Polymers: This Name Hints at How Polymers Are Made

Polymers
This name hints at how polymers are made.
(Poly) Many + (meros) Parts
Polymers are the macromolecules (giant molecules of higher masses) built-up

by the linking together of a large number of small molecules (called monomers).
Monomers
Polymers
Examples
Polyester
Polyvinyl chloride (PVC)
Polyethylene
Few Queries???
• What are some of the polymers that you encounter every day?
Sandwich bags, carpets, nylon stockings, stackable chains, milk cartons, etc.
• Why do different polymers have different properties?

They have different chemical compositions (different monomer units), different
structures, different ways of being fabricated, etc.
• Imagine samples of LDPE (sandwich bag, squeeze bottle) and HDPE (milk jug,
grocery bag). What are some of the differences in the physical properties of these
substances?
LDPE – more transparent, flexible, waxy
HDPE – more opaque, rigid, non-waxy
Functionality
• A substance to act a monomer, it must have at least two reactive sites or bonding sites.
• The number of bonding sites in a monomer is referred to as its functionality.
Monomer Polymer
CH2 CH2
CH2CH2
CH2 CHCl CH2CH2
Cl
O
H2C CH2 CH2CH2O
HOCH2CH2OH CH2CH2O
HO CO2H O C
Functionality
• A substance to act a monomer, it must have at least two reactive sites or bonding sites.
• The number of bonding sites in a monomer is referred to as its functionality.
H H H H
C C C C
H H H H
Ethylene is bifunctional Phenol is trifunctional
• If the monomer is bifunctional,

H H
A linear polymer is formed.
C C O
O
• If the monomer is trifunctional,
H H A cross-linked polymer is formed
Formaldehyde is bifunctional • A mixture of both,
A branched/cross-linked polymer is formed
Definitions
Degree of polymerization: The total number of repeating units contained by the terminal group in a
polymer
Polyester
According to the amount of repeating units

• monomer: one unit
• oligomer: few units
• polymer: many units (poly – many, mer – part)
• macromere (=macro monomer): monomer containing long chain
• telechelic polymer : polymer containing reactive end group
(tele = far, chele = claw)
Drawing polymers – shorthand formulae
Polymers contain thousands of molecules, so how can their structures be easily drawn?
Part of the polymer molecule can be drawn:
A better way is to show a shorthand formula:
The ‘n’ means that the polymer contains a very

large number of the repeating unit shown in the
brackets.
Classification of polymers
Classification based on sources:
1. Natural polymer: which are found in nature in animals and plants etc. like cellulose, protein, nucleic
acids, natural rubber.
2. Synthetic polymer (man made polymer) like polyethylene, polypropylene, polyvinyl chloride,
polystyrene, nylon, etc
Classification based on mechanism of polymerization:
1. Addition polymer: Obtained by addition of monomeric units.
2. Condensation polymer: Obtained by condensation of monomers, followed by elimination of simple

molecules (e.g. water, ammonia, HCl etc.)
Types of polymerization reactions
Classification based on mechanism of polymerization:
1. Addition polymer: Obtained by addition of monomeric units.
Vinyl chloride Polyvinyl chloride (PVC)

Types of polymerization reactions
Addition is a reaction in which elements are added to the starting material.
H H H H H H
light, heat, pressure
n C C n C C C C
H H H H H H
n
Ethene bifunctional molecules polythene
Addition (or chain growth) polymerization reactions:

• Addition or chain polymerization is reaction, which is an exact multiple of the original monomeric
molecules.
• The monomeric molecules usually have one or more double bond which by intermolecular
rearrangement, may make the molecule bifunctional.
• The addition polymerization must be instigated by the application of heat, pressure or catalyst etc. for
breaking down the double covalent bond of monomers.
2. Condensation or step polymerization
A reaction between polar group containing monomer units to yield polymer and elimination of small
molecules (like H2O, HCl, NH3 etc).
Example: hexamethyl diamine and adipic acid condense to form a polymer known as nylon 6:6
Comparison of condensation and Addition Polymerization
Condensation/Step growth polymerization Addition/Chain growth polymerization

1. Growth occurs throughout matrix by 1. Growth occurs by successive addition of
reaction between monomers, monomer units to limited number of
oligomers, and polymers growing chains
2. DP low to moderate 2. DP can be very high
3. Monomer consumed rapidly while 3. Monomer consumed relatively slowly,
molecular weight increases slowly but molecular weight increases rapidly
4. No initiator needed; same reaction 4. Initiation and propagation mechanisms
mechanism throughout different
5. No termination step; end groups still 5. Usually chain-terminating step involved
reactive
6. Polymerization rate decreases steadily 6. Polymerization rate increases initially as
as functional groups consumed initiator units generated; remains
relatively constant until monomer
depleted
DP, average degree of polymerization.
Classification based on Thermal behaviour:
1. Thermoplastic polymer: these polymers are linear, long chain, which can be softened on heating and
hardened on cooling reversibly i.e. their hardness is a temporary properties.
Most thermoplastics are high-molecular-weight polymers whose chains associate through weak Van der
Waals forces (polyethylene); stronger dipole-dipole interactions and hydrogen bonding (nylon). These
polymers have no cross-linking between chains. Examples: Polyethylene, polystyrene etc.
2. Thermosetting polymer: these polymers get hardened during moulding and once they have solidified,
they cannot be softened. So, these polymer once molded, cannot be reprocessed.
This is due to extensive crosslinks between the different polymer chains forming three dimensional
network of bonds. Example: Bakelite and melamine
weak intermolecular forces – these let the chains slide past each other
Plastics made of these polymers are stretchy and have a low melting point. They are called thermoplastic polymer.
strong intermolecular forces (cross-links) – these hold the chains firmly
in place
Plastics made of these polymers cannot be stretched, are rigid and have a high melting point. They are called thermosetting
plastics (or ‘thermosets’).
Classification on the basis of Thermal behavour:
Thermoplastic polymer and Thermosetting polymer: differences
Physical Properties: Thermal behaviour of polymers
• Glass transition temperature (𝐓𝐠 ) → below this temp. amorphous polymers become hard, brittle. Above
this, they are soft and flexible
Physical Properties: Thermal behaviour of polymers
• Glass transition temperature (𝐓𝐠 ) → The glass–liquid transition (or glass transition for short) is the
reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials)
from a hard and relatively brittle state into a molten or rubber-like state
• Factors affecting Tg→

MW – Tg increases with increasing molecular weight
Molecular structure – Tg increases with crosslinking, side chain length, double bond in the backbone
Side groups – aromatics and polar side groups increase Tg
Flexibility – Flexible polymers have low Tg
Branching – Tg increases with branching (a small amount of branching will tend to lower Tg)
Water content – Tg decreases with increasing moisture
• Importance – whether the polymer can be used as plastic or rubber
• The glass-transition temperature (Tg) is always lower than the melting temperature (Tm) of the crystalline
state of the material if there is one
The bulky groups on chain, increases the Tg of the polymer
Polyethylene
Tg = -110 0C
Polypropylene
Tg = -200C
Polystyrene
Tg = 100 0C
The presence of H-bonds between the polymer molecules increases the Tg
Tg of nylon 6,6 (Tg = 50 0C) is higher than PE (Tg = -110 0C)
H  O H  O
H H
nylon 6,6  |  ||  | 
 
|| polyethylene
− N − C  − N −C − C  − N −C −
−C− C−
   
| | | | | H H
H H  6 H H  H
4
: :
: : : : Van der Waals bonds
Hydrogen bonds :

:  : :
: :
H H
H  O H  O
  ||  |  || −C− C−
|
   
− N − C  − N −C − C  − N −C − H H
   
| | | | |
H H  6 H H  H
4

 With H-bonds vs Van der Waals bonds, nylon is expected to have (and does) higher Tg.
➢ The presence of a plasticizer reduces the Tg of a polymer
The plasticizers are usually dialkyl phthalate esters, such as dibutyl phthalate, a high boiling liquid.
O
C
O CH2CH2CH2CH3 The plasticizer separates the individual polymer chains from one another. It
O CH2CH2CH2CH3
C acts as a lubricant which reduces the attractions between the polymer chains.
O
Dibutyl Phthalate
➢ The Tg of a polymer is influenced by its molecular weight

With increase in molecular mass, the Tg increases
PE (low Mw) -110 0C
PE (high Mw) - 90 0C
Classification of polymers based on applications:
1. Elastomer: polymer which can be stretched to at least thrice its length, but it returns to its original
shape and dimensions as soon as stretching force is released. e.g. Rubber.
2. Resins: Resin is a natural or synthetic compound that begins in a highly viscous state and hardens with
treatment. e.g. PF resins , epoxy resins
3. Fibers: Fibers are those polymers whose chains are held by strong intermolecular forces like hydrogen
bonding. They are crystalline in nature. e.g. Nylon
H2 H2
N C N C C C
H H O O
O O H
H
H2 H2
C C C N C N
4. Plastics: Organic materials of high molecular weight, which can be moulded into any desired form,
when subjected to heat and pressure in the presence of a catalyst e.g. Bakelite, PVC
Classification based on chain composition/Structure:
A B
The kinds of applied monomers
• One kind : Homopolymer A-A-A-A-A-A-A-A-
• Two kinds : Copolymer A-B-A-B-A-B-A-B-
• Three kinds : Terpolymer A-B-C-A-C-B-A-B-
Random A and B randomly positioned along chain
Alternating A and B alternate in polymer chain
Block Large blocks of A units alternate with large blocks of

B units
Graft
Chains of B units grafted onto A backbone
Homopolymer is a polymer made up of only one type of monomer
( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n

Teflon Polyethylene Cl
PVC
Copolymer is a polymer made up of two or more monomers
( CH CH2 CH2 CH CH CH2 )n
Styrene-butadiene rubber
Classification based on structure:
1. Linear polymer: monomeric units are joined in the form of
long straight chains. for example: polythene, nylons and
polyesters etc. these polymer possess high density , m.p.
and tensile strength due to close packing of polymer.
2. Branched chain polymer are mainly liner in nature, but

also possess branches along the main chain. e. g. low
density polyethene, glycogen, etc. These polymers possess
low m.p., density, and tensile strength as compared to the
liner polymer
3. Three-dimensional network polymers contain monomers

molecules connected to each other by only covalent bond.
They are giant molecules in which movement of individual
monomeric unit is prevented by strong cross links.
Therefore, they are rigid, hard, and brittle and do not
melt. For example, bakelite, vulcanised rubber, etc.
Classification based on tacticity:
The orientation of monomeric units in a polymer can
take place in orderly or disorderly fashion with
respect to the main chain. The differences in
configuration of polymer is known a tacticity.
1. Isotactic polymer: If the arrangement of all

functional groups are at the same side of the
main chain known as a isotactic polymer.
2. Syndiotactic polymer: if the arrangements of

functional group is in alternative fashion, it is
called syndiotactic polymer.
3. Atactic polymer: if the arrangements of

functional group are at random around the Main
chain, it is called atactic polymer.
Classification based on tacticity:
Which polymer more likely to crystallize? Can it be decided?
alternating random
Poly(styrene-Ethylene) poly(styrene - ethylene) copolymer
Copolymer
Alternating co-polymer more likely to crystallize than random ones, as they are always more easily crystallized as
the chains can align more easily.
Mechanism of addition polymerization
The addition polymerization reaction can take place by three methods –
1. Free radical polymerization mechanism

2. Ionic Mechanism
a) Cationic
b) Anionic
3. Coordination mechanism
Mechanism of Free radical polymerization

Goes through three important steps
i. Chain initiation
ii. Chain propagation
iii. Chain termination
a) Initiation step is considered to involve two reactions:

The first step is the production of free radicals by homolytic dissociation of an initiator to yield pair of
radicals. (benzoylperoxide, tert-butylperoxide, AIBN)
I−I → 2I∗
(free radicals)
tert-butyl peroxide
Azobisisobutyronitrile
Benzoyl peroxide
a) Initiation step is considered to involve two reactions:

In the second step of the initiation, the radical cobines with first monomer unit (M) to produce chain
initiating species
I∗ + M → I − M∗
(free radical) (monomer) (chain is initiated)
b) Propagation step consists of the growth of I–M* free radical by successive reaction of large numbers of
monomers molecules
I − M∗ + M → I − M − M∗
I − M − M∗ + M → I − M − M − M∗
I − M − M − M∗ + M → I − M − M − M − M∗
c) Termination steps
i. Termination by coupling
ii. Termination by disproportionation
iii. Termination by chain transfer
Termination by coupling
Termination by disproportionation
Hydrogen from one growing chain is abstracted by the other growing chain –
forms two polymer chains – 1 saturated and 1 unsaturated.
In chain transfer, hydrogen is abstracted from –

i. Solvent
ii. Impurities
A dead polymer and a radical is formed

Mechanism of Ionic polymerization

2. Ionic Mechanism
a) Cationic
b) Anionic
3. Coordination mechanism
In ionic polymerization,
• the active centers initiating the chain reaction are ions.
• proceeds due to the presence of catalysts – hence it is called catalytic polymerization.
• Depending upon the charge of the ion formed, the polymerization may be
cationic or anionic.
Mechanism of Cationic polymerization
Cationic polymerization:
• Strong Lewis acids (BF3, AlCl3) act as catalysts.
• Water acts as a co-catalyst (proton provider)
• The cationic initiator transfers charge to a monomer which becomes reactive – carbocation
Mechanism of Cationic polymerization
Cationic polymerization:
• Strong Lewis acids (BF3, AlCl3) act as catalysts.
• Water acts as a co-catalyst (proton provider)
• The cationic initiator transfers charge to a monomer which becomes reactive – carbocation
• Like all chain-growth polymerizations, it takes place in three steps:

chain initiation,
chain propagation, and
chain termination.
Mechanism of Anionic polymerization
Anionic polymerization:
• Carried out through a carbanion active species.
• Strong organoalkali compound (n-BuLi, Et-Na) act as catalysts.
• Involves the polymerization of vinyl monomers with strong electronegative (electron withdrawing)
groups.

chain initiation,
chain termination.
Mechanism of Anionic polymerization
Anionic polymerization:
• Carried out through a carbanion active species.
• Strong organoalkali compound (n-BuLi, Et-Na) act as catalysts.
• Involves the polymerization of vinyl monomers with strong electronegative (electron withdrawing)
groups.

