Cy8151 - Engineering Chemistry - by WWW - Learnengineering.in

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UNIT – I Water and its treatment
1.1 HARDNESS
Definition:
1. If the water produces lather with soap, it is soft water. If the water does not produce lather with
soap, it is called as hard water. The property is known as hardness. Hard water will produce a
scummy white precipitate. The hardness is due to Ca2+, Mg2+ and SO42- , Cl- , CO32-, HCO3- ions
and their salts.
2.Test for hardness:
a) Eriochrome Black – T indicator gives red colour in hard water.
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b) With soap, hard water gives a scummy precipitate.
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2C17H35COONa + CaCl2  (C17H35COO)2Ca + 2NaCl
(Sodium stearate) (Scummy precipitate)
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3. Types of Hardness:
a) Temporary Carbonate hardness: The hardness due to carbonates and bicarbonates can be
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removed by simple boiling. So, they are known as temporary or carbonate or alkaline hardness.
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Ca(HCO3)2 (On heating)  CaCO3 + H2O + CO2
b) Permanent hardness (Non-carbonate): The hardness due to chlorides and sulphates

cannot be removed by simple boiling. They need special methods like lime soda process and
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zeolite process. This hardness is called as “Permanent hardness or Non-carbonate or non alkaline
hardness.
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CaCl2 + Na2CO3  CaCO3 + 2NaCl ( Lime soda process)

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CaSO4 + Na2Ze (Zeolite)  CaZe + Na2SO4 (Zeolite process)

4. Units of hardness:
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i) ppm ii) mg/L iii) degree Clarkes iv) Degree French
1 ppm – 1 part by weight of CaCO3 equivalent hardness/106 parts of water

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1 mg/L – 1mg of CaCO3 / 1 Lr of water

Clarkes Degree - 0Cl-1 part of CaCO3 equivalent hardness /70,000 parts of water
1 Degree French – 0F - 1 part of CaCO3 equivalent hardness/105 parts of water
Therefore, 1ppm = 1mg/L = 0.07 0Cl = 0.10F
5.CaCO3 equivalence:
Hardness is expressed in CaCO3 equivalence. Because,
i) It is the most insoluble and forms precipitate quite easily.
ii) Its molecular weight is 100 and equivalent weight is 50. As these are whole numbers, it is very
easy to use them in calculations.
ESTIMATION OF HARDNESS BY EDTA METHOD:
1. Aim:
To estimate the amount of hardness present in the given water sample.
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2. Chemicals required:
a) Standard hard water – 1 g CaCO3 + dil. HCl – made up to 1 L.
b) EDTA solution – 4 g of EDTA sodium salt / 1 L of water
c) EBT Indicator – 0.5 g EBT / 100 ml alcohol
d) Ammonia buffer - 67.5 g Ammoniumchloride +570ml Ammonia-- made up to 1L
3. Principle:
EDTA stands for Ethylene Diamine Tetra Aceticacid. As it is insoluble in water, we use its
disodium salt.
Structure of EDTA:
Na-OOC-H2C CH2 –COO-H

N – CH2 – CH2 – N
H-OOC-H2C CH2 –COO-Na
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By nature, Eriochrome Black T indicator is blue in colour. When EBT indicator is added to water
sample, it forms a wine red coloured unstable Ca-Mg-EBT complex.
This reaction is carried out under a basic PH of 8- 10 using ammonia buffer.
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Ca2+ / Mg2+ in water + EBT - [Ca / Mg –EBT] unstable wine red complex
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When EDTA is titrated against the complex, EDTA replaces all the EBT and forms a stable Ca /
Mg –EDTA complex. The liberated EBT indicates the end point as steel blue.
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[Ca / Mg –EBT] + EDTA  [Ca / Mg –EDTA] + EBT
(Wine red/unstable) (Stable) (Steel blue)
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So, the end point is the colour change from wine red to steel blue.
4. Short Procedure:
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S.No. Content Titration-I Titration-II Titration-III

Standardisation of Total Hardness permanent
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EDTA Hardness
1 Burette EDTA StandardEDTA standardEDTA
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2 Pipette(20 ml) Std. Hardwater Sample water Boiled water

3 Additional solution 10ml of NH3 buffer 10ml of NH3 10ml of NH3 buffer
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buffer
4 Indicator EBT EBT EBT
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5 Endpoint Wine red to steel Wine red to steel Wine red to steel
blue blue blue
6 Volume V1 V2 V3
5. Calculation:
Step1 – Standardisation of EDTA
1 ml of Std. Hard water = 1 mg of CaCO3 (Given)
So, 20 ml of Std. Hard water = 20 mg of CaCO3
V1 ml of EDTA is required for = 20 mg of CaCO3
Therefore, 1ml of EDTA = 20 / V1 mg of CaCO3

Step 2: Finding Total hardness:
20ml of sample water required = V2 ml of EDTA
= V2 X 20 mg of CaCO3
V1
Therefore, 1000ml of sample requires = V2 X 20 X 1000 mg of CaCO3

V1 20
Hence, total hardness = V2 X 1000 ppm

V1
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Step 3: Finding Permanent hardness:
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20ml of boiled water required = V3 ml of EDTA
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= V3 X 20 mg of CaCO3
V1
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Therefore, 1000ml of boiled sample requires = V3 X 20 X 1000 mg of CaCO3
V1 20
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Hence, permanent hardness = V3 X 1000 ppm
V1
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Step 4 : Temporary hardness = Total hardness – permanent hardness

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1.2) Boiler Troubles

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1 .Definition:
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The setup used to produce steam in industries is known as „Boiler‟. Water is fed to the
boiler and heated to produce steam. The water fed into the boiler is known as “Boiler feed water”.
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2. Requirements for boiler water

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S.No. Requirements for boiler water If not, it will cause

1 Free from hardness causing salts Sludge and scale
2 Free from oil and greases, silica Foaming
3 Free from dissolved salts, suspended impurities, Caustic embrittlement
alkalis
4 Free from dissolved gases, suspended salts Boiler corrosion
If the untreated water is fed directly to the boiler, it may cause sludge, scale, priming, foaming,
caustic embrittlement and boiler corrosion which are collectively known as boiler troubles.

Sludge and scale:
Definition: If the water contains hardness causing salts like MgSO4, MgCl2, CaSO4, Ca(HCO3)2
on evaporation, the salts are precipitated .
If they form loose, slim, non-adherent precipitate, It is known as sludge.
If they form hard, thick, adherent precipitate, it is known as scale.
Reasons for sludge and scale:

Sludge: MgCl2, MgSO4, CaCl2
Scale: CaCO3, MgCO3, Ca(HCO3)2
Disadvantages of scales and sludges:
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a) Wastage of fuel:
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Scales have low thermal conductivity. So, the heat transfer from boiler to inside water may not be
sufficient. In order to provide steady supply of heat to water, over heating is to be done which
causes wastage of fuel. The wastage of fuel depends on the thickness and nature of the scale which
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is shown in the table.
Thickness of scale (mm) 0.325 0.625 1.25 2.5 12
Wastage of fuel (%) 10 15 50 80 150
b) Decrease in efficiency: ee
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Scales sometimes deposit in the valves and condensers of the boilers and heat exchangers and cause
choking. This results in decrease in efficiency of the boiler and heat exchangers.
c) Boiler explosion:
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Sometimes due to overheating the thick scales may crack which causes the sudden contact of high
heated boiler material with water. This causes formation of a large amount of steam and it develops
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high pressure. This leads to explosion.
Examples of Scale deposits:

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S.No. Name of the deposit Properties

1 CaCO3 Deposit It is formed due to decomposition of calcium bicarbonate. It has lower
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solubility and forms tenacious scale. The liberated CO2 produces carbonic
acid and produces boiler corrosion.
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2 CaSO4 deposit At high temperature and high pressure boilers, It forms harder and denser
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deposit.
3 Mg(OH)2 deposit It is formed due to decomposition of magnesium bicarbonate. It reacts with

water and liberates corrosive HCl.
4 SiO2 deposit It forms a hard, porcelain coating on the boiler surface.
5 Fe deposit It causes dark coloured magnetic deposits.

Prevention of Scales:
1. At earlier stage, scraper, wire brush, mechanical scrubber can be used to remove scales.
2. Thermal shocks are used to remove brittle scales.
3. By external treatment methods (eg) Ion exchange demineralization, zeolite softening
4. By using boiler compounds in internal treatment (eg) Carbonate, phosphate, calgon, EDTA
5. By acid treatment
Differences between sludge and scale:
S.No. Sludge Scale
1 Loose, slim, non-adherent deposit on the inner Hard, thick, adherent precipitate.
walls of boiler.
2 Due to salts like MgSO4 , MgCl2 Due to salts like CaSO4 , Ca(HCO3)2
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3 Due to poor conductance, they decrease the Due to poor conductance, they decrease the
boiler efficiency to lesser extent and causing boiler efficiency to maximum extent, cause
chocking in the pipelines. reduced fuel economy , improper boiling, boiler
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explosion etc.,
4 It can be prevented by periodical replacement It can be prevented by special methods like
of concentrated hard water by fresh water. This i) External treatment of ion exchange ,
process is known as “blow down” method. ee ii) Internal carbonate, phosphate, Calgon
conditioning
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iii) Mechanical hard scrubbing methods.
iv) Thermal shocks
5 Diagram:
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1.3) External treatment

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Removal of impurities, salts from boiler feed water before feeding it to the boiler is known as
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external treatment.
1.3) - A) ZEOLITE (PERMUTIT) SOFTENING PROCESS
Setup
i) Hydrated sodium alumino silicates available in nature are known as zeolite.

ii) These natural zeolites are green sand. They are non porous in nature.
iii) Zeolites are having the general formula Na2O . Al2O3. xSiO2 . yH2O (x = 2 to 10; y = 2 to 6)
iv) The porous and gel structured synthetic zeolites are known as permutit.
v) These zeolites and permutits are used for water softening.
vi) Synthetic zeolite is represented as Na2Ze.

Principle
i) The sodium ions are loosely held in these zeolites. They are easily replaced by Calcium and
magnesium ions present in the water.
ii) When hard water is passed through a bed of sodium zeolite kept in a cylinder, it exchanges its
sodium ion with Ca2+ and Mg2+ ions present in the water to from Calcium and Magnesium zeolites.
iii) Zeolite softeners may be of pressure type or gravity type.
Reactions:
CaSO4 + Na2Ze  CaZe + Na2SO4
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MgSO4 + Na2Ze  MgZe + Na2SO4
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CaCl2 + Na2Ze  CaZe + 2 NaCl
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MgCl2 + Na2Ze  MgZe + 2 NaCl
The outcoming water is enriched with large amount of sodium salts which do not cause any
hardness. But in cannot be used in boiler.
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Regeneration:
i) On prolonged use, all the zeolite sodium ions are exhausted.

ii) There will be no sodium ions to exchange the Calcium and magnesium ions. So, they have to be
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regenerated.
iii) The exhausted zeolite is regenerated by treating with 10% solution of NaCl.
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Regeneration reaction:
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The regeneration step comprises of a) backwashing b) salting c) rinsing before reuse
CaZe + 2 NaCl  Na2Ze + CaCl2

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MgZe + 2 NaCl  Na2Ze + MgCl2

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Advantages of zeolite process:
1. The outlet water will have least hardness around 1 – 2 ppm only.
2. As the zeolite can be regenerated, the method is cheap.
3. Operation is easy.
4. The space requirement for this setup is minimum.
5. No sludge is formed during this process.
Disadvantages of zeolite process:
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1. Turbid water cannot be treated as it blocks the pores of the zeolite bed.
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2. Acidic water cannot be treated as it decomposes the structure of zeolite.
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3. Water containing Fe, Mn cannot be treated as the regeneration is difficult.
4. Brackish water cannot be treated because it contains Na+ ions. So, the ion exchange reaction will
not occur.
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5. When the softened water contains more dissolved sodium salts, it may result in boiler corrosion
and caustic embrittlement.
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1.3) - B).Ion exchange method - ( Demineralisation)

Working:
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1. Here all the cations and anions are completely removed. It uses two cylinders of cation exchange
cylinder and anion exchange cylinder filled with resins.
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2. Resins are long chain, insoluble, cross linked, organic polymers. There are 2 types.
Cation exchange resins – RH2 (e.g) Sulphonated coals , RSO3H
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i)
ii) Anion exchange resins. R‟(OH)2 (e.g)Ureaformaldehyde,Amines R-NH2
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3. The resins are prepared by copolymerization of styrene and di vinyl benzene.

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The resultant polymer is treated with acid, it forms cation exchange resin. If the polymer is treated
with bases and ammonium chloride, it forms anion exchange resin.
4. The water is fed into cylinder –I where all the cations are replaced by RH2 Resins.
RH2 + CaCl2  R Ca + 2 HCl

5. The cation free water is fed to cylinder II, where all the anions are replaced.
R’(OH)2 + 2 HCl  R’Cl2 + 2H2O
6. So, the resultant water is free from all types of ions.
Regeneration:
–
On prolonged use, as all the resins are exhausted, there will be no H+ orOH ions to
exchange the unwanted ions. So, they have to be regenerated.
Cation resins are regenerated by HCl and anion resins by NaOH.
R Ca + 2 HCl  RH2 + CaCl2

R’Cl2 + 2NaOH  R’(OH)2 + 2NaCl
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Advantages of Ion exchange method:
i) Can be used for high pressure boilers also.
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ii) It can treat highly acidic or alkaline water.
iii) We can get pure water as hardness as low of 2 ppm.
Drawbacks of Ionexchange method:

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i) Expensive
ii) Fe, Mn cannot be removed as they form complexes with resins
iii) Cannot be used for turbid water as they clog the resins.
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Diagram:
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Differences between soft water and demineralized water.
S. No. Soft water Demineralized water

1 It does not contain hardness producing Demineralized water does not contain
calcium and magnesium ions, but it may any ions including hardness producing
contain other ions like K+, Na+, Cl- etc. ions.
2 Softening involves removal of only Demineralization involves removal of
hardness causing ions. all the ions present in water.
Differences between Zeolite and ion exchange process:
S.No. Zeolite process Ion exchange process
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1 It exchanges only cations. It exchanges cations and anions
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2 The cylinder is filled with zeolite. The cylinders are using
Na2O. Al2O3. xSiO2.yH2O cationexchange resin - RH2
Anion exchange resin - R‟(OH)2
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3 NaCl is used for regeneration HCl, NaOH are used for regeneration.
4 Softening involves removal of only hardness Demineralization involves removal of all the ions
causing ions. present in water.
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amount of dissolved Na salts which causes ee
The treated water contains relatively large The treated water does not contain any dissolved
salts. They may not cause any boiler troubles.
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caustic embrittlement in boilers.
6. The setup and operating cost is relatively The setup and operating cost high.
low.
7 The hardness may be upto 10 ppm The hardness may be upto 2 ppm
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8 Acidic water cannot be treated because acid Acidic water can be treated.
decomposes the zeolite.
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1.4. INTERNAL TREATMENT METHODS

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i) The residual salts that are not removed by external methods can be removed by adding some
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chemicals directly into the boiler water.

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ii) These chemicals are known as „Boiler compounds’. This method is known as „Internal
treatment‟ (or) sequesterisation.
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iii) e.g) Carbonate conditioning,

Aluminate conditioning
Phosphate conditioning ,
Calgon conditioning,
colloidal conditioning,
EDTA conditioning
iv) In general, internal treatment methods are followed by blow down operation.

a) Carbonate conditioning:
i) Carbonate conditioning is used for low pressure boilers.
ii) Here the salts like CaSO4 are converted to easlity removable CaCO3.
iii) But in high pressure boilers, the excess Na2CO3 undergoes hydrolysis and is converted to
NaOH.
iv) It leads to caustic embrittlement and boiler corrosion. So it is less preferred.
CaSO4 + Na2CO3  CaCO3 + Na2SO4
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b) Phosphate conditioning:
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i) Phosphate conditioning is used for high pressure boiler.
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ii) It is superior than carbonate conditioning as there is no risk of CO2 liberation, caustic
embrittlement and boiler corrosion.
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iv) For better results, a pH range of 9.5 – 10.5 is recommended.
3CaSO4 + 2 Na3PO4  Ca3(PO4)2 + 3 Na2SO4

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Three types of Phosphate salts are used:
S.No. Salt Name Used for treating
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1 Na3PO4 Tri sodium Phosphate highly acidic water

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2 Na2HPO4 Di sodium hydrogen Phosphate slightly acidic water

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3 NaH2PO4 Sodium di hydrogen phosphate highly alkaline water

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c) Calgon conditioning:
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i) Calgon is the trade name of sodium hexa meta phosphate- Na2 [ Na4 (PO3)6].
ii) With calcium ions it forms a soluble complex .
iii) So, there is no problem of sludge disposal.
iii) It is used for high and low pressure boilers.
2CaSO4 + Na2[ Na4 (PO3)6]  Na2 [Ca2(PO3)6] + 2 Na2SO4

d) Aluminate conditioning by sodium aluminate
i) Sodium aluminate (NaAlO2) gets hydrolysed inside the boiler giving aluminium hydroxide
(Al(OH)3) and sodium hydroxide (NaOH).
NaAlO2+ 2H2O Al(OH)3 + NaOH
ii) The sodium hydroxide formed would react with Mg ions forming Mg(OH)2.
MgCl2 + 2NaOH Mg(OH)2+ 2NaCl
iii) The flocculant precipitates of Mg(OH)2 and Al(OH)3 entraped suspended particles like oil, silica
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and other colloidal impurities.
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iv) The loose precipitate can be removed by below down operation.
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e) Colloidal conditioning:
i) Colloidal conditioning is used for low pressure boilers.
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ii) Here, scale formation is avoided by adding organic substances like kerosene, tannin, agar-agar
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etc., which get coated over the scale forming precipitates.
iii) This converts the scale into sludge and they are removed by blow down operation methods.
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f) EDTA complexometric conditioning:

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i) At basic PH, EDTA is added to boiler water.

