CY3151 Engineering Chemistry - 02 - by 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.

b) With soap, hard water gives a scummy precipitate.
ww 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
a
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
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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.
CaCl2 + Na2CO3  CaCO3 + 2NaCl ( Lime soda process)

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CaSO4 + Na2Ze (Zeolite)  CaZe + Na2SO4 (Zeolite process)
4. Units of hardness:
i) ppm ii) mg/L iii) degree Clarkes iv) Degree French et

1 ppm – 1 part by weight of CaCO3 equivalent hardness/106 parts of water
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.
(Wine red/unstable) (Stable) ngi

[Ca / Mg –EBT] + EDTA  [Ca / Mg –EDTA] + EBT
(Steel blue)
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So, the end point is the colour change from wine red to steel blue.
4. Short Procedure:
S.No. Content Titration-I
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Titration-II
Standardisation of Total Hardness
Titration-III
permanent
1 Burette
EDTA
EDTA g.n
StandardEDTA
Hardness
standardEDTA
2
3
4
Pipette(20 ml)
Additional solution
Indicator
Std. Hardwater Sample water
10ml of NH3 buffer 10ml of NH3
EBT
buffer
EBT
Boiled water
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10ml of NH3 buffer
EBT
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
Step 3: Finding Permanent hardness:
ww20ml of boiled water required = V3 ml of EDTA
w.E = V3 X 20 mg of CaCO3
V1
a
Therefore, 1000ml of boiled sample requires = V3 X 20 X 1000 mg of CaCO3
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Hence, permanent hardness =

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V3 X 1000 ppm
V1
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Step 4 : Temporary hardness = Total hardness – permanent hardness
1.2) Boiler Troubles rin

1 .Definition: g.n
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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”.
2. Requirements for boiler water
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:
a) Wastage of fuel:
Scales have low thermal conductivity. So, the heat transfer from boiler to inside water may not be
wwsufficient. 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
a
b) Decrease in efficiency:
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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: ngi

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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
high pressure. This leads to explosion.
Examples of Scale deposits: rin

S.No. Name of the deposit Properties
1 CaCO3 Deposit g.n
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.
2 CaSO4 deposit At high temperature and high pressure boilers, It forms harder and denser
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
3
ww
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
4 w.E explosion etc.,

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 ,
a
process is known as “blow down” method.
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ii) Internal carbonate, phosphate, Calgon
conditioning
iii) Mechanical hard scrubbing methods.
5 Diagram:
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1.3) External treatment et
Removal of impurities, salts from boiler feed water before feeding it to the boiler is known as
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
MgSO4 + Na2Ze  MgZe + Na2SO4
wwCaCl2 + 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
Regeneration:
a
hardness. But in cannot be used in boiler.
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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
regenerated.
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iii) The exhausted zeolite is regenerated by treating with 10% solution of NaCl.
Regeneration reaction:
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The regeneration step comprises of a) backwashing b) salting c) rinsing before reuse
CaZe + 2 NaCl  Na2Ze + CaCl2
MgZe + 2 NaCl  Na2Ze + MgCl2 et

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:
1. Turbid water cannot be treated as it blocks the pores of the zeolite bed.
ww2. 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: nee
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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.
g.n
2. Resins are long chain, insoluble, cross linked, organic polymers. There are 2 types.
Cation exchange resins – RH2 (e.g) Sulphonated coals , RSO3H
i)
ii) Anion exchange resins. R‟(OH)2 (e.g)Ureaformaldehyde,Amines R-NH2
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
Advantages of Ion exchange method:
ww i) Can be used for high pressure boilers also.

ii)
iii)
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It can treat highly acidic or alkaline water.
We can get pure water as hardness as low of 2 ppm.
i)
ii)
a
Drawbacks of Ionexchange method:
Expensive syE
Fe, Mn cannot be removed as they form complexes with resins
iii)
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Cannot be used for turbid water as they clog the resins.
Diagram:
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g.n
et

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
1 It exchanges only cations. It exchanges cations and anions