chain initiation,
chain termination.
Mechanism of Coordination polymerization
3. Coordination polymerization :
(Ziegler-Natta catalysts)
• An organometallic compound (aluminium co-
catalyst) in combination with transition metal
halides (TiCl3 or TiCl4).
• Can be used to prepare stereospecific
polymers.
Cl C H
3. Coordination polymerization : 2 5
Cl C2H5
(Ziegler-Natta catalysts) TiCl4 + Al(C2H5)3 Ti Al
Cl Cl C2H5
• An organometallic compound (aluminium co- C2H5
catalyst) in combination with transition metal CH2
halides (TiCl3 or TiCl4). H Cl C H
Cl C2 2 5
• Can be used to prepare stereospecific Cl C2H5
Cl
Ti
C2H5
Al
polymers. Ti Al Cl Cl C2H5
Cl Cl C2H5 H2C CH2
CH2 (CH2-CH2)n C2H5

H
Cl C2 Cl H
Cl C2H5 Cl C2H5
Ti Al Ti Al
Cl Cl Cl
C2H5 Cl C2H5
H2C CH (CH2-CH2)n C2H5

3. Coordination polymerization :
(Ziegler-Natta catalysts)
• Coordination polymerisation is a form of addition polymerization in which monomer adds to a
growing macromolecule through an organometallic active center.
• The development of this polymerization technique started in the 1950s with heterogeneous Ziegler-Natta
catalysts based on titanium tetrachloride and an aluminium co-catalyst. Coordination polymerization has
a great impact on the physical properties of vinyl polymers such
as polyethylene and polypropylene compared to the same polymers prepared by other techniques such
as free radical polymerization.
• The polymers tend to be linear and not branched and have much higher molar mass. Coordination type
polymers are also stereoregular and can be isotactic or syndiotactic instead of just atactic.
This tacticity introduces crystallinity in otherwise amorphous polymers.
• From these differences in polymerization type the distinction originates between low-density
polyethylene (LDPE), high-density polyethylene (HDPE).
Molecular Weight of Polymers
Unlike small molecules, polymers are typically a mixture of differently sized molecules. Only an average
molecular weight can be defined.
Number Average Molecular Weight
σ𝑖 𝑛𝑖 𝑀𝑖
𝑀𝑛 =
σ𝑖 𝑛𝑖
Number Average Molecular Weight counts the numbers of molecules in a given volume or mass. Hence
this methods depends on the number of molecules present.
• It is determined by the measurement of the colligative properties (E.g., freezing point depression,
boiling point elevation, lowering of vapors pressure etc.)
Number Average Molecular Weight
σ𝑖 𝑛𝑖 𝑀𝑖
𝑀𝑛 =
σ𝑖 𝑛𝑖
Example: If a polymer has population as:

• a molecules of molecular mass each = A Then,
• b molecules of molecular mass each = B (𝑎×𝐴)+(𝑏×𝐵)+(𝑐×𝐶)+(𝑑×𝐷)
• M𝑛 =
𝑎+𝑏+𝑐+𝑑
• c molecules of molecular mass each = C
• d molecules of molecular mass each = D.
Weight Average Molecular Weight:
σ𝑖 𝑛𝑖 𝑀𝑖2
𝑀𝑤 = σ𝑖 𝑛𝑖 𝑀𝑖
Weight Average Molecular Weight is obtained by averaging the molecular weights according to the weight
of the molecules of each types.
• It is determined by the light scattering methods, ultra-centrifugal techniques.

Weight Average Molecular Weight:
σ𝑖 𝑛𝑖 𝑀𝑖2
Example: If a polymer has population as: Then,

• a molecules of molecular mass each = A (𝑎×𝐴)+(𝑏×𝐵)+(𝑐×𝐶)+(𝑑×𝐷)
• M𝑛 =
𝑎+𝑏+𝑐+𝑑
• b molecules of molecular mass each = B
• c molecules of molecular mass each = C (𝑎×𝐴2 )+(𝑏×𝐵2 )+(𝑐×𝐶 2 )+(𝑑×𝐷2 )
• M𝑤 =
• d molecules of molecular mass each = D. (𝑎×𝐴)+(𝑏×𝐵)+(𝑐×𝐶)+(𝑑×𝐷)
Number Average Molecular Weight Weight Average Molecular Weight:
σ𝑖 𝑛𝑖 𝑀𝑖 σ𝑖 𝑛𝑖 𝑀𝑖2
𝑀𝑛 = 𝑀𝑤 = σ𝑖 𝑛𝑖 𝑀𝑖
σ𝑖 𝑛𝑖
Molecular Weight of Polymers and PDI
Number Average Molecular Weight Weight Average Molecular Weight:
σ𝑖 𝑛𝑖 𝑀𝑖 σ𝑖 𝑛𝑖 𝑀𝑖2
𝑀𝑛 =
σ𝑖 𝑛𝑖
𝑴𝒘
The dispersity index or polydispersity index (PDI)=
𝑴𝒏
PDI gives an idea about the homogeneity of the polymer

Problem 1: If a polymer has population as: 10 molecules of molecular mass each= 5,000; 25 molecules of
molecular mass each= 25,000; 20 molecules of molecular mass each= 15,000; 5 molecules of molecular
mass each= 2,000.
Calculate its number average molecular mass (Mn) and weight-average molecular mass (Mw).
Answer:
(10×5000)+(25×25000)+(20×15000)+(5×2000)
• M𝑛 =
10+25+20+5
(10×50002 )+(25×250002 )+(20×150002 )+(5×20002 )

• M𝑤 =
(10×5000)+(25×25000)+(20×15000)+(5×2000)
Problem 2: Consider a polymer sample containing
• 50 molecules of molecular weight 10000,
• 35 molecules of molecular weight 12000, and
• 15 molecules of molecular weight 14000.
i. Determine Number Average Molecular Weight, Weight Average Molecular Weight.
ii. If the polymer is polypropylene, what will be the degree of polymerization?
50 × 10000 + 35 × 12000 + (15 × 14000)

𝑀𝑛 = = 𝟏𝟏𝟑𝟎𝟎
(50 + 35 + 15)
50×100002 + 35×120002 +(15×140002 )

𝑀𝑤 = = 𝟏𝟏𝟒𝟖𝟔. 𝟕
50×10000 + 35×12000 +(15×14000)
𝑀𝑛 11300
𝐷𝑃 = = = 𝟐𝟔𝟗
𝑀𝑤 𝑜𝑓 𝑝𝑟𝑜𝑝𝑦𝑙𝑒𝑛𝑒 42
Problem 3: In a polymer sample, 30% of the molecules have a molecular mass of 20000, 40% have a
molecular mass of 30000, and the rest have a molecular mass of 60000.
Calculate the mass average and weight average molecular weight.
Answer:
(30×20000)+(40×30000)+(30×60000)
• M𝑛 = = 36000
30+40+30
(30×200002 )+(40×300002 )+(30×600002 )

• M𝑤 = = 43333
(30×20000)+(40×30000)+(30×60000)
Problems
Problem 4: A polymer sample has the following composition.
n = 400, 25% n = 800, 35% n = 600, 40%

Calculate the mass average and weight average molecular weight.
Answer:
25×16800 + 35×33600 +(40×25200)

• M𝑛 = = 26040
25+35+40
25×168002 + 35×336002 +(40×252002 )

• M𝑤 = = 27639
25×16300 + 35×32600 +(40×25200)
Problem 5: A polymer sample analysis indicated presence of 20% (by weight) of macromolecules of
molecular weight 2000, 30% (by weight) of macromolecules of molecular weight 3000 and 50% (by weight)
of macromolecules of molecular weight 5000.
Calculate the number average and weight average molecular weight of the sample.
Answer:
• M𝑛 = σ 𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖 × 𝑀. 𝑊. 𝑖
• M𝑤 = σ 𝑊𝑒𝑖𝑔ℎ𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖 × 𝑀. 𝑊. 𝑖
𝑇𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 100

M𝑛 = = = 3333.3
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 20 30 50
+ +
2000 3000 5000
20 30 50
M𝑤 = × 2000 + × 3000 + × 5000 = 3800
100 100 100
Problem 6: In 10g of PVC sample, (Mn= 30,000; Mw= 60,000), you add 1g of another PVC sample with Mn
20,000, PDI=2. What will be the Mn and Mw of the new polymer mixture?
Answer:
• M𝑛 = 28695.6
• M𝑤 = 58181.8
• M𝑤 = σ 𝑊𝑒𝑖𝑔ℎ𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖 × 𝑀. 𝑊. 𝑖
10 1
= × 60000 + × 40000 = 58181.8
11 11
𝑇𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑖𝑛 𝑔𝑚 11
• M𝑛 = = 10 1 =28695.6
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 +
30000 20000
Natural Rubber No Stress
(Elastomers)
Properties
• Highly amorphous
• Highly random orientation
Stressed In tension
• Elastic properties
Natural rubber is cis−1,4−polyisoprene, a polymer of isoprene (2−methyl−1−3− butadiene). It is a stereo

regular polymer with all the pendent methyl groups in the linear polymer chain lying in one side.
H H
H C H
C C
H C C H
isoprene H H cis-polyisoprene
Natural Rubber
(Elastomers)
Natural rubber is obtained from the exudates of the rubber
trees in the form of a milky colloidal solution called latex
It contains 25-45% of rubber dispersed in a watery medium
with small amounts of protein and other materials.
The latex is tapped by cutting through the bark of the tree
and the liquid that comes out is collected in containers.
The latex is processed either by –

i) coagulation by acid or by heat and processed further
or
ii) mixed with compounding materials and precipitated
directly from the solution.
Raw material extracted from trees
Natural Rubber
Drawbacks
➢ It is plastic in nature: It becomes soft at high temperature and is too brittle at low temperature. So it can
be used in temperature range between 10 to 60˚C only
➢ It is weak: tensile strength is only 200kg/cm2
➢ It has large water absorption capacity
➢ It is non-resistant to non-polar solvents like vegetable and mineral oil
➢ It swells in organic solvent and gradually degrade
➢ It is attacked by oxidizing agent
➢ It has little durability
Natural Rubber
Vulcanization
Vulcanization is a process, through which elasticity of the rubbers increases and reduces plasticity by the
formation of a cross-linked molecular network.
Vulcanization is done by heating the rubber with sulfur or other vulcanizing agents under pressure
Tetramethylthiuram disulfide
Charles Goodyear (December 29, 1800 – July 1, 1860) was an American inventor who developed a process to vulcanize
rubber in 1839 — a method that he perfected while living and working in Springfield, Massachusetts in 1844, and for
which he received patent number 3633 from the United States Patent Office.
Natural Rubber
Vulcanization
Problem 7: 162 gram of poly 1,3-butadiene was treated with sulphur (S) to get a modified polymer.
Calculate the amount of Sulphur required to get the modified polymer. (Atomic weight of S is 32)
68
Compounding of Rubber
Compounding is mixing of the raw rubber (synthetic or natural) with other substances so as to impart the
product specific properties suitable for a particular job
1. Vulcanizing agents: sulfur, sulfur monochloride, benzoyl chloride etc.
2. Accelerators: These materials drastically shorten the time required for vulcanization. E.g. – 2-
mercaptol, Benzothiazole etc.
3. Softener and plasticizers are added to give the rubber greater tenacity and adhesion. E.g. – vegetable
oil, waxes, stearic acid.
4. Antioxidants: Natural rubbers has a tendency to perish due to the oxidation. For this reason
antioxidants are required, such as complex amine, phosphites etc.
5. Reinforcing fillers: theses materials gives strength and rigidity to the rubber products. E.g. – CaCO3, ZnO
etc.
6. Colouring agents
Synthetic Rubber
(Artificially made)
Synthetic rubber, invariably a polymer, is any type of artificial elastomer mainly synthesized from petroleum
byproducts.
An elastomer is a material with the mechanical (or material) property that it can undergo much more elastic
deformation under stress than most materials and still return to its previous size without permanent
deformation.
Examples:
• Buna-S,
• Butyl rubber,
• Buna-N,
• Neoprene
Synthetic Rubber
Buna-S (Styrene rubber)
Buna-S is produced by copolymerization of butadiene (about 75% by weight) and styrene (about 25% by
weight).
Synthetic Rubber
Styrene-butadiene copolymer
Properties:
• Styrene domains act as anchors or junctions
• Butadiene provides flexible linkages
Synthetic Rubber
Buna-S (Styrene rubber)
Properties:
• Styrene rubber resembles natural rubbers in processing characteristics as well as quality of finished
products. It possesses high abrasion-resistance, high load bearing capacity and resilience.
• However, it gets readily oxidized, especially in presence of traces amount of ozone present in
atmosphere.
• Moreover, it swells in oils and solvents.
• It can be vulcanized in the same way as natural rubber either by Sulphur or Sulphur monochloride (S2Cl2)
However it requires less Sulphur, but more accelerator (zinc oxide and stearic acid) for vulcanization.
Uses:
• Mainly used in manufacturing of motor tires.
• Other uses of this elastomer are floor tiles, shoe- soles, gaskets, foot-ware components, wire and cable
insulations, carpet backing, adhesives, tank lining.
Synthetic Rubber
Butyl Rubber
Butyl rubber is made by copolymerization of isobutene with small amount of (1% to 5%) isoprene
Isoprene 1,3 butadiene

Synthetic Rubber
Butyl Rubber
Properties:
• Butyl rubber possesses outstanding low permeability to air and other gases; less than 1/10th of natural
rubber.
• It has excellent resistance to heat, abrasion, ageing, chemicals (such as H2SO4, HNO3, HCl and HF), polar
solvents (such as alcohols, acetone),
• It is soluble in hydrocarbon solvents like benzene.
• It has high resistance to ozone and good electrical insulating properties.
• It can be vulcanized but it cannot be hardened much, due to very low unsaturation.
Uses:
Butyl rubber is used for making cycle and automobile tubes, automobile parts, hoses, conveyer belts for
food and other materials. Tank-linings, insulation for high voltage wires and cables.
Synthetic Rubber
Buna-N (Nitrile rubber)
Buna–N is copolymer of butadiene and acrylonitrile rubber
Synthetic Rubber
Buna-N (Nitrile rubber)
Properties:
• It possesses excellent resistance to heat, sunlight, oils, acids and salts
• It is less resistant to alkalis than natural rubber, because of presence of cyano (-CN) groups.
• As the proportion of acrylonitrile is increased, the resistance to acids, salts, oils, solvents increases but
the low temperature resilience suffers.
• Vulcanized nitrile rubber is more resistant to heat and ageing than natural rubber.
Uses:
For making conveyer belts, high altitude aircraft components, tank lining, hoses, gaskets, printing rollers,
adhesives, oil resistant foams and automobile parts.
Synthetic Rubber
Neoprene
Neoprene is made by polymerization of chloroprene, a chlorinated butadiene
H Cl H H
n C C C C
H H
Chloroprene
Polymerization
H Cl H H
C C C C
H H
n
Polychloroprene or Neoprene
Synthetic Rubber
Neoprene
Properties:
Neoprene is chemically closely related to natural rubber, as indicated by its structural formula.
• The substitution of H atom by chlorine atom produces superior resistance to vegetable and mineral oils,
ageing and high temperature, but at the same time accounts for greater solubility of neoprene in polar
solvents.
• Neoprene can be vulcanized to a considerable extent by heat alone.
• However, its general physical properties are enhanced by compounding it with metallic oxides such as
ZnO or MgO.
Uses:
For making hoses, gaskets, tubing for carrying corrosive gases and liquids. It is also used for making sponges,
conveyer belts, lining of reaction vessels adhesives.
Polyethene Terephthalate (PET)
Properties
➢ PET can exist both in amorphous and semicrystalline form