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ii) EDTA binds the scale forming cations to form soluble complex. Thus scale formation is
prevented.
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[Ca2+ / Mg 2+] + EDTA  [Ca / Mg –EDTA]

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1.5) Desalination of brackish water by Reverse Osmosis method:

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1. Removal of common salt (NaCl) from water is called „Desalination‟.
2. Based on dissolved solids, water can be classified into three types.
S.No Type of water Dissolved solids
1 Fresh water Less than 1000 ppm
2 Brackish water 1000 ppm – 35,000 ppm
3 Sea water More than 35,000 ppm

3. Reverse osmosis is used to convert sea and brackish water to fresh water.
4. Osmosis:
When two different concentrated solutions are separated by a semi permeable membrane, due to
osmotic pressure, low concentrated solvent flows to higher one. This is known as osmosis.
5. Reverse Osmosis:
But when we apply an excess and opposite Hydrostatic pressure of 15 – 40 kg / cm2 to overcome
the osmotic pressure, then higher concentrated solvent will flow to the lower one. This is known as
reverse osmosis.
6. During this RO process, only the water flows across the membrane and it prevents the salt
migration. So, this method is also called as „Super filtration’.
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7. The membrane is madeup of cellulose acetate, cellulose butyrate, polymethacrylate
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Advantages of Reverse Osmosis:
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1. The life time of membrane is quite high. (2- 3 years)
2. Removes ionic, non-ionic and colloidal silica impurities, which can not be removed by
demineralization method.
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3. Low capital cost.
4. Simple operational procedure.

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5. The membrane can be replaced within a few minutes, thereby providing uninterrupted water
supply.
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6. This method is also used to remove bio-molecules, proteins, sugar etc.,

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Disadvantages:
1. Periodical cleaning of membrane is needed.

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2. Pretreatment for bacterial removal is needed.
Diagram:
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UNIT II
SURFACE CHEMISTRY AND CATALYSIS
Some important terms involved in surface chemistry
1.Adsorption:
It is the process of concentration of gas/liquid on the surface of solid/liquid due to
weak or strong forces of attraction.
(e.g.) Adsorption of H2 on Nickel.
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2. Adsorbent:
The surface on which adsorption takes place is known adsorbent. (e.g.) Nickel,
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Charcoal.
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3. Adsorbate:
The substance which gets adsorbed on adsorbent is known as adsorbate. (e.g.) H2 gas
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4. Absorption:
It is a phenomenon in which gas/liquid are slowly penetrate throughout the body of
the solid/liquid is known as absorption.
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(e.g) Absorption of ink on the surface of a chalk.

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5. Sorption:
It is the process in which both adsorption and absorption take place simultaneously.
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Eg. NH3 in water in presence of charcoal.
6. Desorption:
It is reverse process of adsorption. i.e., removal of adsorbate from the adsorbent
surface.

Differences between adsorption and absorption:
ADSORPTION ABSORPTION
NO.
1 Surface phenomenon Bulk phenomenon
2 It is the concentration of gas/liquid It is the concentration of gas/liquid
on adsorbent throughout the body of adsorbent
3 Fast process Slow process
4 Equilibrium is attained easily It takes some time
5 It depends upon the surface of No such effect
adsorbent
6 Eg. Adsorption of water vapour on Absorption of water vapour by CO2
silica gel
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TYPES OF ADSORPTION
1. Physical adsorption/ Physisorption ee
It is a process in which gas/solid/liquid are held on the solid surface through weak
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vander walls forces it is termed as ‘Physisorption’. (e.g) H 2 on charcoal.
2. Chemical adsorption/Chemisorption:
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It is a process in which gas/solid/liquid are held on the solid surface through strong
chemical covalent bonds, it is chemisorption. (e.g) H2 on nickel.
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Differences between the Physical adsorption and Chemical adsorption:

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No PHYSISORPTION
CHEMISORPTION
1 Adsorption is due to weak
Due to strong covalent bonding.
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Vanderwaal’s forces.
2 Adsorption is multilayer. Adsorption is monolayer
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3 Adsorption is completely reversible Adsorption is irreversible

4 The Equilibrium is established rapidly Establishment of equilibrium requires time
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5 No surface compound is formed Surface compound formation is formed

6 Energy of activation (Ea) is low. Energy of activation (Ea) is High
7 Heat of adsorption (∆H) is low (20- Heat of adsorption (∆H) is high (200-
40kcal/mol) 400kcal/mol)
8 Temperature increases adsorption Temperature increases adsorption increases
decreases followed by decreases.
9 Pressure increases adsorption
It independent of pressure
increases
10 It is nonspecific and non-selective in
It is selective and specific in nature
nature
11 e.g - H2 on charcoal. e.g., H2 on nickel.

Factors influencing the adsorption of gases on solid:

(a) Adsorption of gases on solids: (Occulation)
(i). Nature of gases
Easily liquefiable gases like HCl, NH3 adsorbed more easily than the permanent
gases like N2, H2,O2, etc., This is due to (i) Critical temperature (ii) Vander waal’s foreces.
Example,
Gas SO2 NH3 CO2 N2 H2

CT (K) 430 406 304 120 33
Amount of gas Adsorbed (mL) 380 180 48 8 4.5
(ii) Nature and surface area of adsorbent

The greater the surface area, larger pores on the adsorbent larger is the adsorption.
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(eg.) Charcoal and Silica gel.
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(iii) Heats (or) Enthalpy of adsorption
The energy liberated when 1 g mole of a gas is adsorbed on the solid surface. In
physical adsorption it is small due to weak vander waal’s forces, in chemical adsorption it
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is large due to the formation of chemical bonds.
(iv) Reversible character
Physical adsorption is a reversible process. The gas adsorbed on a solid can be
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removes under reverse conditions of temperature and pressure.
Chemical adsorption is not a reversible process, because a surface compound is
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formed.
(v) Effect of pressure
Physical adsorption: It occurs rapidly at lower pressure and increases with increase
in pressure.
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Chemical adsorption: There is no such effect due to chemisorptions is independent

of pressure.
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(vi) Effect of temperature

Physical adsorption: It occurs rapidly at lower temperature and decreases with
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increase in temperature.
Chemical adsorption: It increases with increase in temperature and then decreases.
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(vii) Thickness of adsorbed layer of gas

Multilayer adsorption is formed in physisorption. Monolayer adsorption occur in
Chemisorption.

(viii) Effect of activation of adsorbent

Activation leads to increase in the surface.
(1) Creation of rough surface
(a) by mechanical rubbing,
(b) by subjecting to some chemical reactions on the solid adsorbent.
(2) Increasing effective area of the surface
(a) by sub dividing the solid adsorbent into fine particles.
(b) by heating of solid adsorbent in superheated steam now its pores are opened and
adsorption increases.
ADSORPTION OF SOLUTE FROM SOLUTION:

An adsorbent adsorbs substances (solutes) from the solution in two ways.
1. Solid substances adsorb dissolves substances from solutions.
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Eg. Activated charcoal adsorbs coloring matter present in sugar solution.
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2. An adsorbent also adsorbs certain substance from the solution in preference to other
substances.
Eg. Charcoal adsorbs non-electrolytes more readily than electrolytes from a solution.
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FACTORS INFLUENCING ADSORPTION OF SOLUTES FROM SOLUTIONS
1. Effect of Concentration
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Extent of the adsorption of solute from the solution depends on temperature and
concentration. Effect of the concentration is explained by the Freundlich adsorption
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isotherm.
𝑥
= 𝐾𝐶
𝑚
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(a) Negative adsorption

Adsorption of solvent from the solution results in increase in the concentration of the
solution.
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(b) Positive adsorption

Adsorption of solute from the solution results in decrease in the concentration of the
solution.

2. The area of adsorbent

In increase in the surface area of adsorbent increases the total amount of solute
adsorbed.
3. The nature of the solute adsorbed
The extent of adsorption is usually greater, when the molecular weight of the solute
is high.
Adsorption isotherm:
It may be mathematical relationship or of graphical relation between adsorption and
pressure at constant temperature is known as adsorption isotherm.
= 𝐾𝑃 (at constant T)
Where, x = amount of Adsorbate
m = amount of adsorbent x/m
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x/m= extent of adsorption
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P= pressure
n = whole number
K = adsorption coefficient
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To convert the equation as y = mx + C form, taking log on both sides,

log (x / m) = log k + (1/n) log P (at constant T)
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Where y = log (x / m) ;
m = (1/n) ; C = log k
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so, the plot will be a line with slope 1/n and intercept log k.
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Different types of adsorption isotherm curves: ( P0 = Saturation pressure)

Type I II III IV V
Model Graph
N2 N2 I2 Vapours Benzene Vapours Water vapours
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Adsorbate
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Charcoal Non porous Porous Silica Porous Ferric oxide Porous Charcoal
Adsorbent
silica gel gel gel
-1830C 0
-195 C 0
83 C 500C 1000C
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Temperature
Chemisorption Physisorption Physisorption Condensation in Condensation in

Characteristics
(monolayer) (Multilayer)
Multilayer
ee (Multilayer)
Multilayer
pores/Capillaries
Saturation at the
pores/Capillaries
Multilayer is
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Saturation at the forms after the forms before multilayer formed at the
monolayer completion of the formation beginning of
formation monolayer completion of adsorption
Explanation
monolayer process
en
rn
Diagram
L ea
FREUNDLICH’S ADSORPTION ISOTHERM:

w.
The relation between adsorption and pressure at constant temperature is known as

ww
adsorption isotherm. It may be mathematical relationship or of graphical.
= 𝐾𝑃 (at constant T)
To convert the equation as y = mx + C form, taking log on both sides,
log (x / m) = log k + (1/n) log P (at constant T)
where y axis = log (x / m) ;

m = (1/n) ;
C = log k ;
x axis= log P

so, the plot will be a line with slope 1/n and intercept log k.
From the above graph, there may be three cases:
n
Case 1: At low pressure, adsorption is proportional to pressure.
g.i
∞𝑃
= 𝐾𝑃
rin
Case 2: At high pressure, adsorption is almost constant.
=K
ee
gin
=KP
en
Case 3: At intermediate pressure.

rn
= 𝐾𝑃
This is known as Freundlich adsorption isotherm.
ea
Limitations of Freundlich isotherm:

L
1. It is only an empirical formula and it has no theoretical basis.

w.
2. It is deviated at high pressure.

3. It is not good at high concentration.
4. n and K are temperature dependent.
ww
DERIVATION OF LANGMUIR ADSORPTION ISOTHERM:
Postulates:
1. In adsorbent, surface valencies are not fulfilled.
2. Adsorbate undergoes monolayer adsorption.
3. Adsorbate is uniformly distributed on the surface.
4. No interaction between adjacent gas molecules.
5. The gas molecules do not move around on the surface.

Derivation:
1. As per dynamic equilibrium,

ka
n
Gas + Solid G–S where, ka = Adsorption rate constant
g.i
kd kd = Desorption rate constant
2. Let us consider,
rin
Total area of adsorbent = 1cm2
Surface area adsorbed by gas molecule = θ
Then, surface area available for adsorption =(1-θ)
3. Rate of adsorption, Ra = Ka (1-θ) P

ee --- 1
gin
Rate of desorption, Rd = kd . θ --- 2
4. At equilibrium,
en
𝑅 =𝑅 --- 3
𝐾 𝜃 = 𝐾 (1 − 𝜃)𝑃
rn
𝐾 𝜃 = 𝐾 𝑃 − 𝐾 𝜃𝑃
ea
𝐾 𝜃 + 𝐾 𝜃𝑃 = 𝐾 𝑃
L
𝜃(𝐾 + 𝐾 𝑃) = 𝐾 𝑃
w.
𝜃= --- 4
ww
Dividing equation 4 on right hand side by kd
𝐾
(
)𝑃
𝐾
𝜃=
𝐾
1 + ( )𝑝
𝐾

As, = 𝐾, another constant, known as Adsorption co-efficient,
𝐾𝑃
𝜃=
1 + 𝐾𝑃
But, amount of gas adsorbed (x) is proportional to θ.

𝑥∞𝜃
𝐾𝑃
𝑥 = 𝐾´
1+ 𝐾𝑃
-- 5
Where 𝐾´ is new constant. This equation gives the relation between the amount of gas
adsorbed to the pressure of the gas at constant temperature. It is known as langumuir
n
adsorption isotherm.
g.i
Rearranging the equation 5.
𝐾´𝐾𝑃
1 + 𝐾𝑃 =
𝑥
rin
+ 𝑃= --6
´ ´
ee
gin
en
rn
A plot of P vs gives a straight line with a slope of and an intercept of

´ ´
ea
Case 1: At low pressure, P is very low and 𝑃 term is negligible

´
L
1 𝐾
≫ 𝑃
𝐾´𝐾 𝐾´𝐾
w.
= (or) 𝑥 = 𝑃𝐾´𝐾
ww
𝑥∞𝑃 -- 7
Amount of gas adsorbed is proportional to P.
Case 2: At high pressure, P is very high hence the term negligible

´
1 𝐾
≪ 𝑃
𝐾´𝐾 𝐾´𝐾
𝐾 𝑃
𝑃=
𝐾´𝐾 𝑥

𝑥 = 𝐾´(or) 𝑥 = 𝐾´𝑃 -- 8
Case 3: At normal pressure,
At intermediate pressure equation 8 becomes
𝑥 = 𝐾´𝑃 , where n= 0 to 1
This proves that at normal pressure, Langmuir adsorption resembles Freundlich isotherm.
Limitations:
1. Langmuir adsorption holds good at low pressure but fails at high pressure.
2. Langmuir adsorption explains only monolayer adsorption.
ROLE OF ADSORBENT IN CATALYSIS REACTIONS (OR) ADSORPTION (OR)

CONTACT THEORY
n
Action of heterogeneous catalyst
g.i
Various steps involved in the heterogeneous catalysis are explained with an example
Hydrogenation of ethylene using Ni catalyst
rin
H H
H H Ni(s)
H C C H
H
C C
H
+ H2
H H ee
gin
Ethylene (gas) Ethane (gas)
Step I Adsorption of reactant molecules
Active centers in the catalyst surface adsorbs the gaseous reactant.
en
H H H H
Physisorption Chemisorption
rn
Ni Ni + H2 Ni Ni Ni Ni
ea
Step II Formation of activated complex

L
H H H H
C C C C
H H H H
w.
+
H H H H
ww
Ni Ni Ni Ni
Activated Complex
Step III Decomposition of activated complex
H H H H
C C C C
H H H H
+
H H H H
Ni Ni Ni Ni
Activated Complex
Step IV Desorption of activated complex

H H
C C
H H H H
H H H C C H + Ni Ni
H H
Ni Ni
2. Finely divided state of catalyst is more efficient
E.g.
N N N
i i i
Finely divided N
n
i
g.i
N N N
i i i
Free valencies in combined state = 10 Divided state valencies = (6 x 4)=24
rin
Fineness of the catalyst increase, the free surface area gets increases, thereby free
valencies increases.
ee
3. Enhanced activity of a rough surfaced catalyst
It possess “Cracks”, “Peaks”, “Corners” etc., and consequently have larger number of
gin
active centers. These active centers increase the rate of reaction.
en
rn
ea
4. Action of promoters
Promoters are defined as the substances, which increase the activity of a catalyst.
L
Promoters change the lattice spacing

w.
ww
Promoters increases the peaks and cracks

5. Action of catalytic poisons
Catalytic poison is defined as a substance which destroys the activity of the catalyst.
This process is called catalytic poisoning. Number of free valencies (or) active centres of
catalysts are reduced by the preferential adsorption of the poison. So the rate of reaction
decreases.

6. Specific action of the catalyst

The adsorption depends on the nature of both the adsorbent (catalyst) and the adsorbate
(reactants). So, different catalysts cannot possess the same affinity for the same reactants.
Thus, the action of the catalyst is specific.
7. Ion exchange method ( Demineralisation)
Ion exchange resins adsorb the cations and anions present in hard water.
ROLE OF ADSORBENTS IN POLLUTION ABATEMENT

TREATMENT OF POLLUTED WATER AND AIR
Using Granular Activated Carbon (GAC)
A fixed – bed column is often used for contacting polluted water or air with GAC.It can be
operated singly, in series or in parallel. Among the various type two are important.
n
1. Down flow carbon contactors.
g.i
2. Upflow carbon contactors.
(a) Down flow Carbon Contactors
rin
It usually consist of two (or) three columns operated in series (or) in parallel.
ee
gin
en
Down flow in series Down flow in parallel

rn
The water or air is applied to the top of the column and withdrawn at the bottom. The
AC is held in place with an under drain system at the bottom of the column. Provision for
ea
back washing and surface washing is usually necessary to limit the headless build up due to
the removal of particle material with the carbon column.
L
Advantage
Adsorption of organic materials and filtration of suspended solids are accompanied in a
w.
single step.
Disadvantages
 Down flow filters may require more frequent back washing because of the
ww
accumulation of suspended materials on the surface of the contactor.

