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NOTES OF LESSON
CY3151- ENGINEERING CHEMISTRY

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Unit-I Water and Its Treatment

Water

Water is an abundant, wonderful and very useful resource. Water plays a main role in the
existence of human beings, animals and plants. It is also utilized in steam generation, coolant
in power plants and chemical plants. It occupies a unique position in different industries like,
steel, paper, textile, chemical etc. The main application of water is irrigation and in day today
life activities.

Sources of Water

(i) Rain Water:

It is the purest form of natural water. But during the journey downwards to the surface
through the atmosphere it dissolves gases like CO2, NO2, SO2 and suspended solid particles.

(ii) Surface Water: (River, Lake and Ocean)

River water : It is mainly fed by rains and springs. It flows over the surface and dissolve the
minerals like chlorides, sulfates, carbonates, bicarbonates of Na, Ca, Mg and Fe. River water
also contains organic matter, produced by the decomposition of plants and small
particles of sand and rock suspension.

Lake Water : It has more constant chemical composition. The quantity of organic matters is
high. It contains fewer amounts of dissolved materials.

Sea Water/Ocean Water : It is the most impure form of water. Rivers bring the impurities to
the sea. Continuous evaporation of sea water also increases the impurity. It is more saline in
nature. Sea water contains about 3.5 percent of dissolved salts, principally sodium chloride
NaCl (2.7%), and magnesium chloride and sulphate (0.6%).

(iii) Underground Water: (Wells and springs)

A part of rain water which falls on earth surface percolates through soil into the earth.
During its downward journey, it dissolves a number of salts and meets a hard rock where it
may be stored or come in the form of spring.

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Impurities in Water

Classification of Impurities

1. Suspended Impurities
Physical Impurities
2. Colloidal Impurities

Chemical Impurities 3. Dissolved Impurities Dissolved Salts and Dissolved Gases

Biological Impurities 4. Biological Impurities

Type Source and Properties Removal Methods

Suspended Soil, sand, decayed plant and animal matter. Make Filtration, Sedimentation,
Impurities the water turbid. Particle size is > 10000 A∘ Settlement

Colloidal Finely divided clay and silica, mud organic and Coagulation followed by
Impurities inorganic particles. Particle size is 10 - 1000 A∘ sedimentation, filtration.
Coagulants FeSO4, alum

Dissolved Dissolved salts – Chlorides, sulphates, nitrates, Chemical treatment.

Impurities bicarbonates, carbonates of Ca, Mg, Na, etc.,
Deaeration method for gases
Dissolved gases- CO2, NO2, SO2

Biological Algae, fungi, bacteria and small aquatic animals Sterilization, Bleaching,
Impurities Chlorination, Ozone
treatment

Water Quality Parameters

Physical Parameter Chemical Parameter

Colour pH
Odour and Taste Hardness
Turbidity Alkalinity
Temperature Fluoride
TDS Arsenic
BOD,COD
Physical Parameter

Colour
 Material from decayed organic matter (vegetation), inorganic matter such as soil,
stones, rocks give colour to the water.
 Change in the appearance of water.

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Organic Source: Algae, organic dyes.

Inorganic Source: Cr, Fe & Mn compounds and inorganic dyes from industries.
(Yellow- Cr; Red or Brown – Fe)
Removal Methods: Adsorption, Filtration, Settling

Taste & Odors

Taste and odour in water can be caused by foreign matter such as organic materials, inorganic
compounds, and dissolved gases. These materials may come from natural, domestic, or
agricultural sources.
Organic source: Algae, decaying vegetation
Inorganic Source: Mercaptans, amines & Sulphides

Removal Methods: Aeration, Chlorination, Activated Carbon treatment.

Turbidity

Turbidity is the cloudiness of water. It is the ability of the light to pass through the water.
Caused mainly by suspended material, clay, silt, plankton, greases.

Disadvantages of turbidity:

 Aesthetically unacceptable
 It can increase the cost of water treatment.
 Hiding place for harmful microorganisms. Turbidity shields them from disinfection
process.
 Affecting the life of aquatic organisms like egg, larva maturing.
 Suspended particles provide adsorption media for heavy metals such as mercury,
 Chromium, lead, cadmium, and many hazardous organic pollutants.
 Raises the water temperature (suspended particles absorb more heat). So decreases the
concentration of dissolved oxygen.
 Turbidity is measured by instrument called Nephelometric turbidimeter and the unit
for turbidity is NTU (Nephelometric Turbid Unit)

Removal Methods: Coagulation, Settling, Filtration.

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Temperature

Temperature is measured by the unit degree Celsius (oC). Temperature of the surface water is
influenced by atmospheric conditions. Temperature of ground water is influenced by
characteristics of bedrocks. Temperature raise will decrease the amount of dissolved oxygen
(DO) in the water.

Total Dissolved Solids (TDS)

TDS stands for total dissolved solids, and represents the total concentration of dissolved
substances in water. TDS is made up of inorganic salts such as calcium, magnesium,
chlorides, sulfates, bicarbonates, etc, along with other inorganic compounds that easily
dissolve in water. These dissolved solids not good for health and must be filtered out before
intake. Water purifier with Reverse Osmosis (RO) technology is the best solution to treat
water with high TDS. An RO water purifier doesn’t completely remove TDS, but reduces the
level of TDS to make it palatable and consumable.

Total solid (TS) = Total dissolved solid (TDS) + Total suspended solid (TSS) (2)

Chemical Parameter
pH

pH is one of the most important parameters of water quality. It is defined as the negative
logarithm of the hydrogen ion concentration. pH ranges from 0 to 14, 7 is the neutral. pH less
than 7 indicates acidity, whereas a pH of greater than 7 indicates a basicity.
pH= -log[H+]
Pure water is neutral, with a pH close to 7.0 at 25°C. Safe ranges of pH for drinking water are
from 6.5 to 8.5 for domestic use and living organisms.
 Most aquatic animals and plants have adapted to live in water with a specific pH
even a slight change will affect them.
 A pH below 4 or above 10 will kill most fish.
 Heavy metals such as cadmium, lead, and chromium dissolve more easily in
highly acidic water.

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Alkalinity

The alkalinity of water is its acid-neutralizing capacity. Alkalinity of water is mainly caused
by the presence of hydroxide ions (OH−), bicarbonate ions (HCO3−), and carbonate ions
(CO32−), or a mixture of two of these ions in water. Alkalinity is determined by titration with
a standard acid solution (H2SO4 of 0.02 N) using selective indicators (methyl orange or
phenolphthalein).

 The high level of either acidity or alkalinity in water is the indication of industrial
or chemical pollution.
 It is harmful for aquatic organisms
 Alkaline water cause corrosion in the boiler when used as boiler feed water.

Hardness

Hardness is the term used to express the properties of highly mineralized water. The
dissolved minerals in water cause problems like scale deposits in hot water pipes and
difficulty in producing lather with soap. Calcium (Ca2+) and magnesium (Mg2+) ions cause the
greatest portion of hardness in naturally occurring waters

Temporary Hardness (Carbonate Hardness/Alkaline Hardness) which is due to carbonates

and bicarbonates can be removed by (i) boiling and (ii) treating with lime.

Permanent Hardness (Non-Carbonate Hardness/Non-Alkaline Hardness) which is remaining

after boiling is caused mainly by sulfates and chlorides. It can be removed by (i) lime-soda
process (ii) Zeolite process

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Fluoride
 A moderate amount of fluoride ions (F-) in drinking water contributes to good dental
health.
 About 1.0 mg/L is effective in preventing tooth decay, particularly in children.
 Excessive amounts of fluoride cause discoloured teeth, a condition known as
dental fluorosis
 The maximum allowable levels of fluoride in public water supplies depend on local
climate
Arsenic
 It is a metallic compound and forms number of poisonous compounds.
 Source: Natural deposits run off from agriculture, mining and industries.
Causes
 Long-term intake leads to skin cancer, diabetes, hypertension also affects bladder,
kidney.
 Greater risk found in children.

Biological Oxygen Demand (Biochemical Oxygen Demand) (BOD)

 BOD is the amount of oxygen used by microorganisms (bacteria, yeasts and plankton)
for the oxidation of organic matter.
 It is a measure of the degree of contamination and is expressed in mgO2/L.
 It is a time-consuming biological process. The standard measurement is performed at
20°C for 5 days and is called BOD5.
 In general terms, the greater the pollution, the higher the BOD.

Chemical Oxygen Demand (COD)

 COD is the amount of oxygen required for the oxidation of all the oxidizable
impurities present in the water by K2Cr2O7 in acidic medium.
 This test only takes about 2 hours much less time compared to BOD test.
 The greater the pollution, the higher the COD.
 The main difference between BOD and COD is that, COD measures all organic and
inorganic material, while BOD only measures organic material which can be
biologically degraded.

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Treatment of Water for Domestic Supply (or) Municipal Water treatment

Primary Treatment
Rivers and lakes are the most common sources of water used by municipalities. The water
should be free from colloidal impurities, domestic sewages, industrial effluents and disease
producing bacteria. Hence domestic supply of water involves the following stages in the
purification processes.

Screening
It is a process of removing the floating materials like leaves, wood pieces, etc. from water.
The impure water is allowed to pass through a screen, having large number of holes, which
retains the floating materials and allows only the water to pass.

Aeration
The process of passing air to the water or mixing water with air is known as aeration. The
main purpose of aeration is
(i) To remove gases like CO₂, H₂S and other impurities causing bad taste and odour to water.
(ii) To remove ferrous and manganous salts as insoluble ferric and manganic salts.

Sedimentation
It is a process of removing suspended impurities by allowing the water to stand undisturbed
for 2-6 hours in a big tank. Most of the suspended particles settle down at the bottom, due to
forces of gravity, and they are removed. Sedimentation removes only 75% of the suspended
impurities.