➢ It has high mechanical strength and dimension stability and is
stable over temperature range of -40 oC to 100 oC.
➢ It shows creep and abrasion resistance and good electrical
insulating properties.
➢ At room temperature, it is resistant to water, dilute acids, salts,
aromatic and aliphatic hydrocarbons and alcohols.
Applications
➢ It is used for making video and audio tapes.
➢ It is commonly used in making clear bottles for foods and
beverages.
➢ It is used to make films for shrink packaging.
➢ As an electrical insulator, it is used for making molds for electrical
appliances.
➢ The synthetic fibers can be woven to make fabrics, upholstery,
artificial grass etc.
➢ The fiber may be blended with wool and other natural fibers.
➢ The films may be combined with paper or other polymeric films to
form multilayer materials.
➢ It can be used to produce injection molded articles, such as
switches, valves etc.
80
Synthetic Polymers
Nylon
Polyamides are synthetic polymers, which have recurring amide groups.
Examples:
• Nylon 6:6 H2 H2
N C N C C C
• Nylon 6
• Nylon 11 H H O O
• Nylon 6:10
O O H
H
H2 H2
C C C N C N
Synthetic Polymers
Nylon
Synthetic Polymers
Nylon
Properties of Nylon:
1. One of the very strong fibers. Extremely resistant to abrasion and flexing.
2. The specific gravity is 1.14 Very light, i.e., 80% of that of silk fibers, and 70% of that of cotton fibers.
3. Since nylon fibers absorb little water even though they are wetted., they dry fast and simple in
laundering.
4. Excellent in elasticity and resistant to wrinkle.
5. Resistant to chemicals and oil. Non-attackable by sea water.
7. Non-attackable by molds and insects.
Uses:
1. Nylon-6:6 is primarily used for fibers, which find use in making socks, under-garments, dresses,
carpets etc.
2. Nylon -6 and nylon-11 are mainly used for moulding purposes for gears, bearings etc. Nylon bearing
and gears work quietly without any lubrication.
3. They are also used for making filaments for ropes, bristles for tooth brushes and films, tyre-cords etc.
Synthetic Polymers
Polyethylene
It is the most common plastic you see
Properties:
• Polyethylene is a rigid, waxy, white translucent, non polar material.
• Polyethylene exhibits considerable chemical resistance to strong acids, alkalis and salt solutions at
room temperature.
• It is good insulator of electricity.
• It is swollen and permeable to most oils and solvents.
• It has highly symmetrical chain structure, so polyethylene crystallizes very easily. The degree of
crystallinity may vary from 40 to 95%, depending on the degree of branching in the polyethylene chain
Synthetic Polymers
Polyethylene
Preparation:
Polyethylene (PE)is obtained by polymerization of ethylene.
• The gas is first liquefied under high pressure (up to 1500 atm)
• It is pumped into heated (150 to 250ᵒC) pressure vessel.
• By catalytic effect of traces of oxygen present, ethylene is polymerized into polyethylene.
• A waxy solid which comes out from the bottom of the vessel
• Free radical initiator → Low density polyethylene (LDPE)

• Ionic catalysts → High density polyethylene (HDPE)
Synthetic Polymers
Polyethylene
• Free radical initiator → low density polyethylene (LDPE)
• Ionic catalysts → high density polyethylene (HDPE)
Synthetic Polymers
Polyethylene
LDPE and HDPE
Uses of LDPE & HDPE
LDPE is widely used for manufacturing various containers, dispensing bottles, wash bottles, tubing, plastic bags for
computer components, and various molded laboratory equipment. Its most common use is in plastic bags. Other products
made from it include:
➢ Trays and general purpose containers.
➢ Corrosion-resistant work surfaces.
➢ Parts that require flexibility, for which it serves very well.
➢ Juice and milk cartons are made of liquid packaging board, a laminate of paperboard and LDPE (as the water-proof
inner and outer layer), and often with of a layer of aluminum foil (thus becoming aseptic packaging).
➢ Parts of computer hardware, such as hard disk drives, screen cards, and optical disc drives
HDPE is resistant to many different solvents and has a wide variety of applications, including:
➢ 3-D printer filament
➢ Banners
➢ Bottle caps
➢ Chemical resistant piping systems
➢ Food storage containers
➢ Fuel tanks for vehicles
➢ Electrical and plumbing boxes
➢ Folding chairs and tables
Synthetic Polymers
Polytetrafluoroethylene (PTFE) or Teflon®
Extreme tough, high softening point, exceptionally high chemical-resistance towards all chemicals, high
density, waxy touch. It can be punched, machined, and drilled
Example: Synthesis of phenol-formaldehyde resin (Bakelite)
Phenol-formaldehyde resin (Bakelite and Novolac)
Phenol + excess formaldehyde → Bakelite/Resole

(P/F ratio < 1)
• Hard thermosetting plastic
Excess phenol + formaldehyde → Novolac

(P/F ratio > 1)
• Linear, soluble, low MW polymers
• Used in paints
Properties of Bakelite:
• They are rigid, hard, scratch-resistant, infusible, water resistant, insoluble solid.
• Resistant to non-oxidizaing acids, salts and many organic solvents.
• They are attacked by alkalis
• They possess excellent electrical insulting character
Uses
• For making electric insulators parts like switches, plugs, switch board, heater-handles etc.
• For making moulded articles like telephone parts, cabinets for radio and television.
• For impregnating fabrics, woods and paper
• As adhesives (binder) for grinding wheels.
• In paints and varnish
• As hydrogen exchanger resins in water softening
Polymerization techniques
Condensation polymerization mechanism
Example: Synthesis of urea formaldehyde resin
Synthetic Polymers
Epoxy resins
It is prepared by the condensation polymerization of bisphenol and epicholorohydrin
Properties:
• Stable ether linkages → high chemical resistances
• Excellent adhesion quality due to the presences of polar functional groups
• Tough and heat resistant
• High flexibility
Usage:
• As surface coating , adhesive like ardilite
Syllabus
Module 1: Advanced materials and polymers: Introduction, Definition, classification of

polymers – based on origin, thermal behaviour, Polymerization reactions and
applications, Tacticity. Functionality, Degree of polymerization, Co-polymerization –
alternating, random, block and graft polymers. Mechanism of free radical polymerization
and ionic polymerization. Mechanism of coordination polymerization, Condensation
polymerization reactions, Glass transition temperature & factors affecting it. Molecular
weight of polymers, Number average and weight average molecular weights, Numerical
problems. Preparation, properties and applications of Polythene (LDPE and HDPE), Nylon(
6:6, 6, 6:10, 11), PF resins and Polyester. Natural rubber, Processing of Natural Rubber,
Vulcanization, Compounding of rubber; Synthetic Rubber: Buna-N, Buna-S. Composites,
bio-materials, their properties and applications.
Composites
Composite Materials
A materials system composed of two or more physically and/or chemically distinct phases whose
combination produces aggregate properties that are different from those of its constituents
Plywood Concrete
Examples:
• Cemented carbides (WC with Co binder – Tungsten carbide with Cobalt binder)
• Plastic moulding compounds containing fillers
• Rubber mixed with carbon black
• Wood (a natural composite as distinguished from a synthesized composite)
Composite Materials
A materials system composed of two or more physically and/or chemically distinct phases whose
combination produces aggregate properties that are different from those of its constituents
Plywood Concrete
Composite Materials
Advantages
• High strength to weight ratio (low density high tensile strength) or high specific strength ratio!
• High creep resistance
• High tensile strength at elevated temperatures
• High toughness
• Generally, perform better than steel or aluminum in applications where cyclic loads are encountered
leading to potential fatigue failure (i.e., helicopter blades).
• Impact loads or vibration – composites can be specially formulated with high toughness and high
damping to reduce these load inputs.
• Some composites can have much higher wear resistance than metals.
• Corrosion resistance
• Dimensional changes due to temp changes can be much less.
• Anisotropic – bi-directional properties can be design advantage (i.e., helicopter blades)
Composite Materials
Disadvantages
• Material costs
• Fabrication/ manufacturing difficulties
• Repair can be difficult
• Inspection and testing typically more complex.
• Wider range of variability (statistical spread)

• Operating temperature can be an issue for polymeric matrix (i.e., 500°F). Less an issue for metal matrix
(2,700°F).
• Non-isotropic properties makes design difficult!
Classification of Composite Materials
by Matrix:
1. Ceramic matrix
2. Metal matrix
3. Polymer (Resin) matrix
by Filler type/dispersed phase:

1. Particle-reinforced composites
2. Fiber-reinforced composites
3. Structural composites
by Matrix:
1. Ceramic matrix
2. Metal matrix
Ceramic matrix composites (CMC)

Example: Silicon carbide-silicon carbide (SiC-SiC)
• Both matrix and filler are the same material but …

The filler is in different form such as:
whisker (microcrystalline fibers), chopped fibers or strands

to achieve preferred properties.
by Matrix:
1. Ceramic matrix
2. Metal matrix
Metal matrix composites (MMC)

Metal matrix: Al, Ti, Mg, Fe, Cu, Ni
• Filler: Carbides, oxides etc.
• Examples: Al-SiC (silicon carbide)

Al-Al2O3 (aluminium oxide)
• Advantages: High strength, high stiffness, abrasion resistance, dimensional stability, high
temperature and toughness.
by Matrix:
1. Ceramic matrix
2. Metal matrix
Polymer matrix composites or Fiber Reinforced Polymer (FRP)
Property Glass Carbon fiber Kevlar

• Fibers: glass, carbon or Kevlar
Strength Worst In – between Best
• Matrix:
Stiffness Worst Best In – between
Thermoplastics: PE, Nylon, PS, PP, PVC
Cost Best Worst In – between
Thermosets: Epoxy, polyester, phenolics Weight Worst Best In – between
• Have high strength and stiffness to weight ratio
• Examples:
GFRP aka fiberglass (polyester or epoxy and glass),
CFRP (polyester or epoxy and carbon),
KFRP (polyester or epoxy and Kevlar) Kevlar
Biomaterials
Biomaterials: Definition
Biomaterials is used to make devices to replace a Need for Biomaterials
part or a function of the body in a safe, reliable,
Millions of patients suffer end stage organ and tissue
economic and physiologically acceptable manner
failure annually. – $400 billion annually for treatment. –
[Hench & Erthridge, 1982].
8 million surgical procedures.
Materials of Synthetic as well as of natural origin
Treatment options include transplantation,
in contact with tissue, blood and biological fluids
reconstruction, mechanical devices
and intended for use for prosthetic diagnostic
therapeutic and storage applications without
adversely affecting the living organism and its Evolution of biomaterials
components [Bruck, 1980]. 1st generation (since 1950s) – Goal: Bioinertness
2nd generation (since 1980s) – Goal: Bioactivity
A biomaterial is a nonviable material used in a 3rd generation (since 2000s) – Goal: Regenerate
medical device, intended to interact with functional tissue
biological systems [Williams, 1987].
First Generation Implants
● Ad-hoc’ (unplanned) Implants
● Specified by physicians using common and borrowed materials
● Most successes were accidental rather than by design
● Examples – First generation Implants – Gold fillings, wooden teeth, PMMA dental prosthesis – Steel, gold,
ivory, bone plates etc. – Glass eyes and other body parts
Second generation Implants

● Engineered implants using common and borrowed materials
● Developed through collaborations of physicians and engineers
● Built on first generation experiences
● Used advances in materials science
● Examples – Second generation implants – Titanium alloy dental and orthopedic implants – Cobalt-chromium
implants – UHMW polyethylene bearing surfaces for total joint replacements – Heart valves and Pacemakers.
Third Generation Implants
● Bioengineered implants using bioengineered materials
● Few examples on the market
● Some modified and new polymeric devices
● Many under development
● Example – Third generation implants – Tissue engineered implants designed to re-grow rather than replace
tissues – Some resorbable bone repair cements – Genetically engineered ‘biological’ components.
Characteristics of Biomaterials
Physical Requirements
• Hard Materials
• Flexible Material
Chemical Requirements
• Must not react with any tissue in the body.