2 The cylinder is filled with zeolite. The cylinders are using
ww Na2O. Al2O3. xSiO2.yH2O cationexchange resin - RH2

Anion exchange resin - R‟(OH)2
3
4
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NaCl is used for regeneration HCl, NaOH are used for regeneration.
Softening involves removal of only hardness Demineralization involves removal of all the ions
causing ions. present in water.
5
a
The treated water contains relatively large
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amount of dissolved Na salts which causes
caustic embrittlement in boilers.
The treated water does not contain any dissolved
salts. They may not cause any boiler troubles.
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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
8
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Acidic water cannot be treated because acid Acidic water can be treated.
decomposes the zeolite.
1.4. INTERNAL TREATMENT METHODS rin

g.n
i) The residual salts that are not removed by external methods can be removed by adding some
chemicals directly into the boiler water.
ii) These chemicals are known as „Boiler compounds’.

treatment‟ (or) sequesterisation.
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This method is known as „Internal
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
b) Phosphate conditioning:
ww 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.
a
iv) For better results, a pH range of 9.5 – 10.5 is recommended.
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3CaSO4 + 2 Na3PO4  Ca3(PO4)2 + 3 Na2SO4
Three types of Phosphate salts are used:

S.No. Salt Name ngi Used for treating
1 Na3PO4 Tri sodium Phosphate nee highly acidic water
2 Na2HPO4 Di sodium hydrogen Phosphate

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slightly acidic water
3 NaH2PO4 Sodium di hydrogen phosphate

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highly alkaline water
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
and other colloidal impurities.
wwiv) 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
etc., which get coated over the scale forming precipitates.
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iii) This converts the scale into sludge and they are removed by blow down operation methods.
f) EDTA complexometric conditioning:
i) At basic PH, EDTA is added to boiler water.

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g.n
ii) EDTA binds the scale forming cations to form soluble complex. Thus scale formation is
prevented.
[Ca2+ / Mg 2+] + EDTA  [Ca / Mg –EDTA]
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’.
7. The membrane is madeup of cellulose acetate, cellulose butyrate, polymethacrylate
wwAdvantages 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
a
demineralization method.
3. Low capital cost. syE

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.,
Disadvantages:
1. Periodical cleaning of membrane is needed. g.n

2. Pretreatment for bacterial removal is needed. et
Diagram:

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.
2. Adsorbent:
The surface on which adsorption takes place is known adsorbent. (e.g.) Nickel,
wwCharcoal.
3. Adsorbate:
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The substance which gets adsorbed on adsorbent is known as adsorbate. (e.g.) H2 gas
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4. Absorption:
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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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g.n
(e.g) Absorption of ink on the surface of a chalk.
5. Sorption:
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It is the process in which both adsorption and absorption take place simultaneously.
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
7
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TYPES OF ADSORPTION
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1. Physical adsorption/ Physisorption
It is a process in which gas/solid/liquid are held on the solid surface through weak
vander walls forces it is termed as ‘Physisorption’. (e.g) H 2 on charcoal.
2. Chemical adsorption/Chemisorption: ngi

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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:
No
1
PHYSISORPTION
Adsorption is due to weak g.n
CHEMISORPTION
Due to strong covalent bonding.
2
3
4
Vanderwaal’s forces.
Adsorption is multilayer.
Adsorption is completely reversible
The Equilibrium is established rapidly
Adsorption is monolayer
Adsorption is irreversible
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.
(eg.) Charcoal and Silica gel.
(iii) Heats (or) Enthalpy of adsorption
ww 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
formed.
a
removes under reverse conditions of temperature and pressure.
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Chemical adsorption is not a reversible process, because a surface compound is
(v) Effect of pressure
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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.
(vi) Effect of temperature
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Physical adsorption: It occurs rapidly at lower temperature and decreases with
increase in temperature.
g.n
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.
Eg. Activated charcoal adsorbs coloring matter present in sugar solution.
2. An adsorbent also adsorbs certain substance from the solution in preference to other
ww 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
a
Extent of the adsorption of solute from the solution depends on temperature and
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concentration. Effect of the concentration is explained by the Freundlich adsorption
isotherm.
𝑥
𝑚
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= 𝐾𝐶
(a) Negative adsorption

