Vinayaka Mission’s Research Foundation

Aarupadai Veedu Institute of Technology

Department of Chemistry
Engineering Chemistry

Syllabus
UNIT – I: ELECTROCHEMISTRY, BATTERIES AND FUEL CELLS
Electrode potential - Nernst equation – Electrodes (SHE, Calomel and Glass) - cells - EMF
measurement. Primary battery (Daniel and dry cell) – secondary battery (lead Acid storage
battery and Nickel-Cadmium battery) – Fuel cell (H2-O2 fuel cell)
UNIT – II: WATER TECHNOLOGY AND CORROSION
Sources of water – impurities – Hardness and its determination (problems to be avoided) –
boiler troubles – water softening (Zeolite & Demineralisation) – Domestic water treatment –
Desalination (Electrodialysis & ReverseOsmosis).
Corrosion – Definition, causes and effects, Classification, Types of corrosion- dry corrosion,
Wet corrosion, Factors influencing rate of corrosion, Corrosion control methods – Sacrificial
anode method and impressed current cathodic method
UNIT – III FUELS AND CHEMISTRY OF ADVANCED MATERIALS
Classification of Fuels (Solid, Liquid, Gaseous, Nuclear and Bio fuels) – Calorific Value of a
fuel –Non Petroleum Fuels –Non conventional sources of Energy – combustion.
Basics and Applications:-Organic electronic material, shape memory alloys, polymers (PVC,
Teflon, Bakelite)
TEXTBOOK
1.Engineering Chemistry by VMU.
REFERENCES
1. A text book of Engineering Chemistry by S.S. Dara, S.Chand & company Ltd., New Delhi
2. Engineering Chemistry by Jain & Jain, 15th edition Dhanpatrai Publishing Company (P)
Ltd., New Delhi
3. A text book of Engineering Chemistry by Shashi Chawla, Edition 2012 Dhanpatrai & Co.,
New Delhi.
4. Engineering Chemistry by Dr. A. Ravikrishnan, Sri Krishna Publications, Chennai.
UNIT – I: ELECTROCHEMISTRY, BATTERIES AND FUEL CELLS
Electrode potential - Nernst equation – Electrodes (SHE, Calomel and Glass) - cells - EMF
measurement. Primary battery (Daniel and dry cell) – secondary battery (lead Acid storage
battery and Nickel-Cadmium battery) – Fuel cell (H2-O2 fuel cell)
Electrode Potential
At equilibrium, the potential difference between the metal and solution becomes a
constant value and is termed as “electrode potential.”
A metal (M) consists of metal ions with valance electrons. When the metal (M) is
placed in a solution of its own salt, any one of the following reactions will occur.
(i) Positive metal ions may pass in to the solution
M → Mn+ + ne- (Oxidation)
If the positive ions in the metal come in to equilibrium with those in the solution leaving
behind an equivalent number of electrons of the metal, the metal acquires a negative charge.
Example: Zn in ZnSO4 solution.
(ii) Positive metal ions from the solution may deposit over the metal.
Mn+ + ne- → M (Reduction)
If the positive metallic ion from the solution enters the metallic lattices, then metal
acquires a positive charge.
Example: Cu in CuSO4 solution.

When a metal is placed in the solution of its own salt, the chemical reaction (i) or (ii),
takes place and ultimately a dynamic equilibrium is established, because negative or positive
charge developed on the metal attracts the positively or negatively charged free ions in the
solution. Due to this attraction, the positive or negative ions remain quite close to the metal.
Thus, a short of layer (positive or negative ions) is formed, all around the metal. This layer is
called “Helmholtz electrical double layer.”
This layer prevents further passing of the positive ions from or to the metal. A
difference in potential is consequently set up between the metal and the solution. At
equilibrium, the potential difference becomes a constant value, which is known as the
electrode potential of a metal. Thus, the tendency of an electrode to lose electrons is called
the oxidation potential and the tendency of an electrode to gain electrons is called the
reduction potential.
Nernst Equation
According to Nernst theory, no metal was truly insoluble and all metals have a
tendency to pass in to solution. Based on this concept, the Nernst equation is derived with the
help of reversible cell. Consider the redox reaction
Mn+ + ne- ↔ M
In the above reversible reaction the free energy change (ΔG and its equilibrium
constant k) are related by the following equation which is popularly known as Van’t Hoff
reaction isotherm.
ΔG = -RTlnK + RTln (products/reactants)
= ΔG0 + RTln (products/reactants)
 Where, ΔG0 is known as standard free energy. The free energy change is equivalent to
the electrical energy -nFE .
ΔG = -nFE
ΔG0 = -nFE0
Where n = no of electrons
F = Faraday
E = Electrode potential
E0 = Standard Electrode potential
R = gas constant =8.134 J/K/mole
T = Temperature =273K
Now the equation can be written as,
-nFE = -nFE0+ RTln (products/reactants)
= -nFE0+ RT ln(M/M+)
= -nFE0+ RT 2.303log(M/M+)
if the product activity is taken as 1, then equation becomes
= -nFE0+ RT 2.303 log(1/M+)
It can be written as
= -nFE0—RT 2.303 log (M+)
It is divided by –nF, then the equation becomes,
E = E0 + RT 2.303log(M+)/nF
= E0 +0.0591/n log (M+)

Application Nernst equation can be used to calculate

i. Electrode potential (half cell potential) in a given set of conditions.

ii. EMF and polarity of electrodes in an electro chemical cell.
iii. Corrosion tendency of metals in a given set of environmental conditions.

Cells
A cell is a device consisting of two half cells which are connected by means of a wire.
Type of Cells
In electrochemistry, a cell means an assembly of electrodes (Namely the anode and
the cathode) and an electrolyte. Cells are classified in to two types.
i. Electrolytic cells
ii. Electrochemical cells
 i. Electrolytic cell
Electrolytic cells are cells in which electrical energy is used to bring about the
chemical change. The cells used for electrolysis (where electrical energy is converted to
chemical energy) are called electrolytic cells.
The process of chemical decomposition of an electrolyte by the passage of electricity
is called electrolysis. The device used for electrolysis is called electrolytic cell and it consists
of two electrodes, an electrolyte and an external source of battery is shown in figure Fig 2.1

Electrolytic cell

Example: Electrolysis of HCl

The electrolysis of HCl can be carried out by using an aqueous solution of HCl, in
which two electrodes. (Pt, Ag, Cu or Fe) are immersed at a definite distance from each other.
When electric current passes through an electrolyte, it is dissociated in to positively (Cation)
and negatively (Anion) charged ions. During electrolysis, cation move towards cathode at
cathode reduction takes place. Anion move towards anode. At anode oxidation takes place.
As a result of the electrolysis, evolution of Cl2 gas takes place at the anode and H2 gas at the
cathode.
Mechanism
When HCl is dissolved in H2O, it is dissociated in to H+ and Cl- ions.
HCl H+ + Cl-
On passing electric current
At anode: Oxidation takes place
2Cl- Cl2 + 2e-
At cathode: Reduction takes place
 2e- + 2H+ H2
H+ ions move towards the cathode, where they take up electrons and are reduced to H2. The
overall reaction is,
2HCl H2 + Cl2 (Decomposition)
ii. Electrochemical cell
An electrochemical cell is a device to produce electrical energy by means of chemical
change (Redox reaction). An electrochemical cell is also commonly referred to as voltaic or
galvanic cell. The electrode where oxidation occurs is called anode, while the electrode
where reduction occurs is called cathode. [An electrochemical cell is obtained by coupling
half cells (or two electrodes)].
The practical application of an electrochemical or galvanic cell is Daniel cell. It
consists of Zinc electrode, dipping in ZnSO4 solution (where oxidation takes place) and a Cu
electrode dipping in CuSO4 solution (where reduction takes place). Each electrode is known
as a half cell. The two solutions are interconnected by a salt bridge and the two electrodes are
connected by a wire through a voltmeter.

Electrochemical cell

Reactions occurring in the cell

At the anode
Oxidation takes place in Zn electrode by the liberation of electrons, so this electrode
is called anode.
At the cathode
Reduction takes place in the Cu electrode by the acceptance of electrons, so this
electrode is called cathode.
Zn Zn2+ + 2e- (at anode - oxidation)
Cu2+ + 2e- Cu (at cathode - reduction)
Zn + Cu2+ Zn2+ + Cu

The electrons liberated by the oxidation reaction flow through the external wire and
are consumed by the Cu ions at the cathode. The emf of a Daniel cell is 1.1 volts.

