SWARNANDHRA

College of Engineering & Technology

(Autonomous)
Seetharamapuram, NARSAPUR, W.G. Dt., 534 280.
DEPARTMENT OF BASIC SCIENCE & HUMANITIES
Sub: Engineering Chemistry Year/Sem: 2022-23

UNIT I: WATER TECHNOLOGY

Hardness of water-types of hardness-disadvantages of hard water-determination of hardness by

EDTA complexometric method. Portable water and its specifications-steps involved in purification
of water-chlorination, break point of chlorination. Boiler troubles: Scale and sludge-priming and
foaming-boiler corrosion-caustic embrittlement.
Industrial Water Treatment: Softening methods: zeolite process-ion exchange process.
Brackish water treatment (desalination methods): Reverse osmosis - electro dialysis.

Q.1: Define and classify the hardness of water?

Hardness of water: Hardness is the property of water which does not give good lather with
soap but forms an insoluble precipitate like white scum.
 This property of water is due to the presence of bicarbonates, chlorides and sulphates of
calcium, magnesium salts.
 i.e., CaCl2, CaSO4, MgCl2, MgSO4, Ca(HCO3)2 and Mg(HCO3)2.
 These all above salts completely dissolved in water and we cannot remove by filtration.
Classification of Hardness of Water:
Hardness of water can be classified into two categories.
A. Temporary hardness (or) Carbonate hardness.
B. Permanent hardness (or) Non-Carbonate hardness.

A. Temporary (or) Carbonate hardness:

 This is caused by the presence of dissolved bicarbonates of calcium and magnesium salts.
{Ca(HCO3)2 and Mg(HCO3)2}.
 Temporary hardness can be removed by boiling of water.
 During boiling, the soluble bicarbonates are converted into insoluble precipitates of
carbonates and hydroxides, which can be removed by filtration.
Ca(HCO3)2 CaCO3 + CO2 + H2O
Mg(HCO3)2 Mg(OH)2 + 2 CO2
(Soluble in water) (Insoluble in water)

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 B. Permanent (or) Non-Carbonate hardness:
 Permanent hardness is due to the presence of dissolved chlorides and sulphates of
calcium and magnesium salts. (CaCl2, CaSO4, MgCl2, MgSO4).
 Unlike temporary hardness, permanent hardness is not destroyed on boiling.
 It can be only removed by chemical process such as lime soda and zeolite process.
Total Hardness of Water = Carbonate Hardness + Non Carbonate Hardness
(or) Temporary Hardness + Permanent Hardness
Q.2: Why the hard water doesn’t produce much lather with soap? (2M)
Sodium Sterate (C17H35COONa - Soap) interact with pure water and produces steric acid which
is responsible for lather. The Ca and Mg salts presents in the hard water interacts with soap and
produces Ca/Mg sterates which is cause for a white scum instead of good lather.

Q.3: What is the general expression and units of the Hardness? (2M)
Expression of Hardness: Hardness of water is expressed in terms of number of parts of CaCO3
equivalent. It’s because of…
CaCO3 equivalent = Weight of hardness producing salt x Molecular weight of CaCO3 (100)
Molecular weight of the salt
OR

Units of Hardness:
A. Parts per million (ppm):
 It is the number of parts of calcium carbonate equivalent hardness per million (106) parts
of water.
 1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.
B. Milligram per Litre (Mg/L):
 It is the number of milligram of CaCO3 equivalent hardness present per litre of water.
 1 mg/litre = 1 mg of CaCO3 equivalent hardness in 1 litre of water
1 mg / litre =1 ppm.

Q.4: Summarise the disadvantages of hard water? (2M)

 Hard water cannot be used for drinking and cooking purpose.

 It cannot be used for bathing and washing purposes as it does not give lather with soap.
 Hard water cannot be used in laboratories as it gives unwanted chemical reactions.
 Hard water cannot be used in boilers in steam rising.
 It cannot be used in sugar, paper, textile and leather industries.

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 Q.5: Describe the principle of EDTA method to determine the hardness of Water? (2M)
Explain the EDTA complex-metric method to determine the hardness of given water
sample? (5)
Estimation of Hardness of Water by EDTA Method:
 The hardness of water can be estimated by EDTA method.
 This is a reliable method because of its greater accuracy.
 In this method hardness is estimated by forming complexes.
Molecular structure of EDTA (Ethylene diamine tetra acetic acid)

HOOC-CH2 CH2-COOH
N—CH2 –CH2—N

HOOC-CH2 CH2-COOH

Principle:
 EDTA has ability to form complexes with divalent ions.
 Divalent ions such as Mg+2 and Ca+2 are responsible for hardness in water
 If we measure the how much EDTA consumed to titrate hard water, by that we can estimate
hardness of water.
Theory:

 EDTA forms complex [M-EDTA] with calcium and magnesium ions present in water
 The indicator used in this titration is Eriochrome Black-T (EBT) which also form unstable
complex [M-EBT] with Ca+2 and Mg+2 at pH value about 8-10.
 In order to maintain the pH 8-10, Ammonia-buffer solution is added.
 Generally, EBT has blue colour before formation of a complex with metal ions and its turns to
wine red after formation of the [M-EBT] unstable complex.

 Now the solution contains large number of free metal ions along with few [M-EBT]
complexes.
 As EDTA is added, all free M2+ ions present in hard water sample are first complexes, as it
forms stable complex.

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  When an extra drop of EDTA is added, after all the free M2+ ions have been complexes, EDTA
takes up M2+ ions from the weak M-EBT complex to form stable M-EDTA complex,
simultaneously liberating indicator in the free form.

 The colour change from wine red to blue indicates the end point of the titration.
Determination of Total hardness:
20ml of sample hard water (V2) is pipette out into a conical flask and titrated against EDTA
(M1) taken in burette by adding the buffer and the indicator to get the end point (wine red to
blue). Let the volume of EDTA consumed be V1 ml.

M1V1 =M2V2
V1 = Volume of EDTA consumed in ml V2 =Volume of hard water sample (20 ml)
M1 = Concentration of EDTA M2= Concentration of hardness causing salts

M2 = M1V1
V2
The CaCO3 equivalent harness in ppm = M1V1 x 100 x 1000
V2

Potable Water
Q.6: What is portable water? And give any five specifications of portable water? (2M)
Definition: The water free from contaminants or water that safe for human consumption is
called potable water” or the water which is fit for drinking is called potable water. It is also
called as Municipal Water.
The common specification or standards recommended for potable water are as follows:

 It should be clear, smell-less and have good taste.

 It should be cool.
 Turbidity of water should be less than 10 ppm.
 pH of water should be between 7-8.
 It should be neither too hard nor too soft. The recommended hardness is about
200 mg/L as CaCO3 equivalent.
 It should not contain any harmful dissolved gases like CO2 and H2S
 It should not contain any toxic dissolved solids from led and arsenic.
Domestic water (portable) treatment:

Q.7: Describe the disinfection and sterilization process of portable water? (6M)

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 The filtered water after screening, aeration, sedimentation and coagulation still contains
small amounts of pathogenic (disease producing) bacteria. In order to use this water for
drinking purpose, all the pathogenic bacteria and other micro-organisms present in it must be
killed.
Sterilization and Disinfection:
 Disinfection and sterilization are both decontamination processes.
 Removing or killing of all harmful microorganisms from water sample is called
sterilization and disinfection.
 Some of the important methods of sterilization are as follows:
a) Boiling b) By using ozone c) By using ultraviolet radiations d) by Chlorination
a) Boiling:
The harmful disease producing bacteria can be killed by boiling water for 15-20 minutes.
Boiling is a simple sterilization method but has the following limitations:
 The method is costly for the sterilization of large quantity of water.
 The process does not protect water for long time and it cannot stop future infection.
b) By using ozone:
 Ozone is a powerful disinfectant and is readily absorbed by water.
 Ozone is highly unstable and breaks down to give nascent oxygen.
 The nascent oxygen is powerful oxidizing agent and kills the bacteria.
O3 O2 + [O]
Disadvantages of this process are:
 This process is costly and cannot be used in large scale.
 Ozone is unstable and cannot be stored for long time.