Coagulation
Finely divided clay, silica, ete, do not settle down easily and hence cannot be removed by
sedimentation. Such impurities are removed by coagulation method.
In this method certain chemicals, called coagulants, like alum, Al2(SO4)3 etc. are added to
water. When the Al2(SO4)3, is added to water, it gets hydrolysed to form a gelatinous
precipitate of Al(OH)3, The gelatinous precipitate of Al(OH)3, entraps the finely divided and
colloidal impurities, settles to the bottom and can be removed easily.

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Filtration
It is the process of removing bacteria, colour, taste, odour and suspended particles, etc. by
passing the water through filter beds containing fine sand, coarse sand and gravel.
A typical sand filter is shown in the figure 1.1

The sand filter consists of a tank containing a thick top layer of fine sand followed by course
sand, fine gravel and coarse gravel. When the water passes through the filtering medium, it
flows through the various beds slowly. The rate of filtration decreases slowly due to the
clogging of impurities in the pores of the sand bed. When the rate of filtration becomes very
slow the filtration is stopped and the thick top layer of fine sand is removed and replaced with
clean sand. Bacteria are partly removed by this process.

Fig 1.1 Sand Filtration

Sterilization (or) Disinfection
The processof destroying the harmful bacteria is known as sterilization (or) disinfection. The
chemical used for this method is called disinfectants.
(i) By using Ozone
(ii) By using ultraviolet (UV) radiation
(iii) By Chlorination

(i) By using Ozone

Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly unstable
and breaks down to give nascent oxygen. The nascent oxygen is a powerful oxidising agent
and kills the bacteria.

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Disadvantages
 This process is costly and cannot be used in large scale
 Ozone is unstable and cannot be stored for long time.

(ii) By using ultraviolet (UV) radiation

UV rays are produced by passing electric current through mercury vapour lamp. This is
particularly useful for sterilizing water in swimming pool.
Disadvantages
 This process is costly
 Turbid water cannot be disinfected.

(iii) By Chlorination
The process of adding chlorine to the water is called chlorination. It can be done by following
methods.
 (a) By adding chlorine gas
Chlorine gas bubbled in the water it acts as a very good disinfectant.
 (b) By adding Chloramine
When chlorine and ammonia are mixed and chloramine is formed.

Chloramine compounds decompose slowly to give chlorine. It is a better disinfectant

than chlorine.
 (c) By adding bleaching powder
When bleaching powder is added to the water, it produces hypochlorous acid (HOCl).
HOCl is a powerful germicide.

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Break Point Chlorination

Water contains the following impurities
(i) Bacterias
(ii) Organic impurities.
(iii) Reducing substances (Fe²+, H₂S, etc.).
(iv) Free ammonia.

Chlorine added to water directly as a gas or in the form of bleaching powder. When chlorine
is applied to water, the results obtained can be depicted graphically by the following Fig. 1.2.
The graph shows the relationship between the amount of chlorine added to water and the
residual chlorine.

It is observed from the graph that initially the applied chlorine is used to oxidise all the
reducing substances present in the water and there is no free residual chlorine. (upto A)

Fig 1.2 Break Point Chlorination

As the amount of applied chlorine increases, the amount of combined residual chlorine also
increases. This is due to the formation of chloramine and other chloro organic compounds.
(A to B)

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At one point, on further chlorination, the oxidation of chloramines and other impurities starts
and there is a fall in the combined chlorine content. (B to C) Partial destruction of chloro-
organics and chloramines. Thus, the break point chlorination eliminates bacteria, all the
reducing substances, organic substances responsible for the bad taste and odour, from the
water.
Advantages

 Break point chlorination gives idea of amount of chlorine required for chlorination.
 Removes odour and colour in water.
 Destroys completely all the disease producing bacteria.
 Prevents if any growth of weeds in water.

Desalination of Brackish Water

The process of removing common salt (sodium chloride) from the water is known as
desalination. The water containing dissolved salts with an abnormal salty (or) brackish taste
is called brackish water.

Depending upon the quantity of dissolved solids, water is classified as

Fresh water: < 1000 ppm of dissolved solids

Brackish water: 1000-35,000 ppm of dissolved solids
Sea water: > 35,000 ppm of dissolved solids

Reverse Osmosis (RO)

Sea water and brackish water can be made available as drinking water through desalination
process. Desalination is carried out by reverse osmosis.

When two solutions of different concentrations are separated by a semi-permeable

membrane, solvent (water) flows from a region of lower concentration to higher
concentration. This process is called osmosis and the driving force for this phenomenon is
osmotic pressure.

If a hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration

side, the solvent flow is reversed i.e., solvent flows from higher concentration to lower
concentration. This process is called reverse osmosis (Fig. 1.3). Thus, in the process of

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reverse osmosis pure water is separated from salt water. This process is also known as super-
filtration. The membranes used are cellulose acetate, cellulose butyrate, etc.

Fig 1.3 Reverse Osmosis

Advantages
 The life time of the membrane is high, and it can be replaced within few minutes.
 It removes ionic, non-ionic as well as colloidal impurities.
 It gives us clean and pure water by blocking all contaminants.
 The available RO systems are very compact, and it requires small space.
 Low capital and operating cost & high reliability

Disadvantages of Reverse Osmosis

 Sometimes reverse osmosis leads to clogging of the whole system

 Hard water can damage the system.
Boiler Feed Water

The water fed into the boiler for the production of steam is called boiler feed water. Boiler
feed water should be free from turbidity, oil, dissolved gases, alkali and hardness causing
substances.
Requirements for boiler water
 Free from hardness causing salts
 Free from suspended impurities
 Free from oil and greases
 Free from dissolved salts and gases
 Free from alkalinity

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Boiler troubles (or) Disadvantages of using hard water in boilers

If hard water obtained from natural sources is fed directly into the boilers, the following
troubles may arise.
1. Formation of Scales and Sludges in boilers
2. Priming and foaming (carry over)
3. Caustic embrittlement
4. Boiler corrosion

Formation of Scales and Sludges in boilers

Boilers are employed for the steam generation in power plants, where water is continuously
heated to produce steam. As more and more water is removed in the form of steam,
the boiler water gets concentrated with dissolved salts progressively reaches the
saturation point. At this point the dissolved salts are precipitated out and slowly settle
on the inner walls of the boiler plate. The precipitation takes place in two ways.

Fig 1.4 Formation of Scales and Sludges in boilers

Sludge
Sludge is a soft, loose and slimy precipitate formed within the boiler. The dissolved salts
whose solubility is more in hot water and less in cold water produce sludges. Sludges are
formed by the salts like MgCO3, MgCl2, CaCl2, MgSO4

Disadvantages of sludge
 Sludges are bad conductors of heat and results in the wastage of heat and fuel.
 Excessive sludge formation leads to the settling of sludge in slow circulation
areas such as pipe connections, plug openings leading to the choking of the pipes.
Prevention
 By using softened water
 Blow down operation carried out frequently to prevent sludge formation.

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Scale
Scales are hard, adhering precipitates formed on the inner walls of the boilers. Scales
are stick very firmly on to the inner walls of the boiler. Scales are formed by the salts
like Ca(HCO3)2, Mg(OH)2, CaSO4
Disadvantages of Scale
 Poor conductor of heat, so wastage of heat and fuels.
 Lowering of boiler safety is due to overheating of the boiler.
 Decrease in efficiency of the boiler due to scales deposit.
 Can lead to boiler explosion.
Prevention
 Using softened water.
 External and internal treatment
 By giving thermal shocks
 They can also be removed by scrapers and wire brush
Table 1.1 Comparison of Scales and Sludges

Sludge Scale
1 Sludge is a loose, slimy and non-adherent Scale is a hard adherent coating
precipitate
2 Sludges are formed by the salts like Scales are formed by the salts like
MgCO3, MgCl2, CaCl2, MgSO4 Ca(HCO3)2, CaSO4, Mg(OH)2
3 Sludges are bad conductors of heat. Scales acts as thermal insulators. It
Excess of sludge formation decreases the decreases the efficiency of boiler.
efficiency of boiler. Sometimes leads to the explosion.
4 Prevention  Scale formation can be prevented by
 Sludge formation can be prevented by using acids like HCl, H2SO4
using softened water.  Scale formation can be removed by
 It can also be removed by blow-down External treatment, Internal treatment
operation.  By giving thermal shocks, by sudden
 It is a process of removing portion of heating and sudden cooling which makes
concentrated salt water by fresh water scale brittle and removed by scrubbing.
frequently from the boiler.  They can also be removed by scrapers
and wire brush

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Priming and Foaming (Carry Over)

Priming

During the production of steam in the boiler, some droplets of liquid water are carried along
with the steam. The process of producing wet steam is called priming. The steam with
droplets of liquid water carry some dissolved salts and suspended impurities with them.
Causes Prevention
a) Improper boiler design a) Good boiler design
b) Sudden boiling of water b) Maintain boiling temperature
c) High steam velocity c) Controlling the steam velocity
d) High water level in the boiler d) Fill the water up to low water level
e) Presence of dissolved salts in the water e) By using treated water

Foaming
The formation of stable bubbles over the surface of water is called foaming. It leads to
excess priming.

Causes Prevention
a) Presence of oil and grease a) Adding coagulants - sodium aluminate or aluminium hydroxide.
b) Presence of fine sludges b) Adding anti foaming agents – synthetic polyamides.

Caustic embrittlement
It means inter crystalline cracking of boiler metal due to presence of alkaline water
in the boiler. The boiler water containing Na2CO3 undergoes decomposition to give
NaOH and CO2.

This NaOH flows into the cracks, bends, and joints and dissolves the iron metal of the boiler
by converting to sodium ferroate. This causes embrittlement of boiler wall.

Prevention
 By maintaining the pH value of water and neutralization of alkali.
 By using softening reagents.

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 By adding tannin or lignin or sodium sulphate which blocks the hair-cracks thereby
preventing the flow of NaOH.

Boiler corrosion

It is the decay of boiler material by chemical or electrochemical attack on its environment. It

is due to the presence of
a) Dissolved oxygen
b) Dissolved Carbon dioxide
c) Dissolved salts
Dissolved oxygen in water is mainly responsible for the boiler corrosion. Dissolved oxygen
attacks the boiler material at higher temperature.