• Must be non-toxic to the body.
• Long-term replacement must not be biodegradable.
Features of a Biomaterial
• Absence of carcinogenicity (the ability or tendency to produce cancer)

• Absence of immunogenicity (absence of a recognition of an external factor which could create rejection)
• Absence of teratogenicity (ability to cause birth defects)
• Absence of toxicity
The water resource
• Water Covers 70% – 75% of the earth surface
• Total water available is 1400 million km3
• 97% – locked in sea or oceans (1332 million km3)
• 3% – fresh water
• 2.15% in polar ice caps (29.20 million km3)
• < 1% available as surface water (rivers, streams, lakes) with which we must manage ourselves!
• Only 14 million km3 is fresh water
• Oceans receive about 61% & land 39% of total rainfall.
A graphical distribution of the locations of
water on Earth
The water resource
• No plant or animal species can survive without water.
• If water in our body drops by 1%, we feel thirst, if it drops by 10%, we face death.
• Water is a renewable resource; It may change it’s form but quantity of water on earth has remained
same for millions of years.
• One of the greatest challenges facing the world!
The water resource
Usage
Breakdown → agriculture (70%), industry (22%), domestic (9%)
Domestic
70%
% of total water used
22%
8%
Water uses
in India → agriculture (87%), industry (8%), domestic (5%)
Competing water uses
Types of Impurities Present in water
Micro-organisms:
• Bacteria, Fungi, algae and other forms of animal and plant life
Suspended impurities:
• Inorganic (e.g., clay and sand)
• Organics (e.g., oil, vegetable and animal matters)
Colloidal impurities:
• Clay and finely divided silica colloidal particles of 10-4 – 10-6 mm size
Dissolved impurities:
• Inorganic salts e.g.
(i) Cations: Ca2+, Mg2+, Na+, K+, Fe2+, Al3+, Zn2+, Cu2+
(ii) Anions: Cl-, SO 2-, NO -, HCO -, F-, NO -
4 3 3 2
• Gases: CO2, O2, N2, NH3, H2S
• Organics salts
Hardness of water
• Hardness of water is originally defined as the soap consuming capacity of a water sample.
• The soap consuming capacity of water is mainly due to the certain salt of calcium (Ca2+), magnesium
(Mg2+) and other heavy metals dissolved in it.
• Other metal ions such as Fe2+, Mn2+, Al3+ also contributes to hardness, but they are present in water only
in traces
• The soap consists of sodium salts of fatty acids such as Oleic acid, Palmitic acid and stearic acid.
• Calcium and magnesium react with the sodium salts of long chain fatty acid present in the soap to form
insoluble scums of calcium and magnesium soaps.
Palmitic acid (C₁₆H₃₂O₂)
Stearic acid (C₁₈H₃₆O₂)
Oleic acid (C₁₈H₃₄O₂)

Hardness of water
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + NaCl

(Sodium stearate) (Insoluble)
2 C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

Hardness of water
Temporary hardness
• Temporary hardness is caused by the presences of dissolved bicarbonate of calcium and magnesium and
other heavy metal ions
• Temporary hardness is mostly destroyed by boiling of water
• During boiling bicarbonate are decomposed in the insoluble carbonate and hydroxide, which are
deposited at the bottom of the vessel
ℎ𝑒𝑎𝑡
𝐶𝑎 𝐻𝐶𝑂3 2 𝐶𝑎𝐶𝑂3 + 𝐶𝑂2 + 𝐻2𝑂
ℎ𝑒𝑎𝑡
𝑀𝑔 𝐻𝐶𝑂3 2 𝑀𝑔𝐶𝑂3 + 𝐶𝑂2 + 𝐻2𝑂
Permanent hardness (non-carbonate hardness)

• This is due the presences of chlorides, nitrates, and sulphates of calcium, magnesium, iron and other
heavy metal ions.
Measurement
Hardness is expressed in terms of equivalent of calcium carbonate because it is an insoluble salt that can be
most easily precipitated in water treatment
Equivalent weight of CaCO3 (𝟓𝟎)
Equivalent of CaCO 3 = Mass of salt ×
Equivalent weight of salt
Molecular weight of CaCO3 (𝟏𝟎𝟎)
Equivalent of CaCO 3 = Mass of salt∗ ×
Molecular weight of salt∗
Dissolved salt Molar Mass Chemical Multiplication factor for converting into
equivalent equivalent of CaCO3
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
MgCO3 84 42 100/84
Units of Hardness
• ppm or mg/l
Mass of hardness producing substances x 50
Equivalent of CaCO3 =
Chemical equivalent of hardness producing substances
• Degree Clarke (°Cl)

A Clark degree (°Clark) or English degrees (°e or e) is defined as one grain (64.8 mg) of CaCO3 per Imperial
gallon (4.55 litres) of water, equivalent to 14.254 ppm.
• Degree French (°Fr)

A French degree (°fH or °f) is defined as 10 mg/L CaCO3, equivalent to 10 ppm.
A water sample contains 248 mg CaSO4 per litre. Calculate the hardness of the water in CaCO3 equivalent.
Answer:
• Mol. Wt. of CaSO4 = 136
𝑊𝑡.𝑜𝑓 𝐶𝑎𝑆𝑂 4 ×𝐶ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞.𝑜𝑓 𝐶𝑎𝐶𝑂3 𝑚𝑔
• 𝐸𝑞. 𝐶𝑎𝐶𝑂3 = 𝐶ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞.𝑜𝑓 𝐶𝑎𝑆𝑂 𝐿
𝑜𝑟 𝑝𝑝𝑚
4
100
248×
• 𝐸𝑞. 𝐶𝑎𝐶𝑂3 = 136
2
= 𝑚𝑔 𝑜𝑟 𝑝𝑝𝑚
𝐿
2
• 𝐸𝑞. 𝐶𝑎𝐶𝑂3 =183.35 ppm

A water sample contains 200 mg of CaSO4 per liter. Calculate the hardness in terms of CaCO3 equivalent in
ppm, oCl and oFr.
Answer:
𝑚𝑔 𝐸𝑞. 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂3
= 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝑆𝑂 4 𝑖𝑛 ×
𝐿 𝐸𝑞. 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝑆𝑂4
𝑚𝑔 100/2 𝑚𝑔
= 200 × = 𝟏𝟒𝟕. 𝟎𝟔 𝑜𝑟 𝑝𝑝𝑚
𝐿 136/2 𝐿
𝒎𝒈
𝟏 °𝑪𝒍 = 𝟏𝟒. 𝟐𝟓𝟒 𝒑𝒑𝒎 ⇒ 𝟏 = 𝟎. 𝟎𝟕°𝑪𝒍
𝑳
𝒎𝒈
𝟏 °𝑭𝒓 = 𝟏𝟎 𝒑𝒑𝒎 ⇒ 𝟏 = 𝟎. 𝟏°𝑭𝒓
𝑳
147.06 𝑚𝑔/𝐿 = 𝟏𝟎. 𝟐𝟗 𝒐𝑪𝒍 𝑜𝑟 𝟏𝟒. 𝟕𝟏 𝒐𝑭𝒓
How many grams of MgCl2 dissolved in 1 liter water will give hardness of 76 ppm?
Answer:
Molecular weight of MgCl2 = 95
• Let 𝑥 𝑚𝑔 MgCl2 dissolved in water gives 76 ppm hardness.

𝐿
𝑀.𝑊. 𝐶𝑎𝐶𝑂 3
• 𝑥× = 76
𝑀.𝑊. 𝑀𝑔𝐶𝑙 2
• 𝑥 × 100 = 76
95
• 𝑥 = 72.2 m g = 0.072g
L
The samples A, B, and C were analyzed for their salts contents:
Sample A was found to contain 155 mg of magnesium carbonate per litre.
Sample B was found to contain 800 mg of calcium nitrate, 5.1 mg of sodium chloride, and 2.5 mg of silica
per litre.
Sample C contains 15 mg of potassium nitrate, and 3 g of calcium carbonate per litre.
Determine the hardness in all above three samples in ppm.
Molecular weights: MgCO3=84; Ca(NO3)2=164, NaCl=58.5, silica/SiO2=60, CaCO3=100
Answer:
• A = 184.52 ppm, B = 487.52 ppm, C = 3000 ppm
The samples A and B were analyzed for their salts contents:
Sample A was found to contain 168 mg of magnesium carbonate per 500 mL. Sample B was found to
contain 820 mg of calcium nitrate per 250 mL
Determine the hardness in all above two samples in ppm.
Molecular weights: MgCO3=84; Ca(NO3)2=164
Calculate the temporary hardness and permanent hardness of a sample of water containing: Mg(HCO3)2 =
7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L; CaSO4 = 13.6 mg/L
Molecular weights: Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; MgCl2 = 95; Al2(SO4)3 = 114;
Ca(NO3)2=164
A water sample (500 mL) has hardness equivalent for 50 mL of 0.1 N CaSO4. What is the hardness in ppm?
Answer:
• Mol. Wt. of CaSO4 = 136
• Eq. Wt. of CaSO4 = 68
• 1000 mL 1 N CaSO4 ≡ 68 g/L

• 50 mL 0.1 N CaSO4 ≡ 0.34 g/L = 340 mg/L
• Eq. CaCO 3 = 340×100 𝑚𝑔 𝑜𝑟 𝑝𝑝𝑚 = 250 𝑝𝑝𝑚

136 𝐿
Chemical analysis – Estimation of hardness
Hardness can be determined by the following methods –
• Soap solution method
• EDTA method
1) Soap solution method or Clarke’s method
Soaps gives lather with hard water only after enough soap is added to precipitate all the
hardness causing metal ions present in water.
2 C17H35COONa + CaCl2 or MgCl2 (C17H35COO)2Ca or Mg + NaCl

2 C17H35COONa + MgSO4 or CaSO4 (C17H35COO)2Mg or Ca + Na2SO4

After precipitation of all the hardness causing ions present in water, further addition of
soap gives lather
Method:
1. Standard hard water – pure dry CaCO3 is dissolved in HCl, boiled to evaporate, dissolved in water
2. Soap solution – soap + alcohol + water (80:20)
3. Standardization – soap in burette, water in conical flask, addition of small amount and shaking
4. Lather factor – against distilled water
5. Determination of total hardness – as usual
6. Determination of permanent hardness – as usual (after boiling)
Q. The following data was obtained when 100 ml water was titrated against soap solution. Calculate each
type of hardness present.
• Standard hard water (400 ppm of CaCO3) – 36.6 ml soap solution
• Total hardness – 18.6 ml soap solution
• Permanent hardness – 6.2 ml soap solution
• Lather factor – 0.6 ml soap solution
Answer:
• Standard hard water (400 ppm of CaCO3) = 400 mg in 1000 mL
• 1 mL soap solution ≡ 40/(36.6 – 0.6) mg CaCO3 = 40/36 mg CaCO3
• Total hardness ≡ (18.6 – 0.6) × (40/36) = 20 mg CaCO3 ≡ 200 ppm
• Permanent hardness ≡ (6.2 – 0.6) × (40/36) = 6.22 mg CaCO3 ≡ 62.2 ppm
• Temporary hardness ≡ (200 – 62.2) = 137.8 ppm
Q. 0.2 g of pure and dried CaCO3 was dissolved in 1 lit of distilled water to prepare standard hard water. The
following data was obtained when 50 ml of a sample of hard water was tested. Calculate each type of
hardness present.
• Standard hard water – 20.5 ml soap solution
• Total hardness – 9.0 ml soap solution
• Permanent hardness – 3.0 ml soap solution
• Lather factor – 1.0 ml soap solution
Answer:
• Total hardness = 82 ppm
• Permanent hardness = 20.5 ppm
• Temporary hardness = 61.5 ppm
2) EDTA method
NaOOCH2C CH2COONa
Hard water N CH2 CH2 N
+ HOOCH2C CH2COOH
EBT Indicator
+
10 pH buffer
solution
Ca/Mg
O O
NaO 3 S N N
O2N
2) EDTA method
NaOOCH2C CH2COONa
N CH2 CH2 N
HOOCH2C CH2COOH
Ca/Mg
O O
NaO 3 S N N
O2N
2) EDTA method
Requirements –
• Standard hard water – as before (1mg in 1 L = 1 ppm)
• EDTA solution – Na2-EDTA + distilled water
(3.72 g Na2-EDTA in 1 lit water ➔ 1 ml 0.01 M EDTA ≡ 1 mg CaCO3 equivalent)
• Indicator – EBT + alcohol
• Buffer solution (pH = 10) – NH4Cl + NH4OH
Steps –
• Standardization of EDTA – to get CaCO3 equivalent
• Total hardness – similar process with unknown sample
• Permanent hardness – after boiling
• Temporary hardness – (total – permanent) hardness
Problems
250 ml water sample upon EDTA titration with EBT consumed 13 ml of 0.022 M EDTA till the end point was
reached. Calculate the hardness of the water sample.
Answer:
• 1 ml 0.01 M EDTA ≡ 1 mg CaCO3
• 13 ml 0.022 M EDTA ≡ 13×0.022 ml 0.01M EDTA

0.01
≡ 13×0.022 mg CaCO 3 = 28.6 mg CaCO 3

0.01
• Hardness in 250 ml = 28.6 mg
• Hardness in 1000 ml = 28.6×1000 mg/L = 114.4 mg/L or 114.4 ppm

250
reached. Another part of the sample was boiled to remove temporary hardness. This solution required 8 ml
0.01 M EDTA to reach the end point. Calculate the temporary and permanent hardness of the water sample.
Answer:

Problems
reached. Another part of the sample was boiled to remove temporary hardness. This solution required 8 ml
0.01 M EDTA to reach the end point. Calculate the temporary and permanent hardness of the water sample.
Answer:
• 15 ml 0.01 M EDTA ≡ 1×15×0.01 mg CaCO 3 = 15 mg CaCO 3

1×0.01
• Total hardness in 1000 ml = 15×1000 mg = 150 mg/L or 150 ppm

100
• 8 ml 0.01 M EDTA ≡ 1×8×0.01 mg CaCO 3 = 8 mg CaCO 3

1×0.01
• Permanent hardness in 1000 ml = 8×1000 mg = 80 mg/L or 80 ppm

100
• Temporary hardness = (150 - 80) ppm = 70 ppm

Problems
0.28 g of CaCO3 was dissolved in HCl and the solution was made to 1 lit with distilled water. 100 ml of this
sample upon EDTA titration with EBT consumed 28 ml of EDTA till the end point was reached.
100 ml of a hard water sample required 35 ml of the same EDTA solution on titration. After boiling, filtering,
and titrating 100 ml of this water required 10 ml EDTA solution. Calculate the hardness of the water sample.
Answer:
• 0.28 g = 280 mg in 1 lit water ≡ 280 ppm or 280 mg/L
• 100 ml of this solution (28 mg CaCO3) consumes 28 ml of EDTA i.e., EDTA is of strength 0.01 M
• Total: 35 ml 0.01 M EDTA for 100 ml → 350 ppm
• Permanent: 10 ml 0.01 M EDTA for 100 ml → 100 ppm
• Temporary = (350-100) ppm = 250 ppm

Problems
25 ml of standard hard water consumes 12 ml of standard EDTA solution. 25 ml of hard water sample
consumes 8 ml of EDTA solution. After boiling the sample, 25 ml of this sample consumed 6 ml of standard
EDTA solution. Calculate the hardness of the water sample. Standard hard water = 1000 ppm
Answer:
• Total = 666.67 ppm,
• Permanent = 500 ppm,
• Temporary = 166.67 ppm
Problems
Chemical analysis – Estimation of hardness
Hardness can be determined by the following methods –
• Soap solution method
In CaCO3 equivalent –
• EDTA method
• 300-500 ppm → excessive hardness
high soap consumption
scaling in heating vessels and pipes
• > 150 ppm → consumer objection
• 60-120 ppm → moderate amount
In boilers –
• Hardness → < 0.2 ppm
• Caustic alkalinity (OH–) → 0.15 – 0.45 ppm
• Soda alkalinity (CO3 2-) → 0.45 – 1 ppm
Otherwise, scale & sludge formation, embrittlement, corrosion, foaming happens

Water softening
Removal of hardness –
Hardness is …
• Primarily Ca, Mg
• and Fe, Mn, St, Al salts
Ions like Na/K/NH4 do NOT cause hardness
How do we remove hardness?