 Plugging of carbon pores may require premature removal of the carbon for regeneration,
thereby decreasing the useful life of the carbon.
(b) Upflow Carbon Contactors
In the upflow columns, the polluted water or air moves upward from the base of the
column .

Up flow expanded in series
n
Advantage
 As the carbon adsorbs organic materials, the apparent density of the carbon particles
g.i
increases and encourages migration of the heavier or spent carbon downward.
Disadvantage
rin
 Upflow columns may have more carbon fines in the effluent than downflow columns,
because upflow tends to expand, not compress, the carbon.
 Bed expansion allows the fines to escape through passage ways created by the
expanded bed.
2. Using Powdered Activated Carbon ee
gin
In this method powdered activated carbon is added directly into the effluent.
- The powdered activated carbon and a coagulant are mixed in the contact aeration
tank.
en
- It is then sent to the clarification tank where the heavier carbon settle down due to
gravity.
rn
- The spent carbon can be regenerated.

- The water from the
clarification tank is filtered in a
ea
filtration coloumn.
L
w.
ww
Flow diagram of water treatment using powdered activated carbon

Catalysis
The process of altering (increasing or decreasing) the rate of a chemical reaction with the
help of a catalyst is known as catalysis.
Effect of catalyst
A catalyst increases the rate of reaction by lowering the energy barrier between the reactant
and product.
n
g.i
Types of catalysis
1. Homogeneous catalysis
rin
It is a process in which the catalyst and the reactants are in the same phase.
Examples
(a) Homogeneous catalysis in gas phase
[NO](g)
ee
gin
2SO2(g) + O2(g) 2SO3(g)
(b) Homogeneous catalysis in liquid phase

en
[H+/OH-]
CH3COOC2H5(l) + H2O(l) CH3COOH(l) + CH3OH(l)
rn
2. Heterogeneous catalysis
ea
It is a process in which the catalyst and the reactants are in different phase.
Examples
L
(a) Heterogeneous catalysis in gaseous and solid phase

[Pt](s)
w.
2SO2(g) + O2(g) 2SO3(g)
(b) Heterogeneous catalysis in liquid and solid phase

ww
[Pt](s)
2H2O2(l) 2H2O(l) + O2(g)
Difference between homogeneous and heterogeneous catalysis

S.No. Homogeneous catalysis Heterogeneous catalysis
1. Reactant, product and catalyst are in Reactant, product and catalyst are in
one phase different phase
2. Catalyst cannot be regenerated. Catalyst can be regenerated.
3. Thermal stability of catalyst is low. Thermal stability of the catalyst is low.
4. Reactions are carried out at low Reactions are carried out at high

temperature and pressure. temperature and pressure.

5. Temperature increases the rate of the Temperature increases the rate of the
reaction. reaction.
6. Selectivity of the catalyst does not Selectivity of the catalyst depend on the
depend on the physical nature. physical nature.
Acid-Base Catalysis
A large number of homogeneous catalytic reactions are catalyzed by acids or bases. The
study of kinetics of these reactions is called acid-base catalysis.
Examples
1. Inversion of cane sugar
H+
n
C12H22O11 + H2O C6H12O6 + C6H12O6
g.i
2. Hydrolysis of an ester
H+
CH3COOC2H5 CH3COOH + C2H5OH
rin
Classification of acid base catalysis
Acid catalysis
ee
A reaction may be catalyzed by a proton (H+)- Specifically proton catalyzed.
or
gin
A reaction may be catalyzed by a bronsted acid (proton donors)- General acid catalysis.
Base catalysis
en
A reaction may be catalyzed by a hydroxide ion (OH-)- Specifically hydroxide catalyzed.

or
A reaction may be catalyzed by a bronsted base (proton donors)- General base catalysis.
rn
Mechanism of Acid-Base catalysis

ea
Acid catalysis
Step I: Addition of H+ ion to the substrate forming intermediate complex. (E.g.
L
keto-enol tautomerism of acetone)

w.
CH3CCH3 + H+A CH3CCH3 + A- Step I

O OH
ww
Step II: Removal of proton from intermediate complex by water or base.
CH3C CH2 + H3O+

H2O
OH
CH3CCH3
Step II
OH B
CH3C CH2 + BH+
OH

Base catalysis
Step I: Removal of H+ ions from the reactant forming intermediate complex.
CH3CCH3 + B CH3CCH2 + BH
O O
Step I
CH3CCH2 CH3C CH2
O O
Step II: Addition of proton to the intermediate complex.
CH3C CH2 + BH+ CH3C CH2 + B Step II

O OH
n
g.i
Kinetics of acid-base catalysis
Kinetics of acid-base catalysis is explained by the following mechanism.
rin
Step I
Involves transfer of the H+ ions from an acid AH+ to the substrate S.
k1
Step II
S + AH+
k-1 ee SH+ + A Step I
gin
Involves reaction of the acid form of the substrate with water to give products.
k2
SH+ + H2O P + H3O+ Step II
en
Applying steady state approximation to the intermediate [SH+]

rn
[ ]
= 0 = 𝑘 [𝑆][𝐴𝐻 ] − 𝑘 [𝐴][𝑆𝐻 ] − 𝑘 [𝑆𝐻 ] ---1
ea
The reactions are carried out at low concentration hence concentration of water is not taken
into account in equation 1.
L
𝑘 [𝑆][𝐴𝐻 ] = 𝑘 [𝐴][𝑆𝐻 ] + 𝑘 [𝑆𝐻 ]

w.
[ ][ ]
[𝑆𝐻 ] =
[ ]
---2
ww
The rate of formation of product is given by
[ ]
= 𝑘 [𝑆𝐻 ] ---3
Substituting 2 in 3
[ ] [ ][ ]
𝑅𝑎𝑡𝑒 = = [ ]
---4
Two cases are applied on equation 4.

Case 1 When k2 >> k-1[A], k-1[A] is negligible, so the above equation 4 becomes
𝑘 𝑘 [𝑆][𝐴𝐻 ]
𝑅𝑎𝑡𝑒 =
𝑘
𝑅𝑎𝑡𝑒 = 𝑘 [𝑆][𝐴𝐻 ] ---5
In this case the reaction is general acid catalyzed

Case II
When k-1[A] >> k2, k2 is negligible, the equation 4 becomes
[ ][ ]
n
𝑅𝑎𝑡𝑒 = ---6
[ ]
+
g.i
The ionization constant of the acid AH is
AH+ [H+] + [A]
rin
[𝐻 ][𝐴]
𝐾=
[𝐴𝐻 ]
[𝐴] =ee [
[ ]
]
---7
gin
Equation 7 is substitute in 6
𝑘 𝑘 [𝑆][𝐴𝐻 ]
𝑅𝑎𝑡𝑒 =
𝐾[𝐴𝐻 ]
en
𝑘
[𝐻 ]
rn
𝑘 𝑘 [𝑆][𝐻 ]
𝑅𝑎𝑡𝑒 =
𝑘 𝐾
ea
In this case the reaction is specifically hydrogen-ion catalyzed, because the equation
contains [H+]
L
w.
General applications of catalysis

1. It increases the efficiency of industrial processes.
ww
2. Many fine chemicals are prepared by employing catalysts.

3. Shape selective catalysis is possible.
4. Zeolites are used as catalyst in cracking of hydrocarbon.
5. Catalyts are used in catalytic cracking of petroleum.
6.They are used in functioning of fuel cells.
7. Nickel catalyst is used in hydrogenation of oils.
8. Catalysts are used in green chemistry.

Catalytic converter
- It is a device used to reduce the emission from IC engine.
- Reduced supply of oxygen in IC engine causes emission of toxic gases.
- These gases are oxidized and reduced to less harmful byproducts by catalytic
converters
Construction
- It has a metal housing with a ceramic honey comb like interior with insulating
layers.
- The honey comb interior is coated with aluminium oxide.
- It is porous and it contains metals such as platinum, palladium and rhodium.
n
g.i
rin
Working
- The exhaust fumes are allowed inside compartment A where the reducible
impurities are reduced. ee
- The remaining gases are allowed through the compartment B where all the
gin
oxidisable impurities are oxidized.
- The outgoing fume contains no toxic byproducts.
Function of catalytic converter
en
1. Reduction of nitrogen oxides into elemental nitrogen and oxygen

NOx Nx + Ox
rn
2. Oxidation of CO to CO2
3. Oxidation of hydrocarbons into CO2 and H2O
ea
Enzyme catalysis
L
Enzymes (or) biological catalyst are complex organic substances of high molecular weight
w.
proteins derived from living organisms.

Examples
1. Conversion of starch into maltose
ww
Diatase
2(C6H10O2) + nH2O nC12H22O11
2. Inversion of cane sugar

The enzyme invertase catalyses the conversion of sugar into glucose and fructose.
3. Conversion of glucose into ethanol
The enzyme zymase catalyses the conversion of glucose into ethanol.
zymase
C6H12O6 2C2H5OH + 2CO2
4. Hydrolysis of urea
The enzyme urease converts urea in ammonia.

Urease
H2N C NH2 + H2 2NH3 + CO2
O
Characteristics of enzyme catalysis

1. Enzymes are most efficient catalysts
Enzyme catalyzed reactions proceed at higher rates than the reactions catalyzed by
inorganic catalysts. Enzymes lower the activation energy of a reaction.
2H2O2 2H2O + O2
Activation energy without catalyst = 18 kCal/mol

Activation energy with colloidal platinum = 11.7 kCal/mol
n
Activation energy with enzyme catalyst > 2 kCal/mol
g.i
2. Enzyme catalyzed reactions are more specific
Enzymes are highly specific in catalyzing reactions. An enzyme catalyzes only a particular
reaction.
rin
Urease
H2N C NH2 + H2 2NH3 + CO2
O
ee
H2N C NH CH3 + H2
Urease
No reaction
gin
O
Methy Urea
3. Rate of the enzyme catalyzed reactions is maximum at optimum temperature.

en
Rate of the enzyme catalyzed reactions increases with increase in temperature and enzymes
are denatured at high temperature. Rate is maximum at optimum temperature.
rn
e.g. The optimum temperature of enzymatic reactions in human body is 37 C. The

enzymatic reactions will not happen at high temperature hence high body temperature is
ea
dangerous.
L
w.
4. Rate of the enzyme catalyzed reactions is maximum at optimum pH.

The rate of the enzyme catalyzed reactions is maximum at a particular pH, known as
optimum pH. The rate decreases below and above the optimum pH.
ww
e.g. Many enzymes in human body are highly active at pH 7.4.
5.Catalytic activity of the enzymes is enhanced by activators (or) Co-enzymes.

If activators (metal ions Na+, Mn2+, Co2+, Cu2+, etc., ) (or) co-enzymes (small molecules)
are added to enzymes, they increase the catalytic activity.
6. Enzymes are poisoned by other substances

The catalytic activity is inhibited by the addition of other substances.
e.g. Heavy metal ions (Ag+, Hg2+) react with the SH group of the enzyme and inhibit the
enzyme activity.

Michaelis-Menten Equation
The following mechanism is proposed by Michaelis and Menten to explain the enzyme
catalyzed reactions.
Let the enzyme E react with the substrate S resulting in the formation of intermediate
complex X in first step.
k1
E + S X Step I
The intermediate complex may dissociate back into E
and S (or) may form product P.
k2
X E + S Step II
k3
X P Step III
n
k1, k2 and k3 are rate constant of the respective rections.
g.i
The rate of formation of complex X is given by the following equation.
𝑑[𝑋]
rin
= 𝑘 [𝐸][𝑆] − 𝑘 [𝑋] − 𝑘 [𝑋]
𝑑𝑡
= 𝑘 [𝐸][𝑆] − (𝑘 + 𝑘 )[𝑋] --1

ee
Where, [E][S] and [X] = Molar concentrations of the enzyme, substrate and intermediate
gin
complex.
Rate of formation of the product is given by the following
[ ]
---2
en
= 𝑘 [𝑋]
Since, [E0] = [E] + [X] ---3

rn
Applying equation 3 in 1 gives,

ea
[ ]
= 𝑘 {[𝐸 ] − [𝑋]}[𝑆] − (𝑘 + 𝑘 )[𝑋] ---4
L
Where, [E] = molar concentration of the unreacted enzyme

w.
[X] = concentration of the enzyme in the complex

[E0] = total concentration of the enzyme
ww
The intermediate complex is unstable, it decomposes instantaneously hence
[ ]
=0 ---5
Applying steady state, equation 5 may be applied on 4
𝑘 {[𝐸 ] − [𝑋]}[𝑆] = (𝑘 + 𝑘 )[𝑋] ---6
𝑘 [𝐸 ][𝑆] − 𝑘 [𝑋][𝑆] = (𝑘 + 𝑘 )[𝑋]

𝑘 [𝐸 ][𝑆] = 𝑘 [𝑋][𝑆] + (𝑘 + 𝑘 )[𝑋]
𝑘 [𝐸 ][𝑆] = {𝑘 [𝑆] + (𝑘 + 𝑘 )}[𝑋]
[ ][ ]
[𝑋] =
[ ]
---7
Dividing equation 7 by 𝑘 [𝐸 ] gives
[ ]
[𝑋 ] = ---8
[ ]
Substituting [X] in equation 2 gives
n
[ ] [𝐸0 ]
=𝑘 𝑘 +𝑘 ---9
g.i
1+ 𝑘2 [𝑆]3
1
= 𝐾 = 𝑀𝑖𝑐ℎ𝑎𝑒𝑙𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
rin
[ ] [𝐸0 ] 𝑘3 𝐸0 [𝑆]
= --10 (or) 𝑅𝑎𝑡𝑒 =
𝐾𝑚
1+ [𝑆]
ee [𝑆]+𝐾𝑚
gin
Equation 10 is called Michaelis-Menten equation
Case (i) At low concentration of substrate

en
When the concentration of the substrate [S] is less than Km

[S] << Km then
rn
[ ] [𝐸0 ][𝑆]
=
𝐾𝑚
---11
ea
Case (ii) At high concentration of substrate

When the concentration of the substrate [S] is higher than Km
L
[S] >> Km then

w.
𝑑[𝑃] 𝑘 [𝐸0 ][𝑆]

=
𝑑𝑡 [𝑆]
ww
[ ]
= 𝑘3 [𝐸0 ] ---12
Effect of substrate concentration on rate

The order of the reaction changes with increase in the concentration of substrate.
(i) At low concentration of substrate
When the substrate concentration is low most of the active sites in the enzyme are
unoccupied. At this moment, rate of the reaction increase with increase in the concentration
of the substrate. It is a first order reaction with respect to substrate.

(i) At high concentration of substrate

When all the active sites are occupied, further increase in concentration of enzyme has no
effect on the rate. The reaction becomes zero order with respect to substrate.
Significance of Michaelis-Menten equation

The equation can be simplified by assuming that all the enzyme has reacted with the
substrate. In that case the rate is maximum.
[𝐸 ] = [𝑋]
Substituting the above equation in equation 2 gives
[ ]
= 𝑘 [𝐸 ] = 𝑣 ---13
n
Where, 𝑣 = maximum rate
g.i
The Michaelis-Menten equation can be written as
𝑣 [𝑆]
rin
𝑅𝑎𝑡𝑒 =
[𝑆] + 𝐾
If 𝐾 = [𝑆], then
ee
𝑅𝑎𝑡𝑒 =
𝑣 [𝑆]
[𝑆] + [S]
gin
𝑣 [𝑆]
𝑅𝑎𝑡𝑒 =
2[S]
en
1
𝑅𝑎𝑡𝑒 =
𝑣
rn
2
When the Michaelis-Menten constant is equal to concentration of the substrate, rate of the
reaction is half the maximum rate.
ea
Determination of the Michaelis-Menten constant (Km)

L
Lineweaver-Burk equation is used to determine the value of the Michaelis-Menten constant.

w.
1 1 𝐾
= +
𝑟𝑎𝑡𝑒 𝑣 𝑣 [𝑆]
ww
The plot of reciprocal of rate vs concentration of substrate gives a straight line with
intercept ( ) and slope

Turn over number (k3)

The number of molecules of substrate converted into products in unit time by one molecule
of enzyme.
n
Factors affecting enzyme catalysis
1. pH
g.i
Enzymes work well in the neutral pH but they get denatured at low and high pH values.
2. Temperature
rin
Enzymes works faster at high temperature.
3. Salt Concentration
ee
High concentration of salts increases the activity of the enzyme.
gin
4. Activators and Inhibitors
Activators are small molecules that increase the activity of the enzyme. Inhibitors are small
molecules that decrease the activity of the enzyme.
en
rn
L ea
w.
ww

ALLOYS
INTRODUCTION
Generally metals are insoluble in ordinary solvents like water, alcohol but a metal can dissolve in
another metal in molten state forming a homogeneous liquid mixture. This on cooling solidifies to a solid
mixture called an alloy. Most of the metals can mix up in all proportions forming alloys, e.g. tin and lead.
Alloys are formed not only by metals among themselves, but also by metal and non-metal. From the above
explanation, it is clear that an alloy contains atleast one metal.
DEFINITION
An alloy is defined as “homogeneous solid solution of two or more different elements, one of which
at least is essentially a metal”. Alloys containing Hg as a constituent element are called amalgams.
The metals in excess amount are known as base metal and other elements in lesser amounts are
.in
known as alloying elements.
PROPERTIES OF ALLOY
g
 Alloys are harder, good strength less malleable and ductile.
rin
 Alloys have low electrical conductivity and low melting point than pure metals.
 Alloys resist corrosion and the action of acids. ee
IMPORTANCE (OR) NEED (OR) PURPOSE OF MAKING ALLOYS
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 Generally pure metals possess some useful properties like high melting point, high densities,
malleability, ductility, good thermal and electrical conductivity.
 As said above, the properties of a given metal can be improved by alloying it with some other metal (or)
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non-metal. The purpose of making alloys are as follows:

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1. To increase the hardness of metals

Generally pure metals are soft, but their alloys are hard.
Examples
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(i) Gold and silver are soft metals; they are alloyed with copper to make them hard.
(ii) Addition of 0.5% arsenic makes lead so hard and used for making bullets.
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2. To increase the strength of metals

Pure metals have less strength than their alloys.
Examples
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Pure iron metal has less strength but when alloyed with carbon has more strength.
3. To lower the melting points of metals

Alloying makes the metal easily fusible.
Examples
Wood‟s metal (an alloy of lead, bismuth, tin and cadmium) melts at 60.5° C, which is far below the melting
points of any of these constituent metals.
4. To resist the corrosion of metals

Metals, in pure form, are quite reactive and easily corroded by surroundings, thereby their life is
reduced. If a metal is alloyed, it resist corrosion.
Examples
Pure iron gets rusted, but when it is alloyed with carbon( or) chromium (stainless steel), resists corrosion.