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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
x/m= extent of adsorption
ww 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)
Where y = log (x / m) ;
m = (1/n) ; C = log k g.n
so, the plot will be a line with slope 1/n and intercept log k.
et

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

Adsorbate
Adsorbent
ww Charcoal
-1830C
Non
silica gel
0
-195 C
porous Porous Silica Porous Ferric oxide Porous Charcoal
gel
0
83 C
gel
500C 1000C
Temperature
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Chemisorption Physisorption Physisorption Condensation in Condensation in
Characteristics
a
(monolayer)
Saturation at
(Multilayer)
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Multilayer
the forms after the
(Multilayer)
Multilayer
forms before
pores/Capillaries
Saturation at the
multilayer
pores/Capillaries
Multilayer
formed at the
is
Explanation
monolayer
formation
completion of
monolayer
ngithe
completion of
monolayer
formation beginning
adsorption
process
of
nee
Diagram
rin
g.n
FREUNDLICH’S ADSORPTION ISOTHERM:
The relation between adsorption and pressure at constant temperature is known as

et
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:
Case 1: At low pressure, adsorption is proportional to pressure.
ww ∞𝑃
= 𝐾𝑃
w.E
Case 2: At high pressure, adsorption is almost constant.
a
=K
syE
=KP
ngi
Case 3: At intermediate pressure.
= 𝐾𝑃
nee
This is known as Freundlich adsorption isotherm.
rin
Limitations of Freundlich isotherm:
g.n
1. It is only an empirical formula and it has no theoretical basis.
2. It is deviated at high pressure.
3. It is not good at high concentration.
et
4. n and K are temperature dependent.
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
Gas + Solid G–S where, ka = Adsorption rate constant
ww kd
2. Let us consider,
kd = Desorption rate constant
w.E
Total area of adsorbent = 1cm2
Surface area adsorbed by gas molecule = θ
Then, surface area available for adsorption =(1-θ)
a syE
3. Rate of adsorption, Ra = Ka (1-θ) P
Rate of desorption, Rd = kd . θ
--- 1
--- 2
4. At equilibrium,
ngi --- 3
𝑅 =𝑅
𝐾 𝜃 = 𝐾 (1 − 𝜃)𝑃 nee
𝐾 𝜃 = 𝐾 𝑃 − 𝐾 𝜃𝑃 rin
𝐾 𝜃 + 𝐾 𝜃𝑃 = 𝐾 𝑃 g.n
𝜃(𝐾 + 𝐾 𝑃) = 𝐾 𝑃
𝜃= --- 4
et
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
adsorption isotherm.
Rearranging the equation 5.
ww 1 + 𝐾𝑃 =
𝐾´𝐾𝑃
𝑥
w.E ´
+
´
𝑃= --6
a syE
ngi
nee
A plot of P vs gives a straight line with a slope of
´
rin
and an intercept of
´
Case 1: At low pressure, P is very low and 𝑃 term is negligible

´ g.n
1
≫
𝐾
𝐾´𝐾 𝐾´𝐾
𝑃
et
= (or) 𝑥 = 𝑃𝐾´𝐾
´
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
Action of heterogeneous catalyst
Various steps involved in the heterogeneous catalysis are explained with an example
wwHydrogenation of ethylene using Ni catalyst
H
w.E
H
H2
Ni(s)
H H
H C C H
H
C C
H
Ethylene (gas)
a +
syE
H H
Ethane (gas)
Step I Adsorption of reactant molecules
ngi
Active centers in the catalyst surface adsorbs the gaseous reactant.
Physisorption
H H
nee
Chemisorption
H H
Ni Ni + H2 Ni Ni
rin Ni Ni
Step II Formation of activated complex