• Ion exchange of Ca/Mg with ions Na/K → Ion exchange resin process
• Ion exchange of Ca/Mg with Na → Zeolite process
• Precipitation of Ca and Mg → Soda-Lime process
Water softening
Ion exchange or deionization or demineralization process:
Ion-exchange resins are widely used in different separation, purification, and

decontamination processes.
Ion-exchange resins are –
• insoluble,
• cross linked,
• long chain organic polymer,
• with micro porous structure and,
• the functional groups attached to the chains are responsible for the ion
exchange properties.
Water softening

Ion-exchange resins are widely used in different separation, purification, and decontamination processes.
Water softening

Ion-exchange resins are widely used in different separation, purification, and decontamination processes.
Cation exchange resins
Resins containing acidic functional groups (-COOH, -SO3H, phenolic -OH) are capable of exchanging their H+
ions with other cations which comes in their contacts, known as a cation exchange resins (RH+).
e.g. styrene divinyl benzene (Amberlite IR-120 or Dowex-50), which on sulphonation and carboxylation,
become capable to exchange their hydrogen ions with the cations (Metal ions) in the water.
Anion exchange resins (R+OH-)
Resins containing basic functional groups (-NR 3+OH-) are capable of exchanging their anions with other
anions which comes in their contacts, known as a Anion exchange resins (ROH-).
+
-PR3
Quaternary
Phosphonium
group Quaternary
Sulphonium
group
Quaternary
Ammonium
group
Anion exchange resins (R+OH-)
Resins containing basic functional groups (-NR 3+OH-) are capable of exchanging their anions with other
anions which comes in their contacts, known as an Anion exchange resins (ROH-).
They are styrene divinyl benzene or amine-formaldehyde copolymerization which contains
• quaternary ammonium or
• quaternary phosphonium or
• tertiary sulphonium groups
as an integral part of the resin matrix.
These after treated with dil. NaOH becomes capable of exchanging their OH- ions with anions of water
sample.
Process
• The hard water is passed first through cation exchange column, which remove all the cations from it and
equivalent amount of hydrogen ions are released from this column to water:
2RH+ + Ca2+ → R2Ca2+ + 2H+
2RH+ + Mg2+ → R2Mg2+ + 2H+
• After cation exchange column the hard water is passed through anion exchange resin column, which
remove all the anions from it and equivalent amount of hydroxide ions are released from this column to
water :
ROH- + Cl- → RCl- + OH-
2ROH- + SO42- → R2SO42- + 2OH-
H+ + OH- → H2O
Process
Step 1:
Used up resin
2RH+ + Ca2+ → R2Ca2+ + 2H+
2RH+ + Mg2+ → R2Mg2+ + 2H+
Step 2:
ROH- + Cl- → RCl- + OH-
2ROH- + SO4 → R2SO4 + 2OH-
2- 2-
H + + OH- → H2O
Water coming out from the exchange is free from cations as

well as anions.
Ion free water is known as deionized or demineralized water.

Regeneration
Cation exchange column is regenerated by passing a solution of dil. HCl or dil. H2SO4. The regeneration can
be represented as
R2Ca2+ + 2H+ → 2RH + Ca2+
Exhausted anion exchange column is regenerated by passing a solution of dil. NaOH. The regeneration can
be represented as
R2SO42- + 2OH- →2ROH + SO42-

Ion exchange purifier or softener
Hard
water
Gravel
Cation exchange Resin Anion exchange Resin bed
Injector
Injector
Acid
solution for Wastages to
regeneratio sink Alkaline solution for
n of resin Wastages to
regeneration of resin
sink
pump
Soft water
Pros and Cons
Advantages:
• Can be used to soften highly acidic or alkaline waters.
• It produces water of very low hardness.
Disadvantages:
• The equipment is costly
• Expensive chemicals are needed
• Output of the process is reduced if water contains turbidity. (turbidity must be below 10 ppm)
Zeolite (Permutit) method of Softening of water
Zeolite is a Hydrated Sodium Alumino Silicate (HSAS), capable of exchanging reversibly its sodium ions for
hardness producing ions in water.
The general chemical structure of zeolite is –
Na2O·Al2O3·xSiO2·yH2O
(x = 2-10 and y = 2-6)
• Porosity or cavity size of synthetic zeolite structures can be controlled by varying the Si/Al ratio
• Ion-exchange process of zeolite structure is associated with sodium ions
Process of softening by Zeolite method
• For the purification of water by the zeolite
softener, hard water is passed through the
zeolite bed at a specified rate.
• The hardness causing ions such as Ca2+, Mg2+
are retained by the zeolite bed as CaZe and
MgZe respectively.
• The outgoing water contains sodium salts.
Micro pores of Zeolite
Porous Structure of zeolite

Zeolite softener
Hard water in
Process of softening by Zeolite method
To remove permanent hardness
Hard water spray 𝑁𝑎2𝑍𝑒 + 𝐶𝑎𝐶𝑙2 → 𝐶𝑎𝑍𝑒 + 2𝑁𝑎𝐶𝑙
𝑁𝑎2𝑍𝑒 + 𝑀𝑔𝑆𝑂4 → 𝑀𝑔𝑍𝑒 + 𝑁𝑎2𝑆𝑂4
Zeolite bed
To remove temporary hardness
Gravel
Injector 𝑁𝑎2𝑍𝑒 + 𝐶𝑎 𝐻𝐶𝑂3 2 → 𝐶𝑎𝑍𝑒 + 2𝑁𝑎𝐻𝐶𝑂3

𝑁𝑎2𝑍𝑒 + 𝑀𝑔 𝐻𝐶𝑂3 2 → 𝑀𝑔𝑍𝑒 + 2𝑁𝑎𝐻𝐶𝑂3
Softened water
NaCl storage To
sink Regeneration
𝐶𝑎𝑍𝑒\𝑀𝑔𝑍𝑒 + 2𝑁𝑎𝐶𝑙 → 𝑁𝑎2𝑍𝑒 + 𝐶𝑎𝐶𝑙2\𝑀𝑔𝑆𝑂4
Limitations of Zeolite process
• If the water is turbid: then the turbidity causing particles

clogs the pores of the Zeolite and making it inactive
• The ions such as Mn2+ and Fe2+ forms stable complex
Zeolite which can not be regenerated that easily as both
metal ions bind strongly and irreversibly to the zeolite
structure.
• Any acid present in water (acidic water) should be
neutralized with soda before admitting the water to the
plant.
Advantages of Zeolite process (Zeolite)
• Soft water of 10-15 ppm can be produced by this method
• The equipment occupies less space.
• No impurities are precipitated, hence no danger of sludge formation in the treated water.
• It does not require more time and more skill.
Disadvantages of Zeolite process
• Soft water contains more sodium salts than in lime soda
process
• It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other
ions like HCO 3- and CO 32- in the softened water (then it may
form NaHCO3 and Na2CO3 which releases CO2 when the water
is boiled and causes corrosion)
• It also causes caustic embrittlement when Na2CO3 hydrolyses
to give NaOH
Advantages of Zeolite process (Zeolite)
• Soft water of 10-15 ppm can be produced by this method
• The equipment occupies less space.
• No impurities are precipitated, hence no danger of sludge formation in the treated water.
• It does not require more time and more skill.
How much NaCl is required to regenerate zeolite bed?
3
Hardness = 50×𝑚×𝑉2×10
58.5×𝑉1
V1 = Total vol. of water softened
V2 = total volume of NaCl solution used for regeneration
m = Amount of NaCl present in V2
58.5 = mol. Wt. (also equivalent wt.) of NaCl

A typical problem
A zeolite softener was used to remove the hardness of 10000 litres of hard-water completely. The softener
required 200 litres of NaCl solution containing 150 g/litre of NaCl for regeneration. Calculate the hardness in
ppm.
3
50×𝑚×𝑉2×10
Hardness =
58.5×𝑉1
A typical problem
An exhausted zeolite softener was recovered using 150 lit of 150 gm/L NaCl solution. How much water having
hardness of 500 ppm can be softened using this bed?
50×𝑚×𝑉2×103
Hardness = 58.5×𝑉1
A typical problem
A zeolite softener was used to remove the hardness of 95000 litres of hard-water completely. The softener required 475
litres of NaCl solution containing 18 g/litre of NaCl for regeneration. Calculate the hardness in ppm.
50×𝑚×𝑉2×103
Hardness = 58.5×𝑉1
V1 = Total vol. of water softened
V2 = total volume of NaCl solution used for regeneration
m = Amount of NaCl present in V2
58.5 = mol. Wt. (also equivalent wt.) of NaCl

Lime-Soda process
In this process, all the soluble hardness-causing impurities are converted into insoluble precipitates which
may removed by setting and filtration.
In the lime soda process –

• Calculated amount of lime/Ca(OH)2 and soda/Na2CO3 is added in the hard water.
• The soluble calcium and magnesium salts in water are converted into insoluble compound such as CaCO3
and Mg(OH)2
• They are removed by setting and filtration.
• Coagulants are added (alum, NaAlO2, FeSO4)
Lime-Soda process
Removal of temporary hardness –
Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H2O L

Mg(HCO3)2 + 2 Ca(OH)2 Mg(OH)2 + CaCO3 + H2O 2L
Removal of all calcium based permanent hardness –
CaCl2 + Na2CO3 CaCO3 + NaCl S
CaSO4 + Na2CO3 CaCO3 + Na2SO4 S
Removal of magnesium based permanent hardness –
MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 L+S
MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L+S

Lime-Soda process
Removal of free mineral acids –
2 HCl + Ca(OH)2
CaCl2 + 2H2O L+S
H2SO4 + Ca(OH)2 CaSO4 + 2H2O L+S
Removal of CO2 and H2S –
CO2 + Ca(OH)2 CaCO3 + H2O L
H2 S + Ca(OH) CaS + 2H2O L
Removal of dissolved iron and aluminium –
FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4 L+S
Al2(SO4)3 + 3 Ca(OH)2 2 Al(OH)3 + 3 CaSO4 3L+3S

Lime-Soda process
Now, the 100 parts by mass of CaCO3 are equivalent to:
i. 74 parts of Ca(OH)2 and
ii. 106 parts of Na2CO3
Lime required for softening –

74
= [𝑇𝑒𝑚𝑝. 𝐶𝑎 2+ + 2 × 𝑇𝑒𝑚𝑝. 𝑀𝑔2+ + 𝑃𝑒𝑟𝑚. (𝑀𝑔2+ + 𝐹𝑒 2+ + 3 × 𝐴𝑙3+)]
100
Soda required for softening –

106
= [𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 (𝐶𝑎2+ + 𝑀𝑔2+ + 𝐹𝑒2+ + 3 × 𝐴𝑙3+)]
100
Calculations of the Requirement of Lime and Soda
Step 1. The units in which the impurities are analyzed and expressed are to be noted.
Step 2. Substances which do not contribute towards hardness (KCl, NaCl, SiO2, Na2SO4 etc.) should be
ignored and explicitly stated.
Step 3. A substance causing "hardness should be converted into their respective CaCO3 equivalents.
CaCO3 equivalent of hardness causing impurity

100
= × weight of impurity / chemical equivalent of impurity
2
= multipliction factor × weight of impurity
Step 4. If the impurities are given as Ca(HCO3)2 and Mg(HCO3)2 , they must only be expressed in terms of
CaCO3.
Step 5. The amount expressed as CaCO3 does not require any further conversion.
However, the amount expressed as MgCO3 should be converted into its CaCO3 equivalents by multiplying
with 100/84
Step 6: The amount of lime and soda required are calculated as follows.
74
Lime = {Temp Ca2+ hardness
100
+ (2 × Temp Mg2+ hardness)
+ Perm Mg2+ hardness + CO2
+ HCl + H2SO4+ HCO– 3
+ salts of Fe2+ + 3 × salts of Al3+
– NaAlO2}
106
Soda = {Perm Ca2+ hardness
100
+ Perm Mg2+ hardness
+ salts of Fe2++ 3 × salts of Al3+
+ HCl + H2SO4 + HCO–
3
– NaAlO2}
Step 7. If Ca2+ and Mg2+ is given,

• 1 equivalent of lime and 1 equivalent of soda is required for Mg2+
• 1 equivalent of soda is required for Ca2+.
• The ions Ca2+ and Mg2+ are treated as permanent hardness due to Ca and Mg.
Step 8. If the lime and soda used are impure and if the percentage purity is given, then the actual
requirements of the chemicals should be calculated accordingly.
• Thus, if lime is 90% pure, then the value obtained in step (6) must be multiplied by 100/90 to get actual
lime requirement.
• Similarly, if the soda is 95% pure then the value obtained in step (6) is multiplied by 100/95 to get actual
soda requirement.
Step 9. The value obtained in step (6) is also multiplied by the volume of water which has to be purified.
Thus, the final formula for calculating the amount of lime or soda required is given as
Lime = value obtained from step 6 × volume of water in litre × (100 / % purity)
Soda = value obtained from step 6 × volume of water of in litre × (100 / % purity)
Lime-Soda process
Advantages of lime soda process
• It is very economical.
• If the process is combined with sedimentation/coagulation lesser amounts of coagulants shall be needed.
• In addition to the removal of hardness, the quantities of minerals in the water are reduced.
• Due to alkaline nature of treated water, number of pathogenic bacteria in water is considerably reduced.
Disadvantages of lime soda process

• For efficient and economical softening, careful operation and skilled supervision is required.
• Disposal of large amount of sludge poses a problem.
• This can remove hardness up to 15 ppm which is not good for boilers.
• Cannot be used in high pressure boilers as appreciable number of soluble salts (Na2SO4) might be
present.
• Cannot be used for household purposes as the calculation for required amount of lime and soda is hard.
Lime-Soda process
Intermittent Cold Lime Soda Softener