5. To modify chemical activity of metals
Chemical activity of the metal can be increased or decreased by alloying.
Examples
Sodium amalgam is less active than sodium, but aluminium amalgam is more active than aluminium.
6. To modify the colour of metals

The dull coloured metals are improved by alloying with metals
Examples
Brass, an alloy of copper (red) and zinc (silver-white), is white in colour.
7. To Get Good Casting of metals

Some metals expand on solidification but are soft and brittle. The addition of other metals produce
alloys which are hard, fusible and expand on solidification and thus give good casting.
Examples
An alloy of lead with 5% tin and 2% antimony is used for casting printing type, due to its good
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casting property.
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Functions (or) Effect of alloying elements
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Addition of small amounts of certain metals, such as Ni, Cr, Mo, Mn, Si, V and Al imparts some
special properties like hardness, tensile strength, resistance to corrosion and coefficient of expansion, on
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steel.
Such products are known as special steels (or) alloy steels.
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HEAT TREATMENT OF ALLOYS (Steel)
Heat treatment is defined as, “the process of heating and cooling of solid steel article under carefully
controlled conditions,” During heat treatment certain physical properties are altered without altering its
chemical composition.
Purpose of Heat treatment:
(i) Improvement in magnetic and electrical properties.

(ii) Refinement of grain structure.
(iii) Removal of imprisoned gases.
(iv) Removal of internal stress and strain.
(v) Improves fatique and corrosion resistance.
Types of Heat Treatment of Alloys (Steel)
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The different heat-treatment processes are as follows:
1. Annealing 4. Normalizing
2. Hardening 5. Case-Hardening
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3. Tempering a) Carburizing b) Nitriding c) Cyaniding
1. Annealing
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Annealing means softening. This is done by heating the metal to high temperature, followed by slow
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cooling in a furnace.
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Purpose
(i) It increases the machinability.
(ii) It also removes the imprisoned gases.
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Annealing can be done in two ways

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(i) Low temperature annealing (or) process annealing.

(ii) High temperature annealing (or) full annealing.
Types of Annealing
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(i) Low temperature annealing (or) process annealing

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It involves in heating steel to a temperature below the lower critical temperature followed by slow
cooling.
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Purpose
1. It improves machinability by relieving the internal stress (or) strain.
2. It increases ductility and shock-resistance.
3. It reduces hardness.
(ii) High temperature annealing (or) full-annealing
It involves in heating steel to a temperature about 30 to 50° C above the higher critical temperature
and holding it at that temperature for sufficient time to allow the internal changes to take place and then
cooled to room temperature.
Purpose
1. It increases the ductility and machinability.
2. It makes the steel softer, together with an appreciable increase in its toughness.

2.Hardening (or) Quenching
It is the process of heating steel beyond the critical temperature and then suddenly cooling it either in
oil (or) brine-water (or) some other fluid. Hardening increases the hardness of steel. The faster the rate of
cooling, harder will be the steel produced. Medium and high-carbon steels can be hardened, but low-carbon
steels cannot be hardened.
Purpose
1. It increases its resistance to wear, ability to cut other metals and strength, but steel becomes extra
brittle.
2. It increases abrasion-resistance, so that it can be used for making cutting tools.
3.Tempering
It is the process of heating the already hardened steel to a temperature lower than its own hardening
temperature and then slowly cooling it in air.
In tempering, the temperature to which hardened steel is re-heated is of great significance as it
controls the development of the final properties. Thus
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(i) For retaining strength and hardness, reheating temperature should not exceed 400°C.
(ii) For developing better ductility and toughness, reheating temperature should be within 400 − 600° C.
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Purpose
1. It removes any stress and strains that might have developed during quenching.
2. It reduces the brittleness and also some hardness.
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3.It increases toughness and ductility.
4. Cutting-tools like blades, cutters, tool-bites always require tempering.
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4. Normalizing
It is the process of heating steel to a definite temperature (above its higher critical temperature) and
allowing it to cool gradually in air. Normalized steel will not be as soft as an annealed steel but normalizing
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takes much lesser time than annealing process.

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Purpose
1. It recovers the homogeneity of the steel structure.
2. It refines grain structure.
3. It removes the internal stress and strain.
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4. It increases the toughness.

5. Normalized steel is suitable for the use in engineering works.
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5.Case- Hardening (or) Surface hardening

The process of getting a hard and wear resistant surface over a strong, tough and ductile core are
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known as case–hardening. The steel best suited for this are low-carbon and low-alloy steel.
The different case-hardening processes are as follows:
5.a) Carburizing
The mild steel article is taken in a cast iron box containing small pieces of charcoal (carbon
material). It is then heated to about 900 to 950°C and allowed to keep it as such for sufficient time, so that
the carbon is absorbed to required depth.
The article is then allowed to cool slowly within the iron box itself. The outer surface of the article is
converted into high-carbon steel containing about 0.8 to 1.2% carbon.
Purpose: To produce hard-wearing surface on steel article.
5.b) Nitriding
Nitriding is the process of heating the metal alloy in presence of ammonia at a temperature of about
550°C. The nitrogen (obtained by the dissociation of ammonia) combines with the surface of the alloy to
form hard nitride.
Purpose: To get super-hard surface
5.c) Cyaniding
Cyaniding is the process in which pre-heated steel are dipped in a cyanide bath having sodium
cyanide, sodium carbonate and sodium chloride. During this process, carbon and nitrogen gets diffused into
the surface of steel making it hard. The drawback is that cyanide bath are deadly poison.
CLASSIFICATION (or) TYPES OF ALLOYS
Based on the type of base metals, alloys are classified into two types:
1. Ferrous alloys. (e.g) nichrome, stainless steel
2. Non-ferrous alloys. (e.g) brass, bronze
FERROUS ALLOYS (OR) ALLOY STEELS
Ferrous alloys are the type of steels in which the elements like Al, B, Cr, Co, Cu, Mn are present in
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sufficient quantities, in addition to carbon and iron, to improve the properties of steels.
Properties of Ferrous alloys
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1. It has high yield point and high strength.
2. It has sufficient formability, ductility and weldability.
3. It has good corrosion and abrasion resistance.
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4. Distortion and cracking are less.
5. High temperature strength is greater.
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IMPORTANT FERROUS ALLOYS
Nichrome
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Nichrome is an alloy of nickel and chromium. Its composition are

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Metal Composition
Iron 60%
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Nickel 12%
Chromium 26%
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Manganese 2%
Properties
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1. It shows good resistance to oxidation and heat.

2. It possesses high melting point.
3. It can withstand heat upto 1000 to 1100°C.
4. It possesses high electrical resistance.
Uses
It is widely used for making,

1. Resistance coils and heating elements in stoves.
2. Electric iron box and other household electrical appliances.
3. Boiler parts, steam-lines stills, gas-turbines, aero-engine valves, retorts, annealing boxes.
4. Machineries (or) equipments exposed to very high temperatures.
Stainless Steels (or) Corrosion Resistant Steels
These are alloy steels containing chromium together with other elements such as nickel,
molybdenum, etc., Chromium is effective if its content is 16% (or) more. The carbon content in stainless
steel ranges from 0.3 to 1.5%.Stainless steel resists corrosion by atmospheric gases and also by other
chemicals. Protection against corrosion is mainly due to the formation of dense, non - porous, tough film of
chromium oxide at the surface of metal. If this film cracks, it gets automatically healed-up by atmospheric
oxygen.
Types of Stainless Steels
There are two main types of stainless steels.

1. Heat treatable stainless steels.
2. Non-heat treatable stainless steels.
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Heat Treatable Stainless Steels
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Composition
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Heat - treatable stainless steels mainly contain upto 1.2% of carbon and less than 12-16% of chromium.
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Properties
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1.Heat - treatable stainless steels are magnetic, tough and can be worked in cold condition.
2. They can be used upto 800°C.
3. They have good resistant towards weather and water.
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Uses
They are used in making surgical instruments, scissors, blades, etc.,
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(a) Non - Heat Treatable Stainless Steels
These steels possess less strength at high temperature. They are more resistant to corrosion. There are
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of two types of Non-Heat Treatable Stainless Steel according to their composition:

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(i) Magnetic type

Composition
It contains 12 - 22% of chromium and 0.35% of carbon.
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Properties
1. It can be forged, rolled and machined by the use of specially designed tools.
2. It has better corrosion resistance than heat-treatable stainless steel.
Uses
It is used in making chemical equipments and automobile parts.
(i) Non-Magnetic type
Composition
It contains 18 - 26% of chromium, 8 - 21% of nickel and 0.15% of carbon. The total percentage of Cr
and Ni in such steel should be more than 23%.

18/8 Stainless Steel
The steel having 18% Cr and 8% Ni are known as 18/8 stainless steel. It is the most widely used
stainless steel.
Properties
1.It shows maximum corrosion resistance

2.Corrosion resistance can be further increased by adding small amounts of molybdenum.
Uses
It is used in making household utensils, sinks, dental and surgical instruments.
PHASE RULE
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INTRODUCTION
All chemical reactions are broadly classified into 2 types:
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1) Irreversible Reactions : Zn + H2SO4 −−−−−> ZnSO4 + H2↑
2) Reversible reactions:
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(a) Homogeneous reversible reactions
Eg: N2(g ) + 3H2(g) 2NH3(g)
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(b) Heterogeneous reversible reactions
Eg: CaCO3(s) CaO(s) + CO2(g)
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The reversible reactions are represented by 2 arrows in the opposite directions. The homogeneous
reversible reactions can be studied by the law of mass action and the heterogeneous reversible reactions
using the phase rule, given by Willard Gibbs (1874) which is defined as,
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PHASE RULE:
If the equilibrium between any numbers of phases is not influenced by gravitational/electrical/magnetic
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forces but is influenced by pressure, temperature and concentration, then the number of degrees of freedom
(F) is related to the number of components (C) and the number of phases (P) as: F = C − P + 2
EXPLANATION OF TERMS WITH EXAMPLES

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(1) PHASE (P):

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PHASE is defined as, “any homogeneous physically distinct and mechanically separable portions of
a system which is separated from other parts of the system by definite boundaries”.
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a) Gaseous phase (g):

All gases are completely miscible and have no boundaries between them. Hence all gases constitute a
single phase.
Eg: Air, a mixture of O2, H2, N2, CO2 and water vapor, etc., constitutes a single phase.
(b) Liquid Phase (l):

The number of liquid phases depends on the number of liquids present and their miscibility‟s.
(i) If two liquids are immiscible, they will form two separate liquid phases.
(e.g.) Benzene – Water system.
(ii) If two liquids are completely miscible, they will form only one liquid phase. (e.g.) Alcohol - Water
system.

(c) Solid Phase (s):
Every solid constitutes a separate single phase.
(e.g.) Decomposition of CaCO3

CaCO3(s) CaO (s) + CO2(g)
It involves 3 phases namely solid CaCO3, solid CaO and gaseous CO2.
OTHER EXAMPLES:
1) A water system has 3 phases namely one solid, one liquid and one gaseous phase.
Ice(s) Water(l) Vapour(g)
2) A solution of a substance in a solvent constitutes only one phase. (e.g.) Sugar solution in water.
3) An emulsion of oil in water forms two phases
4) MgCO3 (s) MgO (s) + CO2 (g)
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It involves 3 phases, solid MgCO3, solid MgO and gaseous CO2.
5) Rhombic sulphur (s) −−−−> Monoclinic sulphur (s). It forms 2 phases.
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6) Consider the following heterogeneous system.
CuSO4(s) + 5H2O (l) CuSO4 . 5H2O (s)

It involves 3 phases namely, 2 solids and 1 liquid phase.
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2. COMPONENT (C):
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Component is defined as, “the minimum number of independent variable constituents, by means of
which the composition of each phase can be expressed in the form of a chemical equation”.
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Examples:
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(a) Consider a water system consisting of three phases.

The chemical composition of all the three phases is H2O. Hence the number of component is one.
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(b) Sulphur exists in 4 phases namely rhombic, monoclinic, liquid and vapour, but the chemical
composition is only sulphur. Hence it is a one component system.
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(c) Thermal decomposition of CaCO3

CaCO3s) CaO (s) + CO2(g)
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The system has 3 phases namely, solid CaCO3, solid CaO and gaseous CO2 and 2 components, as the
composition of each of the above phases can be expressed as equations considering any two of the three
components present. When CaCO3and CaO are considered as components, the chemical equations are:
Phase Components
CaCO3 CaCO3 + 0CaO
CaO 0CaCO3 + CaO
CO2 CaCO3 − CaO

(d) PCl5(s) PCl3(l) + Cl2(g)
This system has 3 phases and 2 components namely, PCl3 and Cl2.
(e) An aqueous solution of NaCl is a two component system. The constituents are NaCl and H2O.
(f) CuSO4. 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g)
It is also a two component system as components are CuSO4.3H2O and H2O.
(g) In the dissociation of NH4Cl , the following equilibrium occurs.

NH4Cl (s) NH3 (g) + HCl (g)
The system consists of 2 phases namely solid NH4Cl and the gaseous mixture containing NH3 + HCl.
When NH3and HCl are present in equivalent quantities the composition of both the phases can be
represented by NH4Cl and hence the system will be a one component system.
3. DEGREE OF FREEDOM (F)
Degree of freedom is defined as, “the minimum number of independent variable factors like
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temperature, pressure and concentration, which must be fixed in order to define the system completely”.
A system having 1, 2, 3 or 0 degrees of freedom are called as univariant, bivariant, trivariant and
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non-variant systems respectively.
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Examples:
(b) Consider the following equilibrium

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These 3 phases will be in equilibrium only at a particular temperature and pressure. Hence, this
system does not have any degree of freedom, so it is non-variant (or) zero-variant (or) in-variant system.
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(b) Consider the following equilibrium
Liquid Water(l) Water- vapour(g)

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Here liquid water is in equilibrium with water vapour. Hence any one of the degrees of freedom such
as temperature (or) pressure has to be fixed to define the system. Therefore the degree of freedom is one.
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(c) For a gaseous mixture of N2 and H2, both the pressure and temperature must be fixed to define the
system. Hence, the system is bivariant.
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PHASE DIAGRAM
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Phase diagram is a graph obtained by plotting one degree of freedom against the other.
Types of Phase Diagrams
(i) P-T Diagram

If the phase diagram is plotted between temperature and pressure, the diagram is called P -T diagram.
P -T diagram is used for one component system.
(ii) T-C Diagram

If the phase diagram is plotted between temperature and composition, the diagram is called T-C
diagram.T- C diagram is used for two component system

Uses of Phase Diagram:
It helps in
(i) Predicting whether an eutectic alloy (or) a solid solution is formed on cooling a homogeneous liquid
containing mixture of two metals.
(ii) Understanding the properties of materials in the heterogeneous equilibrium system.
(iii) Studying of low melting eutectic alloys, used in soldering.
APPLICATIONS OF PHASE RULE - TO ONE COMPONENT SYSTEM
The Water System
Water exists in 3 possible phases, namely solid ice, liquid water and water-vapour. Hence, there can
be three forms of equilibria, each involving two phases such as.
Solid Ice Liquid Water
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Liquid Water Water- vapour
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Solid Ice Water- vapour
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The phase diagram for the water system is as follows and it contains curves, areas, and triple point.
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Curve OA
 The curve OA is called vapourisation curve, it represents the equilibrium between water and vapour.
 At any point on the curve the following equilibrium will exist.
Liquid Water Water- vapour
 This equilibrium (i.e. line OA) will extend upto the critical temperature (374°C).
 Beyond the critical temperature the equilibrium will disappear and only water vapour will exist
Curve OB
 The curve OB is called sublimation curve of ice, it represents the equilibrium between solid ice and
water-vapour.
Solid Ice Water- vapour
 This equilibrium (i.e.line OB) will extend up to the absolute zero (− 273°C)
 Beyond absolute zero only solid ice will exist and no water-vapour.
Curve OC
 The curve OC is called melting point curve of ice, it represents the equilibrium between ice and water.
Solid Ice Liquid Water

 The curve OC is slightly inclined towards pressure axis. This shows that melting point of ice decreases
with increase of pressure.
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Curve OB′(Metastable Equilibrium)
 The curve OB′ is called vapour pressure curve of the super-cooled water (or) metastable equilibrium
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where the following equilibrium will exist.
Super- cooled water

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Water- vapour
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 Sometimes water can be cooled below it‟s freezing point (0°C) without the formation of ice, this water is
called super-cooled water.
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 Super cooled water is unstable and it can be converted into solid ice by “seeding” (or) by slight
disturbance.
Along the curves OA,OB,OC and OB′

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The no. of phases(P) is 2 ,component(C) is 1 and the degree of freedom of the system is one i.e., univariant.
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This is predicted by the phase rule:
F = C − P + 2; F = 1 − 2 + 2; F = 1
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Therefore, either temperature (or) pressure must be fixed to define the system.
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Point ‘O’ (Triple point)
 The three curves OA, OB and OC meet at a point „O‟, where three phases namely solid ice, liquid water
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and water-vapour are simultaneously at equilibrium.