Removal of dissolved oxygen

Dissolved oxygen can be removed by chemical or mechanical method.
Chemical method
Sodium sulphite, hydrazines are the chemicals used for removing dissolved oxygen.
Hydrazine is an ideal compound for removing dissolved oxygen in the water since the
products are water and N2 gas

Mechanical de-aeration
In this process water is allowed to fall slowly on the perforated plates fitted inside the tower.
The sides of the towers are heated and a vacuum pump is attached to it. The high temperature
and low pressure inside the tower reduces the amount of dissolved oxygen.

Fig 1.5. Mechanical de-aeration

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Treatment of boiler feed water: Internal treatment

Suitable chemicals are added to the boiler water either to precipitate or to convert the scale
into soluble compounds is called internal treatment of the boiler feed water. Internal
treatment can be done following types.

a) Phosphate conditioning
The addition of sodium phosphate in hard water reacts with the hardness causing agents and
gives calcium and magnesium phosphates which are soft and non-adhere and can be removed
easily by blow-down operation.

Generally three types of phosphates are used,

Na3PO4 – Trisodium phosphate – More alkaline & used for highly acidic water
Na2HPO4 – Disodium hydrogen phosphate – Less alkaline & used for slightly acidic water
NaH2PO4 – Sodium dihydrogen phosphate – More acidic & used for alkaline water

b) Colloidal conditioning
In low pressure boilers, scale formation can be prevented by adding colloidal conditioning
agents like kerosene, tannin, agar-agar gel, gelatin, starch. These substances gets coated over
the scale forming precipitates and gives a loose and non-sticky precipitates which can be
removed by using blow-down operation.

c) Sodium Aluminate conditioning

In boiler water, sodium aluminate (NaAlO2) undergoes hydrolysis to give gelatinous white
precipitate of aluminium hydroxide and sodium hydroxide. The NaOH precipitates
magnesium salts as gelatinous Mg(OH)2. The gelatinous precipitates entrap the colloidal
silica and finely divided solids and settled easily. This can be removed by blow down
operation.

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d) Calgon conditioning
Calgon is sodium hexametaphosphate, Na2[Na4(PO3)6]. With calcium and magnesium ions, it
forms a highly soluble complex and prevents scale and sludge formation. It is used for high
and low pressure boilers.

Treatment of boiler feed water: External treatment

It involves the removal of hardness producing salts from the water before feed in to boiler.
The external treatment can be done by two processes.
1. Demineralisation or Ion-exchange process.
2. Zeolite process.

Demineralisation or Ion-exchange process

In this process, both the cations and anions are completely removed. It is carried out by ion-
exchange resins. Resins with acidic functional group are capable of exchanging H+ ions with
other cations. Resins with basic functional groups are capable of exchanging OH- ions with
other anions.

Cation Exchange Resins

Resins containing –COOH, –SO3H functional groups which responsible for exchanging their
H+ ions with other cations in the water. RH = Cation exchange resin.
Example: Sulphonated coals, sulphonated poly-styrenes

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Anion Exchange Resins

Resins containg NH2-, OH- functional groups which responsible for exchanging their
anions ions with anions in water.
Example: Urea-formaldehyde resin, cross-linked quaternary ammonium salts

Process
In ion-exchange process, hard water is allowed to pass through cation exchange resins, which
remove Ca+2 and Mg+2 ions and exchange equivalent amount of H+ ions. Anions exchange
resins remove bicarbonates, chlorides and sulphates from water exchange equivalent amount
of OH- ions. The water coming out from the exchanger is free from anions and cations. Thus
water of zero hardness is obtained. This water is known as demineralised or deionised water.
Regeneration
When ion exchangers losses its capacity they are said to be exhausted. The exhausted cation
exchanger is regenerated by passing dil. HCl or dil. H2SO4.

The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.

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Merits (or) Advantages of Ion-exchange process

 Very good for use in high pressure boilers also.
 Highly acidic or alkaline water can be treated.
 The residual hardness of treated water is very low (2 ppm).
Demerits (or) Disadvantages of Ion-exchange process
 The equipment is costly and more expensive chemicals are needed.
 Turbid water cannot be treated.
 Water containing Fe, Mn cannot be removed as they form complexes with resins.

Zeolite Process
Zeolites are naturally occurring hydrated sodium alumino silicate minerals
(Na2O.Al2O3.xSiO2.yH2O). Natural zeolites are in green colour and non-porous. The
synthetic zeolite form is called permutit or boiling stone which is porous and gel like
structure. It is represented by Na2Ze.
Process
When hard water is passed through a bed of sodium zeolite, it exchanges its sodium ions with
calcium and magnesium ions present in the hard water.

Regeneration
After some time Zeolite gets exhausted. The exhausted zeolite can be regenerated by treating
with 10% solution of NaCl.

Advantages of Zeolite Process

 Hardness of the water obtained by this process is very low (1-2 ppm).
 The equipment is compact and occupies small space.
 It is a clean and rapid process.
 The operation is simple.
 It is a cheap method. The regenerated zeolite can be used again.
 There is no sludge formation during the process.

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Advantages of Zeolite Process

 Turbid water cannot be treated, which blocks the zeolite’s pore.
 Acidic water cannot be treated, which decomposes the zeolite structure.
 Water containing Fe, Mn salts cannot be treated.
 Brackish water cannot be treated.

Table 1.2 Differences between the zeolite process and ion-exchange

(Demineralisation) process

S.No. Zeolite process Ion-exchange process

It exchanges only cations except It exchanges both anions and
1
Na+ ions. cations.
2 Acidic water cannot be treated. Acidic water can be treated
3 Brackish water cannot be treated. Brackish water can be treated
The treated water contains more The treated water does not contain
4
dissolved salts. any dissolved salts.
5 Soft water is produced Demineralised water is produced
Water containing turbidity, Fe, Water containing turbidity, Fe, Mn
6
Mn salts cannot be treated. salts cannot be treated.

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9

PHASE RULE
Phase Rule
If a heterogeneous system in equilibrium is influenced by pressure,
temperature and concentration and not influenced by electrical, magnetic and
gravitational forces, then the degrees of freedom (F) is related to phases (P) and
components (C) by the phase rule equation.
F = C– P+2
DEFINITION OF TERMS USED
Phase (P):
Phase is any homogeneous, physically distinct part of a system which is
separated from other parts of the system by definite boundary surfaces. A phase
may be a gas, liquid or solid.

Types of Phases

Gas Liquids Solids

All gases are miscible 1. Miscible liquids form one phase Each solid forms
2. Immiscible liquids form two separate phase
and form one phase
phases

Eg.1. Water system:

Ice(s) Water(l) steam(g)
It contains three phases. (One solid, one liquid and one gas)
Eg 2. CaCO3(s) CaO(s) + CO2(g)
It contains three phases. (Two solids and one gas)
Components(C):

It is defined as the minimum number of molecular species in terms of which

the composition of all phases may be expressed in the form of a chemical equation.

Eg.1. Water system:

Ice(s) Water(l) steam(g)
Component of all phases is H2O. Hence C=1.

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Eg 2. CaCO3(s) CaO(s) + CO2(g)

Composition of all three phases can be expressed in terms of two
constituents.
Eg.:- CaCO3 and CaO
Phase CaCO3 CaO CO2
Components CaCO3+ 0CaO 0CaCO3+ CaO CaCO3– CaO
Hence number of Components=2
Degree of freedom (F):
It is defined as the minimum number of independent variable factors such as
temperature, pressure and composition, which must be fixed in order to define the
system perfectly.

Eg.1 Ice(s) Water(l) steam(g)

P=3 and C=1
Then, F=C-P+2=1–3+2=0

Eg.2 CaCO3(s) CaO(s) + CO2(g)

C =2; and P =3
Then, F = C– P+2 = 2–3 +2 = 1
Merits of Phase of Rule
 It is applicable to both physical and chemical equilibria.
 It helps in deciding whether the given number of substances
remains in equilibrium or not.
 It is a convenient method to classify the equilibrium states in
terms of phases, components and degree of freedom.
 It is useful for understanding the heterogeneous equilibrium.
 It indicates that the different systems having the same degree of
freedom behave in a similar manner.

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Limitations of Phase Rule:

1. It takes into account only the variables like temperature, pressure and
concentration.
2. The influence of factors such as electric, magnetic, gravitational force etc.
are ignored.
3. It is applicable only to heterogeneous system in equilibrium.
PHASE DIAGRAM
Phase diagram is a graph obtained by plotting one degree of freedom against
another.
Types of Phase Diagrams:
a) P-T diagram
If the temperature is plotted against pressure, the diagram is called
P-T diagram
b) T-C diagram
If the temperature is plotted against composition, the diagram is called
T-C diagram.
USES OF PHASE DIAGRAM
a) The study of low melting eutectic alloys used in soldering can be carried
out using phase diagram.
b) It is possible to predict whether eutectic alloy or solid solution is formed
on cooling a homogeneous liquid containing mixture of two metals.
APPLICATIONS OF PHASE RULE TO ONE COMPONENT SYSTEM
WATER SYSTEM
Water exists in three possible phases namely solid, liquid and vapour.
Ice(s) Water(l) Vapour(g)
Here only one component (water) is present. Hence it is a one-component
system.

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1) Areas:
Area AOC – Liquid
Area BOC – Solid
Area BOA – Vapour
In the areas, C = 1; and P = 1
F = C–P+2 =1–1+2=2 It is bivariant.
They have two degrees of freedom. (i.e.) To specify a point in an area, we
have to specify both the temperature and pressure.
2) Curves: OA,OB,OC
i) Curve OA: Vapourisation curve
The following equilibrium will exist.
Water (l) Vapour (g)
Here, C = 1; and P = 2
F = C–P+2 =1–2+2=1 It is univariant.
It extends up to 374oC (critical temperature) and 218.5 atm. (critical
pressure). Beyond this, the equilibrium will disappear and vapour only will exist.
ii) Curve OB: Sublimation curve
The following equilibrium will exist.