c) By using ultra violet (UV) rays:

 Ultra violet ray sterilization of water can be done for smaller quantity of water.
 In this process UV light from mercury lamp is focused on flowing water.
 The UV radiation effectively destroys the bacteria but it is found to be a costlier process
when applied to larger quantities of water.
 Mostly used for sterilize the swimming pool water.
d) By chlorination:
Chlorine is the most commonly used sterilizing agent in water treatment. It is capable of killing
B.Coli and other bacteria. The process of adding chlorine to water is known as chlorination.
Chlorination can be done by the following methods:

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 i) By adding chlorine gas:
 When chlorine gas added directly as a gas, it liberates the Hypochlorous acid.
 Chlorine and Hypochlorous acid are strong oxidizing agents and they kill pathogens such
as bacteria.
 Disadvantage of this process is Cl2 produce pungent smell to water.
Cl2 + H2O ⇌ HOCl + HCl
Hypochlorous acid

ii) As bleaching powder:

Bleaching powder contains 30% available chlorine. It reacts with water to produce
Hypochlorous acid which is a powerful disinfectant due to its oxidizing property.
CaOCl2 + H2O Ca(OH)2 + Cl2
(Bleaching powder)

Cl2 + H2O HCl + HOCl

Hypochlorous acid

One kg of bleaching powder is sufficient to sterilize one million litres of water. The use of
bleaching powder as a disinfectant has the following limitations:
a) It is unstable during storage.
b) It introduces calcium in water and thus the water becomes harder.
iii) As Chloramine:
The use of excess chlorine gas or bleaching powder as disinfectants often produces disagreeable
odour and unpleasant taste in water.
This can be avoided by using chloramines.
Chloramines usage is the best method for chlorination.
NH2Cl + H2O HOCl + NH3
Since chloramines decompose slowly to give HOCl, it is particularly useful when the water has
to be stored.

Q.8: Explain break point of chlorination? (2M or 5M)

Definition:
 The Breakpoint is the point at which the chlorine demand has been totally satisfied.
 It reveals the amount of the chlorine required to react with all reducing agents, organic
compounds, ammonia and pathogenic bacteria in the water.
 It also indicates required amount of chlorine to further protection of stored water.

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 Fig. Break point chlorination curve
 Between Points 1&2:
All the chlorine reacts with reducing compounds like H2S & organic matter present in water
until they are destroyed, there is no chlorine residual.
 Between Points 2&3:
Chorine reacts with amino acids, urea and ammonia which come from proteins or from urine,
which is naturally found in pool water.
 Between Points 3&4:
Most of the chloramines are themselves got destroyed until there is nothing left to react and
chlorine residual decreases.
 After point 4:
The water reaches Breakpoint; Shown at point 4 in the above diagram, and at this point
Chlorine begins to appear as “Free available Chlorine”.

BOILER FEED WATER

Q.9: What is boiler feed water and their disadvantages?
Boiler Feed Water:
The water fed into the boiler for the production of steam is called boiler feed water.
Disadvantages of using hard water in boilers:
If the boiler feed water contains impurities (or) if the hard water obtained from natural sources as
fed directly to the boilers, the following troubles may arise
A. Scale and Sludge formation B. Priming and foaming (Carry over)
C. Boiler corrosion D. Caustic embrittlement

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 A. Scale and Sludge Formation in Boilers:
Sludge formation:
1. Sludge is a soft, loose and slimy precipitate forms inside the boiler during steam generation.
2. The sludge is due to MgCO3, MgCl2, MgSO4, CaCl2 etc.
3. Sludges are generally formed at cooler portions of the boiler.
4. Sludges can be easily scrapped off with a wire brush.
Disadvantages of Sludge Formation:
1. Sludges are poor conductors of heat.
2. It decreases the efficiency of boiler.
Prevention of sludge:
Sludge formation in boilers can be
prevented
 By using well softened water.
 By frequent blow down operation.
It can be easily scrapped off with a wire brush. Figure: (a) Sludge Formation in boilers (b) Scale
Formation in boilers
Scale Formation:
1. Scale is a hard, adherent precipitation forms on the inner walls of the boiler during steam
generation.
Scale Formation Reactions:
Scale is mainly produced due to presence of Ca (HCO3)2, CaSO4 and Silica.
Disadvantages of Scale Formation
 Scale has poor thermal conductivity leads to wastage of fuel, lowering boiler safety.
 Wastage of fuel depends on the thickness.
 Scale is a hard adhering precipitation and its leads to boiler failure.
Prevention methods:
Thermal socking and internal softening methods.

B. Priming and Foaming (Carry Over Process):

Carry over process:
 Steam sometimes may be associated with small droplets of water or bubbles and it is
called carry over process.
 This occurs mainly due to Priming and Foaming.

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 Priming: If boiler stream carry the water droplets along with it, is called priming.
Priming may be caused by
i) High steam velocity. ii) Large amount of dissolved salts.
iii) Very high water level in the boiler. iv) Improper boiler design.
v) Sudden boiling of water.
Prevention:
Priming can be controlled by
i) Controlling the velocity of steam. ii) Keeping the water level lower.
iii) Good boiler design.
Foaming: The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried along with steam leading to excessive priming.
Causes:
Foaming may be caused by presence of oil, grease in water and finely divided sludge particles.
Foaming can be prevented by
i) Adding coagulants like sodium aluminate, etc.,
ii) Adding anti-foaming agents.

C. Boiler Corrosion:
The decay of boiler material by its environment is termed as boiler corrosion.
Corrosion in boilers is due to the presence of
i) Dissolved oxygen ii) Dissolved carbon dioxide iii) Dissolved salts
i) Dissolved Oxygen:
The presence of dissolved oxygen in water is the main cause of boiler corrosion.
2Fe + O2+ 2H2O 2Fe(OH)2
4Fe(OH)2 +O2 2 {Fe2O3. 2H2O}
Removal of Dissolved Oxygen
Dissolved oxygen can be removed by chemical (or) mechanical methods.
a) Chemical method
Sodium sulphite, hydrazine is some of the chemicals used for removing oxygen.
2Na2SO3 + O2 2Na2SO4
Sodium sulphite Sodium sulphate

N2H4 + O2 N2 + 2 H2 O
Hydrazine

b) Mechanical method
Dissolved oxygen and CO2 can also be removed from water by mechanical de-aeration.

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 At high temperature and low pressure, gas escapes from the water, so applying the high
temperature and low pressure mechanical Deaeration removes DO and Dissolved CO2.

ii) Dissolved Carbon dioxide

 CO2 will generate due to presence of temporary hardness (Ca(HCO3)2, Mg(HCO3)2)
causing salts in the boiler water.
 First CO2 reacts with water and produces carbonic acid which interacts with Fe lads to
corrosion
H2CO3 + Fe FeCO3 + H2
Removal of dissolved carbon dioxide
a) Carbon dioxide may be removed by adding calculated amount of NH4OH into water.
2NH4OH + CO2 (NH4)2CO3 + H2O
b) Carbon dioxide along with oxygen in water can be removed by mechanical de-aeration.
iii) Dissolved salts
If boiler water contains permanent hardness causing salts, they liberate acids in water.
MgCl2 +2H2O Mg(OH)2 + 2HCl
The liberated acid reacts with iron material of the boiler in a chain-like reaction producing HCl
again and again. Fe + 2HCl FeCl2 + H2
Corrosion by acids can be avoided by the addition of bases to the boiler water.
HCl + NaOH NaCl + H2O
D. Caustic Embrittlement:
 Caustic embrittlement is a type of boiler corrosion.
 It caused by using highly alkaline water in the boiler.
 It leads to the Inter crystalline cracking of boiler metal.
In high-pressure boilers, Na2CO3 decomposes to give sodium hydroxide and carbon dioxide, and
this makes the boiler-water “caustic”.
Na2CO3 + H2O 2NaOH + CO2
This NaOH flows into the minute hair cracking usually present on the boiler material by
capillary action and dissolves the surrounding area of iron as sodium ferroate.
Fe + 2NaOH Na2FeO2 + H2
Sodium Ferroate

Prevention:1. Replace the Na2CO3 by sodium sulphate for softening methods.