Liquid Junction Potential

Liquid junction potential is the one which occurs when two solutions of
different concentrations/compositions are in contact with each other through porous
membrane. It is due to formation of an electrical double layer of positive and negative
charges at the junction of the two solutions as the ions diffuse through membranes.
Salt bridge
Solution of a salt (KCl or KNO3 or NH4NO3) that literally serves as a bridge to
complete the electric circuit, maintain electro neutrality of electrolyte and minimize the
liquid junction potential. For precise measurements of potential, a salt bridge is used.
Difference between Electrolytic Cells and Electrochemical Cells
S. No Electrolytic cells Electrochemical cells
1. In electrolytic cells current is In electrochemical cells, current is produced
passed through an electrolyte from electrolyte solutions.
solution.
2. In electrolytic cells the cathode is In electrochemical cells during discharge of
negative (-) and anode is positive current, the cathode is positive (+) and anode
(+). is negative (-).
3. In electrolytic cells the cathode is In electrochemical cells the half cell with
negative (- ve) and attracts the electrode having reduction reaction is always
cations or positive (+ ve) ions. cathode and positive (+ ve). The half cell with
And attracts the anions or negative electrode having oxidation reaction is always
(- ve) ions. anode which is negative (- ve). This is
applicable for the discharge reaction or
 discharging of current.
4. In electrolytic cells, when current In electrochemical cells two half cells with
is passed through the electrolyte electrode and electrolyte are connected and
solution, movement of ions the flow of electron that produce electric
towards the opposite electrode current. i.e., In one half cell oxidation reaction
takes place. i.e., cations or +ve takes place.
ions moves towards cathode or – M → Mn+ + ne- (Oxidation). In another half
ve electrode. And anions or – ve cell reduction reaction takes place.
ions move towards anode or + Mn+ + ne- → M (Reduction).
electrode.
5. Examples of electrolytic cells are Good examples of electrochemical cells are
mainly mainly
(a) i. Electroplating (a) i. Voltaic cells or Batteries
(b) ii. Extraction or purification of
(b) ii. Corrosion process.
metals.

1.1.6 EMF of a cell

MF of Electrochemical cell: The difference of potential, which causes flow of
electrons from the electrode of higher potential to the electrode of lower potential, is called
electromotive force (EMF). The emf of galvanic cell is calculated from the reduction half-cell
potentials using the following relation.
E(cell) = E(right) – E(left)
Where E(cell) = e.m.f of cell
E(right) = reduction potential of right hand side electrode
E(left) = reduction potential of left hand side electrode
Measurement of EMF of a cell by Poggendorff”s compensation method:
The EMF of an unknown cell can be measured with the help of a potentiometer.
Principle
In this method, the EMF of the cell is compensated or balanced by an external emf, so
that no current flows inside the circuit. At this stage, the applied emf is equal in magnitude to
the emf of the test cell.
Description
 The potentiometer consists of a uniform wire AB of high resistance (Fig 1). A storage
battery is connected to the ends A and B of the wire through a rheostat. A standard cell C,
(cell of known emf) is connected to the end A. At the other end, the C 1 is connected to a
galvanometer (G) through a key K1. The galvanometer is then joined to a sliding contact
which moves on the wire AB.
The cell C2 (unknown cell) whose emf is to be measured is similarly connected with
key K2, the galvanometer and then the sliding contact. By using the key K1, the cell C, is put
in to the along AB. The point of contact X1 is recorded when no current flows through the
galvanometer. Then by using the key K2, the cell C2 is put in to the circuit the procedure is
repeated to find the corresponding X2.

The EMF of the unknown cell C2 is calculated by using the equation.

EMF of the unknown cell (C2) Ex = Distance between AX2

EMF of the standard cell (C1) Es Distance between AX1

Ex AX2
____ = ______

Es AX1
AX2
Ex =_____ ES
AX1
Knowing the emf of the standard cell (ES), EX can be calculated.

Applications of EMF measurement:

1. Potentiometer titrations can be carried out. 2. Transport number of the ions can be
determined. 3. Measurement of pH using hydrogen, quinhydrone and glass electrode. 4. From
the EMF data the free energy changes, equilibrium constant of a reaction can be found out. 5.
Hydrolysis constant can be determined. 6. Solubility of a sparingly soluble salt can be found
out.

Electroctremical Series (EMF series)

The arrangement of metals in the increasing order (downwards) of their standard
(reduction) electrode potential
Application of electrochemical series:
1. Relative ease of oxidation or reduction: The metals on the top are more active, easily
ionized into solution and they are good electron donors.
2. Corrosion: The metal higher in the series is anodic or more active and they are more
prone to corrosion. The metals lower in the series are noble metals and they are less prone to
corrosion.
3. Liberation of Hydrogen: The metal with –ve potential will displace H2 from an acid
solution i.e., active metals are attacked by acids
4. Replacement tendency: The metals which are more active will displace less active ion
from the solution of its salt
5. Calculation of Standard emf of the cell:

6. Predicting the spontaneity of redox reaction: Spontaneity of the redox reaction can be
predicted from the e.m.f value of complete cell reaction. If the value of E cell is +ve , the
reaction is feasible.
If it is -ve the reaction is not feasible. It can predict the direction of oxidation-reduction
reaction.
Electrodes:
Reference Electrodes:
The electrode of standard potential, with which we can compare the potentials of another
electrode, is called a “Reference Electrode”. The best “Primary reference electrode” used is
standard hydrogen electrode, whose electrode potential is taken as Zero.

Batteries:
When two or more electrochemical cells are electrically interconnected, each of which
containing two electrodes and an electrolyte is called a Battery. In everyday usage, “battery”
is also used to refer to a single cell. No one battery design is perfect for every application.
There are many parameters like cost, voltage, duty cycle, dimension, stability with time and
temperature, shelf life, etc., on which a battery is selected for a particular operation. It is
important to prioritize our list of requirements before choosing one and requires compromise.
Here duty cycle refers to conditions the battery experiences during use like, type of discharge
and current drain, e.g. continuous, intermittent, continuous with pulses, etc.
Batteries are classified into two categories depending on their recharging capabilities.
a. Primary batteries
b. Secondary Batteries
Primary batteries: These are non-rechargeable and are meant for a single use and
meant to be
discarded after use.
Primary batteries are non-rechargeable and are less expensive and are often used in
ordinary
gadgets like torch lights, watches and toys. Commercially many kinds of primary
batteries are
available but our discussion only on Leclanche cell, Alkaline cell and Lithium cell.
Secondary batteries:
Secondary batteries are rechargeable and are meant for a multi cycle use. After every
use the electrochemical reaction could be reversed by external application of voltage.
The cycle is reversed till the capacity fades or lost due to leakage or internal short
circuit.
These cells are rechargeable and reusable. A combination of all reversible
electrochemical cells gives secondary batteries. Many kinds of secondary batteries are
available in the market but we are restricting our discussion to Lead-acid cell, Ni/Cd
cells, Ni-Metal hydride cell and Lithium ion
cells.

Fuel Cells
Definition Fuel cell is a voltaic cell. It converts chemical energy of the fuels directly into
electricity without combustion. The reactants flow into the cell, and the reaction products
flow out of it, while the electrolyte remains within it. Fuel cells can operate virtually
continuously as long as the fuels are fed. Examples: Hydrogen - oxygen fuel cell.

Anode H2 gas in porous electrode

Cathode O2 gas in porous electrode
Electrolyte 25% KOH
OCV (open circuit potential) 1.2 V
CCV (closed circuit potential) 1.0 V
Cell representation H2/ H2O // KOH // O2/ OH−