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Ice(s) Vapour(g)
Here, C = 1; and P = 2
F = C–P+2 =1–2+2=1 It is univariant
It extends up to –273oC. At this point, only solid ice will be present.
iii) Curve OC: Melting point curve
The following equilibrium will exist.
Ice(s) Water (l)
Here, C = 1; and P = 2
F = C–P+2 =1–2+2=1 It is univariant
The negative slope of the curve indicates that the melting point of ice is
lowered with increase of pressure.
iv) Curve OB’ : Metastable curve
It is the vapour pressure curve of super-cooled water. It represents the
metastable system.
Super-cooled water Vapour
3) Point O:
The curves meet at point ‘O’. All the three phases coexist at this point. Hence
this point is known as triple point. It occurs at 0.0075oC and 4.58 mm.
Ice(s) Water(l) Vapour(g)
Here, C = 1; and P = 3
F = C–P+2 =1–3+2=0 It is invariant

THERMAL ANALYSIS (or) COOLING CURVE

Thermal analysis is a study of the cooling curves of various compositions of

a system during solidification. The shapes of the freezing point curves can be
determined by thermal analysis.

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Example 1: A pure substance

The pure substance in the fused state is allowed to cool slowly and the
temperature is noted at different time intervals. A graph is drawn between
temperature and time.

Example

Initially, the rate of cooling is continuous. . At point ‘b’, solid begins to

appear. The temperature remains constant until all the liquid is solidified. The line
‘bc’ represents the equilibrium between the solid and the liquid. The corresponding
temperature is the freezing point (or) melting point.
Example 2: Mixture of two substances

A B

C D

At point ‘B’ one substance A or B begins to solidify which is indicated by a

break and the rate of cooling is different. On further cooling at the break point ‘C’
the second compound also begins to solidify. The temperature remains constant
until the liquid melt is completely solidified, which forms the eutectic mixture (line
cd). At the point ‘D’ cooling of solid mass begins. The temperature corresponding
to line CD gives the eutectic temperature.
The experiment is repeated for various compositions of A and B and various
cooling curves are recorded. The phase diagram is constructed by plotting the
freezing point against the composition.
USES OF THERMAL ANALYSIS:
1. Used to derive phase diagram of any two component system.
2. Used to determine the eutectic temperature.

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3. Used to determine the percentage purity of the compounds.

4. Used to understand the behaviour of the compounds.

TWO COMPONENT ALLOY SYSTEM

REDUCED PHASE RULE OR CONDENCED SYSTEM
Solid-liquid equilibrium of an alloy has practically no gaseous phase and the
effect of pressure is negligible. Hence, experiments are conducted under
atmospheric pressure.
The system in which only the solid and liquid phases are present and the gas
phase is ignored is called a condensed system. The phase rule becomes
F=C–P+1
This is called reduced (or) condensed phase rule.

Binary alloy system (or) Simple eutectic system

Eutectic system is a binary system consisting of two components which
are completely miscible in liquid state but immiscible in the solid state.
They do not react chemically. Of different mixtures of two components, the
mixture having the lowest melting point is called eutectic mixture.
Eg. Pb-Ag system , Bi-Cd system

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BINARY ALLOY SYSTEM (or) THE SIMPLE EUTECTIC SYSTEM

LEAD-SILVER SYSTEM
It is a two component system.. At constant pressure, the vapour phase is
ignored and condensed phase rule is used.
Hence, F=C–P+1

(i) Curve AO
It is freezing point curve of silver. It indicates the depression of melting point
of silver by the addition of lead. Point A is the melting point of pure Ag
(961oC).The following equilibrium exits.
Solid Ag (s) Melt (l)
Here, P=2; C=2: Hence, F=C–P+1=2–2+1=1 ; Univariant
(ii) Curve BO
It is freezing point curve of Pb. It indicates the depression of melting point of
lead by the addition of silver. Point B is the melting point of pure Pb (327oC). The
following equilibrium exits.
. Solid Pb(s) Melt (l)
Here, P=2; C=2: Hence, F = C–P+1 = 2–2+1=1 ; Univariant

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(iii) Point O (Eutectic point)

Curves AO and BO meet at Point O, where three phase are in equilibrium.
Solid Pb(s) + Solid Ag(l) Melt(l)
Here P=3; C=2: Hence F=C–P+1=2–3+1=0 ;Non-variant
At point O, the composition of Pb is 97.4% and 2.6% of Ag. The temperature
corresponding to point O (303oC) is eutectic temperature.
(iv) Areas
Area above line AOB contains solution of Pb and Ag.
Here P=1; C=2: Hence F=C–P+1=2–1+1=2 ; Bivariant

Application of Lead-Silver system:

Pattinson’s process for the desilverisation of Argentiferous Lead:-
The process of increasing the composition of Ag in the alloy is known as
Pattinson process.
Argentiferous Lead (small amount of silver≈ 0.1%)
Heated above its melting point
System consist only the Liquid phase (point P)

Cooling
Reaches the point q (Pb crystallised out containing increasing amount of Ag)
Further cooling
More and more Pb separated along line BO

Point O reached (% of Ag = 2.6%)

Uses
 Suitable alloy composition can be predicted.
 Used in preparing solders.

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UNIT-5
FUELS AND COMBUSTION

Introduction
Fuel is a combustible substance, containing carbon as the main constituent,
which on burning gives large amount of heat. During combustion, carbon and
hydrogen combine with oxygen with liberation of heat.
C+O2 → CO2 + 94kcals
2H2+ O2 → 2H2O + 68.5kcals
Characteristics of a good fuel
1. It should be cheap and readily available.
2. It should be safe and economical for storage and transport.
3. It should not undergo spontaneous combustion.
4. It should have higher calorific value.
5. It should have moderate ignition temperature.
6. The combustion should be easily controllable.
7. It should have low moisture content, because the moisture content reduces
the calorific value.
8. The products of combustion should not be harmful.
9. It should have low non combustible matter or ash content.
Classification of fuels
Fuels are classified on occurrence and physical states as follows

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Calorific value
The calorific value of a fuel is the total amount of heat liberated, when
a unit mass of fuel is burnt completely. Its units are kilocalorie or BTU (British
Thermal unit).
Higher calorific value or Gross calorific value (G.C.V)
Gross calorific value (G.C.V) is 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.
Lower calorific value or Net calorific value (N.C.V)
Net calorific value (N.C.V) 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.
The two are related as,
N.C.V = G.C.V − Latent heat of water produced
N.C.V = G.C.V – Mass of Hydrogen X 9 X latent heat of condensation of
water vapour.

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Dulong’s formula for the Theoretical calculation of GCV and NCV.

Calculation of GCV and NCV

1. Calculate the net calorific value if the gross calorific value is 2550 kcal/kg
and contains 6.5% H.
NCV = GCV – [ 0.09H x 587 ] kcal/kg
= 2550 – [ 0.09 x 6.5 x 587 ]
NCV = 2206.6 kcal/kg.

2. Calculate Gross and Net calorific values of a coal having the following
composition.
C = 80%; H = 7%; O = 3%; S = 3.5%; N = 2.5% and Ash = 4.4%
Solution
(i) GCV
GCV = 1/100{8080 x % of C + 34500 (% H - % O/ 8) + 2240 x % S}
= 1/100{8080 x 80 + 34500 (7- % 3/ 8) + 2240 x 3.5}
= 8080 x 80+345(7-0.375) + 2240x 3.5
= 6464 + 2285.6 + 78.4
= 8828kcals/kg.

(ii) NCV

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NCV = GCV – (0.09 H x 587)

= 8828 – (0.09 x 7 x 587)
= 8828 – 369.8
= 8458.2kcals/kg.

SOLID FUEL
Coal
Coal is an important primary solid fuel that has been formed as a result of
alternation of vegetable matter under some favorable condition.
This process of alteration of vegetable matter to coal is called coalification.
Classification of coal
Coal is classified on the basis of its rank/ grade.
Wood →Peat → lignite → Bituminous coal → Anthracite
Analysis of coal
1.Proximate Analysis of Coal

Determination of % of

Moisture content Volatile matter Ash content Fixed carbon

i) Moisture content :

∆, 100 – 1050c
1 g of air-dried coal Loss in weight of coal is calculated
1 hr, electric hot-air oven

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Loss in weight of the coal

% of Moisture in coal = x 100
Weight of air-dried coal

ii) Volatile Matter :

Muffle furnace, 7 min
Moisture removed coal Loss in weight of coal is noted
covered with lid 950 ± 200c

Loss in weight of the coal

% of volatile matter in coal = x 100
Weight of moisture free coal

iii) Ash content :

½ hr
Moisture & Volatile matter Loss in weight of coal is noted
removed coal without lid 700 ± 500c

Loss in weight of the coal

% of ash content in coal = x 100
Weight of dried coal

iv) Fixed Carbon :

% of Fixed carbon in coal = 100 - % of ( Moisture content + Volatile matter
+ Ash content )

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Significance of Proximate Analysis

A good quality coal has High calorific value. For High calorific value,
coal must contain
1. Low Moisture content 2. Low Volatile matter
3. Low Ash content 4. More Fixed Carbon

S.NO CONTENTS SIGNIFICANCE

High i) Reduces Calorific value of

1. Moisture coal
ii) Consumes more heat

2 High volatile i) Reduces Calorific value of coal

matter ii) Burns and produces high smoke

3 High Ash content i) Reduces Calorific value of coal

ii) Blocks the air supply through the fuel

4 More Fixed carbon i) Greater calorific value

ii) Helps in designing the furnace

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2.Ultimate Analysis of Coal

Determination of % of

Carbon & Hydrogen Nitrogen Sulphur Ash Oxygen

i) Carbon & Hydrogen content :
O2
A known amount of coal Formation of CO2 & H2O
Combustion Apparatus
Reactions :
C + O2 CO2
H2 + ½ O2 H2O
KOH Tube :
CO2 vapour is absorbed
Increase in weight of the KOH tube = Weight of CO2
Anhydrous CaCl2 Tube :
H2O vapour is absorbed
Increase in weight of the CaCl2 tube = Weight of H2O
From the weight of CO2 & H2O, % of Carbon & Hydrogen is calculated.
12 x Increase in weight of the KOH tube
% of Carbon in coal = x 100
44 x Weight of coal sample