2. Adding tannin, lignin to the boiler water which blocks the hair cracks.
3. Adjusting the pH of the feed water between 8 and 9.

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 SOFTENING METHODS

Q.10: What is meant by softening water?

The process whereby we remove or reduce the hardness of water irrespective of whether it is
temporary or permanent is called as softening of water.
Q.11: Explain the Zeolite process to softening water?
Zeolites are naturally occurring hydrated sodium aluminium silicate.
 The synthetic form of zeolite is known as Permutit.
 Zeolite can be represent by Na2O.Al2O3.xSiO2.yH2O where x = 2 - 10 and y = 2 - 6.
 Example for natural available zeolite is Natrolite where x=4 and y=2
 Zeolites are simply represents as Na2Ze
Principle:The sodium ions are loosely held in Na2Ze and they are capable to replace by
Ca2+ and Mg2+ ions present in the hard water.
Process:
 In this process, the hard water is passed
through a bed of sodium zeolite (Na2Ze).
 The hardness causing ions (Ca2+, Mg2+) in
hard water is replaced by loosely held
sodium ions in zeolite bed.
 The outgoing soft water contains only
sodium ions.

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgCl2 MgZe + 2NaCl
Regeneration:
 After the softening process, the zeolite is completely converted into calcium and
magnesium zeolites and it gets exhausted.
 At this stage the hard water supply is stopped and the exhausted bed is regenerated by
treating with concentrated 10% brine (NaCl) solution.

CaZe + 2NaCl Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze + MgCl2
Exhausted Regenerated
Zeolite Zeolite

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 Advantages of the process:
 This process removes hardness upto
10ppm.  The equipment used is compact
 Operational cost is less  No sludge formation.
Limitations of the process
 The process exchanges only Ca2+ and Mg2+ ions with Na+ ions.
 This process increases the sodium salts in the water.

Q.12: Explain the deionization of water by ion exchange method?

Demineralization (or) Deionization Process Or Ion exchange process:
Principle:
 In this method ion exchange resins are used as softening material.
 In this process cations (Ca2+, Mg2+) and anions (Cl-, SO42-) are removed respectively by
cation exchange resins and anion exchange resins.
 Ion exchange resins are insoluble, cross linked, long chain organic polymers with a micro
porous structure.
 The functional groups attached to the chains are responsible for the ion-exchanging
properties.
-
Cation exchange resins (R H+)

Resin containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their H+
ions with cations of hard water.
Example: (i) Sulphonated coals. (ii) Sulphonated polystyrene.
-
R-SO3H ; R-COOH ≡ R H+ ≡ RH
+ -
Anion exchange resins (R OH )

Resins containing basic functional groups (-NH2, -OH) are capable of exchanging their OH- ions
with the anions of hard water.
Example: (i) Cross-linked quaternary ammonium salts. (ii) Urea-formaldehyde resin
+
R-NR3OH ; R-OH; R-NH2 ≡ R (OH)- ≡ ROH

Process:
The hard water first passed through a cation exchange column which absorbs all the cations like
Ca2+, Mg2+, Na+, K+ etc., present in the hard water.

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 2 RH + Ca2+ → R2Ca + 2 H+

The cation free water is then passed through an anion exchange column, which absorbs all the
anions like Cl-, SO42- etc., present in the water.
ROH + Cl- → RCl + OH-

Thus the water coming out from the anion exchange is free from both cations and anions. This water
is known as ion-free water (or) deionised (or) demineralised water.

Regeneration
 The saturated cation exchanger is gotten back by passing dilute HCl solution.
R2Ca + 2 HCl → 2 RH + CaCl2
 CaCl2 and MgCl2 are removed as wash
 The saturated anion exchanger is gotten back by passing dilute NaOH solution
RCl + NaOH → ROH + NaCl
 NaCl, Na2SO4 and NaHCO3 are removed as wash
 The washings are thrown away and the regenerated ion exchanger used again.
Advantages: It produced water hardness is very low (2ppm)
It can be also used to soften the high acid or basic hard water.
Disadvantages: Equipment is costly more expensive chemical are required.

DESALINATION OF BRACKISH WATER

Q.13: Define desalination of brackish water and mention two common methods for it?
Desalination:
The process of removing common salt (NaCl) from the sea water is known as desalination.
The water containing high amount of dissolved salts is called Brackish water or saline water.
The common method for the desalination of brackish water is
A. Electro dialysis.
B. Reverse osmosis.

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 Q.14: Explain the electro-dialysis method for desalination of brackish water?
Electro dialysis:
Principle: Electro dialysis involves the removing of dissolved salts from saline water under the
influence of a electrical current and help of membranes.
 An ion-selective membrane is allowed only one kind of ions.
 For example, a cation-selective membrane allows the passage of cations only. It does
not allow passage of anions.
 Similarly, an anion-selective membrane is allows only to anions and not allow passage
of cations.
Process: When a direct current is passed through saline water containing electrodes and ion-
selective membranes,
 The cations are moved towards cathode through cation selective membrane
 The anions are moved towards anode through anion selective membrane
 This decreases the concentration of ions in saline water and after some time the saline
water turns into fresh water.

Advantages: 1. It is the most compact unit. 2. The cost of installation and operation is
economical. 3. If electricity is easily available, this process is best suited.

Q.15: Explain the reverse osmosis method for desalination of brackish water
with sketch?
Reverse Osmosis:
It is a membrane process by which water is separated from saline water.
 Osmosis is defined as the spontaneous flow of ‘water’ from dilute to more concentrated
side through semipermiable membrane.

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  Semi permeable membrane only allows water molecules to pass through it.
 Examples of semi permeable membrane are cellulose acetate, polyamide, etc.,
 This natural process can be reversed by applying pressure higher than the osmotic
pressure on the concentrated side.
 When we apply pressure more than the osmotic pressure on concentrated side, water
molecules moves form concentrated side to diluted side through semi permeable
membrane and is called reverse osmosis.
 In the reverse osmosis, the pure water (free from ions) is separated from the
contaminated brine water (salty water).
 This membrane filtration is also called Super filtration (or) hyper filtration.

Advantages:

1. This method has greater advantages of removing ionic, non-ionic, colloidal and high
molecular weight organic matter.
2. The life time of membrane is quite high (2years).
3. The membrane can be replaced within few minutes.
4. Due to low capital cost, low operating cost and high reliability.
Applications:
1. Reverse Osmosis plays a major role in providing portable water defined by the WHO
criterion of <500 ppm of total dissolved solids. (TDS).
2. Extremely high quality water required for nuclear power plants can be made from sea
water by reverse osmosis process.