g.n
H
H
H
C C
+
H
H
H
H
H
C
H
C
H
H
H
et
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
i
N N N
ww i i i
Free valencies in combined state = 10 Divided state valencies = (6 x 4)=24
w.E
Fineness of the catalyst increase, the free surface area gets increases, thereby free
valencies increases.
a
3. Enhanced activity of a rough surfaced catalyst
syE
It possess “Cracks”, “Peaks”, “Corners” etc., and consequently have larger number of
active centers. These active centers increase the rate of reaction.
ngi
nee
rin
4. Action of promoters
g.n
Promoters are defined as the substances, which increase the activity of a catalyst.
Promoters change the lattice spacing
et
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.
1. Down flow carbon contactors.
2. Upflow carbon contactors.
ww(a) Down flow Carbon Contactors
w.E
It usually consist of two (or) three columns operated in series (or) in parallel.
a syE
ngi
Down flow in series
nee
Down flow in parallel
rin
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
g.n
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.
Advantage
Adsorption of organic materials and filtration of suspended solids are accompanied in a
single step.
Disadvantages
et
 Down flow filters may require more frequent back washing because of the
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

Advantage
 As the carbon adsorbs organic materials, the apparent density of the carbon particles
ww increases and encourages migration of the heavier or spent carbon downward.

Disadvantage
w.E
 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
a
expanded bed.
syE
2. Using Powdered Activated Carbon
In this method powdered activated carbon is added directly into the effluent.
ngi
- The powdered activated carbon and a coagulant are mixed in the contact aeration
tank.
gravity.
- The spent carbon can be regenerated.
nee
- It is then sent to the clarification tank where the heavier carbon settle down due to
- The water
clarification rin from the
tank is filtered in a
filtration
g.n coloumn.
et
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.
wwTypes of catalysis
1. Homogeneous catalysis
Examples w.E
It is a process in which the catalyst and the reactants are in the same phase.
(a) Homogeneous catalysis in gas phase
a
2SO2(g) + O2(g)
[NO](g)
syE
2SO3(g)
(b) Homogeneous catalysis in liquid phase

ngi
CH3COOC2H5(l) + H2O(l)
[H+/OH-] nee
CH3COOH(l) + CH3OH(l)
2. Heterogeneous catalysis rin

g.n
It is a process in which the catalyst and the reactants are in different phase.
Examples
(a) Heterogeneous catalysis in gaseous and solid phase
2SO2(g) + O2(g)
[Pt](s)
2SO3(g) et
(b) Heterogeneous catalysis in liquid and solid phase
[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+
C12H22O11 + H2O C6H12O6 + C6H12O6
ww2. Hydrolysis of an ester
CH3COOC2H5
H+
CH3COOH + C2H5OH
w.E
Classification of acid base catalysis
Acid catalysis
a syE
A reaction may be catalyzed by a proton (H+)- Specifically proton catalyzed.
or
A reaction may be catalyzed by a bronsted acid (proton donors)- General acid catalysis.
Base catalysis ngi

or
nee
A reaction may be catalyzed by a hydroxide ion (OH-)- Specifically hydroxide catalyzed.
A reaction may be catalyzed by a bronsted base (proton donors)- General base catalysis.
Mechanism of Acid-Base catalysis rin

Acid catalysis
g.n
Step I: Addition of H+ ion to the substrate forming intermediate complex. (E.g.
keto-enol tautomerism of acetone)
CH3CCH3 + H A + CH3CCH3 + A- Step I

et
O OH
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
wwKinetics of acid-base catalysis

Kinetics of acid-base catalysis is explained by the following mechanism.
Step I
w.E
Involves transfer of the H+ ions from an acid AH+ to the substrate S.
S + AH+
k1
SH+ + A
Step II a syE k-1
Involves reaction of the acid form of the substrate with water to give products.
k2
Step I
SH+ + H2O
ngi P + H3O+ Step II
Applying steady state approximation to the intermediate [SH+]