2 x Increase in weight of the CaCl2 tube

% of Hydrogen in coal = x 100
18 x Weight of coal sample

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ii) Nitrogen Content (Kjeldahl’s method) :

Con.H2SO4, ∆
Powdered Coal Ammonium sulphate (clear solution)
K2SO4 Catalyst
NaOH

N/10 Std. HCl

Neutralisation takes place NH3

Reactions :
2N + 3H2 + H2SO4 (NH4)2SO4
(NH4)2SO4 + 2NaOH 2 NH3 + Na2SO4 +2 H2O
NH3 + HCl NH4Cl
From the volume of HCl consumed,
% of Nitrogen is calculated.
14 x Volume of acid consumed x Normality of acid
% of Nitrogen in coal = x 100
1000 x Weight of coal sample
i) Sulphur Content :
Burnt in
A known amount of coal Sulphate
Bomb calorimeter
Extracted with water

Extract
BaCl2
Filtered, dried & weighed BaSO4

From the weight of BaSO4, % of Sulphur is calculated.

32 x Weight of BaSO4 tube

% of Sulphur in coal = x 100
233 x Weight of coal sample

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iv) Ash content :

½ hr
Moisture & Volatile matter Loss in weight of coal is noted
removed coal without lid 700 ± 500c

Loss in weight of the coal

% of ash content in coal = x 100
Weight of dried coal

v) Oxygen content :

% of Oxygen in coal = 100 - % of ( Carbon + Hydrogen + Sulphur+ Ash content )

Significance of Ultimate Analysis

A good quality coal has High calorific value. For High calorific value, coal
must contain
1. High Carbon & Hydrogen content 2. Low Nitrogen content
3. Low Sulphur content 4. Low oxygen content

S.NO CONTENTS SIGNIFICANCE

1 High Carbon & Hydrogen i) Increases calorific value of coal

ii) Helps in the classification of coal

2 High Nitrogen No calorific value

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3 High Oxygen content i) Low calorific value

ii) Increases moisture holding capacity of coal

4 High Sulphur content i) Increases calorific value

ii) It produces SO2 , SO3 and corrosion takes

place

Carbonisation
When coal is heated strongly in the absence of air, the volatile matter
escapes out and a hard, strong, porous and coherent mass, called coke is formed.
This process is called carbonization.
Types of carbonization
1. Low temperature carbonization (LTC)
It is carried out 500 - 700°C. The coke formed is soft and
mechanically less strength. The yield is 75 – 85%. The gaseous product
formed has low calorific value.
2. High temperature carbonization (HTC)
It is carried out 900 - 1200°C. The coke formed is hard and mechanically
high strength. The yield is 65 – 75%. The gaseous product formed has high
calorific value.
Metallurgical Coke
When bituminous coal is heated strongly in the absence air, the volatile
matter removed and the mass becomes hard, strong, porous and coherent which is
called Metallurgical Coke.
Characteristics / Requisites of metallurgical coke.
i) Purity : Low moisture, ash and sulphur contents in metallurgical coke

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ii) High Porosity

iii) High Mechanical strength
iv) High Calorific value
v) Easy combustibility
Manufacture of metallurgical coke by Otto-Hoffman’s by-product oven
method.
Otto-Hoffmann oven consists of a number of series of narrow silica
chambers. Each chamber is provided with a charging hole at the top. The oven
is provided with iron door at each end for discharging the coke.
Coal is charged into chambers and the doors are closed. The chambers
are heated by a mixture of preheated air and producer gas at 1200 oC. The coal
undergoes combustion and liberates waste gases. The heat of the waste gases are
used for heat regeneration of oven before leaving the chamber. Therefore, heating
of the oven is continued till the liberation of volatile gases is completed.
After 24 hours, the coke is removed from the oven and quenched with
water. The yield of coke is about 75%. The valuable by- products like coal gas,
tar, ammonia, H2S, benzene etc., are recovered.

Recovery of by-products:
(i) Tar:
The flue gases are first passed through a tower in which liquor ammonia is

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sprayed. Tar and dust get dissolved and collected in a tank below, which is heated
by
steam coils to recover back the ammonia sprayed.
(ii) Ammonia:
The gases are then passed through another tower in which water is sprayed.
Here ammonia gets converted to NH4OH.
(iii) Naphthalene:
The gases are again passed through a tower, in which cooled water is
sprayed.
Here naphthalene gets condensed.
(iv) Benzene:
The gases are passed through another tower, where petroleum is sprayed.
Here benzene gets condensed to liquid.
(v) Hydrogen Sulphide:
The remaining gases are then passed through a purifier packed with moist
Fe2O3. Here H2S is retained.
The final gas left out is called coal gas which is used as a gaseous fuel.
Advantages of Otto Hoffman’s process:
1. Valuable by products like ammonia, coal gas, naphthalene etc. are recovered.
2. The carbonization time is less.
3. Heating is done externally by producer gas.
II Liquid Fuels
Petroleum
Petroleum is naturally occurring liquid fuel of dark brown or black coloured
viscous oil obtained under the earth’s crust consisting a mixture of paraffinic,
olefinic and aromatic hydrocarbons with small amount of inorganic compounds
such as nitrogen, oxygen and sulphure.

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Classification of Petroleum
It is classified into three types.
1. Paraffinic – base type of Petroleum
2. Naphthenic or asphaltic base type of Petroleum
3. Mixed base type of Petroleum.
Refining of petroleum or crude oil.
Crude oil : Mixture of oil, water and unwanted impurities.
Refining of crude oil consists of 3 steps.
Step 1: Removal of water impurities:
Step-1
Crude oil Separation of water by Cottrell‟s process
Flow between two
highly charged
electrodes water removed crude oil
Step 2: Removal of sulphur impurities:
Step - 2
water removed crude oil CuS (removed)
CuO

Purified crude oil

Step 3: Fractional distillation
After the removal of water and sulphur compounds, the purified
crude oil is then heated to about 300° – 400°C in an iron retort, where the
volatile constituent of oil gets vapourised except the residue. The hot vapors
are then passed into the bottom of a fractionating column. Fractions having
higher boiling point condense at lower trays where fractions having
Lower boiling point condense at higher trays. Various fractions obtained at
different trays are given in table. The gasoline obtained by this fractional

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distillation is called straight-run gasoline.

S.No. Fraction Boiling

Composition Uses
range
Uncondensed As a fuel
1. Below 30°C C1 – C4 under the name of LPG.
gases
Petroleum
2. 30 – 70°C C5 – C7 As a solvent.
ether
Fuel for
Gasoline or
3. 40 – 120°C C5 – C9 internal combustion
petrol engines.

Naphtha or As a solvent in paints and in

4. 120 – 180°C C9 – C10 dry cleaning.
solvent spirit

Fuel for stoves

5. Kerosene oil 180 – 250°C C10 – C16 and jet engines.

Diesel oil (or)

6. 250 – 320°C C15 – C18 Diesel engine fuel.
fuel oil
Fuel for ships
and for production of
7. Heavy oil 320 – 400°C C17 – C30 gasoline by cracking.

Synthetic Petrol
The preparation of liquid fuels (petrol) from solid coal is called synthetic petrol.
The process is named hydrogenation of coal.

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Manufactured of synthetic petrol by Bergius process.

Coal - 4.5% hydrogen
Petroleum - 18% hydrogen
When compared to petroleum, coal is a hydrogen deficient compound.
If coal is heated with hydrogen under high temperature and high pressure, solid
coal will be converted into liquid fuel. It is called hydrogenation of coal
and the liquid fuel obtained is called synthetic petrol.
Bergius process for manufacture of synthetic petrol:
In this method, the finely powdered coal is made into a paste with
heavy oil and a powder of catalyst (tin or nickel oleate). This mixture is sent to
a converter and heated with hydrogen gas at 450°C under a pressure of 200 –
250 atm for about 1.5 hours.
During this process, hydrogen combines with coal to form saturated
higher hydrocarbons, which decomposes at higher temperature to yield
mixture of low boiling hydrocarbons.

The mixture is sent into the cooler, where the crude oil is obtained. The
crude oil is then fractionated to get (i) Gasoline (or) Petrol (ii) Middle
oil (iii) Heavy oil
The middle oil is further hydrogenated in the vapour phase in the
presence of solid catalyst to yield more petrol. The heavy oil is recycled for

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making paste with fresh coal dust. The yield of petrol is about 60% of the coal
dust used.
Knocking
Knocking is a kind of explosion due to sudden pressure rise occurring in
internal combustion engine. It can be reduced by adding TEL (Tetra Ethyl
Lead).
The knocking tendency of gasoline mainly depends on their chemical
structures. The knocking tendency decreases in the following order.
Straight chain paraffins > branched chain paraffins (iso paraffins) >
cycloparaffins (naphthalenes) > olefins > aromatics.
Leaded petrol:
When the petrol is mixed with Tetra ethyl lead (TEL), it is called
leaded petrol.
Disadvantages of using TEL
TEL is converted to lead oxide and lead which is harmful to engine life.
It is reduced 1) by adding small amount of ethylene dibromide.

2) by using aromatic phosphates instead of TEL.

Diesel oil:
It is a high boiling fraction of crude oil between 250-320oC. It is a
mixture of C15 – C18 hydrocarbons. Its calorific value is 11000 Kcal/kg. It
is used as good engine fuel.
Octane number
It is used to express the knocking property of petrol. Octane number
is equal to the percentage of isooctane present in a mixture of n-heptane and
isooctane.