Hydrogen - oxygen fuel cell is the simplest and most successful fuel cell. The fuel hydrogen
and the oxidiser-oxygen with the electrolyte. Other fuels include hydrocarbons and alcohols.
Other oxidants include chlorine and chlorine dioxide.
Description/ Construction
The cell has two porous electrodes, anode and cathode. The electrodes are made of
compressed carbon containing a small amount of catalyst (Pt, Pd, Ag) impregnated in it.
Between the two electrodes an electrolytic solution, 25% KOH is filled.
Cell reactions
At anode: 2H2(g) + 4OH− (aq) −→ 4H2O(l) + 4e –
At cathode: O2(g) + 2H2O(l) + 4e − −→ 4OH−
Net reaction: 2H2(g) + O2(g) −→ 2H2O(l)
Working
Hydrogen is passed through the anode compartment, where it is oxidised. Oxygen is passed
through the cathode compartment, where it is reduced.
Advantages of Fuel Cells
1.They are highly efficient in energy conversion and instant in operation.
2. They are pollution free and noise free.
3. Modular and hence parts are exchangeable.
4. Low maintenance cost.
5. Fuel cell holds promises in the energy scenario, replacing to some extend fossil fuel.
6. Continuous discharge takes place.
Disadvantages
1. High initial cost.
2. Large weight and volume of H2 and O2 gas storage.
3. Porous electrodes are affected by CO2 hence gases should be free from CO2.
4. H2 should be pure
Applications
1. H2 - O2 fuel cells are used as energy source in space vehicles, submarines.
2. In H2 - O2 fuel cell, the product water is a valuable source of fresh water for astronauts.
Cells
A cell is a device in which a redox reaction is utilized to get electrical energy. It consists of
two electrodes and an electrolyte. The electrode where oxidation reaction occurs is called
anode, while the electrode where reduction reaction occurs, is called cathode. Cells are
classified based on the electrical energy utilization or production into two kinds:
1. Electrochemical cell:
Here a spontaneous chemical reaction takes place and produces electrical energy.
2. Electrolytic cell:
Here a electrical energy is supplied for a chemical reaction to take place. Further
electrochemical cell is classified on the basis of their nature of chemical reaction taking place
at electrodes as primary or irreversible cell or secondary or reversible cells.
Primary Cell (or) Irreversible cell
In this cell, the electrode reactions cannot be reversed by passing an external electrical
energy. The reactions occur only once. It is a use and throw type of battery. Examples:
Lachlanche cell (Dry cell), Alkaline battery.
2. Secondary Cells (or) Reversible Cells
In these cells, the electrode reactions are reversed by passing an external electrical energy.
They are recharged by passing electric current and used again and again. They are also called
Storage cells (or) Accumulators. Examples: Lead acid storage cell, Nickel-cadmium cell.
Battery is the arrangement of number of cells in series or parallel. Cells connected in series
leads to increase in potential. Cells connected in parallel, leads to addition of energy density.
Daniel cell or Dry cell
The Daniel cell was a great improvement over the existing technology used in the
early days of battery development.
This cell consists of a Cu-vessel containing a concentrated solution of CuSO4.
A porous pot containing dil.H2SO4 is placed in the Cu-vessel which contains CuSO4 solution.
A Zn-rod is dipped into dil.H2SO4. Zn-rod acts as anode and Cu-vessel acts as cathode.
Electrode reactions and the cell reactions are:
Oxidation at anode: Zn(s) Zn2+(aq) + 2e- Eºzn/zn2+ = + 0.77 V
Reduction at cathode: Cu2+(aq) + 2e- Cu(s) Eºcu/cu2+ = + 0.34 V
Cell reaction: Zn(s) + Cu2+ (aq) Cu(s) + Zn2+(aq)

Daniel Cell
Daniel cell can be represented as,
Zn(s) /Zn2+(aq) // Cu2+(aq) /Cu(s)
Anode Cathode
EMF of this cell = Eºzn/zn2+ + Eºcu/cu2+ = 0.77 V + 0.34 V = 1.11 V
Dry Cell Battery
The dry cell battery is one of the most commonly used types, including AA, 9-volt,
and watch batteries. Dry cell batteries are different from wet cells because their electrolytes
are contained in a low-moisture paste; while a wet cell has electrolytes contained in a liquid,
hence the difference in names.
 The most common type of battery used today is the "dry cell" battery. There are many
different types of batteries ranging from the relatively large "flashlight" batteries to the
miniaturized versions used for wristwatches or calculators. Although they vary widely in
composition and form, they all work on the sample principle. A "dry-cell" battery is
essentially comprised of a metal electrode or graphite rod (elemental carbon) surrounded by a
moist electrolyte paste enclosed in a metal cylinder as shown below.

Dry Cell Battery

In the most common type of dry cell battery, the cathode is composed of a form of
elemental carbon called graphite, which serves as a solid support for the reduction half-
reaction. In an acidic dry cell, the reduction reaction occurs within the moist paste comprised
of ammonium chloride (NH4Cl) and manganese dioxide (MnO2):

2NH4+ + 2MnO2 + 2e- Mn2O2 + 2NH3 + H2O

A thin zinc cylinder serves as the anode and it undergoes oxidation:

Zn(s) Zn+2 + 2e-

This dry cell "couple" produces about 1.5 volts. (These "dry cells" can also be linked
in series to boost the voltage produced). In the alkaline version or "alkaline battery", the
ammonium chloride is replaced by KOH or NaOH and the half-cell reactions are:

Zn + 2OH- ZnO + H2O + 2e-

2MnO2 + 2e- + H2O Mn2O3 + 2OH-
Alkaline Battery
Anode Zn
Cathode MnO2/ Carbon rod
Electrolyte 40% KOH
OCV (open circuit voltage) 1.6 V
CCV (closed circuit voltage) 1.5 V
Cell representation Zn/Zn(OH)2 // KOH(aq) // MnO2/Mn2O3

Construction and Working

Alkaline battery is an improved form of the dry cell, in which the electrolyte NH4Cl is
replaced by KOH. Alkaline battery consists of a zinc cylinder filled with an electrolyte
consist of powdered KOH and MnO2 (active cathodic material) in the form of paste using
starch and water. A carbon rod (cathode) is immersed in the electrolyte in the centre of the
cell for electrical contact for the flow of electrons. The outer cylindrical zinc body acts as
anode.
Cell Reactions
At anode: Zn −→ Zn2+ + 2e − Zn + 2OH− (aq) −→ Zn(OH)2
At cathode : 2MnO2(s) + H2O(l) + 2e − −→ Mn2O3(s) + 2OH−
Net Reaction: Zn(s) + 2MnO2(s) + H2O(l) −→ Zn(OH)2(s) + Mn2O3(s)
In cathode reaction, Mn is reduced from +4 oxidation state to +3 oxidation state. Manganese
dioxide is reduced to manganic oxide.
Advantages of alkaline cell
The main advantages of alkaline cell over dry cell are
1. There is no leakage of cell, since Zn does not dissolve readily in a basic medium.
2. The life of alkaline battery is longer than the dry battery, because there is no corrosion of
Zn.
3. Alkaline battery maintains its voltage, as the current is drawn from it.
Uses
It is used in calculators, watches, torch light, transistors, toys etc.

Lead Storage battery or Lead Accumulator or Acid Storage battery

A lead acid storage cell is a secondary cell. It can operate both as a voltaic cell and an
electrolytic cell. When it acts as a voltaic cell, it supplies electrical energy. When it is
recharged, the cell operates as an electrolytic cell.
Anode Pb
Cathode PbO2/ Pb
Electrolyte H2SO4 (1.2 g/cc)
OCV (open circuit voltage) 2.1 V
CCV (closed circuit voltage) 2.0 V
Cell representation Pb/PbSO4// H2SO4(aq) // PbO2/ PbSO4 Cycle life 250-300
A lead storage battery consists of six voltaic cells connected in series to get a 12V battery.
The anode is made of lead. The cathode is made of lead dioxide PbO2 packed on a grid of
lead. Various plates are separated from the adjacent ones by insulators like rubber or glass
fibre. The entire combination is then immersed in dilute H2S O4 (38% by mass) having a
density of 1.2 g/cc. Electrode reaction while discharging When the lead - acid storage battery
operates, the following reaction occurs during discharge.
At anode: (+ve plate)
Pb(s) ⇋ Pb2+ (aq) + 2e –
Pb2+ (aq) + S O2− 4(aq) ⇋ PbS O4(s)
Pb(s) + S O2− 4 ⇋ PbS O4(s) + 2e –
At cathode: (-ve plate)
PbO2(s) + 2e − + 4H + (aq) ⇋ Pb2+ (aq) + 2H2O(l)
Pb2+ (aq) + S O2− 4(aq) ⇋ PbS O4(s)
PbO2(s) + 2e − + 4H + (aq) + S O2− 4(aq) ⇋ PbS O4(s) + 2H2O(l)
Overall cell reaction during discharge
Pb(s) + PbO2(s) + 2H2S O4(aq) ⇋ 2PbS O4(s) + 2H2O(l)
From the cell reaction it is clear that, PbS O4 is precipitated at both the electrodes and H2S
O4 is used up. As a result, the concentration of H2S O4 decreases. Hence the specific gravity
of H2S O4 falls below 1.2 g/cc. So the battery needs recharging.
Recharging of the Battery
The cell is charged by passing electric current in the opposite direction. The electrode
reaction gets reversed and density of acid increases to 1.2g/cc.
At anode (-ve plate):
2PbS O4(s) + 2H2O ⇋ PbO2(s) + 4H + (aq) + S O2− 4(aq) + 2e –
At cathode (+ve plate):
PbS O4(s) + 2e − ⇋ Pb(s) + S O 2− 4
Overall cell reaction during Charge:
2PbS O4(s) + 2H2O(l) ⇋ Pb(s) + PbO2(s) + 2H2S O4(aq)
Disadvantages of lead-acid batteries
1. Recycling of this battery produces environmental hazards.
2. Mechanical strain and normal bumping reduces battery capacity.
3. It is too heavy for handling.
4. It also leaks at times.
Application
1. The cell is used for automobile starting, lighting and ignition batteries.
2. It is used in large backup power supplies for telephone and computer centers, grid energy
and off-grid household electric power systems.
3. They are used in back-up power supplies for computer systems.
4. They are used as fuel in electric scooters, electric wheel chairs, electrified bicycles, marine
applications, battery electric vehicles or micro hybrid vehicles, and motorcycles.
Applications
1. It is used in calculators, electronic flash units, transistors and cordless appliances.
2. It is used in toys like remote-controlled electric model airplanes, boats, and cars.
3. Larger flooded cells are used for aircraft starting batteries, electric vehicles, and standby
power.
Nickel-Cadmium Battery
 Ni–Cd batteries usually have a metal case with a sealing plate equipped with a self-
sealing safety valve. The positive and negative electrode plates, isolated from each other by
the separator, are rolled in a spiral shape inside the case. This is known as the jelly-roll design
and allows a Ni–Cd cell to deliver a much higher maximum current than an equivalent size
alkaline cell. Alkaline cells have a bobbin construction where the cell casing is filled with
electrolyte and contains a graphite rod which acts as the positive electrode. As a relatively
small area of the electrode is in contact with the electrolyte (as opposed to the jelly-roll
design), the internal resistance for an equivalent sized alkaline cell is higher which limits the
maximum current that can be delivered.

