain the mechanism of wet corrosion. Give details of corrosion protection
through sacrificial anodic method and impressed current method
What is meant by differential aeration corrosion?
Illustrate with suitable examples

Write a note on galvanic corrosion

Briefly discuss on galvanic series and galvanic corrosion

8
8
8

10 Write a note on electrochemical corrosion

11 Distinguish between chemical and electrochemical corrosion

12 Give the mechanism of rusting of iron

13 State and explain Pilling-Bedworth rule

Module IV Corrosion Control

No

Questions

Marks

Give details of corrosion protection through sacrificial anodic method and

impressed current method
Mention the essential ingredients of paint. What are their functions?
Give examples

How are metals protected from corrosion by electroplating?

Explain the process of electroplating

What is cathodic and anodic protection for controlling corrosion?

Discuss their merits and demerits

What is anodizing? Explain anodisation of aluminium

Write a note on galvanizing and anodisation of aluminium

Discuss the different types of inorganic coatings

Describe the electrolytic bath for phosphate and chromate coatings

7
7

116

Important Portions

Organometallic
Compounds
Bioinorganic

Green
Chemistry

Electro
chemistry

Storage Cells

Module I
Classification
18-electron rule
Bonding in metal carbonyls
Roles of Bulk and Trace ions
Hemoglobin & Myoglobin
Twelve Principles
Atom Economy
Less toxic chemical synthesis
Avoid chemical accidents
Green Synthesis

Polymer

Lubricants

Fuels

Module III
III
Nernst equation
Electrochemical series and
its applications
Different types of electrodes
pH by using glass electrode
Lead acid accumulators
Nickel-Cadmium cells
Fuel cells
Solar cells

Theory

Internal Continuous Assessment

(Maximum Marks - 50)
% of Marks
Marks
60% - Tests (minimum 2)
30
30% - Assignments (minimum 2)
15
10% - Attendance
05

Corrosion

Water

Module II
Free radical and Ionic
Techniques
Tg and Factors
Mechanism of lubrication
Solid Lubricants
Properties
Cracking
Reforming
Knocking
Cetane & Octane Number
Module IV
Dry and Wet corrosion
Differential aeration
Sacrificial anodic method
Impressed current method
Electroplating
Anodisation
EDTA titration method
Water for domestic use
BOD and COD

Practical

Internal Continuous Assessment

(Maximum Marks - 50)
% of Marks
Marks
50% - Practical and Record
25
40% - Test
20
10% - Attendance
05

University Theory Examination Pattern (Maximum Marks - 100)

Part A: Analytical/problem solving short questions
Candidates have to answer eight questions out of ten.
There shall be minimum of two and maximum of three questions from each

8 x 5 marks =
40 marks

module with total ten questions.

Part B: Analytical/Problem solving descriptive questions
Two questions from each module with choice to answer one question

4 x 15 marks =
60 marks

117

COMBINED FIRST AND SECOND SEMESTER B.TECH. (ENGINEERING)

MODEL EXAMINATION, APRIL 2016
(2014 Scheme)
EN 14 104 Engineering Chemistry
Time: Three hours

Maximum: 100 marks

Part A

Answer any eight questions

Each question carries 5 marks
I

[1] Discuss the 18-electron rule with two examples

[2] What is the importance of bulk and trace metal ions in biological systems
[3] Discuss about green synthesis
[4] Write about the concept of Tg and crystallinity in polymers
[5] Write a note on the term solid lubricants
[6] What is cracking and what for it used? What are the types of cracking?
[7] What is electrochemical series? What are its applications?
[8] How pH is measured by using glass electrode?
[9] Describe the various factors influencing the corrosion
[10] Among BOD and COD, which is greater? Why?
Part B

Answer one full question from each module

Module I
II

(A) (i) What are organometallic compounds? Explain the classification of

organometallic compounds with examples {8 marks}
(ii) Explain the twelve principles of green chemistry {7 marks}
Or
(B) (i) Give elementary idea about hemoglobin and myoglobin{7 marks}
(ii) What are metal carbonyls? Discuss the nature of bonding involved in it and
write examples for mononuclear and polynuclear carbonyls {8 marks}

118

Module II
III

(A) (i) Explain free radical, cationic and anionic mechanism of polymerization
{8 marks}
(ii) Outline the mechanism of lubrication {7 marks}
Or
(B) (i) How does knocking occur in I.C engines? How can it be prevented? {8 marks}
(ii) Briefly explain the techniques of polymerization {7 marks}

Module III
IV

(A) (i) Derive the Nernst equation for electrode potential {7 marks}
(ii) Describe the construction and functioning of lead acid accumulators and
Nickel Cadmium cells {8 marks}
Or
(B) (i) How is EMF of an electrochemical cell determined through Poggendorfs
compensation method? {7 marks}
(ii) Write a descriptive account on Fuel cells and Solar cells {8 marks}

Module IV
V

(A) (i) Give details of corrosion protection through sacrificial anodic method and
impressed current method {8 marks}
(ii) Enumerate the various stages involved in the purification of water for domestic use
{7 marks}
Or
(B) (i) How is hardness of water determined experimentally by EDTA titration method?
Write the structure of EDTA, EBT and necessary calculations {8 marks}
(ii) What is meant by differential aeration corrosion? Illustrate with suitable examples
{7 marks}

119

COMBINED FIRST AND SECOND SEMESTER B.TECH. (ENGINEERING)

MODEL EXAMINATION, APRIL 2016
(2014 Scheme)
EN 14 104 Engineering Chemistry
Time: Three hours

Maximum: 100 marks

Part A

Answer any eight questions

Each question carries 5 marks
I

[1] What are organometallic compounds? How are they classified?

[2] Write short notes on atom economy
[3] Distinguish between polymerization by addition and condensation processes
[4] Explain the classification of lubricants
[5] Write informative notes on biodiesel
[6] Differentiate between electrochemical cell and concentration cell?
[7] Explain the construction and functioning of solar cells
[8] Distinguish between chemical and electrochemical corrosion
[9] Discuss the phosphate and chromate coatings
[10] How is water softened by soda lime process?
Part B

Answer one full question from each module

Module I
II

(A) (i) What are metal carbonyls? Discuss the nature of bonding involved
in it and write examples for mononuclear and polynuclear carbonyls {8 marks}
(ii) Discuss about the prevention of waste, minimization of toxic products and
prevention of chemical accidents in green chemistry {7 marks}
Or
(B) (i) Give elementary idea about hemoglobin and myoglobin{7 marks}
(ii) Explain the twelve principles of green chemistry {8 marks}

120

Module II
III

(A) (i) Distinguish between free radical and ionic mechanism of polymerization
{8 marks}
(ii) Discuss in detail the properties of lubricants {7 marks}
Or
(B) (i) Discuss about petrol knock and diesel knock. Write notes about
octane number and cetane number {8 marks}
(ii) Explain the concept of Tg of polymer and the factors affecting Tg {7 marks}

Module III
IV

(A) (i) Write a descriptive account on different types of electrodes {7 marks}

(ii) Write a descriptive account on Fuel cells and Nickel-Cadmium cell {8 marks}
Or
(B) (i) How pH is measured by using glass electrode? {7 marks}
(ii) Discuss about the concentration cells {8 marks}

Module IV
V

(A) (i) Outline the galvanic corrosion, stress corrosion and corrosion control {8 marks}
(ii)

With relevant chemical equations, outline the estimation of dissolved oxygen

{7 marks}
Or
(B) (i) With a neat diagram, discuss the demineralization of water using ion exchange
method {8 marks}
(ii) Discuss about the metallic coatings {7 marks}

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