In this process –
• Calculated quantity of lime and soda are mixed with water
at room temperature
• The precipitates formed are finely divided, so they do not
settle down easily.
• Therefore, small amounts of coagulants (like alum,
aluminum sulphate, sodium aluminates etc.).
Use of sodium aluminate as coagulant also helps the removal

of silica as well as oil if present in water..
NaAlO2 + 2 H2O → NaOH + Al(OH)3
Al2(SO4)3 + 3 Ca(HCO3)2 → 2 Al(OH)3 + 3 CaSO4 + 6 CO2
Lime-Soda process
Continuous Cold Lime Soda Softener Continuous Hot Lime Soda Process
Lime-Soda process
Hot lime soda process
Calculated quantity of lime and soda are mixed with water at 80°C.
Advantages:
• The reaction proceeds faster.
• Softening capacity is increased.
• No coagulant needed as the precipitate and sludge formed settle down rapidly.
• Much of the dissolved gases are driven out of water.
• Viscosity of soften water is lower, so filtration of water becomes easier.
• This process produces water of comparatively low residual hardness 15 to 30 ppm.
Q. Calculate the amount of lime and soda required for 18000 lit of a water sample which on analysis gave
the following data:
Temporary Ca hardness = 25 ppm, Permanent hardness = 20 ppm, Permanent Mg hardness = 15 ppm
Answer:
Lime = 532.8 gm, Soda = 381.6 gm
Lime = 74/100 × (temp + perm Mg) × Vol of water
= 532.8 gm
Soda = 106/100 × permanent × vol of water
381.6 gm
Problem
Q. Calculate the quantity of lime and soda required for softening 50000 litres of water containing the
following salts per litre:
Ca(HCO3)2 = 8.1 mg; Mg(HCO3)2 = 7.5 mg; CaSO4 = 13.6 mg; MgSO4 = 12.0 mg, MgCl2 = 2.0 mg, NaCl = 4.7 mg.
Calculate the quantities of lime and soda required if purity is 90% for both lime and soda.
Answer:
Constituent Amount (mg/lit) CaCO3 equivalent Lime/soda

requirement
Ca(HCO3)2 8.1 100/162 × 8.1 = 5.0 L
Mg(HCO3)2 7.5 100/146 × 7.5 = 5.14 L
CaSO4 13.6 100/136 × 13.6 = 10.0 S
MgSO4 12.0 100/120 × 12 = 10.0 L+S
MgCl2 2.0 100/95 2 = 2.11 L+S
NaCl 4.7 N.A. ×
Problem
Q. Calculate the quantity of lime and soda required for softening 50000 litres of water containing the
following salts per litre:
Ca(HCO3)2 = 8.1 mg; Mg(HCO3)2 = 7.5 mg; CaSO4 = 13.6 mg; MgSO4 = 12.0 mg, MgCl2 = 2.0 mg, NaCl = 4.7 mg.
Calculate the quantities of lime and soda required if purity is 90% for both lime and soda.
Answer:
74
Lime required for softening = 5.0 + 2 × 5.15 + 10 + 2.11 × 50000 = 1.0134 𝑘𝑔
100
100
Lime is 90% pure, so lime required = 1.0134 × = 𝟏. 𝟏𝟐𝟔 𝒌𝒈
90
106
Soda required for softening = 5 + 10 + 2.11 × 50000 = 0.9068 𝑘𝑔
100
100
Soda is 90% pure, so soda required = 0.9068 × = 𝟏. 𝟎𝟎𝟖 𝒌𝒈
90
Q. A water sample upon analysis was found to contain the following in mg/L:
CaSO4 = 0.45, CaCO3 = 2.5, MgCO3 = 0.5, MgSO4 = 0.85, MgCl2 = 0.8; NaCl = 2.8, SiO2 = 2.9 ppm.
Calculate the amount of lime and soda required to soften 25000 lit of water per day for a year if the purity of
lime and soda is 90%.
Q. A water sample upon analysis was found to contain the following in mg/L:
CaSO4 = 0.45, CaCO3 = 2.5, MgCO3 = 0.5, MgSO4 = 0.85, MgCl2 = 0.8; NaCl = 2.8, SiO2 = 2.9 ppm.
Calculate the amount of lime and soda required to soften 25000 lit of water per day for a year if the purity of
lime and soda is 90%.
Q. Calculate the amount of lime required for softening 50,000 litre of hard water containing CaCO3 = 25
ppm, MgCO3 = 144 ppm, CaCl2 = 111 ppm, MgCl2 = 95 ppm; Na2SO4 = 15 ppm, Fe2O3 = 25 ppm.
MW: Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95
Answer:
• CaCO3 → L → 25 ppm
• MgCO3 → L → 144 × 100/84 = 171.43 ppm
• CaCl2 → S → 111 × 100/111 = 100 ppm
• MgCl2 → L+S → 95 × 100/95 = 100 ppm
• Na2SO4 → x
• Fe2O3 → x
• Lime required = 74/100 [(CaCO3) + 2 (MgCO3) + (MgCl2)] × Volume of water
= 17.311 kg
• Soda required?
Problem
Q. Calculate the amount of lime required for softening 50,000 litre of hard water containing CaCO3 = 25
ppm, MgCO3 = 144 ppm, CaCl2 = 111 ppm, MgCl2 = 95 ppm; Na2SO4 = 15 ppm, Fe2O3 = 25 ppm.
MW: Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95
Answer:
• CaCO3 → L → 25 ppm
• MgCO3 → L → 144 × 100/84 = 171.43 ppm
• CaCl2 → S → 111 × 100/111 = 100 ppm
• MgCl2 → L+S → 95 × 100/95 = 100 ppm
• Na2SO4 → x
• Fe2O3 → x
• Lime required = 74/100 [(CaCO3) + 2 (MgCO3) + (MgCl2)] × Volume of water = 17.311 kg
• Soda required?
Problem
Q. Calculate the amount of lime (84% pure) and soda (92% pure) required for softening 20,000 litre of hard
water containing Ca(HCO3)2 = 40.5 ppm; Mg(HCO3)2 = 36.5 mg; CaSO4 = 34 mg; MgSO4 = 30 mg; CaCl2 =
27.75 mg; NaCl = 4.7 mg.
MW: Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; CaCl2 = 111
Ans: Lime = 1.762 kg, Soda = 1.728 kg

Problem
Q. A water sample on analysis gave the following data:
CaSO4 = 0.45 mg/L; MgCO3 = 0.50 mg/L; CaCO3 = 2.50 mg/L; MgSO4 = 0.85 mg/L, MgCl2 = 0.80 mg/L, SiO2 =
2.90 mg/L
Calculate the quantities of lime and soda required for 25000 lit water if purity is 90% for both lime and soda.
Answer:
• Lime = 39.31 kg, Soda = 20.214 kg
• CaSO4 = S; MgCO3 = 2L; CaCO3 = L; MgSO4 = L+S, MgCl2 = L+S, SiO2 = x
• Eq. CaCO3 = weight x 100/eq. weight

Problem
Q. A water sample have the following impurities : Ca2+ = 20ppm; Mg2+ = 18 ppm; HCO3 - = 183 ppm; SO4 2- = 24
ppm. Calculate the amount of lime and soda needed for softening.
Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]
Soda required for softening:
106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or

=
100 H2SO4) - HCO3-]
Practice Problems
Practice Problems
Q. A water sample on analysis gave the following data:
Ca2+ = 30 mg/L; Mg2+ = 24 mg/L; CO2 = 24mg/L; K+ = 10 mg/L
Calculate the quantities of lime (90%) and soda (94%) required to soften one million litres of water sample.
Q. Explain with chemical equation and calculate the amount of lime and soda needed for softening 1,00,000
litrs of water containing following:
HCl = 7.3 mg/L; Al2(SO4)3 = 34.2 mg/L; MgCl2 = 9.5 mg/L; NaCl = 29.25 mg/L
Purity of lime is 90% and that of the soda is 98%.
MW: Ca(HCO3)2=162; Mg(HCO3)2=146; CaSO4=136; MgSO4=120; MgCl2=95; Al2(SO4)3= 114
Internal treatment
In this process, an ion is prohibited to exhibit its original character by complexing or converted into other
more soluble salt by adding appropriate reagent.
An internal treatment is accomplished by adding a proper chemical to water either:

• To precipitate the scale forming impurities in the form of sludge, which can be removed.
• To convert them into compounds, which will stay dissolved in water and thus do not cause any harm.
Important Internal Treatments are –

a) Colloidal treatment
b) Carbonate treatment
c) Phosphate conditioning
d) Calgon conditioning
Internal treatment
a) Colloidal treatment
• This treatment involves addition of conditioning agents such as glue, seaweed extract, agar-agar, tannin
to the boiler water.
• The residual precipitates get surrounded by molecules of the conditioning agents and effectively
maintains non-sticky colloidal state.
• Once colloidal solution become concentrated, the colloids may be easily removed by blow-down
operation.
b) Carbonate treatment
• Addition of sodium carbonate prevents the precipitation of scale forming calcium sulphate.
• By increasing the concentration of carbonate ions, the equilibrium can be shifted to facilitate
precipitation of calcium carbonate (CaCO3).
• The CaCO3 forms loose precipitate which can be easily removed.
Na2CO3 + CaSO4 → CaCO3 + Na2SO4
loose precipitate
Internal treatment
c) Phosphate conditioning
Scale formation can be avoided by adding sodium phosphate which reacts with hardness of water forming
non-adherent and easily removable soft sludge of calcium or magnesium phosphate.
3CaCl2 + 2Na3PO4 → Ca3(PO4)2 + 6NaCl
The choice of salt depends upon the alkalinity of the boiled water because calcium cannot be precipitated
below a pH 9.5.
• Trisodium phosphate (Na3PO4) is most suitable for treatment when alkalinity is low
• Disodium phosphate (Na2HPO4) is used when the water alkalinity is sufficient.
• Monosodium phosphate (NaH2PO4) is used when the alkalinity of boiler water is too high.
Internal treatment
d) Calgon conditioning:
It involves adding calgon - Sodium hexa-meta phosphate (NaPO3)6 to boiler water. It prevents the scale and
sludge formation by forming soluble complex compound with CaSO4.
[Na6(PO3)6] → 2 Na+ + [Na4P6O18]2-
2 CaSO4 + [Na4P6O18]2- → [Ca2P6O18]2+ + 2 Na2SO4

soluble complex ion
Scale and Sludge Formation In Boilers
In boilers, water evaporates continuously, and the concentrations of the dissolved salts increases
progressively.
When concentrations of dissolved salts reach saturation point, they form loose and slimy precipitates, it is
called sludge.
On the other hand, if the precipitate matter form a hard adhering crust/coating on the inner walls of the
boiler, it is called scale.
Disadvantages of sludge formation –
• Sludges are poor conductor of heat, so they tend to waste a portion of heat generated.
• Sludge’s get entrapped in the scale and both get deposited as scales.
• Excessive sludge formation, disturbs the working of the boiler. It settles in the regions of poor water
circulation such as pipe connection etc.
Prevention of sludge formation –

• By using well softened water
• By frequently ‘blow-down operation’, i.e., drawing off a portion of the concentrated water.
Scales
Scales are hard deposit, which stick very firmly to the inner surface of boiler. Scales are very difficult to
remove.
Formation of scales may be due to –
• Decomposition of Ca(HCO3)2
• Deposition of CaSO4
• Hydrolysis of magnesium salts
• Presence of silica
Disadvantages of scale formation
• Wastage of fuel: Scales have a low thermal conductivity, so that rate of heat transfer from boiler to inside
water is greatly decreased
• Lowering of boiler safety: Due to scale formation, over heating of boiler is done, which causes distortion of
boiler tube.
• Decrease in efficiency: Scales may deposit in the valve and condensers of the boiler and choke them partially.
• Danger of explosion: When thick scales crack, the water comes suddenly in contact with over heated iron
plates.
Removal of scales
• With the help of scraper or piece of wood or wire brush.
• By giving thermal shocks, if they are brittle.
• By dissolving them by adding chemicals, (5-10% HCl, EDTA) if they are adherent and hard.
• By frequent blow-down operation, if the scales are loosely adhering.
Prevention of scales formation

1. External Treatment: Includes efficient ‘softening of water’ (i.e., removing hardness-producing
constituents of water)
2. Internal Treatment: Accomplished by adding a proper chemical to the boiler water.
(i) Colloidal conditioning
(ii) Phosphate Conditioning
(iii) Carbonate Conditioning
(iv) Calgon Conditioning
Caustic embrittlement
This is very dangerous form of stress corrosion, occurring in mild steel exposed to alkaline
solution at high temperature and stresses.
The failure is often associated with steam boiler and heat transfer equipment in which
water of high alkalinity attacks the mild steel plates, particularly at the crevices near
rivets.
Boiler water, usually contains a certain portion of sodium carbonate, added for water softening purposes. In
high pressure boilers
𝑁𝑎2𝐶𝑂3 + 𝐻2𝑂 → 2 𝑁𝑎𝑂𝐻 + 𝐶𝑂2
• Sodium hydroxide makes water alkaline in nature.