Nickel-Cadmium Cell Battery

The chemical reactions during discharge are:
At cadmium electrode,
Cd + 2OH- Cd(OH)2 + 2e-
At nickel electrode,
2NiO(OH) + 2H2O + 2e 2Ni(OH)2 + 2OH-
The net reaction during discharge is,
2NiO(OH) + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2
During recharge, the reactions go from right to left. It can be used in cordless razors,
ash units and power tools.
Advantages: Lightweight
 Unit – II – Water Technology
Introduction:

Water is the most important compound for the existence of human beings, animals and
plants. About 80% of the earth’s surface is occupied by water. The main sources of
water are
1. rain
2. rivers and lakes (surface water),
3. wells and springs (underground water),
4. sea water.

Among the above sources of water, rain water is the purest form of water but it is very
difficult to collect whereas sea water is the most impure form.

So, surface and underground water are normally used for domestic and industrial
purposes. Such water must be free from undesirable impurities.

The process of removing all types of impurities from water and making it fit for
domestic or industrial purposes is called water technology (or) water treatment.

Before treating the water, we should know the nature as well as the amount of
impurities.

HARD WATER AND SOFT WATER

Hard Water
Water, which does not produce lather with soap solution, but produces white
precipitate (scum) is called hard water.
This is due to the presence of dissolved Ca and Mg salts.

Soft water
 Water, which produces lather readily with soap
solution is called soft water.
  This is due to the absence of Ca and Mg Salts.
HARDNESS OF WATER
 Hardness is the property or characteristics of water, which does not
Produce lather with soap.
How to detect hardness?
 Hardness of water can be detected in two ways.

1.3.1 TYPES OF HARDNESS

o Depending upon the types of dissolved salts present in

water,

hardness of water can be classified into two types

1. Temporary hardness.

2. Permanent hardness.
 1. Temporary Hardness (or) Carbonate Hardness (CH)
(or) Alkaline hardness
 This is due to the presence of bicarbonates of calcium and
magnesium. It can be removed by (i) boiling the water (ii)
adding lime to the water.

 The above two processes convert the bicarbonates

into insoluble carbonates and hydroxides, which can
be removed by filtering.

2. Permanent hardness (or) Non-carbonate hardness (NCH) (or) Non-alkaline

hardness
 This is due to the presence of chlorides and sulphates of calcium
and magnesium. It cannot be removed by boiling the water. But,
it can be removed by
i. Lime-soda process
ii. Zeolite process.

Expression of hardness in terms of equivalents of CaCO3

The concentration of hardness producing salts are usually expressed in terms of an
equivalent amount of CaCO3. CaCO3 is chosen as a standard because,
(i) Its molecular weight (100) and equivalent weight (50) is a whole number, so the
calculations in water analysis can be simplified.
 (ii) It is the most insoluble salt, that can be precipitated in water treatment. If the
concentration of hardness producing salt is x mgs/lit, then
Procedure:
Titration:1
Standardisation of EDTA:

Burette Solution: EDTA

Pipette Solution: 20 ml of standard hardwater + 5 ml of buffer solution
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V1 ml

Titration : 2
Estimation of total hardness:
Burette Solution: EDTA
Pipette Solution: 20 ml of Sample hardwater + 5 ml of buffer solution
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V2 ml

Titration: 3
Estimation of permanent hardness:

Burette Solution: EDTA

Pipette Solution: 20 ml of Boiled hardwater + 5 ml of Ammonical buffer
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V3 ml

Boiler Feed Water
The water fed into the boiler for the production of steam is called boiler feed water.
Boiler feed water should be free from turbidity, oil, dissolved gases, alkali and hardness
causing substances. If hard water obtained from natural sources is fed directly into the
boilers, the following troubles may arise.

1. Formation of Scales and sludges in boilers.

2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion.

Formation of Scales and Sludges in boilers

When water is continuously converted into steam in boilers (or) heat exchangers, the
concentration of dissolved salts in water increases progressively. When the
concentration of the salts reaches their saturation point, they are thrown out in the form
of precipitates on the inner walls of the boilers (or) heat exchangers. The least soluble
one gets precipitated first.
Sludge:
If the precipitate is loose and slimy it is called sludge. Sludges are formed by the
substances like MgCl2, MgCO3, MgSO4 and CaCl2. They have greater solubilities in hot
water than cold water.
Scale:
On the other hand, if the precipitate forms hard and adherent coating on the inner
walls of the boiler, it is called scale. Scales are formed by substances like Ca(HCO3)2,
CaSO4 and Mg(OH)2

Comparison of Scales and Sludges

S.No Sludge Scale

1. Sludge is a loose, slimy and Scale is a hard, adherent coating
non-adherent precipitate
2. The main sludge forming The main scale forming substances are
substances are MgCO3, MgCl2, Ca(HCO3)2, CaSO4, Mg(OH)2
MgSO4 and CaCl2 etc
3. Disadvantages : Disadvantages:
Sludges are poor conductors of Scales act as thermal insulators. It decreases
heat. Excess of sludge the efficiency of boiler. Any crack developed
formation decrease the on the scale, leads to explosion
 efficiency of boiler
4. Prevention: Prevention:
(i) Sludge formation can be (i) Scale formation can be prevented by
prevented by using softened dissolving using acids like HCl, H2SO4
water
(ii) Sludges can also be removed (ii) Scale formation can be removed by
by “blow-down operation”. (a) External treatment
(b) Internal treatment
(iii) Blow-down operation is a (iii) They can also be removed by applying
process of removing a portion thermal shocks, scrapers, wire brush etc.
of concentrated water by fresh
water frequently from the
boiler during steam production

2. Priming and Foaming (Carry over)

During the production of steam in the boiler, due to rapid boiling, some droplets of
liquid water are carried along with steam. Steam containing droplets of liquid water is called
Wet steam. These droplets of liquid water carry with them some dissolved salts and
suspended impurities. This phenomenon is called carry over. It occurs due to priming and
foaming.
Priming:
Priming is the process of production of wet steam.
Priming is caused by
(i) High steam velocity
(ii) Very high water level in the boiler
(iii) Sudden boiling of water
(iv)Very poor boiler design
Priming can be controlled by
(i) Controlling the velocity of steam
(ii) Keeping the water level lower
(iii) Modified boiler design
(iv) Using treated water
Foaming:
 The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried over by steam leading to excessive priming. Foaming is caused by the
presence oil, grease and finely divided particles.
Foaming can be prevented by
(i) Adding coagulants like sodium aluminates, aluminium hydroxide
(ii) Adding anti foaming agents like synthetic polyamides.
Caustic embrittlement
Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler water
usually contains a small proportion of Na2CO3. In high pressure boilers this Na2CO3
undergoes decomposition to give NaOH.
Na2CO3 + H2O 2NaOH + CO2
This NaOH flows into the minute hair cracks and crevices usually present in the boiler
material by capillary action and dissolve the surrounding area of iron as sodium ferrate.
Fe + 2NaOH Na2FeO2 + H2↑
This causes embrittlement of boiler parts, particularly stressed parts like bends, joints,
rivets etc., causing even failure of the boiler.
Prevention
Caustic embrittlement can be prevented by
(i) Using sodium phosphate as softening agent instead of sodium carbonate
(ii) By adding tanning, lignin to the boiler water, which blocks the hair cracks.
4. Boiler corrosion
Corrosion in boiler is due to the presence of
1. Dissolved oxygen
2. Dissolved Carbon dioxide
3. Dissolved salts
(i) Dissolved oxygen:
The dissolved oxygen in water attacks the boiler material at higher temperature.
Dissolved oxygen can be removed by chemical or mechanical methods
4Fe + 2H2O + O2 4Fe (OH)3↓
(a) Chemical method
Sodium sulphite and hydrazine are some of the chemical used for removing oxygen.
2Na2SO3 +O2 2Na2SO4
N2H4+O2 N2 + 2H2O
(b) Mechanical de-aeration
 Dissolved oxygen can also be removed from water by mechanical de-aeration. (In
Figure) In this process, water is allowed to fall slowly on the perforated plates fitted inside
the tower. The sides of the tower are heated, and a vacuum pump is also attached to it. The
high temperature and low pressure produced inside the tower reduce the dissolved oxygen
content of the water.