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 SWARNANDHRA
College of Engineering & Technology
(Autonomous)
Seetharamapuram, NARSAPUR, W.G. Dt., 534 280.
DEPARTMENT OF BASIC SCIENCE & HUMANITIES
Sub/Branch: Engineering Chemistry/CIVIL & CSE-A Year/Sem: 2019-20/I Faculty: Dr G. Srinivasa Rao
UNIT-II: POLYMERS AND COMPOSITE MATERIALS
Polymers: Introduction-types of polymers-degree of polymerization-functionality-preparation
properties and applications of individual polymers-Bakelite-PVC-Poly styrene.
Plastics: Types (thermosetting and thermoplastic)-compounding of plastics-moulding Process-
recycling of e-waste.
Rubbers and elastomers: Introduction-natural rubber-vulcanization of rubber-synthetic rubbers-
Buna-N, Buna-S.
Composite materials: Fiber reinforced plastics-biodegradable polymers-biomedical polymers-
conducting polymers

Q.1: Define the following terms: polymer, polymerization, degree of polymerization and
functionality.

Polymer: Polymers are large or macro molecules, which are formed by combining of a many
small repeating units (monomers). This phenomenon is called polymerization. Example:
Polyethylene, Poly styrene, PVC, Bakelite, etc.

Degree of Polymerization (DP): The number of repeating units in a polymer is known as the “degree
of polymerization”.

Functionality: The number of active bonding sites of a monomer is known as Functionality.

Example: Ethylene has two reactive sites. So, it is bi functional monomer.

Q.2: Distinguish between additional polymerization and condensation polymerization?

Addition Polymerization Condensation polymerization

Monomers joined by simple addition process. Monomers joined by condensation process.
There is no elimination of small units. There is an elimination of small units like H2O, NH3.

It is a chain mechanism. It is a step wise mechanism.

It is a rapid polymerization process It is a slow polymerization process.
Initiator is required to start reaction Catalyst is required to start a reaction
Ex: PVC, PE, PS… Ex: Bakelite, Nylon, Poly ester….

1
Q.3: Describe the Preparation, properties and Uses of PS, PVC and Bakelite?

1. Poly Styrene (PS):

 It is a synthetic aromatic polymer.
 It is an additional polymer.
 The monomers involved in polymerization are styrene. (Homo polymer)
 It is a thermoplastic polymer.
 It is an inexpensive and widely used plastic material.
Preparation: Poly styrene is prepared by polymerization of styrene in the presence of catalyst such as
benzoyl Peroxide (radical mechanism) or KNH2 (Anionic mechanism through additional
polymerization.

n
Properties:
 Polystyrene is slow to biodegrade.
 It is an amorphous polymer. (Not a close packed due to presence of bulky phenyl groups)
 PS is transparent and solid (glassy) at room temperature.
 PS has hard & brittle nature.
 It has good optical properties.
 Its softening temperature (82-1000C) is low.
 It acts as good electrical insulators.
Uses: PS used in making of
 Audio cassettes, Bottle caps, CD & DVD
 Containers for talcum powder, soft drinks and baby feeding bottles.
 House wares (small jars, storage containers), combs & brush handles.

2. Polyvinyl chloride (PVC):

 It is a synthetic non-aromatic polymer.
 It is an additional polymer.
 Vinyl chloride is the monomer in this polymer (Homo polymer)
 It is a thermoplastic polymer.
 These are mainly two types: Rigid PVC and plasticized PVC:

Preparation: It is prepared by free radical addition polymerization process.

2 Dr.GSR
Properties:
 PVC is colourless, odour less & non-inflammable substance.
 It has excellent resistance to oil as well as weathering.
 It has superior chemical resistance.
 It is a good insulator to heat and electricity.
Uses:
A. Rigid PVC:
 It can be used in construction field as drainage pipes, doors, window frames.
 It is used to make consumable liquid bottles like edible oils & house hold liquid bottles
like mineral water, cosmetics & detergents.
 It can be used to making sheets, safety helmets, refrigerator components, tyres, and
bicycle etc.
B. Plasticized PVC: The above rigid PVC polymer is added by plasticizers like camphor then
plasticized PVC obtained.
Applications:
Its flexibility is high and rigidness, brittleness is low compare to the rigid PVC
 It is cheaper than rubber, leather & latex. So, it is widely used in making leather cloths,
ladies hand bags etc.
 It can be used in cable wires as insulators.
 It can be used in manufacture of handles, radio-components, conveyor belts, chemical
containers etc.
---------------------------------------------------------------------------------------------------------------------------
3. Bakelite (phenol-formaldehyde resin):
 It is a synthetic aromatic polymer.
 It is a co-polymer obtained from condensation of formaldehyde and phenol monomers.
 It is a thermosetting polymer.
 It is a cross linked polymer.
 It is first synthetic plastic developed by Dr. Leo bakeland.
 It is also called as phenol-plastics or phenol-resins.
Preparation:
 It is prepared by condensation of phenol with formaldehyde in the presence of acidic/alkaline
catalyst.
 First phenol reacts with formaldehyde in presence of acid catalyst produce O-hydroxy methyl
phenol then it produces Novolac linier polymer.
 In presence of excess formaldehyde, Novolac results 3-D cross linked Bakelite polymer.

3
Properties:
 It is hard, rigid & strong.
 It is water resistant polymer.
 It is an excellent electrical and heat insulator.
 It is a very good adhesive and abrasion resistance.
 It has ion exchange ability.
Uses:
 It is used for making electrical insulator parts like switch boards, heater handles etc.
 For making moulded articles like telephone parts, cabinets for radio & television.
 It can be used as an adhesive (binder) for grinding wheels etc.
 It is used in paints & varnishes.
 It is used as an anion exchanger in water purification.

------------------------------------------------------------------------------------------------
PLASTICS
What is Plastic? Explain their advantages and disadvantages?***
 “Plastics” are high molecular weight organic polymers which can be moulded into desirable
shapes by the applications of heat & pressure.
 Plasticity is the property of material due their ductility and malleability.
 All plastics are polymers but all polymers are not plastics.

4
  Most plastics do not conduct electricity well, low in density and are often tough.
Advantages:  Low maintenance cost
 Lightness in weight  They do not absorb water
 Good thermal & electrical insulation  Good strength
 Corrosion resistance  It can be melted & reused
 Low fabrication cost  Resistant to weather conditions

Disadvantages:
 Recycling process of plastics is costly  Low combustibility
 It takes very long period to biodegrade  The manufacture of plastic process
 Low-heat resistance causes harmful environment.
 Deformation under load.
 On burning some plastics emit toxic
gases
-----------------------------------------------------------------------------------------------------------------

Q.4: Identify the Differences between the Thermoplastics and Thermosetting Plastics?

Q.5: What is compounding of Plastics? Explain various constituents?

Compounding of plastics:
The mechanical mixing (heat, bend, and solidification) of various additives with polymers is called
compounding of plastics. This process changes the physical, thermal, chemical and aesthetic
properties of the plastic.
The main types of compounding materials and their functions are discussed below:

5
The additives are 1. Resins 2. Plasticizers 3. Fillers 4. Lubricants 5. Colorants 6. Stabilizers & 7.
Anti-oxidants.
1. Resins:
 These are thermoplastics & thermosetting plastics.
 Each type required its specific moulding process.
 Examples: PE, PVC, PS, Nylons, Phenol-formaldehyde, Urea-formaldehyde resin etc.
2. Plasticizers:
 These are added to polymers to increase plasticity & flexibility.
 They improve process ability of the plastics & reduce the brittleness of the products.
Example: Vegetable oils, camphor, esters of phthalic acids & some phosphates etc.
3. Fillers:
 These are added to give the final plastic, better hardness, tensile strength.
 These provide good finish & workability during processing.
 It reduces the cost, shrinkage & brittleness of plastic.
 Examples: Sand, quartz, asbestos, chalk, limestone, zinc oxide & metallic oxides.
4. Lubricants:
 A lubricant prevents the plastic material from sticking to the fabrication equipment.
 These proved flawless finishing to materials.
 It gives good finishing to the plastic. Examples: oils, waxes & soaps.
5. Colouring materials:
 They provide attractive colours to plastics.
 Examples: Black – Carbon black White – Zinc oxide
Red – Ferric oxide Green – Chromium oxide Crimson red – Antimony sulphide.
6. Stabilizers:
 The purpose of adding stabilizers is to improve the thermal stability during processing.
 Examples: organic metallic salts, amines & alkali earth metals.
7. Anti oxidants:
 It protects against oxidation degradation.
 Example: di-t-butyl cresol, phenyl β- naphthylamine etc.