 This point is called triple point, at this point the following equilibrium will exist
At this point the no. of phases(P) is 3, component(C) is 1 and the degree of freedom of the system is zero
i.e., nonvariant. This is predicted by the phase rule:
F = C − P + 2; F = 1 − 3 + 2; F = 0
This takes place only at a constant temperature (0.0075°C) and pressure (4.58 mm of Hg).

Areas
Areas AOC, BOC, AOB represents liquid water, solid ice and water-vapour respectively where the no.
of phases(P) and component(C) are one. Hence the degree of freedom of the system is two i.e., bivariant.
This is predicted by the phase rule:
F = C − P + 2; F = 1 − 1 + 2; F = 2
Therefore, both temperature and pressure must be fixed to define the system at any point in the areas.
TWO COMPONENT ALLOY SYSTEM (or) MULTI COMPONENT EQUILIBRIA
Reduced Phase Rule (or) Condensed System
The maximum number of degrees of freedom for a two component system will be three, when the
system exists as a single phase.
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F = C − P + 2; F = 2 − 1 + 2; F = 3
In order to represent the conditions of equilibrium graphically, it requires three co-ordinates, namely
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P, T and C. This requires three dimensional graph, which cannot be conveniently represented on paper.
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Therefore, any two of the three variables must be chosen for graphical representation.
A solid-liquid equilibrium of an alloy has practically no gaseous phase and the effect of pressure is
negligible. Therefore, experiments are conducted under atmospheric pressure.
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Thus, the system in which only the solid and liquid phases are considered and the gas phase is
ignored is called a condensed system.
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Since the pressure is kept constant, the phase rule becomes
F′ = C − P + 1
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This equation is called reduced phase rule (or) condensed phase rule.
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Classification of Two Component System
Based on the solubility and reactive ability, the two component systems are classified into three
types.
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(ii) Simple eutectic formation.

(ii) (a) Formation of compound with congruent melting point.
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(b) Formation of compound with incongruent melting point.

(iii) Formation of solid solution.
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(i) Simple Eutectic Formation
A binary system having two substances, which are completely miscible in the liquid state, but
completely immiscible in the solid state, is known as eutectic (easy melt) system. They do not react
chemically. Of the different mixtures of two substances, a mixture having the lowest melting point is known
as the eutectic mixture.
(ii)(a) Formation of compound with congruent melting point
The binary alloy system with two substances form one or more compounds with definite proportions.
Of the compounds, a compound is said to have congruent melting point, if it melts exactly at a constant
temperature into liquid, having the same composition as that of the solid.

(ii) (b) Formation of compound with incongruent melting point
Of the above compounds, a compound is said to have incongruent melting point,

if it decomposes completely at a temperature below its melting point forming a new solid phase with a
different composition from that of the original.
(iii) Formation of solid solution
A binary system in which two substances, especially metals, are completely miscible in both solid and
liquid states form solid solutions and their mixing takes place in the atomic levels. This happens only when
the atomic radius of the two metals
not differ by more than 15%.
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EXPERIMENTAL METHOD OF CONSTRUCTION OF A SIMPLE EUTECTIC PHASE
DIAGRAM
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Thermal Analysis (or) Cooling Curves
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Thermal analysis is a method of studying the cooling curves of various compositions of a system
during solidification. The shapes of the freezing point curves for any system (involving metals) can be
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determined by thermal analysis. The form of cooling curves indicates the composition of the solid.
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Example 1:
A pure solid substance in the fused state is allowed to cool slowly and the temperature is noted at
different time intervals. Then a graph is plotted between temperature and time and it is the cooling curve for
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the pure solid substance.

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Initially the rate of cooling of liquid melt is continuous from „a‟ till the point „b‟, where solid begins
to appear. Then the temperature remains constant until the liquid melt is completely solidified and
solidification completes at the point „c‟.
The horizontal line „bc‟ represents the equilibrium between the solid and liquid melt. After the point
„c‟, along the curve „cd‟ cooling of solid mass begins and the temperature begins to decrease.
Example 2:
If a mixture of two substances (say A and B) in the fused state are allowed to cool slowly, the cooling
curve is obtained as above:

Initially the rate of cooling of liquid melt is continuous from ‘a’ till the point ‘b’. When it reaches the
point ‘b’ one substance (either A or B) begins to solidify out of the melt. This is indicated by a break where
the rate of cooling is different. On further cooling at the break point ‘c’ the second substance also begins to
solidify. Now the temperature remains constant until the liquid melt is completely solidified, which forms
the eutectic mixture along the line ‘cd’. After the break point ‘d’ cooling of solid mass begins. The
temperature of horizontal line „cd‟ gives the eutectic temperature.
The experiment are repeated for different compositions of A and B and the various cooling curves are
recorded.
From the cooling curves of various compositions, the main phase diagram can be drawn by taking
composition in X-axis and the temperature in Y-axis.
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Uses of Cooling Curves:

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1. Melting point and eutectic temperature can be noted.

2. Percentage purity of the compounds can be noted.
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3. The behavior of the compounds can be clearly understood.

4. The composition corresponding to its freezing point yields the composition of the alloy.
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5. The phase diagram for any two component system can be obtained.
BINARY ALLOY SYSTEM (OR) THE SIMPLE EUTECTIC SYSTEM
The Lead-Silver System
The Lead-Silver system is studied at constant pressure and the vapour phase is ignored. Hence the
condensed phase rule is used:
F′ = C − P + 1
The phase diagram of lead-silver system is shown as follows. It contains curves, areas and eutectic
point.

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(i) Curve AO
The curve AO is known as freezing point curve of silver. Point A is the melting point of pure Ag
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(961°C). The curve AO shows the melting point depression of Ag by the successive addition of Pb. Along
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this curve AO, solid Ag and the melt are in equilibrium.
Solid Ag Liquid Melt
F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1
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(ii) Curve BO
The curve BO is known as freezing point curve of lead. Point B is the melting point of pure lead
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(327°C). The curve BO shows the melting point depression of Pb by the successive addition of Ag. Along
this curve BO, solid Pb and the melt are in equilibrium.
Solid Pb Liquid Melt
F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1
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Along the curves AO and BO

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The system is univariant which means either temperature (or) composition must be fixed to define the
system.
(iii) Point ‘O’ (Eutectic point)

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The curves AO and BO meet at point „O‟ at a temperature of 303°C, where three phases (solid Ag,
solid Pb and their liquid melt) are in equilibrium.
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Solid Ag + Solid Pb Liquid Melt

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According to reduced phase rule equation.
F′ = C − P + 1; F′ = 2 − 3 + 1; F′ = 0
The system is non-variant.
The point „O‟ is called eutectic point or eutectic temperature and its corresponding composition,
97.4%Pb + 2.6%Ag, is called eutectic composition.
Below this point the eutectic compound and the metal solidify.
(iv) Area
The area above the line AOB has a single phase (molten Pb+Ag) or liquid melt.
According to reduced phase rule the degree of freedom.
F′ = C − P + 1; F′ = 2 − 1 + 1; F′ = 2

The system is bivariant which means both the temperature and composition have to be fixed to define the
system completely.
The area below the line AO (solid Ag + liquid melt), below the line BO (solid Pb + liquid melt) and
below the point „O‟ (Eutectic compound + solid Ag or solid Pb) have two phases and hence the system is
univariant
F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1.
Application of Pattinson’s process for the desilverisation of Argentiferous lead
The argentiferous lead, having a very small amount of silver (say 0.1%), is heated to a temperature
above its melting point, so that the system has only the liquid phase represented by the point „p‟ in the phase
diagram .
It is then allowed to cool where the temperature decreases along the line „pq‟. As soon as the point
„q‟ is reached, Pb is crystallised out and the solution will contain relatively increasing amounts of „Ag‟. On
further cooling, more and more of „Pb‟ is separated along the line „BO‟. The melt continues to be richer and
richer in Ag until the point „O‟ is reached, where the percentage of Ag rises to 2.6%.
.in
Thus, the process of raising the relative proportions of Ag in the alloy is known as Pattinson‟s
process.
g
Uses of Eutectic system
1. Suitable alloy composition can be predicted.

rin
2. Making solders, used for joining two metal pieces together.
ee
Differences between Melting point, Eutectic point and Triple point
gin
1.Melting Point: It is the temperature at which the solid and liquid phases, having the same composition,
are in equilibrium.
en
Solid A Liquid A
2. Eutectic Point: It is the temperature at which two solids and a liquid phase are in equilibrium
arn
Solid A + Solid B Liquid

3. Triple Point
Le
It is the temperature at which three phases are in equilibrium.
Solid Liquid Vapour

w.
 All the eutectic points are melting points

 All the melting points need not be eutectic points.
ww
 Similarly all the eutectic points are triple points, but all the triple points need not be eutectic points.

UNIT V ENERGY SOURCES AND STORAGE DEVICES

SYLLABUS
Nuclear fission - controlled nuclear fission - nuclear fusion - differences
between nuclear fission and fusion - nuclear chain reactions - nuclear energy -
light water nuclear power plant - breeder reactor - solar energy conversion -
solar cells - wind energy. Batteries, fuel cells and supercapacitors: Types of
batteries – primary battery (dry cell) secondary battery (lead acid battery,
n
lithium-ion-battery) fuel cells – H2-O2 fuel cell.
g.i
Nuclear fission:
Nuclear fission is defined as the process of splitting of heavier nucleus
rin
into two or more smaller nuclei with simultaneous liberation of large amount of
energy.
Example:
92U235+ 0n1 → [92U236] → 56Ba141
ee
+ 36Kr92 + 30n1 + 200.5 MeV (Energy)
gin
Mechanism of nuclear fission:
When U-235 is bombarded by slow moving neutron, unstable U-236 is
en
formed. This nucleus disintegrates into two equal nuclei with the release of
huge amount of energy and few neutrons.
rn
L ea
w.
ww
Characteristics of nuclear fission reaction: (Part-B)

1. Heavy nucleus splits into two or more nuclei.
2. Two or more neutrons are produced by fission of each nucleus.
3. Large quantity of energy is produced during the nuclear fission reaction.

4. All the fission fragments are radioactive in nature, giving off gamma
radiations
5. The atomic weights of nuclear fission product ranges from 70 to 160.
6. All the fission reactions are self-propagating chain reaction because one of
the fission products is neutron.
7. The nuclear reactions can be controlled by absorbing the neutrons using Cd,
Boron.
8. Every secondary neutron released in the fission reaction does not strike the
n
nucleus. Some neutrons escape into air. Hence a chain reaction cannot be
g.i
maintained.
rin
9. The number of neutrons resulting from a single fission is known as
multiplication factor. When it is less than 1, nuclear chain reaction does not
take place.
Nuclear fusion:
ee
gin
The process of combination of lighter nuclei to form heavier nuclei, with
simultaneous liberation of huge amount of energy is called as nuclear energy.
en
Example:
Fusion reaction in sun (Thermo nuclear reactions)
rn
41H1 2 He4 + 2+1e0 + Energy

ea
Characteristics of nuclear fusion:

L
1. There is no limit on the amount of nuclear fusion that can occur.

w.
2. It is possible only when the distance between the nuclei is of the order of
ww
one Fermi.
3. The amount of energy in fusion is four times more than that of fission.
4. Sufficient amount of kinetic energy must be provided to facilitate the
fusion reaction.
5. Only lighter nuclei can undergo nuclear fusion reaction.

Differences between nuclear fission and nuclear fusion: (Part-B)

S.No. Nuclear fission Nuclear fusion
It is the breaking of heavier It is the combination of lighter
1
nucleus. nuclei.
2 It emits radioactive rays. It does not emit radioactive rays.
It takes place at very high
3 It occurs at ordinary temperature.
temperature (>106K).
The mass number and atomic The mass number and atomic
n
g.i
4 number of the fission product is number of the fusion product is
less than the heavier nucleus. higher than the starting elements.
rin
It does not give rise to chain
5 It gives rise to chain reaction.
reaction.
6
7
Neutrons are emitted.
It can be controlled.
ee Positrons are emitted.
It cannot be controlled.
gin
Example:
Example:
8 92U235+ 0n1 → [92U236] →
en
41H1 2He4 + 2+1e0 + Energy

56Ba141 + 36Kr92 + 30n1 + Energy
rn
Nuclear chain reaction:

ea
A fission reaction, where the neutrons from the previous step continue to
L
propagate and repeat the reaction is called nuclear chain reaction.

w.
ww

Reason for less energy:

Some neutrons, released in the fission of U235 may escape into the air
and some absorbed by U239 present as impurity. This will result in breaking
of the chain and the amount of energy released will be less than expected.
How to improve the amount of energy?
1. For a nuclear chain reaction to continue, sufficient amount of U235 must be
present to capture the neutrons.
Critical mass
n
The minimum amount of fissionable material requited to continue the
g.i
nuclear chain reaction is called critical mass.
rin
The critical mass of U-235 is between 1 to 100 Kg.
a) Super critical mass
ee
If the mass of the fissionable material is more than the critical
mass, it is called super critical mass.
gin
b) Sub critical mass.
If the mass of the fissionable material is less than the critical
en
mass, it is called sub critical mass.

2. The super and sub-critical mass may hinder the propagation of the chain
rn
reaction.
ea
Nuclear energy:
The energy released by the nuclear fission is called nuclear fission energy
L
or nuclear energy.
w.
Cause of the release of energy:

ww
The sum of the masses of the products is slightly than the sum of the
masses of the reactants.
The loss in mass gets converted into energy according to the Einstein
equation, E= mc2
Where m- loss in mass, c- velocity, E- energy
Hazards of using nuclear energy:
1. The nuclear radiation can damage the structure of cells in the human
body.
4

2. It causes diseases like cancer and blindness.

3. It causes genetic disorder in a human body.
4. It causes sterility in young generation.
Types of nuclear fission reaction
1. Uncontrolled nuclear fission reaction. Example- Atom bomb
2. Controlled nuclear fission reaction. Example- Nuclear power plant.
LIGHT WATER NUCLEAR POWER PLANT (Part-B)
The arrangement or equipment used to carry out fission reaction under
n
controlled conditions is called nuclear reactor.
g.i
The energy released by the fission reaction in the nuclear reactor can be
rin
used to produce steam which can turn turbines and produce electricity.
COMPONENTS OF A NUCLEAR REACTOR
1. Fuel rods
2. Control rods
ee
gin
3. Moderators
4. Coolant
en
5. Pressure vessel
6. Protective shield
rn
7. Heat exchanger
ea
8. Turbine
1. Fuel rods:
L
The fissionable material used in the nuclear reactor is enriched U-235. It

w.
is used in the form of rods or strips.

ww
Example: U235, Pu239

Function:
It produces fuel and neutrons. This neutron starts nuclear chain
reaction.
2. Control rods
To control the rate of fission of U-235, movable rods made of cadmium
(Cd) or boron (B) are suspended between fuel rods.

These rods absorb the excess neutrons. So the fission reaction proceeds
at steady rate. These rods are lowered and raised as of need.
If the rods are deeply inserted inside the reactor, they will absorb more
neutrons and the reaction becomes very slow. If the rods are pushed outwards,
they will absorb less neutrons and the reaction will be very fast.
113
43𝐶𝑑 + 10𝑛 → 114
43𝐶𝑑 + 𝛾
10 11
5𝐵 + 10𝑛 → 5𝐵 + 𝛾
Example: Cadmium, Boron
n
g.i
Function: It controls the nuclear chain reaction and avoids the damage to the
reactor.
rin
3. Moderators
The substances used to slow down the neutrons are called moderators.
ee
Example: Ordinary water, Heavy water, graphite, beryllium.
Function: The kinetic energy of fast neutron (1meV) is reduced to slow
gin
neutrons (0.25 eV).
en
rn
Fast neutron Slow neutron

Moderator
ea
4. Coolant
L
In order to absorb the heat produced during fission reaction, the coolant
w.
is circulated in the reactor core. It enters the base and leaves at the top. The
ww
heat carried by outgoing liquid is used to produce steam.

Example: Water (act as coolant and moderator), Heavy water, liquid metal (Na or K)
Function: It cools the fuel core.
5. Pressure vessel
It encloses the core and also provides the entrance and exit passages for
coolant.
Function: It withstands the pressure as high as 200 atm.