(ii) Dissolved carbon dioxide

Dissolved carbon dioxide in water produces carbonic acid, which is acidic and
corrosive in nature.
CO2 + H2O H2CO3
Carbon dioxide gas is also produced from the decomposition of bicarbonate salts
present in water.
∆
Ca(OH3)2 CaCO3↓ + H2O + CO2↑
Removal of dissolved Carbon dioxide
(a) Carbon dioxide can be removed from water by adding a calculated amount of
NH4OH into water.
2NH4OH + CO2 (NH4)2CO3 + H2O
(b) Carbon dioxide along with oxygen can also be removed mechanically by de-aeration
method.

(iii) Dissolved MgCl2

Acids produced from salts dissolved in water are also mainly responsible for the
corrosion of boilers. Salts like MgCl2, CaCl2 etc, undergo hydrolysis at higher temperature to
give HCl, which corrode the boiler.
MgCl2 + 2H2O Mg(OH)2↓ + 2HCl
 Fe + 2HCl FeCl2 + H 2↑
FeCl2 + 2H2O Fe(OH)2 + 2HCl
Removal of acids
Corrosion by acids can be avoided by the addition of alkali to the boiler water
HCl + NaOH NaCl + H2O
2.1.3. Softening methods
Water used for industrial purposes should be free from hardness producing
substances, suspended impurities and dissolved gases etc. The process of removing hardness
producing salts from water is known as softening of water.
Softening of water can be done in two methods
1. Internal treatment
2. External treatment
External treatment
It involves the removal of hardness producing salts from the water before feeding in
to the boiler. The external treatment can be done by the following methods.
i. Zeolite or Permutit process
ii. Demineralisation or Ion – exchange process
i. Zeolite or permutit process:
Zeolites are naturally occurring hydrated sodium aluminoSilicate. Its general formula
is Na2O. Al2O3. xSiO2. yH2O. (x = 2 – 10, y = 2- 6). Natural zeolites are green sand and non-
porous. The synthetic form of Zeolite is known as permutit, which is porous and possess gel
structure, hence it is generally used for water softening. Synthetic zeolite is represented by
Na2Ze. The sodium ions which are loosely held in Na2Ze are replaced by Ca2+ and Mg2+ ions
present in the water.
Process
When hard water is passed through a bed of sodium zeolite (Na2Ze), kept in a cylinder
(Fig), it exchanges its sodium ions with Ca2+ and Mg2+ ions present in the hard water to form
calcium and magnesium zeolite. The various reactions taking place during softening process
are
CaCl2 + Na2Ze CaZe + 2NaCl
CaSO4+ Na2Ze CaZe + Na2SO4
Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3
CaCl2 + Na2Ze CaZe + 2NaCl
MgCl2+ Na2Ze MgZe+ 2NaCl
 Mg (HCO3)2 + Na2Ze CaZe + 2MgHCO3

Zeolite process
The softened water is enriched with large amount of sodium salts, which do not cause
any hardness, but cannot be used in boilers.
Regeneration process:
After some time zeolite gets exhausted. The exhausted zeolite is again regenerated by
treating with 10% solution of NaCl.
CaZe + NaCl Na2Ze + CaCl2
MgZe + NaCl Na2Ze + MgCl2
Advantages:
1. It reduces hardness up to 10ppm
2. The equipment is quit compact.
3. Less time for softening.
4. Its operation is easy.
5. No sludge is formed during this process.

Disadvantages:
1. The treated water containing sodium ions, which cannot be used as boiler feed water.
2. Highly turbid water cannot be treated by this method. Because it blocks the pores of the
Zeolite bed.
3. Acidic water cannot be treated, because it decomposes the structure of Zeolite.
4. This process cannot be used for softening brackish water, because brackish water contains
Na+ ions. So the ion exchange reaction will not occur.
5. Water containing Fe, Mn cannot be treated, because regeneration is very difficult.
ii. Ion-exchange or demineralization process
This process removes almost all the ions (both anions and cations) present in the hard
water. The soft water, produced by lime-soda and zeolite processes, does not contain
hardness producing Ca2+ and Mg2+ ions, but it will contain other ions like Na+, K+, SO24-, Cl-
etc. on the other hand D.M. (Demineralised) water does not contain both anions and cations.
Thus a soft water is not demineralised water whereas demineralised water is soft water.
This process carried out by using ion exchange resins, which are insoluble, cross-
linked, long chain organic polymers with a micro porous structure and the “functional
groups” attached to the chains are responsible for the ion-exchanging properties.
Cation exchanger:
Resins containing acidic functional groups (-COOH, -SO3H, etc.) are capable of
exchanging their H+ ions with other cations of hard water. Cation exchange resin is
represented as RH2.
Example
1. Sulphonated coals
2. Sulphonated poly styrene
Anion exchanger:
Resins containing basic functional groups (-NH2, -OH, etc.) are capable of
exchanging their anions with other anions of hard water. Anion exchange resin is represented
as R(OH)2.
Example
1. Cross linked quaternary ammonium salts
2. Urea-formaldehyde resin.
Process
The hard water first passed through a cation exchange column, (Fig) which absorbs all
the cations like Na+, K+, SO24-, Cl-+, etc., present in the hard water.
  The water coming out of the anion exchanger is completely
f ree f rom cations and anions. This water is known as demineralised
water or deionised water.
Sri Krishna Hitech Publishing Com pany Pvt. Ltd.

Demineralization process
RH2 + CaCl2 RCa + 2HCl
RH2 + MgSO4 RCa + 2HCl
RH + NaCl RNa + HCl
The cation free water is then passed through an anion exchange column, which
absorbs all the anions like Cl-, SO42-, HCO3- etc., present in the water.
R’(OH)2 +2HCl R’Cl2 + 2H2O
R’(OH)2 +2H2SO4 R’SO4 + 2H2O
The water coming out of the anion exchanger is completely free from cations, anions
and gases. This water is known as demineralised or deionised water.
Regeneration of resin:
When the cation exchange resin is exhausted, it can be regenerated by passing a
solution of dil.HCl or dil.H2SO4.
RCa + 2HCl RH2 + CaCl2
RNa2 + HCl RH2 + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated by
passing a solution of dil.NaOH.
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl
Advantages:
It produces very pure water of hardness nearly 2ppm.
Highly acidic or alkaline water can be treated by this process.
The softened water is completely free from any salts and fit for use as boiler feed water.
Disadvantages:
1. The equipment is little expensive.
2. This process can not treat highly turbid water.
Comparison between zeolite and ion-exchange process
S.No. Zeolite process Ion-exchange process
1. Only cations are exchanged Cations and anions are removed.
2. Acidic water cannot be treated. Acidic water can be treated.
3. Zero hardness cannot be achieved. Zero hardness can be achieved.
Treated water has more sodium
4. Water is free from sodium ions.
ions.