Q.6: Explain the moulding process (Fabrication process) for the preparation of plastic
materials?
Fabrication of plastics:
This is also called as “Moulding of plastics into articles”. To give suitable shapes to plastics, several
methods of fabrication are used. The important fabrication methods are:
1. Compression moulding 2. Injection moulding
3. Transfer moulding 4. Extrusion moulding

6
1. Compression moulding:

 It is a method applied for both thermoplastic & thermosetting resins.

 The plastic ingredients (components) are filled between the two half-pieces of mould which
are capable of being moved relative to each other.
 Heat & pressure are applied. Two halves are closed very slowly.
 The cavities get filled with fluidized plastic finally curing is done either by heating
(thermosetting) or cooling (thermoplastic).
 After curing the moulded article is taken out.

2. Injection moulding:
 This is mainly applicable to thermoplastic resins.
 In this, the moulded plastic powder is fed into a heated cylinder from an injector at a
controlled rate.
 The mould is kept cooled and thus it becomes rigid then the article is ejected.

3 .Transfer moulding:
 Transfer moulding is a method, which uses the principle of injection moulding for
thermosetting materials.
 The moulding material is preheated and loaded into a chamber. A plunger is then used to
force the material from the chamber to moulding cavity through orifice.
 The mould remains closed as the material is inserted and apply high pressure and heat.
 The moulded article is then ejected after curing process (by heating).

7
4. Extrusion moulding:
 It is used mainly for continuous moulding of thermo plastics material into articles of uniform
cross-section like tubes, rods, strips, cables.
 The thermoplastic ingredient are heated to plastic condition and then pushed by means of a
screw conveyor into heated chamber where it softens & is forced out through a die having the
required outer shape.
 Then the plastics cooled due to the atmospheric exposure.

Q.7: What is an e-waste, why should it recycled and explain the process?
E-waste: Discarded electrical or electronic devices are called e-waste or electronic waste.
Source: E-waste is created from anything electronic: computers, medical devices, TVs, monitors, cell
phones, tablets, lap tabs, VCRs, CD players, fax machines, printers, etc.
Consequences:
 Used electronic devices are rapidly filling the landfills of the globe.
 Electronic scrap components contain potentially harmful materials such as lead, cadmium,
beryllium, or brominates, which pollute the soil, water.
 The damage to the atmosphere is one of the biggest environmental impacts from e-waste.

8
  When electronic waste is thrown away in landfills their toxic materials discharge into
groundwater, affecting both land and sea animals.
E-waste recycling:
 E-waste recycling is the process of recovery and reprocessing of waste materials for use in
new products.
 Typical materials that are recycled include iron and steel scrap, aluminum cans, glass bottles,
paper, wood, and plastics.
 Recycling can help reduce the quantities of solid waste deposited in landfills.
 Recycling also reduces the pollution of air, water, and land resulting from waste disposal.
Plastics recycling:
 Recycling process depends on the type of polymers present in the plastics.
 Different types of polymers must be sorted by the type before recycling process.
 Various thermoplastics are remelted and reformed into new products.
 Thermosetting plastics such as Bakelite, polyurethane and epoxy resins are cannot be
remelted.
 These are usually ground or shredded for use as fillers or insulating materials.
 However, biodegradable plastics are not required to recycle, they are degrading naturally, but
suitable additives are required for effective degradation.

Explain the Engineering applications of Plastics?***

Engineering applications of Plastics:
 Plastics are playing important role in every one life.
 They replaced metals and also decrease the usage of paper.
 Their low cost, less weight and ease of manufacture make them very useful in everyday life.
 They have many applications in demanding areas like automobiles, defences, electrical &
electronics, telecommunications, textiles, satellite, robots, computer components etc..
Each engineering plastic usually has a unique combination of properties.
 Different plastics having different applications in as follows…
Carry bags, home appliances, playing toys, health instruments, and construction materials.
 Bottles, containers, heat and electric insulators, bullet proof jackets, aeroplane and rocket
components.

RUBBER & ELASTOMERS

What is Elastomers and what are their properties?
Elastomers:

9
  The polymers which are able to extended their length 2 to 3 times more than their original
length is known as Elastomers or Rubber.
 These are amorphous polymers and coil like structure molecules.
 They deformed by stretching & regain original form when stretching force is removed.
Important properties of rubber are its
 Flexibility: Strength: Impermeability to water: High resistance to abrasion.
Due to these properties rubber is highly useful for industrial as well as domestic purposes.

What is Natural Rubber?

Natural rubber:
 Natural Rubber consists of basic material Latex which contains Isoprene.
 Hevea Brasiliensis is the source for the Latex and it is a milky colloidal emulsion.
 During the treatment, isoprene molecules polymerise to form, long coiled chains of Cis-poly-
isoprene is called as natural rubber.
 The molecular weight of raw rubber is about 1,00,000- 1,50,000.

Gutta percha:
 It is another variety of Natural Rubber.
 It is obtained from the nature leaves of Dichopis gutta trees.
 It is also has a polymer of isoprene but it is a trans-poly Isoprene.

---------------------------------------------------------------------------------------------------------------------------
Q.8: Explain why natural rubber needs vulcanization (Drawbacks of natural rubber)? What is
Vulcanization of rubber? How is it carried out?
Drawbacks of natural rubber: As prepared natural rubber has following drawbacks…
 It is soft at high temperature & brittle at low temperatures.
 Weak, low tensile strength (200 kg / cm2).
 It has high water absorption capacity.
 No resistance to mineral oils, solvents.

10
  It is attacked by Oxidizing agents.
 It has little durability.
 It perishes due to oxidation in air.
 It swells in organic solvents & gradually disintegrates.
 Its applicable temperature range is 10-60o C.
To overcome these limitations rubber is need to vulcanize.
Vulcanization of rubber:
 Vulcanization is compounding of rubber it involves heating of raw rubber with sulphur at
100-140o C.
 Sulphur enters the double bonds of rubber and forms cross-linkages.
 These cross linkages formed by sulphur, anchor and restricting intermolecular movements
between polymer chains leads to stiffing character of rubber.
 Vulcanization facilitates excellent changes in properties, resistance to changes in temperature,
decreased elasticity and increased tensile strength, durability, chemical resistance.

 The toughness or stiffness of vulcanization depends on the amount of sulphur included.

 For flexible tyre rubber, sulphur content is from 3-5% whereas for tougher variety like
ebonite, content of sulphur is 32 %.
The superior properties of vulcanized rubber compared to raw rubber are summarized below.

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Q.9: Demonstrate the preparation, properties and uses of Buna-S, Buna-N (Commercial
rubbers OR artificial Rubbers OR Synthetic Rubbers)?

1. Buna-S / SBR ( Styrene-Butadiene) / GR-S:

 Buna-S is obtained by co-polymerization of butadiene and styrene in the presence of
sodium catalyst or cumene hydro peroxide.
 It is an additional polymerized rubber.
 It is also called as Styrene rubber or GRS rubber.
 This copolymer contains 75% Butadiene and 25% Styrene.

Properties:
 Properties of Buna–S depends on % of monomers.
 It possess high abrasion- resistance, high load – bearing capacity
 It oxidizes in presence of ozone, It swells in oils and solvents
 It can be vulcanized.
Uses:
It is used for the manufacture of tyres, floor tiles, shoe soles, gaskets, footwear components, wire and
cable insulators, carpet packing, adhesives, tank linings.
2. Nitrile Rubber / Buna-N / GR-A:
 Buna-N is obtained by co-polymerization of butadiene and acrylonitrile in the presence of
sodium catalyst or cumene hydro peroxide.
 It is an additional polymerized rubber.
 It is also called as Nitrile rubber or GRA rubber.