6. Protective shield
The moderator, control rods and fuel element are enclosed in a chamber
which has a thick concrete shield (10m thick).
Function: The environment and the operating persons are protected from
destruction in case of leakage of radiation.
7. Heat exchanger
It transfers the heat liberated from the reactor core to boil water and
produce steam at about 400Kg/cm2.
n
8. Turbine
g.i
The steam generated in the heat exchanger is used to operate a steam
rin
turbine, which drives a generator to produce electricity.
Working of light water nuclear reactor:
ee
It is the one in which U-235 fuel rods are submerged in water. Here
water acts as coolant and moderator.
gin
en
rn
L ea
w.
ww
Light water nuclear power plant
The fission reaction is controlled by inserting or removing control rods of

B10 automatically from the space in between the fuel rods. The heat emitted is
absorbed by the coolant (light water).

The heated coolant then goes to the heat exchanger containing sea water,
which is converted to steam. The steam drives the turbines, generating
electricity.
Breeder reactor
Breeder reactor is the one which converts non-fissionable material (U238,
Th232) into fissionable material (U235, Pu239). Thus the reactor produces or
breeds more fissionable material than it consumes.
Illustration:
n
g.i
𝑼𝟐𝟑𝟖 𝟏 𝟐𝟑𝟗
𝟗𝟐 + 𝒏𝟎 → 𝑷𝒖𝟗𝟒 + 𝟐𝒆
−
𝑷𝒖𝟐𝟑𝟗 𝟏 𝟏
𝟗𝟒 + 𝒏𝟎 → 𝑭𝒊𝒔𝒔𝒊𝒐𝒏 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 + 𝟑𝒏𝟎
rin
In breeder reactor, three neutrons are emitted during the fission of U239.
Among the three neutrons, only one neutron is used for propagation step. The
ee
other two neutrons are allowed to react with U238. Thus two fissionable atoms
of Pu239 are produced from one fissionable U235. Therefore breeder reactor
gin
produces more fissionable material than it uses. Pu239 is known as secondary
fuel or man-made fuel.
en
rn
L ea
w.
ww
Significance:
1. The non-fissionable materials such as U238 and Th232 are called as fertile
materials.

2. The fissionable materials such as U235 and Pu239 are called as fissile
materials.
3. Efficiency of breeder reactor is more since regeneration of fissile
materials takes place.
Solar energy (Part-B)
Solar energy conversion:
It is the process of conversion of direct sunlight into more useful forms.
It occurs by the following two mechanisms.
n
(i) Thermal conversion
g.i
(ii) Photo conversion
rin
Thermal conversion:
It involves absorption of thermal energy in the form of IR radiation.
ee
Solar energy is an important source for low temperature heat which is
useful for heating buildings, water and refrigeration.
gin
Methods of thermal conversion
1. Solar heat collectors:
en
It consists of natural materials like stones, bricks or materials like glass,

which can absorb heat during day time and release it slowly at night.
rn
Uses: It used in cold places, where houses are kept in hot condition using heat
ea
collectors.
2. Solar water heater:
L
It consists of an insulated box inside of which is painted with black

w.
paint. It is also provided with a glass lid to receive and store solar heat. The
ww
black painted copper coil allows the cold water in and heats it up and flows out
into a storage tank.
Solar water heater

9

Photo conversion:
It involves conversion of light energy directly in to electrical energy.
Example: Photo galvanic cell or solar cell
Photo galvanic cell or solar cell
It is the one which converts the solar energy directly into electrical
energy.
Principle:
The basic principle is based on the photovoltaic effect. When solar rays
n
fall on a two layer of semiconductor devices, a potential difference between two
g.i
layers is produced. This potential difference causes flow of electrons and
rin
produces electricity.
Construction:
ee
Solar cell consists of a p-type semiconductor (Si doped with B) and n-
type semiconductor (Si doped with P). They are in close contact with each
gin
other.
en
rn
ea
Working:
L
When solar rays fall on n-type semiconductor the electrons from the
w.
valence band get promoted to the conduction band and cross p-n junction into
p type semiconductor. Thereby potential difference is produced which causes
ww
flow of electrons and hence current is generated.

Thus when this p and n layers are connected to an external circuit,
electrons flow from n- layer to p-layer and hence current is generated.
10

Applications of solar cells

1. Lighting purpose.
n
g.i
2. Solar pumps can be run by solar battery.
rin
ee
gin
en
rn
ea
Solar pump run by solar cells
3. Used in calculators, electronic watches, radios and TV.

L
4. Used to drive vehicles.

w.
5. Used in space craft and satellites.

ww
Advantages:
1. Solar cells can be used in remote areas and hilly regions.
2. Maintenance cost is low.
3. Solar cells are non-polluting and eco-friendly.
4. Their life time is long.
5. They need not be charged.
11

Disadvantages:
1. Capital cost is high.
2. Storage of solar energy is not possible.
3. It produces only DC current.
4. Solar energy is not available in night time.
Wind energy (Part-B)
• Moving air is called wind.
• Energy recovered from the force of the wind is called wind energy.
n
g.i
• The wind energy is harnessed by making use of wind mills.
Wind mills
rin
The strike of blowing wind on the blades of the wind mill makes it
rotating continuously. The rotational motion of the blade drives a number of
ee
machines like water pump, flour mills and electric generators.
gin
en
rn
L ea
w.
Wind Energy
ww
Nowadays windmill uses large sized propeller blades and connected to a

generator through a shaft. Wind mills are capable of generating about100 kW
electricity.
Wind farms:
When a large number of wind mills are installed and joined together in a
definite pattern it forms a wind farm. The wind farm produces a large amount
of electricity.
12

Condition:
The minimum speed required for satisfactory working of a wind generator is
15Km/hr.
Advantages:
(i) It does not cause any pollution.
(ii) It is very cheap.
(iii) It is renewable.
Disadvantages:
n
1. Public resists for locating the wind forms in populated areas due to noise
g.i
generated by the machines.
rin
2. Wind forms located on the migratory routes of birds will cause hazards.
3. Wind mill interferes with electromagnetic signals.
Batteries
Definition
ee
gin
A battery is an arrangement of several electrochemical cells connected in
series that can be used as a source of direct electric current.
en
Cell: It contains only one anode and one cathode.

Battery: It contains several anodes and cathodes.
rn
Requirements of a battery:
ea
1. It should be light and compact for easy transport.

2. It should have long life both when it is being used and when it is not used.
L
3. The voltage of the battery should not vary appreciably during its use.
w.
Types of battery:
ww
1. Primary battery or Primary cell or Non – reversible battery

2. Secondary battery or Secondary cell or reversible battery
3. Fuel cell or Flow battery
1. Primary battery:
It is the device in which the cell reaction is non-reversible and it cannot
be recharged.
Example: dry cell, mercury cell
13

2. Secondary battery or storage cells.

These cells are rechargeable and reusable. Its electrode reaction can
proceed in either direction. During charging, electrical work is done on the cell
to provide the free energy needed to force the reaction in the non-spontaneous
reaction.
Example: Lead acid cell, Nickel cadmium cell
3. Fuel cell
It is similar to a battery and produce electricity using chemicals. They do
n
not run down like batteries.
g.i
Example: Hydrogen-oxygen cell, methanol fuel cell.
rin
Dry cell or Leclanche’s cell (Part-B)
It is a primary cell which works without fluid component.
Description:
ee
gin
en
rn
L ea
Leclanche’s Cell
w.
ww
✓ A dry cell consists of zinc cylinder which acts as anode.

✓ This zinc cylinder is filled with ammonium chloride, zinc chloride and
MnO2 in the form of paste using starch and water.
✓ A graphite (carbon) rod acts as cathode.
✓ Cathode is immersed in the centre of the cell.
✓ The zinc cylinder has an outer insulation of cardboard case.
14

Working:
❖ When the cell is working, zinc loses electrons and Zn2+ ion gets dissolved
in the electrolyte.
❖ The electrons pass through the circuit and are consumed at the cathode.
❖ This causes discharge of NH4+ ions from the electrolyte.
❖ In the cathode reaction Manganese is reduced from +4 oxidation state to
+3 oxidation state.
❖ The liberation of ammonia gas disrupts the current flow.
n
❖ This is prevented by the presence of ZnCl2
g.i
𝒁𝒏𝑪𝒍𝟐 + 𝟐𝑵𝑯𝟑 → [𝒁𝒏(𝑵𝑯𝟑 )𝟐 ] 𝑪𝒍𝟐 (𝒔)
rin
1. Anode – Zinc powder
2. Cathode – Carbon rod
3. Electrolyte – NH4Cl, ZnCl2 and MnO2
4. Cell representation- Zn(s) /NH4Cl/MnO2(s)
ee
gin
5. Anode reaction (oxidation) (loss of electron):
𝒁𝒏 → 𝒁𝒏𝟐+ + 𝟐𝒆−
en
6. Cathode reaction (reduction) (gain of electron):

rn
𝑵𝑯+ − −
𝟒(𝒂𝒒) + 𝑴𝒏𝑶𝟐(𝒔) + 𝟐𝒆 → 𝑴𝒏𝑶(𝑶𝑯) + 𝑵𝑯𝟑
ea
7. The net reaction is

L
𝒁𝒏 + 𝑵𝑯+
𝟒(𝒂𝒒) + 𝑴𝒏𝑶𝟐(𝒔) → 𝒁𝒏
𝟐+
+ 𝑴𝒏𝑶(𝑶𝑯)− + 𝑵𝑯𝟑
w.
8. The cell develops an e.m.f of 1.5 volt.

9. Disadvantages:
ww
• Its lifetime is less. Since NH4Cl corrodes the zinc container easily.
• Voltage drop occurs.
10. Uses:
It is used in radios, tape recorders, torches and electronic photographic
flash units.
Lead acid battery or Lead storage accumulator (Part-B)
✓ It was invented by Gaston Plante in 1859.
15

✓ It acts both as voltaic cell and electrolytic cell.

✓ On supplying electrical energy, this acts as a voltaic cell.
✓ On recharging, the cell acts as an electrolytic cell.
Description:
❖ It consists of a 3-to 6 number of voltaic cells connected in series.
❖ In each cell, lead acts as a node and PbO2 acts as cathode.
❖ Anode and cathodes are separated by insulators like rubber.
❖ The entire arrangement is immersed in dilute sulphuric acid of 38% by
n
mass with density 1.30 g/ml
g.i
rin
ee
gin
en
Lead storage cell
1. Anode – Lead
rn
2. Cathode – PbO2
ea
3. Electrolyte - dil. H2SO4 (density- 1.38 g/ml)

4. Insulator- rubber or glass fiber.
L
5. Cell representation- Pb /PbSO4 // H2SO4(aq) // PbSO4/ PbO2

w.
6. Anode reaction (oxidation) (loss of electron):

ww
𝑷𝒃(𝒔) + 𝑺𝑶𝟐−
𝟒 → 𝑷𝒃𝑺𝑶𝟒(𝒔) + 𝟐𝒆
−
E0anode=-0.36V
7. Cathode reaction (reduction) (gain of electron):

𝑷𝒃𝑶𝟐(𝒔) + 𝟒𝑯+ + 𝑺𝑶𝟐− −
𝟒 + 𝟐𝒆 → 𝑷𝒃𝑺𝑶𝟒(𝒔) + 𝑯𝟐 𝑶 E0cathode=+1.69V
8. The net reaction:

𝑷𝒃(𝒔) + 𝑷𝒃𝑶𝟐(𝒔) + 𝟒𝑯+ + 𝟐𝑺𝑶𝟐−
𝟒 → 𝟐𝑷𝒃𝑺𝑶𝟒(𝒔) + 𝑯𝟐 𝑶 E0cell=+2.05V
E0cell = E0cathode − E0 anode
E0cell = 1.69 − (−0.36) = 2.05V
16

9. The cell develops an e.m.f of 2 volts.

10. Uses:
1. It is used to supply current mainly in automobiles such as cars,
Buses, trucks etc.
2. It is also used in gas engine ignition, telephone exchanges, hospitals,
power stations.
11. Advantages:
1. It is made easily.
n
2. It produces high current.
g.i
3. Self-discharging rate is low.
rin
4. It acts effectively at low temperature.
12. Disadvantages:
ee
1. Recycling of the battery causes environmental hazards.
2. Mechanical strain reduces the battery capacity.
gin
Lithium ion batteries (LIB) (Part –B)
Lithium ion battery is a secondary battery.
en
It has three components

1. Cathode – positive electrode – Layers of lithium cobalt oxide
rn
2. Anode – negative electrode – Layers of porous carbon (graphite)

ea
3. Electrolyte – Polymer gel

Construction:
L
Both anode and cathode are dipped in a polymer gel and are separated
w.
by perforated plastic separator.

ww
Working:
During charging Li+ ion flows from the positive electrode (cathode) to
negative electrode (anode) through the polymer electrolyte.
Electrons also flow from the positive electrode to negative electrode
through the wire.
The electrons and Li+ ions combine at the negative electrode and deposit
there as Li.
17

Charging reaction:
𝑳𝒊𝑪𝒐𝑶𝟐 + 𝑪 → 𝑳𝒊𝟏−𝒙 𝑪𝒐𝑶𝟐 + 𝑪𝑳𝒊𝒙
n
Discharging reaction:
g.i
𝑳𝒊𝟏−𝒙 𝑪𝒐𝑶𝟐 + 𝑪𝑳𝒊𝒙 → 𝑳𝒊𝑪𝒐𝑶𝟐 + 𝑪
rin
ee
gin
en
During discharging reaction, reverse reaction occurs. That is Li+ ions flow
from negative electrode to positive electrode through electrolyte. Similarly,
rn
electrons also flow from negative electrode to positive electrode through wire.
ea
Thus Li deposits at positive electrode.

Uses:
L
It is used in cell phone, note PC, portable LCD TV, power tools and
w.
electric vehicles.
Lithium battery is the cell of future, why?
ww
1. Its cell voltage is high, 3.0V

2. Since Li is a light weight metal, only 7g (1mole) material is required to
produce 1 mole of electrons
3. Since it has the most negative E0 value, it generates a higher voltage than
the other types of cells.
4. Since all the constituents of the battery are solids, there is no risk of leakage
from the battery.
18

5. This battery can be made in variety of sizes and shapes.

Fuel cells (Part –B)
Fuel cell is a voltaic cell, which converts the chemical energy of the fuels
directly into electricity without combustion.
𝑭𝒖𝒆𝒍 + 𝑶𝒙𝒚𝒈𝒆𝒏 → 𝑶𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 + 𝑬𝒍𝒆𝒄𝒕𝒓𝒊𝒄𝒊𝒕𝒚
Example: 1. Hydrogen – Oxygen fuel cell
2. Methyl alcohol –Oxygen fuel cell
Description:
n
✓ In a fuel cell, the electricity can be generated as long as the fuel and
g.i
oxygen are supplied into the cell.
rin
✓ It consists of anode, cathode and electrolyte.
✓ In a fuel cell, fuel is sent through the anode and the oxygen is supplied
through the cathode.
ee
✓ The electrolyte carries the charged particles from anode to cathode and
gin
vice versa.
Hydrogen – Oxygen fuel cell
en
rn
L ea
w.
ww
1. Anode- Hydrogen gas

2. Cathode- Oxygen gas
3. Electrolyte- 25-40% KOH
4. Electrode- Two porous carbon electrode impregnated with a finely
platinum or nickel as catalyst.
5. Cell representation: H2, C, Pt or Ni /KOH/ C, Pt or Ni, O2
6. Anode reaction:
19

𝑯𝟐 + 𝟐𝑶𝑯− → 𝟐𝑯𝟐 𝑶 + 𝟐𝒆−

7. Cathode reaction:
𝟏
𝑶𝟐 + 𝑯𝟐 𝑶 + 𝟐𝒆− → 𝟐𝑶𝑯−
𝟐
8. Net reaction:
𝟏
𝑯𝟐 + 𝑶𝟐 → 𝑯𝟐 𝑶
𝟐
9. The cell develops the emf of 1.23V.
n
10. The efficiency of hydrogen – oxygen fuel cell is 70 %.
g.i
11. The operating temperature is 60-70 °C.
Advantages:
rin
1. It is highly reliable.
2. It does not cause any pollution.
3. It produces portable water. ee
gin
4. It is used in space vehicles, submarines.
Disadvantages:
en
1. Hydrogen gas is expensive.

2. As hydrogen is a gas, it is difficult to compress in liquid form.
rn
3. High pressure is needed when it is used in automobiles.

Applications:
ea
1. It is used in Apollo spacecraft to produce electricity and water.

L
2. It is used in military and other commercial vehicles of all types.

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Super capacitor (Electro chemical capacitor) (Part –B)

✓ It is high capacity capacitor.
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✓ They store 10 to 100 times more energy per unit volume and deliver
charge much faster than batteries.
✓ Super capacitor use electrostatic double layer capacitance not
conventional solid dielectric.
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Design of the super capacitor
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✓ It consists of two electrodes.
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✓ The electrodes are made of metal coated porous substance like
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powered activated carbon.
✓ The two electrodes are separated by an ion permeable membrane and
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dipped in the electrolyte.