2.1.4. Domestic water treatment:

Municipal water supply has been one of the most challenging problems of water
technology. Water supplied by municipalities or corporation must be free from pathogenic
bacteria, dissolved salt, suspended impurities, colour and odour. It must be clear and pleasant
taste.
Generally, the treatment of this water involves removal of suspended impurities and
colloidal impurities and microbes. Hence domestic supply of water involves the following
purification processes.
Purification of water:
1. Screening
2. Aeration
3. Sedimentation
4. Coagulation
5. Filtration
6. Sterilisation
1. Screening:
It is a process of removing the floating materials like leaves, wood pieces etc. from
water. The raw water is allowed to pass through a screen, having large number of holes,
which retains the floating materials and allows the water to pass.
2. Aeration
The process of mixing water with air is known as aeration. The main purpose of
aeration is,
(i) To remove gases like CO2, H2S and other volatile impurities causing bad taste and odour.
(ii) To remove ferrous and manganous salts as insoluble ferric and manganic salts.
3. Sedimentation:
Sedimentation is the process of removing the sludge and other solid impurities by
allowing the water to stay undisturbed for few days. Different kinds of sedimentation tanks
are used for the settling of solid impurities.
In the horizontal flow tank the water is released at the bottom of the tank where it has
to come through a series of constricted walls. The solid materials automatically settle down.
The water at the top of the other end of the tank is free from suspended impurities.
There are other kinds of sedimentation tanks like ‘radial flow circular tank’ and
‘vertical flow hopper bottom tank’ which can be effectively used to remove the suspended
impurities.
4. Coagulation:
Finely divided clay, silica etc. do not settle down easily and hence cannot be removed
by sedimentation. Such impurities are removed by coagulation method.
In this method certain chemicals called coagulants like alum, Al2(SO4)3 etc., are
added to water. When the Al2(SO4)3 is added to water, it gets hydrolysed to form a gelatinous
precipitate of Al(OH)3. The gelatinous precipitate of Al(OH)3 entraps the finely divided and
colloidal impurities, settles to the bottom and can be removed easily.
5. Filtration: It is the process of removing bacteria, colour, taste, odour and suspended
particles, etc. by passing the water through filter beds containing fine sand, coarse sand and
gravel.
The sand filter consists of a tank containing a thick top layer of fine sand followed by
coarse sand, fine gravel and coarse gravel. When the water passes through the filtering
medium, it flows through the various beds slowly. The rate of filtration decreases slowly due
to the clogging of impurities in the pores of the sand bed. When the rate of filtration becomes
very slow, the filtration is stopped and the thick top layer of fine sand is scrapped off and
replaced with clean sand. Bacteria are also partly removed by this process.
6. Sterilisation or Disinfection
The process of destroying the harmful bacteria is known as sterilization or
disinfection. The chemicals used for this purpose are called disinfectants. This process can
be carried out by the following methods.
(a) By Boiling
When water is boiled for 10-15 minutes, all the harmful bacteria are killed and water
becomes safe for use. Disadvantages of boiling are
(i) Boiling alters the taste of drinking water
(ii) It is impossible to employ it in municipal water-works.

(b) By using Ozone

Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly
unstable and breaks down to give nascent oxygen.
O3 O2 + [O]
The nascent oxygen is a powerful oxidizing agent and kills the bacteria.
Disadvantages of this process are
(i) This process is costly and cannot be used in large scale
(ii) Ozone is unstable and cannot be stored for long time.
(c) By Using Ultraviolet Radiations
UV rays are produced by passing electric current through mercury vapour lamp. This
is particularly useful for sterilizing water in swimming pool.
Disadvantages
(i) It is costly
(ii) Turbid water cannot be treated
(d) By Chlorination
The process of adding chlorine to water is called chlorination. Chlorination can be
done by the following methods.
(i) By adding chlorine gas:
Chlorine gas can be bubbled in the water as a very good disinfectant.
(ii) By Adding Chloramine:
When chlorine and ammonia are mixed in the ratio 2:1 compound chloramines is
formed.
Cl2 + NH3 ClNH2 + HCl
Chloramine compounds decompose slowly to give chlorine. It is a better disinfectant
than chlorine.
(iii) By adding bleaching powder: When bleaching powder is added to water, it produces
hypochlorous acid (HOCl). HOCl is a powerful germicide.
CaOCl2 + H2O Ca(OH)2 + Cl2
Bleaching powder
Cl2 + H2O HCl + HOCl
HOCl + Bacteria Bacteria are killed
Break point chlorination
Water contains the following impurities
(i) Bacteria
(ii) Organic impurities
(iii) Reducing substances (Fe2+, H2S etc)
(iv) Free ammonia
Chlorine may be added to water directly as a gas or in the form of bleaching powder.
When chlorine is applied to water, the results obtained can be depicted graphically in the
following fig. The graph shows the relationship between the amount of chlorine added to
water and the residual chlorine.
It is seen from the graph that initially the applied chlorine is used to kill the bacteria and
oxidizes all the reducing substances present in the water and there is no free residual chlorine.
As the amount of applied chlorine increases, the amount of combined residual
chlorine also increases. This is due to the formation of chloramines and other chloro
compound.
At one point, on further chlorination, the oxidation of chloramines and other
impurities starts and there is a fall in the combined residual chlorine content. Thus the
combined residual chlorine decreases to minimum point at which oxidation of chloramines
and other impurities complete and free residual chlorine begins to appear this minimum point
is known as “break point chlorination”.

Thus, the break point chlorination eliminates bacteria, reducing substances, organic
substances responsible for the bad taste and odour, from the water.

Advantages of break – point chlorination

1. It oxidizes completely organic compounds, ammonia and other reducing compounds.
2. It removes colour in water, due to the presence of organic matters.
3. It destroys completely (100%) all the disease – producing bacteria.
4. It removes both odour and taste from the water.
5. It prevents the growth of any weed in water.
2.1.5. Desalination of brackish water
Removal of common salt from sea water is known as desalination process. The water
containing dissolved salts with a peculiar salty or brackish taste is called brackish water.
Sea water or brackish water can be made available as drinking water through
desalination process. Desalination process can be carried out by reverse osmosis,
electrodialysis, solar distillation, freezing etc. The successful methods are reverse osmosis
and electrodialysis.
Electrodialysis:
Principle:
Electrodialysis is the process of separating ions of the salt from the salt water through
ion-selective membranes by passing direct current.
Description:
 An electrodialysis cell consists of alternate cation (C) and anion (A) selective
membranes. An ion selective membrane has permeability for only one kind of ions with
specific charge. Therefore cation selective membrane is permeable to cations only but not to
anions while anion selective membrane is permeable to anions only but not to cations. The
cathode is placed near the cation selective membrane and the anode is placed near the anion
selective membrane.
Process
Saline water is fed into the electrodialysis cell and direct current is applied through
the electrodes perpendicular to the direction of water flow. As the current passes through the
electrodes, from the centre compartment cations (Na+) move towards the cathode through
cation selective membrane (C) and anions (Cl-) move towards the anode through anion
selective membrane (A). The net result is the decrease of ions (salt) from the centre
compartment while the concentration of ions (Salt) in the adjacent compartments is increased.
Now the centre compartment is filled with pure water and the other compartments are filled
with concentrated brine solution. Thus, the salinity is removed from salt water.

Electrodialysis
Examples for ion selective membranes
Cation selective membrane – Poly styrene containing sulphonic acid group
Anion selective membrane – Poly styrene containing tetra ammonium chloride
Advantages:
(i) It is the most compact unit, the cost of installation and operation is economical.
(ii) If electricity is easily available, this process is best suited.
Reverse osmosis:
 When solutions of different concentrations are separated by a semi-permeable
membrane, solvent flows from a region of lower concentration to higher concentration.
This process is called osmosis. The driving force in this phenomenon is called osmotic
pressure.
If a hydrostatic pressure in excess of osmotic pressure is applied on the higher
concentration side, the solvent flow is reversed. i.e., solvent flows from higher
concentration to lower concentration. This process is called reverse osmosis. Thus, in the
process of reverse osmosis pure water is separated from salt water. This process is also
known as super – filtration. The membranes used are cellulose acetate, cellulose butrate etc.