nee
rin
[ ]
= 0 = 𝑘 [𝑆][𝐴𝐻 ] − 𝑘 [𝐴][𝑆𝐻 ] − 𝑘 [𝑆𝐻 ] ---1
g.n
The reactions are carried out at low concentration hence concentration of water is not taken
into account in equation 1.
𝑘 [𝑆][𝐴𝐻 ] = 𝑘 [𝐴][𝑆𝐻 ] + 𝑘 [𝑆𝐻 ]
[𝑆𝐻 ] =
[ ][
[ ]
]
---2
et
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
[ ][ ]
𝑅𝑎𝑡𝑒 = ---6
[ ]
+
The ionization constant of the acid AH is
ww AH+ [H+] + [A]
w.E
𝐾=
[𝐻 ][𝐴]
[𝐴𝐻 ]
a
Equation 7 is substitute in 6
syE[𝐴] =
[
[ ]
]
---7
𝑅𝑎𝑡𝑒 = ngi
𝑘 𝑘 [𝑆][𝐴𝐻 ]
𝐾[𝐴𝐻 ]
𝑘
[𝐻 ]
nee
𝑅𝑎𝑡𝑒 =
𝑘 𝑘 [𝑆][𝐻 ]
𝑘 𝐾
rin
g.n
In this case the reaction is specifically hydrogen-ion catalyzed, because the equation
contains [H+]
General applications of catalysis

1. It increases the efficiency of industrial processes.
et
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.
ww
Working w.E
- The exhaust fumes are allowed inside compartment A where the reducible
a
impurities are reduced.
syE
- The remaining gases are allowed through the compartment B where all the
oxidisable impurities are oxidized.
ngi
- The outgoing fume contains no toxic byproducts.
Function of catalytic converter
NOx nee
1. Reduction of nitrogen oxides into elemental nitrogen and oxygen
Nx + Ox
2. Oxidation of CO to CO2
3. Oxidation of hydrocarbons into CO2 and H2O rin
Enzyme catalysis g.n
Enzymes (or) biological catalyst are complex organic substances of high molecular weight
proteins derived from living organisms.
Examples
et
1. Conversion of starch into maltose
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
Activation energy with enzyme catalyst > 2 kCal/mol
2. Enzyme catalyzed reactions are more specific
wwEnzymes are highly specific in catalyzing reactions. An enzyme catalyzes only a particular
reaction.
w.E
Urease
H2N C NH2 + H2 2NH3 + CO2
O
a syE
H2N C NH CH3 + H2
O
Urease
No reaction
Methy Urea
ngi
3. Rate of the enzyme catalyzed reactions is maximum at optimum temperature.
nee
Rate of the enzyme catalyzed reactions increases with increase in temperature and enzymes
are denatured at high temperature. Rate is maximum at optimum temperature.
rin
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
dangerous.
g.n
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
et
optimum pH. The rate decreases below and above the optimum pH.
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
k1, k2 and k3 are rate constant of the respective rections.

The rate of formation of complex X is given by the following equation.
ww 𝑑[𝑋]
= 𝑘 [𝐸][𝑆] − 𝑘 [𝑋] − 𝑘 [𝑋]
w.E 𝑑𝑡
= 𝑘 [𝐸][𝑆] − (𝑘 + 𝑘 )[𝑋] --1
a syE
Where, [E][S] and [X] = Molar concentrations of the enzyme, substrate and intermediate
complex.
Rate of formation of the product is given by the following
[ ]
= 𝑘 [𝑋] ngi ---2
Since, [E0] = [E] + [X] nee ---3
Applying equation 3 in 1 gives, rin

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

[X] = concentration of the enzyme in the complex
et
[E0] = total concentration of the enzyme
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
[ ] [𝐸0 ]
=𝑘 𝑘 +𝑘 ---9
1+ 𝑘2 [𝑆]3
ww = 𝐾 = 𝑀𝑖𝑐ℎ𝑎𝑒𝑙𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
1
w.E [ ]
=
[𝐸0 ]
--10 (or) 𝑅𝑎𝑡𝑒 =
𝑘3 𝐸0 [𝑆]
a 𝐾𝑚
1+ [𝑆]
syE
Equation 10 is called Michaelis-Menten equation
[𝑆]+𝐾𝑚
Case (i) At low concentration of substrate