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Improvement of Octane number:

i) By adding anti-knock agents like tetra ethyl lead or aromatic phosphates
ii) By mixing with petrol of higher octane number
Cetane number:
It is used to express the knocking property of diesel. Cetane
number is the percentage of hexadecane (cetane) present in a mixture of
hexadecane and 2-methyl naphthalene which has the same ignition lag as the fuel
under test.

Improvement of cetane number:

Cetane value of diesel can be increased by adding dopes like ethyl
nitrate, iso-amyl nitrate.

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Comparison / Difference between gasoline oil and diesel oil

S.No. Petrol (Gasoline) oil Diesel oil

Low boiling fraction of petroleum,
High boiling fraction of petroleum, C15 – C18
1. C5 –C9 hydrocarbons.
hydrocarbons.
2. It is a fuel for Spark It is a fuel for Compression
Ignition (SI) engine. Ignition (CI) engine.
Knocking tendency of
Knocking tendency of diesel is
3. petrol is measured in octane
measured in cetane number or rating.
number or rating.
4. Knocking is due to premature Knocking is due to delay in the ignition.
ignition.
Anti-knocking is improved by the
Anti-knocking is improved by Ethyl nitrate.
5. addition of Tetra Ethyl Lead
(TEL).
Higher amount of pollutants. Lesser amount of pollutants.
6.
7. Consumption is more. Consumption is less.
8 Thermal efficiency is low.
Thermal efficiency is high.

III Gaseous Fuels

CNG (Compressed Natural Gas):
When the natural gas is compressed under pressure of 1000 atm , it is
called CNG.
Its calorific value is 1200 – 1400 Kcal/m3.
Properties of CNG:
(i) It is a light weight gas, cheapest and eco friendly
(ii) The ignition temperature is 540°C
(iii) Less expensive than petrol and diesel.
(iv) It produces less CO and hydrocarbon emission.
(v) For ignition, it requires more air.
Uses of CNG:
Used as an alternate to petrol and diesel for vehicles.
Advantages over other fuels:

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Uses
1. Used in the synthesis of ammonia
2. Used to synthesis of gasoline.
3. Used in the manufacture of power alcohol
4. Used in the manufacture of carbureted water gas (water gas + oil gas)
5. A fuel gas.
Power alcohol:

When 10 % absolute ethyl alcohol is blended with petrol , it is called

power alcohol. Its calorific value is 7000 Kcal./Kg

Manufacture: It consists of 2 steps.

Step-I : Synthesis of ethyl alcohol

Ethyl alcohol is synthesized by fermentation of carbohydrates (sugar
material).
Example: Fermentation of molasses with yeast generates alcohol.

Yeast
C6H12O6 2C2H5OH + 2CO2
Glucose (Sugar) Ethanol

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It yields only above 20% alcohol. The concentration of alcohol can

be increased up to 97.6% by fractional distillation. It yields rectified spirit.

Step-II : Synthesis of power alcohol

The last traces of water from rectified spirit is removed by distilling

the alcohol with benzene or dehydrating agent. Then, 10 % absolute ethyl
alcohol is blended with petrol to form power alcohol.
Properties:
1. Low calorific value 2. High octane number
2. 3. Good anti-knocking property
4. High compression ratio 5. Generates 10% more power than petrol
Uses: Very good fuel.
Advantages:
(i) Cheaper than petrol (ii) Biodegradable fuel
(iii) Minimum emission of greenhouse gases (iv) Decreases the damage of
ozone layer (v) Burns more cleanly
Disadvantages of power alcohol:
(i) Production of ethanol requires significant energy and land.
(ii) Fuels with more than 10% ethanol may cause corrosion.
(iii) It requires specially designed engine. (iv) It causes starting trouble.
(v) It may undergo oxidation to give acetic acid, which corrodes engine part.
Biodiesel :
Biodiesel is the methyl esters of fatty acids derived from vegetable
oils or animal fats.
Problems of using vegetable oil directly:
 Viscosity and molecular weight of vegetable oils are higher than
diesel.

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 Atomization is very poor, hence incomplete combustion.

 It causes deposit formation on engine.
 Misfire and ignition delay.
Manufacture: Trans-esterification or Alcoholysis
Biodiesel fuel is produced from a variety of crops like soya bean,
mustard, flax, sunflower, palm oil, hemp, jatropha, rape seed, canola and
animal fats.
Biodiesel is synthesized by trans-esterification of vegetable oil and fat
by methanol in the presence of catalyst (NaOH, KOH) to give monomethyl
esters of fatty acids and glycerin.

Uses:
It is a pure fuel. It can be used in existing diesel engines without
modification.
Advantages:

(i) Biodegradable fuel (ii) Renewable fuel (iii) Less expensive (iv) Less
toxic (v) Less smoke emissions (vi) Clean-burning fuel (vii) Best engine
performance.

Disadvantages: (i) It requires energy to produce biodiesel (ii) It gels in

cold weather (iii) It degrades and soften the rubber (iv) It absorbs the
water from atmosphere (v) It decreases the horse power of engine.

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hence 2.34 kg of O2 supplied = (100/23) x 2.34 = 10.174kg of air.

The amount of air required by the
complete combustion of 100kg of fuel = 10.174 x 100 = 1017.4kg of air.
IGNITION TEMPERATURE
It is the minimum temperature at which a fuel will burn smoothly.

Spontaneous Ignition Temperature (SIT)

It is the minimum temperature at which the fuel catches fire

spontaneously without external heating.

Explosive range

It is the range of composition of a gas-air mixture that will burn if

an ignition source is introduced. Beyond which the gas - air mixture will not
ignite and continue to burn.

e.g Natural gas – lower limit 5

- upper limit 14.

Flue gas analysis by Orsat apparatus method.

The mixture of gases (like CO2, O2, CO and N2) coming out from the
combustion
chamber is called flue gas.

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Principle :
This method is based on the absorption principle. The gases like CO2 ,
O2 and CO are absorbed by KOH, alkaline pyrogallol and ammoniacal
cuprous chloride solutions respectively.
Significance :
i) It gives an idea about the complete combustion of fuel or not.
ii) If CO is high in the flue gas, it shows incomplete combustion of
the fuel and
short supply of oxygen.
iii) If CO2 and O2 are high in the flue gas, it shows complete
combustions of the fuel and excess supply of oxygen.
Description of Orsat's apparatus
 It consists of a horizontal tube having three way stop cock.
 One end of the tube is connected to a U- tube containing fused CaCl2.
 Another end of the tube is connected to a graduated burette.
 The burette is surrounded by a water jacket.
 The lower end of the burette is connected by a water reservoir.
 The middle of the horizontal tube is connected with 3 bulbs (I, II
and III) for
absorbing flue gases as follows:
i) Bulb I - KOH solution and it absorbs only CO2
ii) Bulb II - alkaline pyrogallol solution and it absorbs only O2
iii) Bulb III - ammoniacal cuprous chloride solution and it absorbs CO.
Working of Orsat apparatus:
 The three – way stop cock is opened.

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 The burette is filled with water, by raising the water reservoir

to remove air from the burette.
 Then, the flue gas is taken in the burette upto 100 cc by
raising and lowering the reservoir.
 The three way stop cock is now closed.
Absorption of gases in bulbs
i) Absorption of CO2
 The stopper of the bulb I is opened.
 The flue gas is allowed to pass into the bulb I.
 CO2 present in flue gas is absorbed by KOH.
 It is repeated several times.
 The decrease in volume of burette indicates the volume of
CO2 .
 Now the stopper is closed.
ii) Absorption of O2
 The stopper of the bulb II is opened.
 The flue gas is allowed to pass into the bulb II.
 O2 present in flue gas is absorbed by alkaline pyrogallol.
 It is repeated several times.
 The decrease in volume of burette indicates the volume of O2.
 Now the stopper is closed.
iii) Absorption of CO
 The stopper of the bulb III is opened.
 The flue gas is allowed to pass into the bulb III.
 CO present in flue gas is absorbed by ammoniacal cuprous
chloride solution. It is repeated several times.

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 The decrease in volume of burette indicates the volume of

CO.
 Now the stopper is closed.
iv) Nitrogen
The remaining gas in the burette after the absorption of CO2, O2 and
CO is nitrogen.
The % of N2 in flue gas = [100 − (% of CO2 + % of O2 + % of CO)]

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UNIT - 5
ENERGY SOURCES
INTRODUCTION
We mainly depend on the conventional sources of energy like coal,
petroleum, gas, etc. These sources are limited in quantity and can be exhausted
in future. To overcome this energy crisis, the renewable energy sources can be
used.

NUCLEAR FISSION
Nuclear Fission is a process of splitting heavier nucleus into two or
more smaller nuclei on bombardment by thermal neutrons with simultaneous
liberation of large amount of energy.
235
92U +0n1 → 36Kr
92
+ 56Ba
141
+ 3 0n1 + energy
Mechanism of fission

Illustration of fission

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Characteristics:
1. Heavy nucleus splits into two or more smaller nuclei.
2. Two or more neutrons are produced by each fission.
3. Large amount of energy is produced.
4. All the fission products are radioactive and emits β and γ rays.
5. The atomic weights of fission products ranges from about 70 to 160.
6. All fission reactions are self-propagating chain-reactions.
7. It can be controlled and maintained by control rods - nuclear reactor.
8. Multiplication factor:
It is the no of neutrons, resulting from a single fission. If it is
less than 1 , chain reaction does not take place.
Classification of nuclear fission:
There are 2 types.
(i) Uncontrolled fission reaction:
If a nuclear fission reaction is made to occur in an uncontrolled manner, it
is an uncontrolled nuclear fission.
Eg. Atom bomb
(ii) Controlled fission reaction:
If a nuclear fission reaction is made to occur in an controlled manner, it is
an controlled nuclear fission.
Eg. Nuclear reactor
Advantages of nuclear fission energy:
 Nuclear energy requires very small amount of nuclear fuel
 Once the nuclear fission reaction starts, we get nuclear energy over a long
period of time in a nuclear reactor.
Disadvantages of nuclear fission energy:
 It causes nuclear pollution.
 It causes genetic mutation.
 Safe disposal of nuclear waste is difficult.