Properties:
 It possesses good resistance to heat, sunlight, acids, chemicals.
 It is less resistant to alkalis than natural rubber. It has good tensile strength.
Uses:
In making conveyor belts, air craft components, tank linings, gaskets, printing rollers, oil- resistant
foams ,oil seals, hoses and automobiles parts.

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 COMPOSITE MATERIALS
Q.10: Write a note on Fibre-reinforced plastic (FRP) with suitable examples.

(Or) Describe the Preparation, properties and Uses of Bullet Proof Plastics?

 Fibre-reinforced plastics are composite materials.

 In FRP, polymer matrix is reinforced with fibres.
 Commonly used fibres are glass, carbon, aramid, paper, wood, asbestos.
 Bakelite was the first polymer used for fibre-reinforced plastic.
 Polymers are combined with these fibres and produce FRP, which have superior thermal,
electrical, mechanical and optical properties than normal polymers.

Aramid fibres reinforced plastics: (Bullet Proof Plastics):

 Aramid means aromatic polyamides which are used as fibre material.
 Example for Aramid is Nomex & kelvar mainly used for bullet proof vests & puncture
resistance bicycle tyres.
Kelvar:
 It is a para-aramid synthetic fibre. It is also known as poly (p-phenylene terephthal amide).
 Kelvar is formed by condensation reaction of p-phenylene di amine & isophthaloyl chloride.

Nomex:
 It is a meta-aramid synthetic fiber.
 It is formed by condensation reaction of m-phenylene di amine & meta-phthaloyl chloride.

 Kelvar and Nomex are high strength fibres due to the many inter-chain bonds.
 These inter-molecular hydrogen bonds form between the carbonyl groups and
 NH canters.

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  Additional strength is derived from aromatic stacking interactions between adjacent
strands.

Properties and applications of Aramid fibres:

Properties: Applications:
 Usually yellow in appearance.  As bullet proof vests & puncture
 Low density & High strength. resistant bicycle tyres
 Good impact, abrasion & chemical  Aircraft body parts
resistance.  Boat hulls, tennis strings, hockey sticks
 Excellent heat & flame resistance.  Gaskets & motorcycle protective
 Low thermal shrinkage. clothing
 Self-extinguishing flame retardant  Protective gloves, helmets, body
properties. armor
 Ropes and cables
 Optical fiber cable systems.

Q.11: Write a Note on Bio-Degradable polymers?

 Bio-degradable polymers are naturally degradable polymer
 Degradation due to the action of natural micro-organisms such as bacteria, fungi & algae.
 Bio-degradable polymers are non-toxic and these are break down into environment as CO2,
N2, H2O, and biomass.
 If bio-degradation carried in presence of water, called hydro bio-degradable plastics (HBP).
 If it carried by oxidation, it called as oxo-bio-degradable plastics (OBP).
 The natural bio-degradable polymers are starch, cellulose, proteins, nucleic acids etc.
 The synthetic bio degradable polymers are PVA (Poly vinyl alcohol), PLA (Poly lactic
acid) and PHBV (Poly β-Hydroxy Butyrate-co-β-hydroxy Valerate).
PHBV Synthesis:

Uses:
 PHBV find its application in controlled release of drugs, capsules, medical implants and
repairs.
 It is also used in specialty packing & in orthopaedic device.

Q.12: Write a note on bio-medical polymers.

 Biomedical polymers (BMP) are essentially made by a biomaterial, which is used in
application of medical field.
 Biomedical polymers are classified mainly as natural BMP and synthetic BMP.

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  Natural BMP are derived from living creatures and synthetic BMP are derived from non
living substances.
 Ex for Natural BMP is cellulose, collagen, Chitosan etc.
 Ex for Synthetic BMP is Polyethylene (PE), poly propylene (PP) and polytetrafluoroethene
(PTFE) etc.
Properties: Applications: To make
 They are flexible  Medical disposables
 Great resistance to biochemical attacks  Dental materials
 Light weight, easily manufactured into  Implants,
items.  Synthetic bones and valves
 Good biocompatibility.  Dressing materials
 Non toxic and non inflammatory.  Tissue engineering materials
 Control drug delivery systems

Q.13: Write a note on conducting polymers.

 Conducting polymers are organic polymers which are able to conduct electricity.
 The structure of these materials has conjugated chains, that is, an alternating single and
double bond between the atoms.
 They are three types: 1. Electron conducting polymer. 2. Proton conducting polymer. 3. Ion
conducting polymer.
 Ex for conducting polymers are Poly-acetylene, Poly-aniline, poly-pyrrole etc.
Properties and applications:
 They have conductive properties as metals.
 They are relatively inert and good mechanical properties as normal polymers.
 There are many applications of these materials in electronics, such as batteries, sensors, and
microelectronics devices.
 In the medical field, the conductive polymers can be used in the production artificial muscles,
biosensors, and drugs controlled-release agents.

15
 SWARNANDHRA
College of Engineering & Technology
(Autonomous)
Seetharamapuram, NARSAPUR, W.G. Dt., 534 280.
DEPARTMENT OF BASIC SCIENCE & HUMANITIES
Sub/Branch: Engineering Chemistry/CIVIL & CSE-A Year/Sem: 2019-20/I Faculty: Dr G. Srinivasa Rao
UNIT-III: ELECTROCHEMICAL CELLS AND CORROSION
Electrochemical Cells
Introduction-single electrode potential-electrochemical cell-electrochemical series and applications. Reference electrodes-
standard hydrogen electrode and calomel electrode-construction of glass electrode.
Batteries: Construction, working and cell reaction of primary (dry cell and Zinc-Air battery), Secondary (Pb-acid, Ni-Cd and Li-
ion) battery, Fuel cells (H2-O2, Methanol-Air cells).
Corrosion
Definition-theories of corrosion (Chemical and Electrochemical corrosion)-types of corrosion (Galvanic, Differential aeration
(waterline and pitting corrosion), stress Corrosion). Factors influencing rate of corrosion-nature of metal-nature of corrosive
atmosphere.
Corrosion Prevention methods: Cathodic protection-Sacrificial anodic method-Impressed voltage method. Metallic coatings:
Galvanization-Tinning-Electro plating-Electro less plating.

A: Electrochemistry

Introduction: Electrochemistry is the study of production of electricity from spontaneous

redox chemical energy and the use of electrical energy to do a non-spontaneous chemical
reaction.

Q.1: Define the following terms: Single Electrode potential, oxidation potential,
reduction potential and standard electrode potential? (2M)
Electrode Potential:
 The electrode potential also defined as the tendency of an electrode to lose or gain
electrons when it is in contact with solution of its own ions.
Oxidation Potential: It is a tendency of giving or loosing electrons of an electrode.
Reduction Potential: It is a tendency of gaining electrons of an electrode.
Standard Electrode Potential:
“The electrode potential of a given electrode measured at 298K and concentration of
electrolyte is 1M then potential of that electrode is said to be Standard Electrode Potential”.

1
2: Define Single Electrode Potential? Or What is significance of reference electrode?
(2M)
The potential associated with single electrode is called single electrode potential. It is
impossible to know the absolute value of a single electrode potential. If we can fix arbitrarily
the potential value of any one electrode, then we can measure the other electrode potential by
using potentiometer. For this purpose the reference electrode is introduced.
Q.3: Describe the Electrochemical Cell or Galvanic cell or Voltaic cell or Daniel cell?
 An electrochemical cell is device which produces electrical energy by performing
a spontaneous redox reaction.
 Redox reaction is a combination of oxidation and reduction reactions.
 Galvanic cell consists of two half cells with corresponding electrode and electrolyte.
Each of cells conducts one of the redox reactions.
 Generally, at anode oxidation and at cathode reduction takes place.