Reverse Osmosis
Advantages:
1. The life time of the membrane is high and it can be replaced easily.
2. It removes ionic as well as non – ionic and colloidal impurities.
3. Due to low capital cost, simplicity, low operating, this process is used for converting
sea water in to drinking water.
CORROSION
2.2. Introduction:
Most metals (with the exception of noble metal such as Au, Pt etc) exist in nature in
combined forms as their oxides, carbonates, hydroxyl carbonates, sulphides, chlorides and
silicates. These are reduced to their metallic state from their ores, during their extraction
processes. Hence, when metals are put in to use, in various forms, they are exposed to
environment; the exposed metal surfaces begin to decay more or less rapidly, when they
come in contact with gaseous and / or liquid environment.
Metals and alloys are generally used as fabrication or construction materials in
engineering. If the metal or alloy structures are not properly maintained, they deteriorate
slowly by the action of atmospheric gases, moisture and other chemicals. This phenomenon
of deterioration or destruction of metals and alloys is known as corrosion.
Definition
 “Corrosion is defined as the gradual destruction or deterioration of metals or alloys
by the chemical or electrochemical reaction with its environment”.
Consequences of corrosion
1. Plant shut – down
2. Replacement of corroded equipment
3. Preventive maintenance
4. Necessity for over design to allow for corrosion
5. Loss of efficiency
6. Contamination or loss of the product
7. Safety
8. Health
Cause of corrosion:
Metals in the uncombined condition have 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.
2.2.1 Principles of corrosion:
Acid theory
This theory suggests that the presence of acids (such as carbonic acids) is essential for
corrosion.
This acid theory is particularly applicable to rusting of iron in the atmosphere.
According to this theory, rusting of iron is due to the combined action of moisture, O2 and
CO2 on iron converting the metal into ferrous bicarbonate which is further oxidised to basic
ferric carbonate and finally to hydrated ferric oxide.
2Fe + O2 + 4CO2 + 2H2O 2Fe(HCO3)2
4Fe(HCO3)2 + O2 4Fe(OH)CO3 + 4CO2 + H2O
2Fe(OH)CO3 + 2H2O Fe2O3.3H2O + 2CO2
The acid theory is supported by the fact that rust analysis generally shows the
presence of ferrous and ferric carbonates along with hydrated ferric oxide.
Classification of corrosion
On the basis of medium attack, corrosion can be classified in to two types.
(i) Chemical or Dry corrosion
(ii) Electrochemical or Wet corrosion
(i) Direct chemical attack or chemical or dry corrosion:
 Dry corrosion is due to the attack of metal surfaces by the atmospheric gases such as
O2, H2S, N2, SO2 etc. in the dry environment.
There are three main types of dry corrosion
(a) Oxidation corrosion or corrosion by oxygen
(b) Liquid - Metal corrosion
(c) Corrosion by other gases
(a) Oxidation corrosion or corrosion by oxygen
Oxidation corrosion is brought about by the direct action of oxygen at low or high
temperatures on metal surface in the absence of moisture. Alkali metals (Li, Na, K etc) and
alkaline – earth metals (Mg, Ca, Sn etc) are rapidly oxidized at low temperature, almost all
metals (except, Ag, Au and Pt) are oxidized.
Mechanism of corrosion
Step; 1 Oxidation occurs first at the surface of the metal resulting in the formation of metal
ions (M2+) which occurs at the metal / oxide interface
M M2++2e-
Step; 2
Oxygen changes to ionic form (O2-) due to the transfer of electron from metal, which
occurs at the oxides film / environment interface.
1/2O2+2e- O2-
Step; 3
Oxide ions react with the metal ion to form the metal / oxide film.
M+1/2O2- M2++O2- ≡ MO (Metal – Oxide film)
Once the metal surface is converted to a monolayer of metal – oxide, for further
corrosion (oxidation) to occur, the metal ion diffuses outward through the metal –oxide
barrier. Thus the growth of oxide film commences perpendicular to the metal surface.
Oxidation corrosion is depends on the nature of oxide film.
Nature of oxide film
The nature of oxide film formed on the metal surface plays an important role in
oxidation corrosion.
(1) Stable oxide layer
A stable oxide layer is a fine grained in structure, and get adsorbed tightly to the metal
surface. Such a layer is impervious in nature and stops further oxygen attack through
diffusion. Such a film behaves as a protective coating and no further corrosion can develop.
Example
Oxide of Al, Sn, Cu
(2) Unstable oxide layer
Unstable oxide layer is mainly produced on the surface of noble metals, which
decomposes back in to the metal and oxygen.
Metal oxide Metal+Oxide
Example: Oxide of Pt, Ag etc.
(3) Volatile oxide layer
The oxide layer volatilizes as soon as it is formed, leaving the metal surface for
further corrosion.
Example: MoO3 (Molybdum oxide)

(4) Porous oxide layer

In this case, further corrosion is possible through pore or cracks of the metal oxide.
Example: Oxide of Fe
Pilling Bedworth rule / Protective or Non – productive oxide film
The volume of the oxide layer formed is less than the volume of the metal; the oxide
layer is porous or non-protective.
Example:
The volume of oxides of alkali and alkaline earth metals such as Na, Mg, Ca etc., is
less than the volume of the metal consumed. Hence the oxide layer formed is porous and
non-protective.
On the other hand, if the volume of the oxide layer formed is greater than the volume
of the metal, the oxide layer is non-porous and protective. For example, the volume of oxides
of heavy metals such as Pb, Sn etc., is greater than the volume of the metal. Hence, the oxide
layer formed is non-porous and protective.
Pilling – Bed worth ratio
The ratio of the volume of the oxide formed to the volume of the metal consumed is
called Pilling – Bed worth ratio.
(b) Liquid – Metal corrosion
This is due to the chemical action of flowing liquid metal at high temperature. The
corrosion reaction involve,
1. Either dissolution of a solid metal by a liquid metal
2. Liquid metal may penetrate in to the solid metal
(c) Corrosion by other gases
 Besides oxygen, the dry corrosion is caused by CO2, Cl2, SO2, F2 etc. The extent of
corrosion effect depends on the chemical affinity between the metal and the gases involved.
The gases chemically react with the meal surface forming either the protective oxide
layer or the porous or volatile oxide layer which are non – protective.
Example: Hydrogen corrosion or Hydrogen embrittlement
When metals contact to H2S at ordinary temperature causes evolution of atomic
hydrogen.
Fe+H2S FeS +2H
This atomic hydrogen diffuses readily in to the metal and collects in the voids, where
it recombines to form molecular hydrogen.
H+H H2↑
Collection of these hydrogen gases in the voids develops very high pressure, which
causes cracks and blisters on metal. This process is called hydrogen embrittlement.

(ii) Electrochemical theory or wet corrosion:

This type of corrosion where the conducting electrolytic liquid is contact with metal
or two dissimilar metals or alloy is called electrochemical corrosion.
One part of the metal becomes anode, another cathode. Anodic metal oxidation, takes
place with the liberation of electron where the actual corrosion takes place. Cathodic metal
reduction takes place, with the absorption of electron liberated from the anode.
The main basis of electrochemical corrosion involves the formation of anodic and
cathodic parts in the contact with each other through the presence of a conducting electrolyte
media.
Mechanisms of wet corrosion
Under the above conditions, one part of the metal becomes anode and another part as
cathode
(i) At anode
In anodic part, oxidation or dissolution of metal occurs.
M M2++2e-
(ii) At cathode
In cathodic part reduction reaction occurs, which depends on nature of the corrosive
environment.
1. Acidic environment
 If the corrosive environment is acidic, hydrogen evolution occurs at cathodic part.
2H++2e- H2↑
2. Neutral environment
If the corrosive environment is slightly alkaline or neutral, OH- ion forms at cathodic
part.
1/2O2+ 2e-+H2O 2OH-
Thus, the metal ion (from anodic part) and non – metallic ion (from cathodic part)
diffuse towards each other through conducting medium and form a corrosion product
between anode and cathode.
Galvanic Corrosion
When two different metals are in contact with each other in presence of an aqueous
solution or moisture, galvanic corrosion occurs.
The more active metal (with more –ve electrode potential) acts as anode and the less
active metal (with less –ve electrode potential) acts as cathode.
Fig (a) represents Zn-Fe couple, in which Zn (more active or higher in Emf series)
dissolves in preference to iron (less active metal). i.e., Zn acts as anode and undergoes
corrosion and Fe acts as cathode.