• Dilute alkaline boiler water flow into the minute hair-cracks and crevices by capillary action.
• Water evaporates and the concentration of caustic soda builds up.
• The concentrated alkali dissolve iron as sodium ferroate (Na2FeO2) in cracks and crevices (where the
metal is stresses and the concentration of alkali is much higher than that in the body of the liquid)
• The sodium ferroate (Na2FeO2) decomposes, a short distances from its point of formation.
3𝑁𝑎2𝐹𝑒𝑂2 + 4𝐻2𝑂 → 6 𝑁𝑎𝑂𝐻 + 𝐹𝑒3𝑂4 + 𝐻2
6𝑁𝑎2𝐹𝑒𝑂2 + 6𝐻2𝑂 + 𝑂2 → 12 𝑁𝑎𝑂𝐻 + 2𝐹𝑒3𝑂4
Corrosion → degradation of a material by chemical means.
(Reverse process of metal extraction)
Metal Ore
Reduction Refining
Pure Metal
Oxidation Corrosion
Corrosion product
Corrosion - Energetics
Metal Ore Pure Metal Corrosion product
Reduction Corrosion
Reaction Coordinate
Corrosion
Corrosion may be considered to be the degradation of a material
by chemical means.
• Although all materials will degrade in some way, the term
corrosion is usually applied to metals, hence metallic corrosion.
• When considering metals, corrosion is essentially the reverse of
the refining process. When metals are extracted from the earth
they are refined into pure metals from the various ores (metal
oxides, hydroxides, carbonates, etc).
• As a result of corrosion, the metal reacts with chemicals in the
environment and progressively returns to the combined form,
rust is a form of iron oxide.
Metal Ore Pure Metal Corrosion product

Reduction Corrosion
Effects of corrosion
Corrosion is a slow process but highly detrimental to metals
• Metallic properties are lost
• Frequent replacement and maintenance
• Reduced Strength
• Life time is reduced
• Wastage of metal
• Contamination
• Especially problematic for hazardous containers
25% of the annual production of iron is wasted because of

corrosion
Theories of corrosion
1. Acid theory:
• The presence of acid is essential.
• Example: rusting of iron.
O2 , CO2 , H2 O Oxidation
Fe Fe HCO3 2 Fe OH CO3 → 2 Fe OH 3
2. Direct chemical attack: This theory explains the so-called

chemical or dry corrosion. Example: direct chemical attack by
dry gases
3. The electrochemical theory: This theory explains the indirect
or wet corrosion. The modern electrochemical theory is based
on Nernst theory.
Acid theory:
• This theory suggests that the presence of acid (such as carbonic
acid) is essential for corrosion.
• This theory is particularly applicable to rusting of iron in the
atmosphere.
• The rusting is due to continued action of oxygen, carbon
dioxide and moisture, converting the metal into soluble ferrous
bicarbonate which is further oxidized to basic ferric carbonate
and finally to hydrated ferric oxide.
1
Fe + O2 + 2 CO2 + H2 O → Fe HCO3 2
2
Fe HCO3 2 + O2 → Fe OH CO3 + CO2 + H2 O
2 Fe OH CO3 + 2 H2 O → 2 Fe OH 3 + 2CO2
Theory of corrosion
Chemical (or) Dry Corrosion
What is it?
The direct chemical attack on the atmospheric content on the
metal surfaces in the absence of moisture
1. Oxidation Corrosion: Direct action of oxygen at high (or) low

temperature on metal surfaces.
2. Corrosion by other Gases: Attack of gases like SO2, CO2, H2S,
Cl2, F2 etc. on metal surfaces.
3. Liquid Metal Corrosion : Attack of inorganic liquid metals on
solid metallic surfaces.
1. Oxidation Corrosion
2 𝑀 → 2 𝑀2+ + 4 𝑒 − → (Loss of electrons = Oxidation)

𝑂2 + 4 𝑒 − → 2 𝑂2− → (Gain of electrons = Reduction)
−−−−−−−−−−−−−−−−−−−−− −
2 𝑀 + 𝑂2 → 2 𝑀2+ + 2 𝑂2−
If the formed metal oxide is stable,

further corrosion of metal is prevented
(Example: Al, Sn, Pb, Cu)

If the formed metal oxide is stable, further corrosion of metal is prevented
(Example: Copper)
If the formed metal oxide is stable, further corrosion of metal is prevented
(Example: Bronze)
If the formed metal oxide is unstable,

corrosion does not occur*
(Example: Ag, Au, Pt) → Nobel metals

Energetics
Metal oxide
Metal
Reaction Coordinate
If the formed metal oxide is volatile,

surface is rapidly exposed, and evaporated
(Example: Mo)
If the formed metal oxide is porous,

surface is rapidly exposed, and evaporated
(Example: Iron, Steel)

Three types of oxides may
form, depending on the
volume ratio between the
metal and the oxide:
a. Magnesium produces
a porous oxide film,
b. Aluminum forms a
protective, adherent,
nonporous oxide
film,
c. Iron forms an oxide
film that spills off the
surface and provides
poor protection.
Pilling-Bedworth rule
The Pilling-Bedworth rule →
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍 𝒐𝒙𝒊𝒅𝒆
𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍
Pilling-Bedworth rule
The Pilling-Bedworth rule →
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍 𝒐𝒙𝒊𝒅𝒆
𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍
Three types of oxides may form, depending on the volume ratio

between the metal and the oxide:
a. Magnesium produces a porous oxide film,
b. Aluminum forms a protective, adherent, nonporous oxide film,
and
c. Iron forms an oxide film that spills off the surface and provides
poor protection.
Pilling-Bedworth Ratio
The Pilling-Bedworth ratio (P-B ratio), in corrosion of metals, is
the ratio of the volume of the elementary cell of a metal oxide to
the volume of the elementary cell of the corresponding metal
(from which the oxide is created).
Volume of the elementary cell of a metal oxide

𝐏 − 𝐁 𝐫𝐚𝐭𝐢𝐨 =
Volume of the elementary cell of the metal
On the basis of the P-B ratio, it can be judged if the metal is likely
to passivate in dry air by creation of a protective oxide layer.
The Pilling-Bedworth ratio (P-B ratio), in corrosion of metals, is
the ratio of the volume of the elementary cell of a metal oxide to
the volume of the elementary cell of the corresponding metal
(from which the oxide is created).
MOxide
VOxide ρOxide MOxide × ρMetal
𝐑 𝐏𝐁 = = =
VMetal M
𝑛 × Metal 𝑛 × MMetal × ρOxide
ρMetal
where,
RPB : is the Pilling-Bedworth ratio,
V : the molar volume
ρ : density,
M : the atomic or molecular mass,
n : number of atoms of metal per one molecule of the oxide
On the basis of measurements, the following connection can be shown:
VOxide MOxide × ρMetal

𝐑 𝐏𝐁 = =
VMetal n × MMetal × ρOxide
𝐑 𝐏𝐁 < 𝟏: the oxide coating layer is too thin, likely broken and
provides no protective effect (for example magnesium)
𝐑 𝐏𝐁 > 𝟏: the oxide coating provides protective effect
However, the exceptions to the above P-B ratio rules are numerous. Many of
the exceptions can be attributed to the mechanism of the oxide growth: the
underlying assumption in the P-B ratio is that oxygen needs to diffuse through
the oxide layer to the metal surface; in reality, it is often the metal ion that
diffuses to the air-oxide interface.
Calculation of Pilling-Bedworth Ratio

𝐑 𝐏𝐁 = =
Oxide Oxide Density Atomic Metal Molecular P-B Ratio

(g/cc) weight of Density Weight of
Metal (g/cc) Oxide
MgO 3.65 24.3 1.74 40.3 0.79
CaO 3.40 40.08 1.55 56.1 0.04
Al2O3 3.70 27.00 2.70 102.0 1.37


𝐑 𝐏𝐁 = =
Oxide Oxide Atomic Metal Molecular P-B Ratio

Density Weight of Density Weight of
(g/cc) Metal (g/cc) Oxide
Cr2O3 5.22 52 7.19 152.0 ?
Na2O 2.27 23 0.97 62.0 ?
NiO 6.67 58.69 8.91 74.7 ?
K2O 2.13 39.09 0.86 94.2 ?


𝐑 𝐏𝐁 = =
Oxide Oxide Atomic Metal Molecular P-B Ratio

Density Weight of Density Weight of
(g/cc) Metal (g/cc) Oxide
Cr2O3 5.22 52 7.19 152.0 2.01
Na2O 2.27 23 0.97 62.0 0.57
NiO 6.67 58.69 8.91 74.7 1.70
K2O 2.13 39.09 0.86 94.2 0.48

2. Corrosion by gases
The gases such as SO2, CO2, H2S, Cl2, F2 etc., when come in direct
contact with metal surface corrosion occurs.
• The extent of corrosion depends on the chemical affinity
between the metal and the gas concerned.
• The prevention of metal corrosion can be known from the
nature of corrosion product.
Whether the layer of corrosion product is protecting or non-

protecting in nature.
• If the formed corrosion product is protecting (or) non porous metal is
prevented. Ex: AgCl layer on metallic silver by the action of Cl2 gas.
• If the formed corrosion product is non protecting (or) porous , the corrosion
of metals occurs non stop. Ex: H2S gas attacks on steel at high temperature
forming FeS , a corrosion product which is porous.
3. Liquid metal corrosion
The chemical action of the flowing liquid metal at high
temperature, on a solid metal or alloy produces liquid metal
corrosion.
There are two reasons for this corrosion –

• Dissolution of the solid metal by liquid metal
• Internal penetration of the liquid metal into the solid phase,

weakening the solid metal.
Example: liquid Na used as a coolant in a nuclear plants, these

causes cadmium corrosion.
Dry or chemical corrosion: Wet or electrochemical corrosion:

• This occurs at dry • This occurs at wet conditions
conditions (electrolytic medium)
• Corrosion is uniform • Corrosion Is not uniform

• It is a slow process • It is a rapid process
• It involves direct chemical • It involves formation of
attack electrochemical cells
• Explained by absorption • Explained by mechanism of
mechanism electrochemical reactions
Electrochemical corrosion
The metal surface undergoes an electrochemical reaction with the
moisture and oxygen in the atmosphere. This theory is known as
electrochemical theory of corrosion.
Mechanism :
• Anodic reaction : Oxidation of metal (corrosion)
• Cathodic reaction : Consumption of electrons
Corrosion always occurs at the anode

Mechanism of wet corrosion
(Oxidation) (Reduction)
2 H+(aq) + 2e- → H2
M(s) → M2+(aq) + 2e- (Acidic medium)
(Dissolution or corrosion ½ O2(g) + H2O (aq) +2 e- → OH-
of metal takes place)
(Neutral medium)
Mechanism of wet corrosion
1. The formation of anodic and cathodic areas or parts in contact

with each other.
2. Presence of a conducting medium.
3. Corrosions of anodic areas only.
4. Formation of corrosion product somewhere between anodic

and cathodic areas.
1) Mechanism of wet corrosion
Wet corrosion takes place by the following two ways based on

the nature of medium:
1) Evolution of H2 (acidic medium)
Anode: Fe (s) → Fe2+ (aq) + 2e-
Cathode: 2 H+ (aq) + 2e- → H2
Displacement of hydrogen ions from the acidic solution by metal ions)

Wet corrosion takes place by the following two ways based on

the nature of medium:
2) Absorption of O2 : Neutral medium
Anode: Fe(s) → Fe2+(aq) + 2e-
Cathode: ½ O2(g) + H2O (aq) +2 e- → 2OH-
Salt speeds up the process
Water
Fe2+ Rust
e-
Iron Dissolves- O2 + 2H2O +4e- → 4OH-
Fe → Fe+2
4Fe2+ + O2 + 4H2O → 2Fe2O3 + 8 H+
Galvanic Corrosion
Galvanic corrosion is an electrochemical process in which

one metal corrodes preferentially to another when both metals
are in electrical contact and immersed in an electrolyte.
Galvanic cell
Galvanic Corrosion

Galvanic Corrosion

Galvanic Corrosion
• Possibility when two dissimilar metals are electrically
connected in an electrolyte.
• Results from a difference in oxidation potentials of metallic
ions between two or more metals. The greater the difference
in oxidation potential, the greater the galvanic corrosion.
• Galvanic coupling is a galvanic cell in which the anode is the
less corrosion resistant metal than the cathode
• The less noble metal will corrode (i.e. will act as the anode) and
the more noble metal will not corrode (acts as cathode).
• Perhaps the best known of all corrosion types is galvanic
corrosion, which occurs at the contact point of two metals or
alloys with different electrode potentials.
Standard electrode potential
Galvanic series
PASSIVE – will not

corrode – act as
cathode. These
elements are least likely
to give up electrons!
The Galvanic series
The galvanic series (or electro-potential series) determines the
nobility of metals and semi-metals.
When two metals are submerged in an electrolyte, while
electrically connected, the less noble (base) will experience
galvanic corrosion.
The rate of corrosion is determined by
• the electrolyte and
• the difference in nobility.
The difference can be measured as a difference in voltage
potential.
Galvanic reaction is the principle upon which batteries are based.

Design for Galvanic Corrosion
Severity of Galvanic corrosion depends on:

• Amount of separation in the galvanic series
• Relative surface areas of the two. Severe corrosion if anode area
(area eaten away) is smaller than the cathode area.
It does NOT depend upon:

• Amount of contact
• Volume
• Mass
Example

corrode – act as
cathode. These
Iron screws and brass

Example

corrode – act as
cathode. These
Iron screw in Mg
Example
Iron screws and brass Iron screw in Mg
Dissimilar metals, the damage occurs at the anode.

Example

corrode – act as
cathode. These
Example
Large Cathode, Small Anode = Big Trouble

Design for Galvanic Corrosion
Prevention:
◼ Material Selection: Do not connect dissimilar
metals! Or if you can’t avoid it:
❑ Try to electrically isolate one from the other (rubber
gasket).
❑ Make the anode large and the cathode small
◼ Bad situation: Steel siding with aluminum fasteners
◼ Better: Aluminum siding with steel fasteners
◼ Eliminate electrolyte
◼ Galvanic of anodic protection
Examples
Steel bolt (less noble) is isolated from copper plates.

Question
An iron rod and a copper rod are immersed in a conducting
solution and two of the electrodes are connected by a wire. The
surface area of iron rod and copper rod are x cm2 and y cm2
respectively. Consider the two cases-
(i) x: y > 1 and
(ii) x: y < 1
• Which one of the metals will be corroded?