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NUCLEAR FUSION
It is the process of combination of lighter nuclei into heavier nucleus
with simultaneous liberation of large amount of energy.
(e.g) solar system
2
1H + 1H2  2 He4 + Energy
2
1H + 1H3  2 He4 + 0n1

The energy of stars and sun is arised from the fusion reactions in which
hydrogen is converted into helium. The fusion reactions can start only when the
atoms are heated to very high temperatures. Such a high temperature required is
produced by fission reaction.
Eg. In hydrogen bomb, fusion occurs by the fission of atom bomb which acts
as trigger.
Characteristics of nuclear fusion:
 There is no limit on the amount of nuclear fusion that can occur.
 It is possible only when the distance between the nuclei is of the order of
one Fermi.
 The amount of energy in fusion is four times greater than fission.
 Sufficient amount of kinetic energy must be provided.
 Only lighter nuclei can undergo nuclear fusion reaction.
Disadvantages of fusion:
 Utilization of fusion energy is problem, because no known material can
withstand at high temperature.
 It cannot be controlled easily.
 Design of thermonuclear fusion power plant is very difficult.

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Difference between nuclear fission and fusion

S.NO NUCLEAR FISSION NUCLEAR FUSION
1. It is the process of breaking of It is the process combination of
heavier nucleus into smaller nuclei smaller nuclei in to a heavy nucleus
2. It emits radioactive rays It does not emit rays
3. It occurs at ordinary temperature It occurs at high temperature
4. The mass number and atomic The mass number and atomic
number of new elements are number of product is higher than
lower than that of parent nucleus that of starting elements
5. It gives chain reaction It does not give chain reaction
6. It emits neutron It emits positrons
7. It can be controlled It cannot be controlled
Eg: Atom bomb Eg: Hydrogen bomb

NUCLEAR CHAIN REACTIONS

A fission reaction, where the neutrons from the previous step
continue to propagate and repeat the reaction is called nuclear chain
reaction.
Criteria for nuclear chain reaction:
235
1. For continuous nuclear chain reaction, sufficient amount of 92U

must be present to capture the neutrons. Otherwise neutrons will

escape from the surface.
a) Critical mass:
235
The minimum amount of fissionable materials 92U or Pu239
required to continue the nuclear chain reaction is called critical mass.
b) Super- Critical mass :
235
If the mass of the fissionable material 92U is more than the
critical mass, then it is called super- critical mass.

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c) Sub- Critical mass:

If the mass of the fissionable material 92U235 is lesser than the
critical mass, then it is called sub- critical mass.
2. The super or sub critical mass will hinder the propagation of the chain
reaction.
Illustration of the Nuclear chain reaction:
235
When 92U nucleus is bombarded by thermal neutron, it
undergoes the reaction with release of three neutrons.
235
92U +0n1 → 36Kr
92
+ 56Ba
141
+ 3 0n1 + energy

Each of the three neutrons, produced in the reaction, strikes

235
another 92U nucleus causing (3*3) 9 subsequent reactions. This is
called chain reaction.
NUCLEAR ENERGY
The energy released by nuclear reaction is called nuclear energy or
nuclear energy.
Example:
235 92 141
92U +0n1 → 36Kr + 56Ba + 3 0n1 + energy

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Causes of the release of nuclear energy:

Hazards of using nuclear energy:

 Nuclear radiation can damage the structure of cells in human body.
 It causes diseases like cancer and blindness.
 It causes genetic disorder

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 It causes sterility in young generation

Applications of nuclear energy:
 Used as eco-friendly energy resources
 Used for electricity generation
 The water discharged from the nuclear reactors is free from radiation and
is clean enough to conserve animals
 Health care:
Used in treatment of cancer.
Eg. Radioactive isotopes
 Used for sterilization to destroy microorganism
 Used to control agricultural pests

NUCLEAR REACTOR
Nuclear reactor is a device used to produce electricity in
which nuclear fission takes place in a controlled rate.
Components of a Nuclear Power Plant (Or) Light Water Nuclear Power
Plant
1. Reactor core
2. Fuel elements
3. Moderator
4. Coolant
5. Control rod
6. Pressure vessel
7. Protective shield
8. Turbine
1. Reactor core
It consists of fuel elements, moderator, coolant and control rods.
(i) Fuel elements:

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They are of fissile isotope . Used in the form of rods or strips.

Example: 92U235 , 94Pu
239

Functions:
(i) It produces high heat energy.
(ii) It produces neutron for nuclear chain reaction.
(ii)Moderators:
These are used to convert the fast moving neutrons (1 MeV to
0.25 eV) into slow moving neutron by colliding with them.
Example: Ordinary water, Heavy water, Graphite, Beryllium

(iii) Coolants:
The heat produced inside the reactor is absorbed by the coolant. It
is circulated, enters at the base and exit at the top.
Example: Ordinary Water, heavy water, liquid metal (Na, K), organic liquids.
(iv) Control rods (Movable rods) :
These are used to control the fission rate . It is suspended between fuel
rods. If the rods are inserted inside, they will absorb more 0n1 , reaction
becomes very slow. If the rods are raised, reaction becomes very fast.
Example:5 B10, 43Cd113
113
43Cd +0n1 →43Cd114 +γ-ray
5 B10+0n1 →5 B11+γ-ray
Functions:
(i) It controls the nuclear chain reaction.
(ii) It prevents the damage of the reactor.

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2. Pressure vessel:
It encloses the core and also provides the entrance and exit passages for
the coolant.
Function:
It withstands the pressure as high as 200 kg/cm2 .
3. Protective shield:
It is a thick massive concrete shield of 10 m thickness, that encloses
the nuclear reactor.
Function:
It prevents the γ-rays and harmful radiation.
4. Turbine:
In heat exchanger, the heat from the coolant is exchanged to sea water
and produce steam at high pressure. It is used to rotate the turbine to
produce electricity.
Working:
The U235 is bombarded with thermal 0n1 produces fission products
and three secondary neutrons which initiate nuclear chain reaction. It can
be controlled by control rods (B10). The heat produced during fission

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is absorbed by coolant (light water). The hot coolant (water at 300 ° C)

then goes to the heat exchanger containing sea water. The coolant
transfers heat to sea water which is converted into steam , the steam
then drives the turbines to generate electricity.
Disadvantages:
(i) Nuclear reactor cause nuclear pollution to environment.
(ii) The radioactive fission products release harmful radiation for several
100 years.
(iii) It causes genetic mutation.
(iv) Problem on Disposal of radioactive waste
Disposal of radioactive waste is a problem. It causes radioactive
pollution for several hundred years. The radioactive waste is
packed in concrete barrels, which are buried in the sea.

BREEDER REACTOR
Breeder reactor is a reactor which converts non-fissionable material
(U238, Th232) into fissionable material (U235, Pu239). This reactor produces more
fissionable material than it consumes.

Illustration
238 1 239
92U + 0n → 94Pu + 2 e-
Non –fissionable (from fission) Fissionable

239 1 90 147
94Pu + 0n → 38Sr + 56Ba + 3 0n1 + energy
(fission products)

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235
Out of three neutrons emitted in the fission of 92U , only one is
used in propagating the fission chain with U235 . The other two neutrons
238
are allowed to react with 92U . Thus, two fissionable atoms of Pu239 are
produced for each atom of U235 consumed. So breeder reactor produces
more fissionable materials than it consumes.
Significance:
(i) The non-fissionable nucleides converted into fissile nucleides .
(ii) As regeneration of fissile nucleides, efficiency increases.

SOLAR ENERGY CONVERSION

Solar energy conversion is the process of conversion of direct
sunlight into thermal energy and electrical energy.
Two methods:
1. Photo conversion
2. Thermal conversion
THERMAL CONVERSION OF SOLAR ENERGY
It involves absorption of thermal energy from sunlight in the form
of IR radiation.
Eg.: Solar water heater, solar cooker, solar heat collector, etc.
1. Solar water heater:

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It consists of an insulated box inside of which is painted with

black paint. It is provided with a glass lid to receive and store solar
heat. The water is allowed to flow inside the copper coil. The water gets
heated up and flows out.

2. Solar heat collector:

It consists of natural materials like stones, bricks, glass which can
absorb sun light during day time, and releases it slowly at night.
Uses:
It is used in cold places to keep houses in hot condition.

PHOTO CONVERSION OF SOLAR ENERGY

It involves conversion of solar energy into electrical energy by the
photoelectric effect.
Solar energy → Electrical energy
Methods of photoconversion:
It can be made by photo galvanic cell or solar cell
SOLAR CELL OR PHOTOGALVANIC CELL:
Solar cells or batteries are the devices that convert the solar energy
into electrical energy.
Solar energy → Electrical energy

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Principle:
It is based on PV effect, when the solar rays falls on a two layer of
semiconductor devices, a potential difference between the two layer is
produced. This potential difference causes flow of electrons and produces
electricity.
Construction:

Solar cells consist of a p-type semiconductor (Si with B) and n-type

semiconductor (Si with P). They are in close contact with each other.
Working:
When solar rays fall on the top layer of p-type semiconductor, the
electrons from the valence band get promoted to the conduction band and
cross the p-n junction into n-type semiconductor. When the p and n layer are
connected to an external circuit, electrons flow from n-layer to p-layer and
hence current is generated.
SOLAR BATTERY:
When large numbers of solar cells are connected in series, it forms a solar
battery. Solar battery produces more electricity and run water pump, street light
etc.
Uses:
1. Lighting purpose: Street lights are replaced by solar street light.

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2. Water pumps run by solar battery.