When the concentration of the substrate [S] is less than Km
ngi
[S] << Km then
nee
[ ]
=
[𝐸0 ][𝑆]
𝐾𝑚
rin
---11
Case (ii) At high concentration of substrate g.n

When the concentration of the substrate [S] is higher than Km
[S] >> Km then
𝑑[𝑃] 𝑘 [𝐸0 ][𝑆]

et
=
𝑑𝑡 [𝑆]
[ ]
= 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
Where, 𝑣 = maximum rate
wwThe Michaelis-Menten equation can be written as
𝑣 [𝑆]
w.E
If 𝐾 = [𝑆], then
𝑅𝑎𝑡𝑒 =
[𝑆] + 𝐾
a syE 𝑅𝑎𝑡𝑒 =
𝑣 [𝑆]
[𝑆] + [S]
ngi
𝑅𝑎𝑡𝑒 =
𝑣 [𝑆]
2[S]
1
𝑅𝑎𝑡𝑒 =
𝑣 nee
2
rin
When the Michaelis-Menten constant is equal to concentration of the substrate, rate of the
reaction is half the maximum rate.
Determination of the Michaelis-Menten constant (Km) g.n

Lineweaver-Burk equation is used to determine the value of the Michaelis-Menten constant.
1
=
1
+
𝐾
et
𝑟𝑎𝑡𝑒 𝑣 𝑣 [𝑆]
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.
Factors affecting enzyme catalysis
1. pH
wwEnzymes work well in the neutral pH but they get denatured at low and high pH values.
2. Temperature
w.E
Enzymes works faster at high temperature.
3. Salt Concentration
a syE
High concentration of salts increases the activity of the enzyme.
4. Activators and Inhibitors
ngi
Activators are small molecules that increase the activity of the enzyme. Inhibitors are small
molecules that decrease the activity of the enzyme.
nee
rin
g.n
et

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
Solid Wood, peat, coal, lignite, dung Coke, charcoal, petroleum
Liquid Crude oil Tar, kerosene, diesel, Petrol
Gas
ww Natural gas Coal gas, water gas, bio Gas, coke oven gas,
producer gas, CNG, LPG
w.E
1.2.PRIMARY SOLID FUEL - COAL
Coal is an important primary solid fuel that has been formed as a result of alteration of
asy
vegetable matter under some favorable conditions.
1.Coalification (or) Metamorphism

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

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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
(i) decrease in moisture content, g.n
(ii)
(iii)
(iv)
(v)
decrease in volatile content,
decrease in hydrogen, oxygen, nitrogen and sulphur contents,
increase in carbon content,
increase in hardness,
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(vi) increase in calorific value
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
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
. asy Significance
1 Moisture
content
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High percentage of moisture is undesirable because
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(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
2 Volatile
matter
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High percentage of volatile matter is undesirable because
(ii) produces sooty and smoky flame
(iii) cocking is not possible
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3 Ash
content
(iv) toxic gases will be evolved
High percentage of ash content is undesirable because
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(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 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. Download From : www.EasyEngineering.net
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.
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
over and is absorbed in a known volume of standard N/10 HCl.
(NH4)2 SO4+ 2NaOH −−−> 2NH3 + Na2SO4+ 2H2O
w.E NH3 + HCl −−−> NH4Cl

The volume of unused N/10 HCl is then determined by titrating it against standard N/10 NaOH.
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Thus the amount of acid neutralised by liberated ammonia from coal is determined.
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2. Sulphur content
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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
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
(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
When coal is heated strongly in the absence of air (called destructive distillation) it is converted
into lustrous, dense, porous and coherent mass known as coke. This process of converting coal into
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coke is known as Carbonisation.
Types of carbonization (i) Low temperature carbonization (ii) High temperature carbonization
w.E S.No.
1
low temperature carbonization high temperature carbonization
It is carried out at 500 - 700˚C It is carried out at 900 - 1200˚C
2
3 asy
Produces soft semi coke
Yield of coke 75 – 85 %
Produces hard metallurgical coke
Yield of coke 65 – 75 %
4
5
6
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Used for domestic purpose
Volatile matter is 5 – 15%
Low calorific value ngi
Used for metallurgy
Volatile matter is 1-3%
High calorific value
7 Strength of coke is low
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Strength of coke is high
Caking coals and coking coals