The following redox reaction occurs in Daniell cell

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
This reaction is a combination of two half reactions whose addition gives the overall cell
reaction:
At Anode (-ve electrode): Zn(s) → Zn2+ + 2e– (Oxidation reaction)
At Cathode (+ve electrode): Cu2++2e– → Cu(s) (Reduction reaction)
Overall Redox reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Salt bridge saturated with KCl (or) KNO3 to complete the cycle of the cell and
also maintain the electrical neutrality during redox reaction.
Representation of the electrochemical cell:
Zn ; Zn+2 (M) // Cu+2 (M); Cu
Anode Reaction // Cathode Reaction
Because of potential difference between the two electrodes electron move from anode to
cathode leads to flow of electricity in opposite direction.

2
Q.4: What is an electrochemical series and its applications?
It is a series of chemical elements arranged in order of their standard electrode
potentials (reduction potential) on hydrogen scale. The hydrogen electrode is taken as having
zero electrode potential: Li<Mg<Pb<Zn<Fe<Sn<H<Cu<Ag<Au

Q.5: Explain the Electromotive force (EMF) of Electrochemical cell? (2M)

The potential difference between the two electrodes of a galvanic cell is called the
Electromotive force or cell potential and is measured in volts.
Ecell = Ecathode – Eanode

Q.6: What is meant by Reference electrode and give two examples of it? (2M)
Reference electrode:
Reference electrodes whose potentials are extremely known and can be used for
construction of electrochemical cell and by which we can determined the unknown single
electrode potentials.
Reference electrodes are divided into two types, primary (Standard Hydrogen Electrode) and
secondary reference electrode (Calomel Electrode).
Q.7: Explain the construction and working of Standard hydrogen electrode (SHE) or
Normal hydrogen electrode (NHE)? OR
How to measure the pH of unknown solution (electrolyte) by using Standard Hydrogen
Electrode?
 It is impossible to know the absolute value of a single electrode potential.
 If we can fix arbitrarily the potential value of any one electrode, then we can measure
the other electrode potential by using potentiometer.
 For this purpose the reference electrode is introduced. Most commonly used reference
electrode is Standard or Normal Hydrogen Electrode (S.H.E or N.H.E).
 Standard Hydrogen electrode (SHE) is the example for primary reference
electrode. Its electrode potential is taken as zero at all the temperatures.
 This electrode may serve as anode or cathode depending upon the nature of another
electrode to which it is connected.
Reactions: The reaction, when SHE acts as the
anode i.e. oxidization
takes place

When SHE acts as the cathode i.e. reduction takes place

3
Representation: SHE is usually represented as: Pt,H2 (g),1atm/ H+ (1M)
Disadvantage: But it is not always convenient to use SHE as reference electrode because it is
difficult to maintain the activity of [H+] in solution at one molar and also keep pressure of the
gas uniformly at 1 atm.

Q.8: What is a Secondary reference electrode and explain with one example? Or
Write a note on Calomel electrode?
 It is impossible to know the absolute value of a single electrode potential.
 If we can fix arbitrarily the potential value of any one electrode, then we can measure
the other electrode potential by using potentiometer.
 For this purpose the reference electrode is introduced.
 Example of the secondary reference electrode is calomel electrode.
 Calomel electrode is also called as Mercury -Merqurous chloride electrode.
 Calomel electrode consists of mercury (Hg), solid merqurous chloride (Hg2Cl2), and
KCl solution.
Electrode potential of saturated calomel is 0.2422 V
Construction:
 Pure Hg placed at bottom of the glass tube having a side tubes on each side.
 Hg is covered with a paste merqurous chloride Hg2Cl2 (calomel)
 A solution of KCL is placed over paste through the one side of the tube
 Pt wire is dipped into glass tube to make electrical contact of the electrode with the
circuit.
Reactions:

4
Q.9: What is Ion Selective Electrode (ISE) and give an example? (2M)
 The electrodes which only respond for specific ions is called ion selective electrode.
 Glass electrode is example for ion selective electrode and potential selectively
depends on [H+] ions only.

Batteries
Q.11: Define and classify the batteries? (2M) differentiate the primary and secondary
battery.
Battery is a device which stores and converted the chemical energy into electrical
energy, and it is also called as storage battery. Generally, in battery number of
electrochemical cells is connected in series.
Batteries are classified as follows,
I) Primary battery ii) Secondary battery iii) Fuel battery or Flow battery
Primary battery: Primary battery is a cell in which the cell reaction is not reversible. They
are not rechargeable. They are use and throw type. Example: Dry cell, Zinc-Air cell etc.
Secondary battery: Secondary battery is a cell in which the cell reaction is reversible. They
are rechargeable cells. Once the battery gets exhausted, it can be recharged.
Example: Nickel-Cadmium cell, Lead-acid cell, etc.
Flow or Fuel battery: Flow battery is an electrochemical cell that converts the fuel energy
into electrical energy. Here fuel and oxidants continuously supply to the cell, so it never
exhausted. Example: Hydrogen-oxygen cell, Methanol-oxygen cell, etc.

Q.12: Explain the construction, working and applications of the primary battery (Dry
cell or Laclanche cell)?

Dry Cell: A cell without fluid component is called as dry

cell. Example: Laclanche cell.
It is a primary cell and not rechargeable.
Construction and working:
Anode: Zinc Sheet
Cathode: Carbon/graphite rod.
Electrolyte: NH4Cl, ZnCl2 and MnO2 to which starch is

5
added to make it thick paste and it will not leak.
A graphite rod serves as the cathode, which is immersed in the electrolyte in the
centre of the cell. The electrode reactions are given below.

Anodic reaction: (Oxidation): Zn (s) Zn+2 + 2e-

Cathodic reaction: (Reduction):
2MnO2(s) + 2NH4Cl(aq) + 2e- Mn2O3(s) + 2NH3(g) + 2 Cl- + H2O
Overall Redox reaction:
Zn (s) + 2MnO2(s) + 2NH4Cl(aq) Mn2O3(s) +Zn[NH3]2Cl2(s) + H2O

The formed complex [Zn[NH3]2Cl2] is stable it cannot be reversed by recharging.

 The dry cell is a primary battery, since no reaction is reversible by supplying

electricity.
 Dry cell is very cheap to make. It gives voltage of about 1.5V.
 Dry cells are used in flash-lights, transistor radios, calculators, etc.
But, it has few demerits:
 Since the electrolyte is acidic, Zn dissolves slowly even if it is not in use.
Q:13. Explain the construction, working and applications of the Zn-Air battery.
 Zn-Air is an example of Metal Air batteries.
 It is a primary battery and not rechargeable in normal conditions.
 They have a high capacity, low cost, low toxicity
Construction and working:
Anode: Zinc Sheet
Cathode: Air adsorbed Carbon.
Electrolyte: KOH
 In zinc-air batteries, zinc is oxidized by
oxygen taken from the surrounding air.

Cell Reactions:
Anodic Reaction: Zn + 2OH− ZnO + H2O + 2e−
Cathodic Reaction: 1/2 O2 + H2O + 2e− 2OH−
Overall: Zn + ½ O2 ZnO
Applications:
They are commonly used for watches and hearing aids.
Used in telecoms and railways as remote signalling, safety lamps.

6
 Secondary-Rechargeable Batteries
Q.14: Explain the construction, working and applications of the storage cell/secondary
battery/ Led acid storage cell/ Lead acid Accumulator? Write discharging and charging
reactions? (6M)
 The typical example for storage cell
is Lead-acid storage cell.
 It is a secondary battery which can
operate as an electrochemical cell
and as an electrolytic cell.
 When it acts as an electrochemical
cell, it supplies electrical energy and
becomes run down.
 During recharge it acts as electrolytic cell and after recharged, the cell is ready to
operate as an electrochemical cell.