✓ The electrolyte contains positive ions and negative ions and connects
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the electrodes.
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Working:
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❖ When the electrodes are connected to the power source, ions in the
electrolyte forms electrical double layer.
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❖ This electrode/electrolyte interface creates an electric field between

them. Thus electrical energy stores at an electrode/electrolyte interface.
❖ Example: Positive electrode has a layer of negative ions at the
electrode/electrolyte interface and vice versa.
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Advantages:
1. It is highly safe.
2. Its life time is high.(10 to 20 years)
3. It can be charged in seconds.
4. It provides high power density and high load currents.
5. Its performance is good at low temperature.
Disadvantages:
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1. Cost is high.
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2. It cannot be used as source for continuous power supply.
3. If higher voltage is required, the cells must be connected in series.
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4. Self-discharge is high.
Applications:
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1. Voltage stabilization in start /stop system
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2. Energy harvesting
3. Kitchen appliances
4. Consumer electronics
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5. Wind energy
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6. Utility meters
7. Remote power sensors, LEDs, switches
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UNIT IV
FUELS AND COMBUSTION
1. FUEL
A fuel is a combustible substance, containing carbon as the main constituent, which on burning
gives large amount of heat. During the process of combustion of a fuel, the atoms of carbon, hydrogen,
etc., combine with oxygen with simultaneous liberation of heat.
C + O2 → CO2 + 94 k cals.
2H2 + O2 → 2H2O + 68.5 k cals.
The main source of fuel is coal and crude petroleum oil. These are stored fuels available in
Earth‟s crust and are generally called fossil fuels, because they were formed from fossilized remains of
plants and animals.
Classification of fuel: Fuels can be classified:

Types of fuel Natural or primary fuels Artificial or secondary fuels
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Solid Wood, peat, coal, lignite, dung Coke, charcoal, petroleum
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Liquid Crude oil Tar, kerosene, diesel, Petrol
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Gas Natural gas Coal gas, water gas, bio Gas, coke oven gas,
producer gas, CNG, LPG
1.2.PRIMARY SOLID FUEL - COAL eri

Coal is an important primary solid fuel that has been formed as a result of alteration of
vegetable matter under some favorable conditions.
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1.Coalification (or) Metamorphism

The process of conversion (or alteration) of vegetable matter to anthracite (coal) is called
coalification or metamorphism of coal.
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1.2.1 Classification of Coal

Coal is classified on the basis of its rank. The rank of coal indicates its degree of maturity.
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Various types of coal categorized based on carbon content, calorific value, hardness, moisture content,
H, O, N, S content, volatile matter increases
The progressive transformation of wood to anthracite results in
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(i) decrease in moisture content,

(ii) decrease in volatile content,
(iii) decrease in hydrogen, oxygen, nitrogen and sulphur contents,
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(iv) increase in carbon content,

(v) increase in hardness,
(vi) increase in calorific value
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1.3 ANALYSIS OF COAL:

In order to assess the quality of coal the following two types of analysis are made.
1.3.1. Proximate Analysis

It involves the determination of percentage of (i) Moisture content (ii) Volatile
matter (iii) Ash content (iv) Fixed carbon in coal.
1. Moisture Content
About 1 gm of powdered coal sample is taken in a crucible, and is heated at 100 − 105°C in an
electric hot-air oven for 1 hour. The loss in weight of the sample is found out and the percentage of
moisture is calculated as

2. Volatile matter
After the analysis of moisture content the crucible with residual coal sample is covered with a
lid, and is heated at 950 ± 20°C for 7 minutes in a muffle furnace. The loss in weight of the sample is
found out and the % of volatile matter is calculated as loss in weight of the coal.
3. Ash content
After the analysis of volatile matter, the crucible with residual coal sample is heated without lid
at 700 ± 50°C for half an hour in a muffle furnace. The loss in weight of the sample is found out and
the % of ash content is calculated as
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4. Fixed carbon
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It is determined by subtracting the sum total of moisture, volatile and ash contents from 100.
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Significance (or) Importance of Proximate Analysis
S.No Analysis
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Significance
.
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1 Moisture High percentage of moisture is undesirable because

content (i) it reduces the calorific value of coal,
(ii) most of the supplied energy will be wasted for evaporation
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(iii) it increases the transport cost

(iv) produces smoke
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2 Volatile High percentage of volatile matter is undesirable because

matter (i) it reduces the calorific value of coal,
(ii) produces sooty and smoky flame
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(iii) cocking is not possible

(iv) toxic gases will be evolved
3 Ash High percentage of ash content is undesirable because
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content (i) it reduces the calorific value of coal,

(ii) ash causes clinkers, which disturbing the oxygen supply
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(iii) forms flying ash which causes air and land pollution
(iv)it increases the transporting, handling and storage costs,
(v) it involves additional cost in ash disposal.
4 Fixed High percentage of fixed carbon is desirable because

carbon (i) higher the percentage of fixed carbon in a coal, greater is its calorific value,
(ii) the percentage of fixed carbon helps in designing the furnace
1.3.2 Ultimate Analysis

It involves the determination of percentage of (i) carbon and hydrogen contents, (ii) nitrogen
content (iii) sulphur content (iv) ash content (v) oxygen content
1. Carbon and Hydrogen contents

A known amount of the coal sample is burnt in a current of O2 in a combustion apparatus. The
carbon and hydrogen, present in the coal sample, are converted into CO2 and H2O respectively according
to the following equations. For More Visit : www.Learnengineering.in
C + O2 −−−> CO2 ↑
H2 + 1/2 O2 −−−> H2O ↑
The liberated CO2 and H2O vapours are absorbed respectively in KOH and anhydrous CaCl2
tubes of known weights. The increase in weight of KOH tube is due to the formation of CO2 while
increase in weight of CaCl2 tube is due to the formation of H2O. From the weights of CO2 and H2O
formed, the % of carbon and hydrogen present in the coal can be calculated as follows.
2. Nitrogen content
The determination of nitrogen content is carried out by Kjeldahl‟s method. A known amount of
powdered coal sample is heated with con. H2SO4 in presence of K2SO4 (catalyst) in a long necked flask
(called Kjeldahl‟s flask). Nitrogen in the coal is converted into ammonium sulphate and a clear solution
is obtained.
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N2 + 3H2 + H2SO4 −−−> (NH4)2 SO4
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The clear solution is then heated with excess of NaOH and the liberated ammonia is distilled
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over and is absorbed in a known volume of standard N/10 HCl.
(NH4)2 SO4+ 2NaOH −−−> 2NH3 + Na2SO4+ 2H2O
NH3 + HCl −−−> NH4Cl
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The volume of unused N/10 HCl is then determined by titrating it against standard N/10 NaOH.
Thus the amount of acid neutralised by liberated ammonia from coal is determined.
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2. Sulphur content
A known amount of coal sample is burnt completely in a bomb calorimeter. During this process
sulphur is converted into sulphate, which is extracted with water. The extract is then treated with BaCl2
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solution so that sulphates are precipitated as BaSO4. The precipitate is filtered, dried and weighed.
From the weight of BaSO4 obtained, the sulphur present in the coal is calculated as follows.
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3. Ash content
Determination of ash content is carried out as in proximate analysis
4. Oxygen content
The percentage of oxygen is calculated as follows.
Significance (or) Importance of Ultimate Analysis

S.No. Analysis Significances
1 Carbon and (i) Higher the % of carbon and hydrogen, better is the quality of coal and higher is its
hydrogen calorific value.
contents (ii) The % of carbon is helpful in the classification of coal
(iii) Higher % of carbon in coal reduces the size of combustion chamber required.
2 Nitrogen (i) Nitrogen does not have any calorific value, and its presence in coal is undesirable.
content (ii) Good quality coal should have very little nitrogen content.

3 Sulphur its presence in coal is undesirable because
content (i) The combustion products of sulphur, i.e., SO2 and SO3 are toxic and have
corrosion effects on equipments.
(ii) The coal containing sulphur is not suitable for the preparation of metallurgical
coke as it affects the properties of the metal.
3 Ash content High percentage of ash content is undesirable because
(i) it reduces the calorific value of coal,
(ii) ash causes clinkers, which disturbing the oxygen supply
(iii) forms flying ash which causes air and land pollution
(iv) it increases the transporting, handling and storage costs,
(v) it involves additional cost in ash disposal.
4 Oxygen (i) Lower the % of oxygen higher is its calorific value.
content (ii) As the oxygen content increases its moisture holding capacity increases, and the
calorific value of the fuel is reduced.
1.4 CARBONISATION
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When coal is heated strongly in the absence of air (called destructive distillation) it is converted
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into lustrous, dense, porous and coherent mass known as coke. This process of converting coal into
coke is known as Carbonisation.
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Types of carbonization (i) Low temperature carbonization (ii) High temperature carbonization
S.No. low temperature carbonization high temperature carbonization
1
2
It is carried out at 500 - 700˚C
Produces soft semi coke
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It is carried out at 900 - 1200˚C
Produces hard metallurgical coke
3 Yield of coke 75 – 85 % Yield of coke 65 – 75 %
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4 Used for domestic purpose Used for metallurgy

5 Volatile matter is 5 – 15% Volatile matter is 1-3%
6 Low calorific value High calorific value
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7 Strength of coke is low Strength of coke is high

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Caking coals and coking coals

When coals are heated strongly, the mass becomes soft, plastic and fuses to give a coherent
mass. Such type of coals are called Caking Coals. But if the mass so produced is hard, porous and
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strong then the coals are called Coking Coals. Coking coals possess lower volatile matter and are used
for the manufacture of metallurgical coke. Thus all coking coals are caking coals but all caking coals
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are not coking coals.

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SECONDARY SOLID FUEL - METALLURGICAL COKE

When bituminous coal is heated strongly in the absence of air, the volatile matter escapes out
and the mass becomes hard, strong, porous and coherent which is called Metallurgical Coke.
1.5.1 Requisites (or) characteristics of good metallurgical coke
S.No. Requisites Explanation
Purity It should be high. The impurities like moisture, ash, sulphur and phosphorus
1
may contaminate the metal and reduce the calorific value.
2 Porosity Coke should be highly porous so that oxygen will have intimate contact with carbon
3 Strength It should be high to withstand high load
4 Calorific value It should be very high.
5 Combustibility The coke should burn easily.
6 Reactivity The reactivity of the coke should be low because low reactive cokes produce high
temperature
7 Cost It should be cheap and readily available.

1.5.2. MANUFACTURE OF METALLURGICAL COKE (Otto-Hoffman’s by-product oven)
There are so many types of ovens used for the manufacture of metallurgical coke.
But the important one is Otto-Hoffman‟s by product oven.
Objectives & Advantages

(i) increase the thermal efficiency of the carbonisation process and,
(ii) recover the valuable by products (like coal gas, ammonia, benzol oil, etc.,
(iii) heating is done externally by producer gas hence we can save fossil fuel
(iv) the carbonisation time is less.
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1. The oven consists of a number of silica chambers. Each chamber is about 10 − 12 m long, 3 − 4
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m height and 0.4 − 0.45 m wide. Each chamber is provided with a charging hole at the top, it is also
provided with a gas off take valve and iron door at each end for discharging coke.
2. Coal is introduced into the silica chamber and the chambers are closed. The chambers are heated
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to 1200°C by burning the preheated air and the producer gas mixture in the interspaces between the
chambers.
3. The air and gas are preheated by sending them through 2nd and 3rd hot regenerators. Hot flue
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gases produced during carbonisation are allowed to pass through 1st and 4th regenerators until the
temperature has been raised to 1000°C. While 1st and 4th regenerators are heated by hot flue gases,
the 2nd and 3rd regenerators are used for heating the incoming air and gas mixture.
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4. For economical heating, the direction of inlet gases and flue gases are changed frequently. The
above system of recycling the flue gases to produce heat energy is known as the regenerative
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system of heat economy. When the process is complete, the coke is removed and quenched with
water.
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5. Time taken for complete carbonisation is about 12-20 hours. The yield of coke is about 70%.The
valuable by products like coal gas, tar, ammonia, H2S and benzol, etc. can be recovered from flue
gas.
Recovery of by – products
S.No. By - products Recovered by
1 Tar By spraying Liquid Ammonia to dissolve tar. NH3 is again recovered by the
heating the solution.
2 Ammonia By spraying water. Here ammonia gets converted to NH4OH.
3 Naphthalene By spraying cooled water, naphthalene gets condensed.
4 Benzene By spraying petroleum, benzene gets condensed to liquid.
5 Hydrogen The remaining gases are then passed through a purifier packed with moist
Sulphide Fe2O3. Here H2S is retained.
6 Gaseous fuel The final gas left out is called coal gas which is used as a gaseous fuel.

1.6. PRIMARY LIQUID FUELS – PETROLEUM / CRUDE OIL
Crude oil is a mixture of paraffinic, olefinic and aromatic hydrocarbons with small amounts of
organic compounds like N, O and S. The approximate composition of petroleum is:
Constituents Percentage (%)

C 80-87
H 11-15
S 0.1-3.5
N and O 0.1-0.5
Petroleum may be of three types:
1. Paraffinic based – straight chain hydrocarbons
2. Naphthenic based – Cycloparaffins and aromatic
3. Mixed based – both paraffinic and naphthenic
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1.6.1. REFINING OF PETROLEUM (or) CRUDE OIL
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The process of removing impurities like water, sulphur, dissolved salts like MgCl2 and
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separating the crude oil into various fractions having different boiling points is called refining of
petroleum. This process of refining involves the following four steps.
S.No. Various steps

Separation of water
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The crude oil is fed between two highly charged electrodes. Where colloidal
(Cottrell’s Process) water droplets combine to form large drops, which is then separated out from the
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oil.
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2 Removal of harmful Sulphur compounds are removed by adding copper oxide. The copper sulphide
sulphur compounds formed is separated out by filtration.
This process follows electrolysis, which removes dissolved salts like NaCl,
3 Electrical desalting
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MgCl2 etc from oil.

4 Fractional distillation The purified crude oil is heated to 400°C and the vapours are passed at the
bottom of fractionating column. The column has a number of horizontal
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stainless steel trays. On passing the vapours through the trays, they get
condensed and collected according to their boiling points.
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Fractional distillation of crude petroleum
When the vapours of the oil go up in the fractionating column, they become cooler and get
condensed at different trays. The fractions having higher boiling points condense at lower trays
whereas the fractions having lower boiling points condense at higher trays. The gasoline obtained by
this fractional distillation is called straight-run gasoline. Various fractions obtained at different trays
are given in table For More Visit : www.Learnengineering.in
Name of the fraction B.Pt. (˚C) C- atoms Uses

Uncondensed gases Below 30 C1-C4 Liquified petroleum gas
Petroleum ether 30-70 C5–C7 As a solvent
Gasoline or petrol 40-120 C5–C9 Fuel for IC engines.

Naphtha or solvent spirit 120-180 C9–C10 As a solvent, dry cleaning
Kerosene oil 180-250 C10–C16 Fuel for stoves, jet
engines
Diesel oil 250-320 C15–C18 Diesel engine fuel
Heavy oil 320-400 C17–C30 Fuel for ships, production
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of gasoline by cracking
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S.No. Name of the fraction Uses
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1 Lubricating oil As lubricants
2
3
Petroleum jelly or vaseline
Grease
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Used in medicines and cosmetics
As lubricant
4 Paraffin wax Used in candles, boot polishes
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5 Pitch above 400˚C Used for making roads and water proof
roofing.
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1.8. MANUFACTURE OF SYNTHETIC PETROL

The gasoline, obtained from the fractional distillation of crude petroleum oil, is called straight
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run petrol. As the use of gasoline is increased, the amount of straight run gasoline is not enough to
meet the requirement of the present community. Hence, we are in need of finding out a method of
synthesizing petrol.
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Hydrogenation of coal (or) Synthetic petrol

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Coal contains about 4.5% hydrogen compared to about 18% in petroleum. So coal is a
hydrogen deficient compound. If coal is heated with hydrogen to high temperature under high pressure,
it is converted to gasoline. The preparation of liquid fuels from solid coal is called Hydrogenation of
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coal (or) synthetic petrol.