Fig (b) represents Fe – Cu couple, in which iron (more active, when compared to Cu)
dissolves in preference to copper (less active) i.e., Fe acts as anode and undergoes corrosion
and Cu acts as cathode.
Example
(i) Steel screw in a brass marine hardware corrodes.
(ii) Bolt and nut made of same metal is preferred.
Prevention:
Galvanic corrosion can be minimized by providing insulating material between the
two metals.
Differential aeration or concentration cell corrosion:
This type of corrosion occurs when a metal is exposed to varying concentration of
oxygen or any electrolyte on the surface of the base metal.
Example:
Metals partially immersed in water or conducting solution (called water line
corrosion).
If the metal is partially immersed in a conducting solution (in Fig) the metal part
above the solution is more aerated and hence become cathodic. On the other hand, the metal
part inside the solution is less aerated and thus, become anodic and suffers corrosion. A good
example of this kind is a metal like zinc partially dipped in a brackish solution (NaCl + H2O).
The zinc rod above the solution is more strongly oxygenated and hence is a cathode.
On the other hand the zinc rod dipped inside the solution have less access to oxygen and the
poorly oxygenated area acts as an anode. Hence a difference of potential is developed on the
same metal and the flow of electrons takes place from anode producing metal ions or
corrosion.
At anode (less aerated) corrosion occurs
Zn Zn2++2e-
At cathode (more aerated part) OH- ions are produced
1/2O2+ 2e-+H2O 2OH-
 Differential aeration or concentration cell corrosion
Examples for this type of corrosion are
Pitting or localized corrosion
Crevice corrosion
Pipeline corrosion
Corrosion on wire fence
2.2.2. Factors influencing corrosion
Corrosion is a kind of reaction that takes place in the metal by the influence of its
environment. Hence both the nature of the metal and the environment play equal part in the
corrosion of the metal. The following are the factors responsible for the corrosion.
1. Nature of the metal
(i) Position in the galvanic series - Metals higher in the electrochemical or galvanic series
(positive values of electrode potential compared with hydrogen) are less prone to corrosion.
(ii) Relative areas of the anode and cathode - When two different metals are in contact, the
corrosion in the anodic area is directly proportional to the areas of cathode and anode.
Corrosion will be severe if the anodic area is smaller and cathodic area is large. The larger
cathodic area of the cathode will create a great demand of electron which can be met by the
smaller area of the anode only by undergoing more corrosion.
(iii) Over potential - The increase of corrosion is related to decease in hydrogen over
potential. The normal hydrogen over potential of zinc metal when it is dipped in 1M
sulphuric acid is 0.7 volt. By adding few amount of copper sulphate to zinc metal directly, the
hydrogen over voltage is reduced to 0.33 and the increase of the dissolution of the metal (or
corrosion) takes place.
(iv) Purity of metals - Impurities present in the pure metal creates heterogeneity. It causes
galvanic cell type corrosion.
(v) Physical state of metals - Metal parts under stress can become anodes and undergo stress
corrosion. Also the smaller grain size of the metal or its alloy can undergo corrosion easily
since the solubility of the metal is high.
(vi) Nature of the surface film - Metals like Mg, Fe etc form oxides whose specific volume
is less than the volume of the metal. Hence the oxide film formed will be porous and mere
oxygen diffuses through the pores to bring about more corrosion.

Metals like Al, Cr, Ni, W etc form oxides whose specific volume is greater than that
of the metal. Hence the oxide film once formed is compact and impervious for further
diffusion of oxygen through the oxide film and corrosion is prevented.
(vii) Nature of corrosion product If the corrosion product is soluble in the corroding
medium, then further corrosion takes place. On the other hand if the corrosion product is
insoluble (eg. PbSO4), it acts as a barrier between the metal and environment and stops
further corrosion.
Volatile metal oxide film also can produce further corrosion. For example
molybdenum metal forms MoO3 when exposed to atmosphere, molybdenum oxide layer
voltalises immediately and fresh attack of oxygen corrosion continues on the metal.
2. Nature of the environment
(i) Temperature
Increase in temperature increases the reaction rate as well as the diffusion rate so
naturally the rate of corrosion is increased.
(ii) Humidity
Humidity of air is directly related to the corrosion rate. Critical humidity is the relative
humidity above which the atmospheric corrosion rate of the metal increases sharply. The
basic principle of enhancement of corrosion in humid conditions is that atmospheric gases
like CO2, O2 etc., and dissolves in water to produce the electrolyte which is essential for
electrochemical corrosion.
(iii) Presence of corrosive gases
In industrial areas atmosphere is polluted with acidic gases like CO2, SO2, H2S and
fumes of HCl, H2SO4 etc., These gases produces electrolyte which are acidic and increases
the electrochemical corrosion. Similarly in the marine atmosphere, the electrolyte produced
will have more chloride ions (Cl-) which increases the corrosion rate.
(iv) Presence of solid suspended particles or compounds
Particles like NaCl, (NH4)2SO4 along with moisture act as powerful electrolyte and
enhances the electrochemical corrosion.
(v) Effect of pH
Generally acidic medium is more corrosive than alkaline medium. The corrosion of iron
in oxygen free water is very slow up to pH = 5. But in presence of oxygen the corrosion rate
of iron is very high at pH = 5. But at pH = 4 the corrosion rate of iron is considerably
increased due to the change in oxidation states of iron from Fe2+ to Fe3+. Zinc which is
readily corroded in acidic solution suffers very less corrosion in alkaline medium i.e., pH =
11 aluminium has less corrosion at pH = 5.5 while corrodes rapidly at pH = 8.5.
(vi) Nature of ions present
Anions like silicates in the presence of medium leads to the formation of insoluble
reaction products which stops further corrosion. Whereas the chloride ions (Cl-) in the
medium destroy the protective oxide film and expose the metal for further corrosion.
(vii) Formation of oxygen concentration cell
Increase in oxygen in one part of the metal which becomes cathodic and the less
oxygenated part becomes anodic and the oxygen concentration cell is set up resulting, in
corrosion. This is explained by the reaction.
1/2O2+ 4e-+H2O 4OH- (Cathodic reaction)
The reaction takes place with more oxygen concentration (Cathodic reaction)
Fe Fe2++2e-
This reaction causes the ionization of the metal. i.e., corrosion in the anodic region
where there is less oxygen concentration.
Corrosion of buried pipelines, cables etc. passing from one kind of soil to another are
due to the differential aeration in the soil.
2.2.3 Corrosion control methods
Corrosion is a process very harmful for the metals or alloys. Since the metals and
alloys disintegrated or wasted every year through corrosion costs a huge amount. It is
necessary to protect the metals or alloys against corrosion. A few methods of corrosion
control are given below.
1. Proper designing
It is necessary that before the fabrication of machine parts or equipment, proper
selection of metal or alloy and the design part of the engineering system have to be properly
studied according to the environmental conditions.
Important design principles are:
(i) “Avoid the contact of dissimilar metals in the presence of a corroding solution”: If
this principle is not followed, then corrosion is localized on the more active metal
(in the immediate vicinity of contact); while the less active metal remains
protected.
(ii) When two dissimilar metals are to be in contact, the anodic material should have
as large area as possible; whereas the cathodic metal should have as much
smaller are as possible.
(iii) If two dissimilar metals in contact have to be used, they should be as close as
possible to each other in the electrochemical series.
(iv) Whenever the direct joining of dissimilar metals, is unavoidable, an insulating
fitting may be applied in between them to avoid direct metal – metal electrical
contact.
(v) The anodic metal should not be painted or coated, when in contact with a
dissimilar cathodic meal, because any break in coating would lead to rapid
localized corrosion.
(vi) It is desirable that the design allows for adequate cleaning and flushing of the
critical parts (i.e., susceptible to dirt, deposition, etc.) of the equipment. Sharp
corners and recesses should be avoided, because they favour the formation of
stagment areas and accumulation of solids, etc.
(vii) Uniform flow of corrosion liquid is desirable, since both stagnant areas and highly
turbulent flow and high velocities can cause accelerated corrosion. So, it is
practically possible.
(viii) A proper design should prevent condition subjecting some areas of structure to
stress (cold – worked part). Such an area could set up a galvanic couple with non
– stressed (not worked) areas of the metal.
2. Use of pure metals
Impurity metal present in the base metal can act as anode and produces
electrochemical corrosion. Purification of metals like Al, Mg etc. makes them corrosion
resistant by its impervious oxide film formation. But the production of purer metals is costly
as well as the metal looses some of its mechanical properties.
3. By cathodic protection
The principle of this method is that the base metal to be protected turn into cathode by
connecting it to a powerful anode metal plate. There are two kinds of it.
(i) Sacrificial anodic protection
The metallic structure to be protected is connected through a metallic wire to a more
anodic metal. So that all the corrosion will takes place only on the anodic metal. The
artificially made anode thus gradually gets corroded protecting the original metallic structure.
And hence this process is otherwise known as sacrificial anodic protection. Metals commonly
used as sacrificial anodes are Al, Zn, Mg and their alloys.

Sacrificial anodic protection

 This method is used for the protection of ships and boats. Sheets of Mg or Zn are hull
of the ship as in figure. Zn or Mg will act as anode compared to iron (ship or boat is made of
iron), so corrosion concentrates on Zn or Mg. Since they are sacrificed in the process of
saving iron, they are called sacrificial anodes.
Application
1. This method is used for the protection of ships and boats.
2. Sheets of Mg or Zn are hung around the hull of the ship.
3. Copper metal is employed to minimize engine corrosion.
(ii) Impressed current cathodic protection
In this method, an impressed current is applied in the opposite direction of the
corrosion current to nullify it and the corroding metal is converted from anode to cathode.
This can be done by connecting –ve terminal of the battery to the metallic structure to
be protected and +ve terminal of the battery is connected to an inert anode. Inert anodes used
for this purpose are graphite, platinised titanium.
The anode is buried in a ‘‘back fill’’ (containing mixture of gypsum, coke, breeze,
sodium sulphite). The ‘‘back fill’’ provides good electrical contact to anode.

Impressed current cathodic protection

Applications of impressed current protection
1. Structures like tanks, pipelines, transmission line towers and laid – up strips etc.
2. Underground water pipe lines, oil pipelines, ships etc can be protected by this
method.