• Among the two cases where the corrosion will be more and
why?
3) Concentration cell corrosion
Because of differential aeration, the concentration of O2 is varied
and causes Oxidation of metal .
Examples:
1. Pitting corrosion
2. Water line corrosion
3. Crevice corrosion
3) Concentration cell corrosion
Because of differential aeration, the concentration of O2 is varied
and causes Oxidation of metal .
3.a) Water line corrosion
When water is stored in a metallic tank, it is observed that the

metal below the waterline gets corroded.
• The water below the waterline is poorly oxygenated and acts as
an anode.
• The metal above the waterline is highly oxygenated and acts as
a cathode.
General facts about differential aeration corrosion
• Corrosion may be accelerated in apparently inaccessible places,
because the oxygen deficient areas serve as anode, therefore,
cracks serve as foci for corrosion.
• Corrosion is accelerated under accumulation of dirt sand, scale
and other contamination. This is because accumulation of rust
and scale restricts the access of oxygen and establish an anode
to promote greater accumulation.
• Metal exposed to aqueous media under blocks of wood or
piece of glass, which screen that portion of metal from oxygen.
Example
Anode: Fe(s) → Fe2+(aq) + 2e-
Cathode: ½ O2(g) + H2O (aq) +2 e- → 2OH-

3.b) Pitting corrosion
Pitting corrosion, is a form of extremely localized corrosion that

leads to the creation of small holes in the metal.
3.b) Pitting corrosion
Pitting Corrosion is an extremely localized corrosion mechanism

that causes destructive pits.
3.c) Crevice corrosion
• Here, corrosion take place in crevices because solutions
retained at this place and takes longer time to dry out.
• When this occurs, the attack is more severe at crevices.
• Crevices are formed because of the metal contact with another
piece of the same or other metal or with a nonmetallic
material.
• Corrosion in crevice is due to deficiency of O2, acidity changes,.
Measures to Reduce Pitting and Crevice Corrosion
• Fully understand the environment.
• Control the environment to low chloride content and low
temperature if possible.
• Use alloys sufficiently high in chromium, molybdenum and/or
nitrogen to ensure resistance.
• Prepare surfaces to best possible finish. Mirror-finish resists
pitting best.
• Remove all contaminants, especially free-iron, by passivation.
• Design and fabricate to avoid crevices.
• Design and fabricate to avoid trapped and pooled liquids.
• Weld with correct consumables and practices and inspect to
check for inadvertent crevices.
3.d) Stress corrosion
Stress corrosion is combined effects of static tensile stress and the
corrosive environments on a metal.
It is characterized by the highly localized corrosion. For stress

corrosion to occurs:
1. Presence of tensile stress
2. A specific corrosive environments
For e.g. caustic alkali and strong nitrate solution for mild steel,
traces of ammonia for brass, acids chloride solution for stainless
steel
Stress corrosion
Stress corrosion is combined effects of static tensile stress and the
corrosive environments on a metal.
Tensile stress is caused by:

• Deformation during fabrication
• Unequal rate of cooling from high temp.
• Internal stress rearrangement involving volume changes
• Stress induced by rivets, bolts and shrink fits.
• Eliminating high stress areas prevent this type of corrosion.
Stressed corrosion and cracking
Stressed corrosion and cracking
This is very dangerous form of stress corrosion, occurring in mild
steel exposed to alkaline solution at high temperature and
stresses.
The failure is often associated with steam boiler and heat transfer
equipment in which water of high alkalinity attacks the mild steel
plates, particularly at the crevices near rivets.
Boiler water, usually contains a certain portion of sodium
carbonate, added for water softening purposes. In high pressure
boilers
𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂 → 2 𝑁𝑎𝑂𝐻 + 𝐶𝑂2
• Sodium hydroxide makes water alkaline in nature.

• Dilute alkaline boiler water flow into the minute hair-cracks and crevices by
capillary action.
• Water evaporates and the concentration of caustic soda builds up.
• The concentrated alkali dissolve iron as sodium ferroate (Na2FeO2) in cracks
and crevices (where the metal is stresses and the concentration of alkali is
much higher than that in the body of the liquid)
• The sodium ferroate (Na2FeO2) decomposes, a short distances from its point
of formation.
3𝑁𝑎2 𝐹𝑒𝑂2 + 4𝐻2 𝑂 → 6 𝑁𝑎𝑂𝐻 + 𝐹𝑒3 𝑂4 + 𝐻2
6𝑁𝑎2 𝐹𝑒𝑂2 + 6𝐻2 𝑂 + 𝑂2 → 12 𝑁𝑎𝑂𝐻 + 2𝐹𝑒3 𝑂4
Design for Stress Corrosion Cracking
• Material selection for a given environment.
• Reduce applied or residual stress – Stress relieve to eliminate
residual stress (i.e. stress relieve after heat treat).
• Introduce residual compressive stress in the service.
• Use corrosion alloy inhibitors.
• Apply protective coatings.
Factors affecting the rate of corrosion
1. Nature of metal
2. Nature of the corroding environment
3. Solution pH
4. Oxidizing agent
5. Temperature
6. Velocity
7. Surface films
8. Other factors
1. Nature of the metal
• Position in the Galvanic series

• Relative areas of the cathodic and anodic parts
• Purity of metal (tiny electrochemical cells)
• Physical state of the metal (grain size, crystal faces)
• Nature of the surface film
• Passive character of the metal
• Volatility of the corrosion product
• Solubility of the corrosion product
2. Nature of the corroding environment
• Temperature
• Humidity of air
• Presence of impurities in atmosphere
• Nature of ions present in environment
• Conductance of corroding medium
• Amount of oxygen in atmosphere
• Velocity of ions which flow in the medium
• pH value of the medium
• Suspended impurities
3. Solution pH
• Metals such as Fe dissolve rapidly in acidic solution. In the

middle pH range the concentration of H+ ions is low. Hence,
the corrosion rate is controlled by the rate of transport of
oxygen.
• Certain amphoteric metals dissolve rapidly in either acidic or

basic solution. e.g. Al and Zn.
• Noble metals are not affected by pH e.g. Au and Pt.
• H+ ions capture electrons and promote anodic corrosion.

4. Oxidizing agents
• Oxidizing agents accelerate the corrosion of one class of

materials, whereas retard another class.
• Oxidizing agent retard corrosion due to formation of surface
oxide films, which makes the surface more resistant to
chemical attack.
• Thus a balance between the power of oxidizing agent to
preserve the protective layer and their tendency to destroy the
protective film determine the corrosion of metal.
5. Temperature
• Rise in temp increase rate of corrosion.
• Increase in temp reduce the solubility of oxygen or air. The
released oxygen enhances the corrosion.
• Increase in temp induces phase change, which enhance the
rate of corrosion.
6. Velocity
• High velocity of corrosive medium increases corrosion.
• Corrosion products are formed rapidly, because chemicals are
brought to the surface at a high rate.
• The accumulation of insoluble film on the metallic surface is
prevented. So corrosion resistance of these films decreases.
• The corrosion products are easily stifled and carried away,
thereby exposing the new surfaces for corrosion.
7. Surface Films
• The oxide films are formed on the surface of S.S. these films
absorb moisture, which delay time of drying and hence
increases the extent of corrosion.
• Insoluble slats such as carbonates and sulphates may be
precipitated from hot solution on the metal surfaces. These
protects the metal surfaces.
• If the film is porous (e.g. ZnO) corrosion continues. Nonporous
films (CrO on iron) prevents further corrosion.
• Oil and grease films may occur on the surface either
intentionally or naturally. These films protect surface from
direct contact with corrosive substance. e.g. metals submerged
in sewage .
Corrosion control methods
• Selection of metals
• Proper design
• Use pure metal
• Modifying the environment
• Sacrificial anodic protection
• Corrosion inhibitors
• Surface coatings (Paints, Electroplating, etc.)
1. Proper design
• Minimal contact with medium
• Prevention from moisture
• Adequate ventilation and drainage
• Welding
• Avoid cervices between adjacent parts
• Bend should be smooth
• Bimetallic contacts should be avoided
• Paint cathodic portion
• Prevent uneven stress
1. Proper design
1. Proper design
2. Modifying the environment
The corrosive nature of the environment can be reduced either
1. By the removal of harmful constituents
2. By the addition of specific substances which neutralize the effects of
corrosive constituents of the environments
Deactivation involves the addition of chemicals, capable of
combining with the oxygen in aqueous solution by using
• Sodium sulphite
𝑁𝑎2 𝑆𝑂3 + 𝑂2 → 2𝑁𝑎2 𝑆𝑂4
• Hydrazine hydrate
𝑁2 𝐻4 + 𝑂2 → 𝑁2 + 2𝐻2 𝑂
Also,
• Dehumidification: Silica gel, Alumina
• Alkaline neutralization: NH3, NaOH
3. Cathodic protection
The method of protection given to a metal by forcibly making it to
behave like a cathode
Two methods –
1. Sacrificial anodic protection
2. Impressed current cathodic protection
The method of protection given to a metal by forcibly making it to
behave like a cathode
1. Sacrificial anodic protection:

In this method of protection , the metallic structure to be
protected called “base metal” is connected to more anodic
metal through a wire.
2. Impressed current cathodic protection:
In this method an impressed current is applied in the
opposite direction to nullify the corrosion current, thus
the anodic corroding metal becomes cathodic and
protected from corrosion.
Cathodic protection of a buried steel pipeline:

(a) A sacrificial magnesium anode assures that the galvanic cell makes the
pipeline the cathode.
(b) An impressed voltage between a scrap iron auxiliary anode and the
pipeline assures that the pipeline is the cathode.
Examples: Mg sacrificial anode of an iron storage tank
Anodic protection (AP) is a technique to control the corrosion of a

metal surface by making it the anode of an electrochemical
cell and controlling the electrode potential in a zone where the
metal is passive.
Examples: Zinc is attached to the steel hull of the vessel
Examples:
Corrosion inhibitors
A substance which when added in small quantities to the
aqueous corrosive environment, effectively decrease the
corrosion of a metal.
Anodic inhibitors:
These inhibitors avoid the corrosion reaction occurring at the
anode, by forming the sparingly soluble compounds. They are
adsorbed on the metal surface , forming a protective film or
barrier, thereby reducing the corrosion rate
Ex: Chromates , Phosphates , Tungstates
Corrosion inhibitors
Cathodic inhibitors:
In acidic medium corrosion may reduced by:
2𝐻 + 𝑎𝑞 + 2𝑒 − → 𝐻2 (𝑔)
1. Slowing down the diffusion of H+ ions by adding organic inhibitors like
amines, mercaptans, heterocyclic nitrogen compounds.
2. By increasing the over voltage of hydrogen evolution by adding inhibitors
like Antimony and Arsenic oxides
In neutral medium corrosion may reduced by :
1
𝑂2 𝑔 + 𝐻2 𝑂 𝑎𝑞 + 2𝑒 − → 2𝑂𝐻−
2
1. Eliminating oxygen from the corrosion medium by the addition of Na2SO3,
Na2S ;
Electroplating
Electroplating is a process of depositing a thin layer of a fine and
superior metal (like Cr, Zn, Ni, Au etc.) over the article of a baser
and cheaper metal (like iron), with the help of electric current.
Popular methods:
• Electroplating with Ni
• Electroplating with Cu
**Role of pH in electroplating
Electroplating – Steps:
• Before electroplating the metal surface is cleaned thoroughly.
Firstly, an alkaline solution is used to remove grease and then it
is treated with acid to remove any oxide layer. It is then
washed with water.
• The article to be electroplated is made cathode since metallic
ions are positive and thus get deposited on the cathode.
• The anode is made of pure metal, which is to be coated on the
article.
• The electrolyte is the salt of the metal to be coated on the
article.
• A direct (D.C.) current is passed through the electrolyte. The
anode dissolves, depositing the metal ions from the solution on
the article in the form of a metallic coating.
Electroplating with Ni:
• Electrolyte - Aqueous solution of nickel sulphate
• Cathode - Article to be electroplated (nail)
• Anode - Block of nickel metal.
• Dissociation of nickel sulphate: 𝑁𝑖𝑆𝑂4 → 𝑁𝑖 2+ + 𝑆𝑂42−
Electroplating with Ni:
Electroplating with Cu:
Metals Coatings
• It is possible to coat metals that are susceptible to destructive
corrosion with metals that will protect them from further
corrosion.
• Probably the best known coated material is galvanised steel,
which is steel coated with zinc.
• Zinc is a good choice for two reasons: it forms a passive layer
that prevents further corrosion and it is anodic when compared
to steel, so in the event of the underlying steel becoming
exposed the zinc will still corrode to protect the steel.
Metals Coatings
Electrode potential
The potential difference developed when an electrode of an
element is placed in a solution containing ions of that element.
The potential difference between an anode and a cathode can be

measured with a voltage measuring device. The absolute potential
of the anode and cathode cannot be measured directly. Defining a
standard electrode, all other potential measurements can be
made against this standard electrode. If the standard electrode
potential is set to zero, the potential difference measured can be
considered as the absolute potential.

Polymers: This Name Hints at How Polymers Are Made

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Polymers: This Name Hints at How Polymers Are Made

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Polymers

This name hints at how polymers are made.

(Poly) Many + (meros) Parts

Polymers are the macromolecules (giant molecules of higher masses) built-up

Polyvinyl chloride (PVC)

• Why do different polymers have different properties?

CH2 CHCl CH2CH2

Ethylene is bifunctional Phenol is trifunctional

• If the monomer is bifunctional,

According to the amount of repeating units

Part of the polymer molecule can be drawn:

A better way is to show a shorthand formula:

The ‘n’ means that the polymer contains a very

2. Condensation polymer: Obtained by condensation of monomers, followed by elimination of simple

Vinyl chloride Polyvinyl chloride (PVC)

Addition (or chain growth) polymerization reactions:

Condensation/Step growth polymerization Addition/Chain growth polymerization

• Factors affecting Tg→

• Importance – whether the polymer can be used as plastic or rubber

Tg of nylon 6,6 (Tg = 50 0C) is higher than PE (Tg = -110 0C)

➢ The Tg of a polymer is influenced by its molecular weight

PE (low Mw) -110 0C

Random A and B randomly positioned along chain

Alternating A and B alternate in polymer chain

Block Large blocks of A units alternate with large blocks of

( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n

( CH CH2 CH2 CH CH CH2 )n

2. Branched chain polymer are mainly liner in nature, but

3. Three-dimensional network polymers contain monomers

1. Isotactic polymer: If the arrangement of all

2. Syndiotactic polymer: if the arrangements of

3. Atactic polymer: if the arrangements of

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

a) Initiation step is considered to involve two reactions:

1. Free radical polymerization mechanism

a) Initiation step is considered to involve two reactions:

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

1. Free radical polymerization mechanism

In chain transfer, hydrogen is abstracted from –

A dead polymer and a radical is formed

1. Free radical polymerization mechanism

• Like all chain-growth polymerizations, it takes place in three steps:

• Like all chain-growth polymerizations, it takes place in three steps:

• Like all chain-growth polymerizations, it takes place in three steps:

CH2 (CH2-CH2)n C2H5

H2C CH (CH2-CH2)n C2H5

Number Average Molecular Weight

Number Average Molecular Weight

Example: If a polymer has population as:

Weight Average Molecular Weight:

• It is determined by the light scattering methods, ultra-centrifugal techniques.

Weight Average Molecular Weight:

Example: If a polymer has population as: Then,

Number Average Molecular Weight Weight Average Molecular Weight:

Number Average Molecular Weight Weight Average Molecular Weight:

PDI gives an idea about the homogeneity of the polymer

(10×50002 )+(25×250002 )+(20×150002 )+(5×20002 )

50 × 10000 + 35 × 12000 + (15 × 14000)