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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
are not coking coals. t
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
m height and 0.4 − 0.45 m wide. Each chamber is provided with a charging hole at the top, it is also
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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
chambers.
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to 1200°C by burning the preheated air and the producer gas mixture in the interspaces between the
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
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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.
above system of recycling the flue gases to produce heat energy is known as the regenerative
system of heat economy. When the process is complete, the coke is removed and quenched with
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4. For economical heating, the direction of inlet gases and flue gases are changed frequently. The
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water.
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
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
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. w.E
Various steps
Separation of water
Process
The crude oil is fed between two highly charged electrodes. Where colloidal
1 (Cottrell’s Process)
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water droplets combine to form large drops, which is then separated out from the
oil.
3
Removal of harmful
sulphur compounds
Electrical desalting
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Sulphur compounds are removed by adding copper oxide. The copper sulphide
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formed is separated out by filtration.
This process follows electrolysis, which removes dissolved salts like NaCl,
4 Fractional distillation
MgCl2 etc from oil.
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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 Download From : www.EasyEngineering.net
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

of gasoline by cracking
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1
Name of the fraction
Lubricating oil
Uses
As lubricants
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3
Petroleum jelly or vaseline
Grease
Used in medicines and cosmetics
As lubricant
4
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Paraffin wax
Pitch above 400˚C
Used in candles, boot polishes
5
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Used for making roads and water proof
roofing.
1.8. MANUFACTURE OF SYNTHETIC PETROL

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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
Coal contains about 4.5% hydrogen compared to about 18% in petroleum. So coal is a e
hydrogen deficient compound. If coal is heated with hydrogen to high temperature under high pressure,
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it is converted to gasoline. The preparation of liquid fuels from solid coal is called Hydrogenation of
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. The 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:
The sudden explosion (unwanted sound) due to rapid rise in pressure inside the engine is
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
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regular way, there is no problem in knocking. But in some cases, the rate of combustion
(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
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instantaneously producing an explosive sound known as “Knocking”. Knocking petrol engine is
rated by “ Octane number”
1. OCTANCE NUMBER OR OCTANCE RATING
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The octane number is defined as „‟the percentage of iso-octane present in a mixture of iso-
octane and n-heptane.‟‟
CH3 rin
CH3
CH CH2 C CH3
CH3 –( CH2)5−CH3
g.n
(Octane number = 0)
CH3 CH3
2. Structure knocking property is based on the Chemical

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The knocking tendency of fuel hydrocarbons mainly depends on their chemical structures.
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
this, small amount of ethylene dibromide is added along with TEL. This ethylene dibromide reacts
with Pb and PbO to give volatile lead bromide, which goes out along with exhaust gases. But this
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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
0
. Now,
the diesel oil is sprayed. This further increases the temperature and pressure. The expanding
gases push the piston and power stroke begins.
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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‟
6. CETANE NUMBER OR CETANE RATING g.n
decane
and α-methyl naphthalene, which has the same ignition lag as the fuel under test".
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The cetane number is defined as "the percentage of hexa decane present in a mixture of hexa
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
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
w.E Constituents
Methane
Ethane
Percentage (%)
88.5
5.5
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Butane
3.7
1.8
Properties
E Pentane
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0.5
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.
Advantages of CNG over LPG g.n
1. CNG produces less pollutants than LPG.
2. CNG is cheaper and cleaner than LPG.
3. The octane rating of CNG is high; hence the thermal efficiency is more.
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4. It does not evolve sulphur and nitrogen gases.
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