Construction and Working:

 A lead – acid storage cell consists of a number of electrochemical cells (3 to 6)
connected in series to get 6 to 12 V battery.
 In each cell, a number of Pb plates used as anodes (-ve) are connected in parallel and
a number of PbO2 plates used as cathodes (+ve) are connected in parallel.
 The plates are separated by insulators like rubber or glass fibre.
 The entire combinations are immersed in dil.H2SO4 (Electrolyte).

Cell reactions: During discharging process: Acts as electrochemical cell:

Anodic reaction: Oxidation Reaction
Lead is oxidized to Pb+2 ions, which further combines with SO4-2 forms insoluble PbSO4.
Pb + H2SO4 ———> PbSO4(s)+ 2H++ 2e-
Cathodic reaction: Reduction reaction:
PbO2 is reduced to Pb+2 ions, which further combines with SO4-2 forms insoluble PbSO4.
PbO2 + H2SO4 + 2H+ + 2e- ———> PbSO4 +2H2O
Overall cell reaction during discharging:
Pb(s) + PbO2(s) + 2H2SO4(aq) ———> 2PbSO4(s) + 2H2O + Energy
Charging of the cell: Acts as electrolytic cell:

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  From the above cell reactions, it is clear that PbSO4 is precipitated at both the
electrodes and the concentration of H2SO4 decreases.
 So, the battery needs recharging. The cell can be charged by passing electric current
in the opposite direction.
2PbSO4(s) + 2H2O + Energy ———> Pb(s) +PbO2(s) + 2H2SO4(aq)
Advantages of Lead – acid batteries:
1. It is made easily. 2. It produces very high current.
3. The self discharging rate is low. 4. It works effectively even at low temperatures.
Uses: Lead – acid batteries are used in cars, buses and trucks. It is used in gas engine
ignition, telephone exchanges, power stations, etc.
----------------------------------------------------------------------------------------------------------------
Q.15: Explain the construction, working and applications of the Ni-Cd battery.
The nickel–cadmium battery (Ni-Cd battery or NiCad battery) is a type of rechargeable
battery using nickel oxy hydroxide (NiOOH) and metallic cadmium as electrodes.
It is an example of alkaline rechargeable battery. Ni-Cd cells can supply extremely high
currents and can be recharged rapidly.

Construction and working:

Anode: Cadmium (Cd) undergo oxidation
Cathode: NiO(OH) undergo reduction
Electrolyte: KOH
Cell reaction:
During discharging: Electrochemical cell:

- -
Anodic reaction: Cd + 2OH Cd(OH)2 + 2e

- -
Cathodic reaction: 2 NiOOH + 2H2O + 2e 2 Ni(OH)2 + 2OH

Overall redox reaction Cd + 2NiOOH + 2H2O Cd(OH)2 + 2 Ni(OH)2 + Electricity

During Charging: Electrolytic reaction:

Cd(OH)2 + 2 Ni(OH)2 + Electricity Cd + 2NiOOH + 2H2O
Applications: Calculators, digital cameras, pagers, lap tops, tape recorders, flashlights,
medical devices (e.g., defibrillators), electric vehicles, space applications
----------------------------------------------------------------------------------------------------------------

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Q.16: Describe Lithium ion battery with cell reactions?
 It is a rechargeable battery in which lithium ions move from one electrode to other
electrode during charging and discharging process.
 It works on intercalation mechanism.
 Li-ion batteries use an intercalated
lithium compound as cathode material,
and the porous carbon as anode (negative
electrode).
 Anodes: Hard Carbons (LiC6), Graphite (C6)
 Cathodes: LiCoO2
 Separator: Fine porous polymer film.
 Electrolytes: Non aqueous lithium salts such
LiPF6, LiBF4 in an organic solvent.
During discharge, lithium ions (Li+) carry the current and moves from the negative (Anode)
to the positive (Cathode) electrode, through the non-aqueous electrolyte. (DAC)
During charging the Li+ ions migrate from the positive (Cathode) to the negative (Anode)
electrode. (CCA)
Charging: LixCoO2 + C6 ----> Lix-y CoO2 + LiyC6
Discharging: Lix-yCoO2 + LiyC6 ----> LiXCoO2 + C6
+
Thus charging and discharging cycle is simply migration of Li ions from electrode to
another with flow of electrons through the external circuit
Applications:
Because of the excellent voltage control they are used in electronic devices and circuit
boards, military and space applications, medical devices such as simulators, drug delivery
systems Etc.....

Fuel cells
Q.17: What is a Fuel cell and give examples of any two fuel batteries? (2M)
 Fuel cells are an electro chemical cell which converts the Fuel-chemical energy which
into electrical energy.
 Examples of fuel cells are H2-O2 cell, CH3OH-Air Cell
Advantages of Fuel cell are:
1. High efficiency 2. Low noise levels
3. Free from vibration, heat, transfer and thermal pollution.

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 8. What is green fuel (H2-O2) cell and why it is called so? (2M)
Explain the H2-O2 fuel cell working and construction?
H2 –O2 Fuel cell (Green fuel cell):
A typical example of pollution free cell is H2–O2 fuel
cell in which the fuel is hydrogen and the oxidizer is
oxygen gas.
A full cell converts the chemical energy of the fuels
directly to electricity.
It doesn’t produce any pollutant gases during
production of electricity; hence it is called as green fuel cell.
Fuel + Oxygen ———> Oxidation products + Electricity
Construction and working:
 Hydrogen–oxygen fuel cell consists of two porous carbon electrodes coated with
small amount of catalysts (Pt, Pd, Ag).
 KOH or NaOH solution as the electrolyte.
During working, Hydrogen (the fuel) is bubbled though the anode compartment,
where it is oxidized. The oxygen (oxidizer) is bubbled though the cathode compartment,
where it is reduced.
The following cell reactions occur.
Anodic reaction: 2H2 +4OH- ———> 4H2O+ 4e-
Cathodic reaction: O2 + 2H2O+ 4e- ———> 4OH-
Overall cell reaction: 2H2(g) + O2(g) ———> 2H2O(l)
From the above cell reactions, hydrogen molecules are oxidized to water. When a large
number of fuel cells are connected in series, it is called fuel battery.
Advantages of fuel cells:
1. Fuel cells are efficient and take less time for operation.
2. No harmful chemicals are produced in fuel cells.
3. It is used as auxiliary energy source in space vehicles, submarines etc.
4. It is used in producing drinking water for astronauts in the space.
Limitations:
1) The life time of the fuel cells are not accurately known.
2) Their initial cost is high.

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Q.19: Write a note on Methanol Oxygen cell? (6M)
 Another important fuel cell is ethanol oxygen
fuel cell.
 In this fuel cell, methanol and water are
circulated at anode and air is circulated at
cathode of the cell.
 Methanol and water are adsorbed on
electrodes and lose protons until carbon
dioxide is formed.
 The H+ ions produced in this reaction migrate to cathode through the membrane and
these H+ ions react as with O2 at cathode and produce water.
 Electrons produced at anode moved to cathode through external circuit it leads
production of power.
At anode: (oxidation) CH3OH + H2O ———> CO2 + 6H+ + 6e-
At Cathode: (Reduction) 3/2 O2 + 6H+ +6e- ———> 3H2O
Overall reaction: CH3OH + 3/2 O2 ———> CO2 + 2H2O
Limitations:
1) Methanol is toxic and flammable.
2) They produce limited power.
During the oxidation of methanol CO2 is formed which is reactive towards platinum and
lowering the performance.
Advantages:
1) Storage of methanol easy then H2.
2) The energy density of method is greater than highly compressed H2.

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