There are two methods available for the hydrogenation of coal
1. Bergius process (or direct method).
2. Fischer-Tropsch process (or indirect method).
1. Bergius process (or) direct method

1. In this process, the finely powdered coal is made into a paste with heavy oil and a catalyst
powder (tin or nickel oleate) is mixed with it.
2. The paste is pumped along with hydrogen gas into the converter, where the paste is
heated to 400 − 450°C under a pressure of 200 − 250 atm.
3. During this process hydrogen combines with coal to form saturated higher hydrocarbons,
which undergo further decomposition at higher temperature to yield mixture of lower
hydrocarbons.
4. The mixture is led to a condenser, where the crude oil is obtained.
5. The crude oil is then fractionated to yield (i) Gasoline (ii) Middle oil (iii) Heavy oil.
6. For
TheMore Visit : www.Learnengineering.in
middle oil is further hydrogenated in vapour phase to yield more gasoline. The heavy
oil is recycled for making paste with fresh coal dust.
7. The yield of gasoline is about 60% of the coal used.
1.9.KNOCKING:
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The sudden explosion (unwanted sound) due to rapid rise in pressure inside the engine is
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known as knocking. It is common in petrol and diesel engine.
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1. Causes of knocking in S.I (Spark Ignition) Engine [Petrol engines]
In a petrol engine, a mixture of gasoline vapour and air at 1:17 ratio is used as fuel. This mixture
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is compressed and ignited by an electric spark. The product of oxidation reaction (combustion)
increases the pressure and pushes the piston down the cylinder. If the combustion proceeds in a
regular way, there is no problem in knocking. But in some cases, the rate of combustion
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(oxidation) will not be uniform due to unwanted chemical constituents of gasoline. The rate of
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ignition of the fuel gradually increases and the final portion of the fuel-air mixture gets ignited
instantaneously producing an explosive sound known as “Knocking”. Knocking petrol engine is
rated by “ Octane number”
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1. OCTANCE NUMBER OR OCTANCE RATING

The octane number is defined as „‟the percentage of iso-octane present in a mixture of iso-
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octane and n-heptane.‟‟

CH3 CH3
CH3 –( CH2)5−CH3
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CH CH2 C CH3
(Octane number = 0)
CH3 CH3
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2. Structure knocking property is based on the Chemical

The knocking tendency of fuel hydrocarbons mainly depends on their chemical structures.
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Knocking property of the fuel reduces the efficiency of engine. So a good gasoline should resist
knocking. The knocking tendency decreases in the following order.
Straight chain paraffins > Branched chain paraffins > Cycloparaffins > Olefins > Aromatics.
Thus olefins of the same carbon-chain length possess better anti-knock properties than the corresponding
paraffins.
Reduction of knocking (or) Improvement of Antiknocking Characteristics
(i) by adding anti-knock agents like Tetra-Ethyl Lead (TEL)
(ii) by blending low octane numbered fuel with high octane numbered fuel.
(iii) now a days aromatic phosphates are used as antiknock agent because it avoids lead pollution.
(iv) by proper cracking

3. LEADED PETROL (ANTI – KNOCKING AGENT)
The anti-knock properties of a gasoline can be improved by the addition of suitable additives.
Tetraethyl lead (TEL) (C2H5)4Pb is an important additive added to petrol. Thus the petrol containing
tetra ethyl lead is called leaded petrol.
4. Mechanism of Knocking
TEL reduces the knocking tendency of hydrocarbon. Knocking follows a free radical mechanism,
leading to a chain growth which results in an explosion. If the chains are terminated before their
growth, knocking will cease. TEL decomposes thermally to form ethyl free radicals which combine
with the growing free radicals of knocking process and thus the chain growth is stopped.
5. Disadvantages of using TEL

When the leaded petrol is used as a fuel, the TEL is converted to lead oxide and metallic lead.
This lead deposits on the spark plug and on cylinder walls which is harmful to engine life. To avoid
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this, small amount of ethylene dibromide is added along with TEL. This ethylene dibromide reacts
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with Pb and PbO to give volatile lead bromide, which goes out along with exhaust gases. But this
creates atmospheric pollution. So nowadays aromatic phosphates are used instead of TEL.
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1.10. KNOCKING IN DIESEL ENGINE:
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1. In diesel (Compresssion) engine, the diesel and air are not sent at same time.
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2. The compressed air is sent first. The compression raises the temperature around 500 C . Now,
the diesel oil is sprayed. This further increases the temperature and pressure. The expanding
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gases push the piston and power stroke begins.

3. The time difference between the diesel injection and its ignition is known as “ignition lag”.
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4. If diesel contains any impurity, the ignition will be delayed. This delayed ignition lag increases
the accumulate pion of vapour, hence increases the pressure rapidly and knocking occurs.
5. Knocking of diesel engine is rated by „cetane number‟
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6. CETANE NUMBER OR CETANE RATING

The cetane number is defined as "the percentage of hexa decane present in a mixture of hexa
decane
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and α-methyl naphthalene, which has the same ignition lag as the fuel under test".
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Cetane number is introduced to express the knocking characteristics of diesel. Cetane (hexa
decane) (C16H34) has a very short ignition lag and hence its cetane number is taken as 100. On
the other
hand α-methyl naphthalene has a long ignition lag and hence its cetane number is taken as zero.
7. The cetane number decreases in the following order.
Straight chain paraffins > Cycloparaffins > Olefins > Branched paraffins > Aromatics.
8. The cetane number of a diesel oil can be increased by adding additives called
dopes. Ex:Ethyl nitrate, Iso-amyl nitrate.

9. Differences between petrol (gasoline) and Diesel
S.No. Petrol Diesel
1. Fuel for SI engines Fuel for CI engine
2 Low boiling fraction High boiling fraction
3 Liberates more pollutants Less pollutants
4 It is rated by octane number It is rated by cetane number
5 Knocking is due to premature ignition Knocking is due to delayed ignition lag
6 Knocking is prevented by anti-knocking Knocking is prevented by dopes (Eg. Iso amyl
agent (Eg. TEL) nitrate)
1.11. SECONDARY GASEOUS FUELS - COMPRESSED NATURAL GAS (CNG)

When the natural gas is compressed, it is called Compressed Natural Gas (CNG). The primary
component present in CNG is methane. It is mainly derived from natural gas. The natural gas can
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either be stored in a tank of a vehicle as compressed natural gas (CNG) at 3,000 or 3,600 psi or as
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liquified natural gas (LNG) at typically 20-150 psi. The average composition of CNG is as follows
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Methane
Ethane
Propane
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5.5
3.7
Butane 1.8
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Pentane 0.5
Properties
1. CNG is the cheapest, cleanest and least environmentally impacting alternative fuel.
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2. Vehicles powered by CNG produce less carbon monoxide and hydrocarbon (HC) emission.
3. It is less expensive than petrol and diesel.
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4. The ignition temperature of CNG is about 550°C.

5. CNG requires more air for ignition.
Uses : CNG is used to run an automobile vehicle just like LPG.
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Advantages of CNG over LPG

1. CNG produces less pollutants than LPG.
2. CNG is cheaper and cleaner than LPG.
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3. The octane rating of CNG is high; hence the thermal efficiency is more.
4. It does not evolve sulphur and nitrogen gases.
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5. It mixes very easily with air than the other gaseous fuels.
6. Noise level is much less than diesel
7. CNG vehicle limit 40% less of nitrogen oxide, 90% less of hydrocarbons, 25% less of CO2
Comparison of emission levels between CNG - driven vehicles and petrol driven vehicles
Emission levels
Pollutants
Petrol driven vehicle CNG driven vehicle
CO (g/km) 0.92 0.05
HC (g/km) 0.36 0.24
1.12. LIQUEFIED PETROLEUM GAS (LPG)

It is obtained as a by-product during fractional distillation of crude petroleum oil or by
cracking of heavy oil. It consists of propane and butane. It can be readily liquefied under pressure, so it
can be economically stored and transported in cylinders. The average composition of LPG is as follows

n-Butane 38.5
Isobutane 37
Propane 24.5
3
Calorific value 25,000kcal/m
Uses: (1) It is used as a domestic and industrial fuel (2) It is also used as a motor fuel.
Advantages of LPG over gaseous fuels
1. LPG consists of hydrocarbons, so it burns cleanly without leaving any residue.
2. The LPG (hydrocarbons) has higher calorific value than the other gaseous fuels containing H2 or
CO. The calorific value is 7 times higher than coal gas and 3 times higher than natural gas.
3. LPG is characterized by high thermal efficiency and heating rate.
4. It is easy to manipulate.
5. Comparatively it is less of health hazard, even in case of leakage.
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6. It is free from CO, so it is less hazardous.
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Disadvantages of LPG over other gaseous fuels.
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1. Due to its faint odour, leakage cannot be easily detected.
2. Its octane value is low.
3. Handling must be done under high pressure.
COMBUSTION OF FUELS
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4. LPG is suitable only for the engines working under high compression ratio.
2.1. INTRODUCTION
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Combustion is a process of rapid exothermic oxidation in which a fuel burns in the presence of
oxygen with the evolution of heat and light.
Aim of combustion is to get the maximum amount of heat from a combustible substance in the
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shortest time. Most of the combustible substances are enriched with carbon and hydrogen. During
combustion they undergo thermal decomposition to give simpler products, which are oxidised to CO 2,
H2O, etc.,
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C + O2 −−−> CO2 ; Exothermic.

H2+ ½O2 −−−> H2O ; Exothermic.
Since the above reactions are exothermic, large quantity of heat is given out.
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2.2. CALORIFIC VALUE

The efficiency of a fuel can be understood by its calorific value. The calorific value of fuel is
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defined as the total amount of heat liberated, when a unit mass of fuel is burnt completely.
UNITS OF CALORIFIC VALUES
The quantity of heat can be measured by the following units:
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(i) Calorie.
(ii) Kilocalorie.
(iii) British Thermal Unit (B.T.U).
(iv) Centigrade Heat Unit (C.H.U).
Calorie: It is defined as the amount of heat required to raise the temperature of 1 gram of water
through 1°C (15 to 16°C).
2.3 HIGHER AND LOWER CALORIFIC VALUES ( Dulong’s Formula) 2.3.1 Higher (or) Gross
calorific value (GCV)
It is defined as the total amount of heat produced, when a unit quantity of the fuel is
completely burnt and the products of combustion are cooled to room temperature. GCV (or)
HCV
[ ( ) ]

2.3.2 Lower (or) Net Calorific Value (NCV)
It is defined as the net heat produced, when a unit quantity of the fuel is completely burnt and the
products of combustion are allowed to escape.
Thus * ( )+
2.5 PROBLEMS BASED ON CALORIFIC VALUE :

Calculate the gross and net calorific value of coal having the following composition carbon - 85%,
hydrogen – 8%, sulphur – 1%, nitrogen – 2%, ash – 4%, latent heat of steam – 587 cals/g
Solution:
[ ( ) ]
GCV= 1/100[8080*85+34500*(8-0/8)+2240*1] Kcal/Kg
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= 1/100[686800+276000+2240] Kcal/Kg
= 9650.4 Kcal/Kg
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[ ( )]
= 9650.4 - 0.09*8*587
= 9227.76 Kcal/Kg
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2.6 FLUE GAS ANALYSIS (ORSAT’S METHOD)
The mixture of gases (like CO2, O2, CO, etc) coming out from the combustion chamber is called flue
gases. The analysis of a flue gas would give an idea about the complete or incomplete combustion process.
The analysis of flue gases is carried out by using Orsat‟s apparatus.
Description of Orsat’s apparatus
It consists of a horizontal tube. At one end of this tube, U-tube containing fused CaCl2 is connected
through 3-way stop cock. The other end of this tube is connected with a graduated burette. The burette is
surrounded by a water-jacket to keep the temperature of gas constant. The lower end of the burette is
connected to a water reservoir by means of a rubber tube. The level of water in the burette can be raised or
lowered by raising or lowering the reservoir.
The horizontal tube is also connected with three different absorption bulbs I, II, and III for absorbing
CO2, O2 and CO.
I-Bulb: It contains potassium hydroxide solution, and it absorbs only CO2.
II-Bulb: It contains alkaline pyrogallol solution, and it absorbs CO2 and O2.
III-Bulb:It contains „ammoniacal cuprous chloride solution and it absorbs CO2, O2 and CO.
Precautions
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1. Care must be taken in such a way that, the reagents in the absorption bulb 1, 2 and 3 should be
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brought to the etched marked level one by one by raising and lowering reservoir bottle.
2. All the air from the reservoir bottle is expelled to atmosphere by lifting the reservoir bottle.
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3. It is essential that CO2, O2 and CO are absorbed in that order only.
4. As the CO content in flue gas is very small, it should be measured quite carefully.
Working:
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The 3-way stop-cock is opened to the atmosphere and the reservoir is raised, till the burette is
completely filled with water and air is excluded from the burette. The 3-way stop-cock is now connected to
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the flue gas supply and the flue gas is sucked into the burette and the volume of flue gas is adjused to 100 cc
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by raising and lowering the reservoir. Then the 3-way stop cock is closed.
(a) Absorption of CO2: The stopper of the absorption bulb-I, containing KOH solution, is opened
and all the gas is passed into the bulb-I by raising the level of water in the burette. The gas enters into the
bulb-I, where CO2 present in the flue gas is absorbed by KOH. The gas is again sent to the burette. This
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process is repeated several times to ensure complete absorption of CO2. The decrease in volume of the flue
gas in the burette indicates the volume of CO2 in 100 cc of the flue gas.
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(b) Absorption of O2: Stop-cock of bulb-I is closed and stop cock of bulb-II is opened. The gas is
again sent into the absorption bulb-II, where O2 present in the flue gas is absorbed by alkaline pyrogallol.
The decrease in volume of the flue gas in the burette indicates the volume of O2.
(c) Absorption of CO: Now stop-cock of bulb-II is closed and stop-cock of bulb-III is opened. The
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remaining gas is sent into the absorption bulb-III, where CO present in the flue gas is absorbed by
ammoniacal cuprous chloride. The decrease in volume of the flue gas in the burette indicates the volume of
CO. The remaining gas in the burette after the absorption of CO2, O2 & CO is taken as nitrogen.
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Significance (or) uses of flue gas analysis

1. Flue gas analysis gives an idea about the complete or incomplete combustion process.
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2. If the flue gases contain considerable amount of CO, it indicates that incomplete
combustion is occuring and it also indicates that the short supply of O2.
3. If the flue gases contain considerable amount of O2, it indicates that complete combustion
is occuring and also it indicates that the excess of O2 is supplied.

IGNITION TEMPERATURE
The lowest temperature to which the fuel must be heated for its smooth burning is known as ignition
temperature. In case of liquid fuels, ignition temperature is known as flash point.
Examples
S.No. Type of fuel Ignition temperature (oC)
1 Solid coal 300
2 Liquid fuels 200 – 450
3 Gaseous fuels 800
The minimum temperature at which the fuel catches fire spontaneously without any external heating is
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known as Spontaneous Ignition Temperature (SIT). Pulvarised coal, oil rags, cotton wastes get oxidized
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slowly. If the heat evolved is unable to escape, the temperature in the system goes on increasing and when
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SIT is reached, the system catches fire on its own.
Significance of SIT:
EXPLOSIVE RANGE (LIMITS OF INFLAMMABILITY)

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A low SIT value indicates the ready ignition of the fuel and also means a fire hazard.
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For a fuel to burn, it should be mixed with air in proper ratio.
The fuel should be present in the fuel – air mixture in a particular range.
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The gaseous fuels have two extreme limits in the mixture – a) Upper limit b) Lower limit
The range covered by these two extreme (Upper and lower) limits are known as explosive range or limits of
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inflammability.
Significance:
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For continuous burning , the amount of fuel present in fuel – air mixture should not go below the lower limit
or above the upper limit.
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For example, the explosive range of petrol is 2 – 4.5. This means, when the concentration of petrol vapour
in petro-air mixture is between 2 – 4.5 by volume, the mixture will burn on ignition. When it is below 2%
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or above 4.5% by volume, the burning will not be proper.
Example:
S.No. Fuel Explosive range %

1 Hydrogen 4 – 75
2 Carbon monoxide 13 – 74
3 Acetylene 3 – 80
4 Natural gas 5 – 14

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UNIT – I Water and its treatment

a) Eriochrome Black – T indicator gives red colour in hard water.

b) Permanent hardness (Non-carbonate): The hardness due to chlorides and sulphates

CaCl2 + Na2CO3  CaCO3 + 2NaCl ( Lime soda process)

CaSO4 + Na2Ze (Zeolite)  CaZe + Na2SO4 (Zeolite process)

i) ppm ii) mg/L iii) degree Clarkes iv) Degree French

1 ppm – 1 part by weight of CaCO3 equivalent hardness/106 parts of water

1 mg/L – 1mg of CaCO3 / 1 Lr of water

ESTIMATION OF HARDNESS BY EDTA METHOD:

Na-OOC-H2C CH2 –COO-H

S.No. Content Titration-I Titration-II Titration-III

2 Pipette(20 ml) Std. Hardwater Sample water Boiled water

Step1 – Standardisation of EDTA

1 ml of Std. Hard water = 1 mg of CaCO3 (Given)

So, 20 ml of Std. Hard water = 20 mg of CaCO3

V1 ml of EDTA is required for = 20 mg of CaCO3

Therefore, 1ml of EDTA = 20 / V1 mg of CaCO3

Step 2: Finding Total hardness:

20ml of sample water required = V2 ml of EDTA

Therefore, 1000ml of sample requires = V2 X 20 X 1000 mg of CaCO3

Hence, total hardness = V2 X 1000 ppm

Step 4 : Temporary hardness = Total hardness – permanent hardness

1.2) Boiler Troubles

2. Requirements for boiler water

S.No. Requirements for boiler water If not, it will cause

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Reasons for sludge and scale:

Disadvantages of scales and sludges:

high pressure. This leads to explosion.

Examples of Scale deposits:

S.No. Name of the deposit Properties

3 Mg(OH)2 deposit It is formed due to decomposition of magnesium bicarbonate. It reacts with

4 SiO2 deposit It forms a hard, porcelain coating on the boiler surface.

5 Fe deposit It causes dark coloured magnetic deposits.

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Differences between sludge and scale:

S.No. Sludge Scale

1.3) External treatment

i) Hydrated sodium alumino silicates available in nature are known as zeolite.

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iii) Zeolite softeners may be of pressure type or gravity type.

CaSO4 + Na2Ze  CaZe + Na2SO4

i) On prolonged use, all the zeolite sodium ions are exhausted.

The regeneration step comprises of a) backwashing b) salting c) rinsing before reuse

CaZe + 2 NaCl  Na2Ze + CaCl2

MgZe + 2 NaCl  Na2Ze + MgCl2

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2. As the zeolite can be regenerated, the method is cheap.

4. The space requirement for this setup is minimum.

5. No sludge is formed during this process.

Disadvantages of zeolite process:

1.3) - B).Ion exchange method - ( Demineralisation)

3. The resins are prepared by copolymerization of styrene and di vinyl benzene.

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6. So, the resultant water is free from all types of ions.

R Ca + 2 HCl  RH2 + CaCl2

i) Can be used for high pressure boilers also.

Drawbacks of Ionexchange method:

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S. No. Soft water Demineralized water

Differences between Zeolite and ion exchange process:

S.No. Zeolite process Ion exchange process