Constituents Percentage (%)
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.
6. It is free from CO, so it is less hazardous.
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.
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3. Handling must be done under high pressure.
4. LPG is suitable only for the engines working under high compression ratio.
COMBUSTION OF FUELS
2.1. INTRODUCTION asy
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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.
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Aim of combustion is to get the maximum amount of heat from a combustible substance in the
shortest time. Most of the combustible substances are enriched with carbon and hydrogen. During
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combustion they undergo thermal decomposition to give simpler products, which are oxidised to CO 2,
H2O, etc.,
C + O2 −−−> CO2 ; Exothermic.
H2+ ½O2 −−−> H2O ; Exothermic. rin
Since the above reactions are exothermic, large quantity of heat is given out.
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2.2. CALORIFIC VALUE
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The efficiency of a fuel can be understood by its calorific value. The calorific value of fuel is
defined as the total amount of heat liberated, when a unit mass of fuel is burnt completely.
UNITS OF CALORIFIC VALUES
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The quantity of heat can be measured by the following units:
(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

= 1/100[686800+276000+2240] Kcal/Kg
= 9650.4 Kcal/Kg
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w.E = 9650.4 - 0.09*8*587

= 9227.76 Kcal/Kg
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22
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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
1. Care must be taken in such a way that, the reagents in the absorption bulb 1, 2 and 3 should be
brought to the etched marked level one by one by raising and lowering reservoir bottle.
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2. All the air from the reservoir bottle is expelled to atmosphere by lifting the reservoir bottle.
3. It is essential that CO2, O2 and CO are absorbed in that order only.
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4. As the CO content in flue gas is very small, it should be measured quite carefully.
Working:
The 3-way stop-cock is opened to the atmosphere and the reservoir is raised, till the burette is
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completely filled with water and air is excluded from the burette. The 3-way stop-cock is now connected to
the flue gas supply and the flue gas is sucked into the burette and the volume of flue gas is adjused to 100 cc
by raising and lowering the reservoir. Then the 3-way stop cock is closed.
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(a) Absorption of CO2: The stopper of the absorption bulb-I, containing KOH solution, is opened
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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.
(b) Absorption of O2: Stop-cock of bulb-I is closed and stop cock of bulb-II is opened. The gas is
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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.
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(c) Absorption of CO: Now stop-cock of bulb-II is closed and stop-cock of bulb-III is opened. The
remaining gas is sent into the absorption bulb-III, where CO present in the flue gas is absorbed by
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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.
Significance (or) uses of flue gas analysis t
1. Flue gas analysis gives an idea about the complete or incomplete combustion process.
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
known as Spontaneous Ignition Temperature (SIT). Pulvarised coal, oil rags, cotton wastes get oxidized
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.
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Significance of SIT:
A low SIT value indicates the ready ignition of the fuel and also means a fire hazard.
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EXPLOSIVE RANGE (LIMITS OF INFLAMMABILITY)
For a fuel to burn, it should be mixed with air in proper ratio.
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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
inflammability.
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Significance:
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or above the upper limit.
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For continuous burning , the amount of fuel present in fuel – air mixture should not go below the lower 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%
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.

ww 2C17H35COONa + CaCl2  (C17H35COO)2Ca + 2NaCl

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

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

ESTIMATION OF HARDNESS BY EDTA METHOD:

Na-OOC-H2C CH2 –COO-H

(Wine red/unstable) (Stable) ngi

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 3: Finding Permanent hardness:

ww20ml of boiled water required = V3 ml of EDTA

Hence, permanent hardness =

1.2) Boiler Troubles rin

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:

c) Boiler explosion: ngi

Examples of Scale deposits: rin

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

4 w.E explosion etc.,

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

MgSO4 + Na2Ze  MgZe + Na2SO4

wwCaCl2 + Na2Ze  CaZe + 2 NaCl

CaZe + 2 NaCl  Na2Ze + CaCl2

MgZe + 2 NaCl  Na2Ze + MgCl2 et

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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:

ww2. Acidic water cannot be treated as it decomposes the structure of zeolite.

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

Advantages of Ion exchange method:

ww i) Can be used for high pressure boilers also.

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S. No. Soft water Demineralized water

Differences between Zeolite and ion exchange process:

S.No. Zeolite process Ion exchange process

1 It exchanges only cations. It exchanges cations and anions

ww Na2O. Al2O3. xSiO2.yH2O cationexchange resin - RH2