3. Used in calculators, electronic watches, street lights, water pumps, radios &
TVs.
4. Used to drive vehicles, space craft, satellites.
5. It can be stored in Ni-Cd and lead-acid batteries.
Advantages:
1. Pollution free energy
2. Eco friendly
3. Used in remote areas, forest and hilly regions
4. Maintenance cost is low
5. Long life time
6. It does not require recharge
Disadvantages:
1. The Solar energy is not available at night
2. The Solar power decreases during cloudy
3. It produces only DC voltage
4. High capital cost

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Recent Development in solar cell materials

 Crystalline Si
 Thin films
 Next generation Perovskite Solar Cells (PSCs)
 Solar paints
 Transparent solar windows

 Thermo radiative PV devices

Crystalline silicon (c-Si)

Crystalline silicon is the most used (90% of the global PV market) semiconducting
material in solar panels.
But, its efficiency is only 30%. So, solar cells with low-cost and high-efficiency
materials are needed.
Ex: III – V multijunction materials: (efficiency > 30%)
Hybrid tandem III – V/Si solar cells: (efficiency > 30%)
Six-junction III – V solar cells under concentrated light: (efficiency > 47.1%)
Si-based bifacial technology: (efficiency is 11% more compared to standard panels)

Thin films
Due to their narrow design (light weight, flexibility and ease of installation)
secondgeneration thin-film solar cells are growing as one of the most promising PV
technologies.
This films are 350 times smaller light absorbing layers compared to standard Si
panels.
Ex:
Cadmium-telluride (CdTe)
Amorphous silicon
Gallium – Arsenide (GaAs)
Copper – Indium – Gallium – Selenide (CIGS)
Of all, CIGS is the more efficient with efficiency upto 21%.

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Perovskite solar cells

Among the next generation solar cells, hybrid metal halide perovskite solar cells
(PSCs), play an important role due to their low price, thinner design, low
temperature processing and excellent light absorption properties.
Ex: Combined pervoskite and S – PV materials shows a record efficiency of upto
28%

Solar paints
Solar paint is the another transformative technology. These can be coated over the
polymer films.
Ex: Solar paint hydrogen generated energy from photovoltaic water splitting.
Quantum dots (Photovoltaic paint). Perovskite – based paints.

Transparent solar windows

They possess highly innovative applications. Their solar – to – electricity conversion

efficiency is 10% more.

Thermoradiative PV devices (or) Reverse solar panels

They can generate electricity at night by utilizing the heat irradiated from the panels
to the optically coupled deep space, which serves as a heat sink.

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Wind Energy
 Energy generated from the force of wind is called wind energy
 It is stored in the form of electricity through wind mills.

Wind energy is harnessed by Wind Mills and Wind Farms

Windmills

 The device used to convert wind energy into electrical energy.

 The minimum speed of air required is 1.5km/h.

 It produce electricity of about 100kw.
 It consist of a wheel containing number of blades.
 The blades of the wind mill keep on rotating continuously due to the
force of striking wind which produce electricity

Windfarms

 A large number of wind mills are linked in a definite pattern

 A large amount of electricity is produced.
Working of a wind mill

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Working of a wind mill

 It consists of a wheel containing number of blades.

 The wheel rotates about an axle mounted on a pole.
 The wind energy is used to rotate the wheel.
 One end of the axle is connected to the armature of a generator, which
rotates between two poles of a strong magnet.
 Another end of the axle is connected to the shaft of the wind mill.
 When wind falls on the wheel of a wind mill, it rotates and
electric current is produced.
 Thus, the kinetic energy of the wind is converted into electrical
energy
Disadvantages
 The direction of the wind is not predictable.
Advantages
 It produces noise pollution.
 Pollution free
 Wind turbines interfere with electromagnetic
 Renewable energy signals (TV, radio signal).
 Very cheap
 It causes hazards to birds.
 Freely available

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Uses

 It is used to produce large amount of electricity.

 Used to move sail boats in lakes, rivers and seas.
 Used to operate water pumps.
 Used to run the flour mill.

Other Methods To Harness The Wind Energy

 Sky sail
 Ladder mill
 Kite ship
 Sky wind power
 Briza technologies
 Sequoia automation

Geothermal energy

 Geothermal energy is the thermal energy present inside the Earth's crust in high
temperature and pressure.
 It is a renewable energy source because heat is continuously produced inside the
earth.
 Temperature of the earth increases at a rate of 20-75 oC per km, when we move
down the earth surface.

Resources of Geothermal energy

• Geysers
• Hot springs
• Volcanoes
• Hot boiling mud pots
• Magma

Usage of geothermal energy can be classified into two types

Direct usage

The energy extracted is directly used without processing or converting

it into any other form of energy which could be implied for other uses.

E.g : spas, springs, etc

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Indirect usage

The energy extracted is processed, converted or transformed into an

another form using turbines and generators, which could be
used for other applications.

E.g; power plants, generators, turbines, etc.

The three types of power plants used to convert geothermal energy to

electricity are,

• Dry steam power plant

• Flash steam power plant
• Binary cycle power plant

ADVANTAGES DISADVANTAGES
 It is not a widespread source
 Available all the year around of energy .
 Doesn’t involve any  Its installation costs more .
combustion of fuel
 It cant function when the
 Independent of weather steam runs out , which is the
conditions Economically good main source
alternative
 It may release harmful gases
 It is a sustainable source of
energy  Natural calamities like
earthquake , etc.. Can
 Used for direct uses such as hot damage the system
water bath, resorts, aquaculture,
greenhouses

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MSAJCE-DEPARTMENT OF CHEMISTRY

BATTERIES AND FUEL CELLS

In the electrochemical cells, the chemical energy is converted into
electrical energy. The cell potential is related to free energy change (ΔG).
ΔG = maximum useful work
ΔG = - nFE (or) ΔG < 0
When cell operates, work is done on the surroundings (i.e. flow of
electricity).
BATTERY
Battery is an electrochemical device containing 2 or more cells
which converts chemical energy into electrical energy.
A Cell contains only one anode and cathode.
A battery contains several anodes and cathodes.
Requirements of a battery:
1. It should be light and compact
2. It should have long life
3. The voltage of battery should not vary
Types of battery:
It is classified into 3 types.
1. Primary or 2. Secondary or 3. Flow or Fuel battery
Irreversible battery Reversible battery
1 Non-rechargeable Rechargeable battery Fuel cells are the galvanic cells
battery in which chemical energy of fuel
is directly converted into
electrical energy. Reactants are
continuously passing through
the cell.
2 Electrode reactions Electrode reactions can Eg: H2-O2 fuel cell
cannot be reversed. be reversed by passing
external current.
3. Discarded after use. Used over and over
again.
4. Eg: Dry cell, Eg: Lead acid, Nicad,
Alkaline battery Lithium batteries.

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MSAJCE-DEPARTMENT OF CHEMISTRY

IMPORTANT PRIMATRY BATTERY

DRY CELL (OR) LECLANCHE’S CELL
It is a primary cell, which works without fluid component.
Description:
Anode : Zn
Cathode : Carbon rod (graphite)
Electrolyte : NH4Cl, ZnCl2 and MnO2 paste
Voltage : 1.5 V
It consists of a zinc cylinder which acts as anode. The zinc cylinder is
filled with in the electrolytic mixture of NH4Cl, ZnCl2 and MnO2 paste. The
carbon rod is immersed in the electrolyte in the Centre of the cell. During use,
the zinc cylinder gets consumed and at the end, it will develop holes which are
responsible for leakages.
Construction and Working:

When the cell is working, zinc loses electrons and Zn 2+ ions gets
dissolved in the electrolyte. The electrons pass through the circuit and are
consumed at cathode. This causes discharge of NH4+ ions from the electrolyte.
Cell reactions:
At anode:
Zn → Zn2+ + 2e-
At cathode:
NH4+(aq) + MnO2(s) + 2e- → MnO(OH)- + NH3
Overall reaction:
Zn + NH4+(aq) + MnO2(s) → Zn2+ + MnO(OH)- + NH3

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The liberation of NH3 gas disrupts the current flow and is prevented by
the following reaction.
2 NH3 + ZnCl2 → [Zn(NH3)2]Cl2(s)
Advantages:
1) Corrosion of Zn occurs
2) Zinc dissolves readily in basic medium
3) No Long life time
4) While using, voltage drop occurs; because the products are build up on the
electrodes.
Uses:
Used in torches, toys, flash lights, calculator, transistor radios, etc.

IMPORTANT SECONDARY BATTERY

LEAD-ACID BATTERY OR LEAD ACCUMULATORS
Lead-acid battery is a secondary battery. When it acts as voltaic
cell, it supplies electrical energy and run down. When it is recharged, it
acts as an electrolytic cell.
Description:
Anode : Pb
Cathode : PbO2
Electrolyte : 20% Dil.H2SO4 (density 1.20 gm/ml)
Voltage : 2.0 V
Representation : Pb│ PbSO4││ H2SO4(aq)│ PbO2│ Pb
Construction and working:

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A lead storage battery consists of 3 or 6 voltaic cell. A number of

anode and cathode plates are connected in series. Plates are separated
from adjacent ones by insulators like rubber. This arrangement is immersed
in dil. H2SO4.
Working (On discharging):
At anode :
Lead is oxidized to Pb2+ ions.
Pb (s) + SO42- → PbSO4 (s) + 2e-
At cathode:
PbO2 is reduced to Pb2+ ions.
PbO2(s) + SO42- + 4H+ + 2e- → PbSO4+ 2H2O
Overall reaction:
discharging
Pb (s) + PbO2(s) + 2H2SO4 2PbSO4 + 2H2O + Energy
charging

On discharging, PbSO4 is deposited at both the electrodes and

H2SO4 is consumed. So concentration of H2SO4 decreases gradually.
On Recharging:
The cell is recharged by applying electricity externally.
At anode :
PbSO4 (s) + 2e- → Pb (s) + SO42-
At cathode:
PbSO4 + 2H2O → PbO2(s) + SO42- + 4H+ + 2e-
Overall reaction:
charging
2PbSO4 + 2H2O + Energy Pb (s) + PbO2(s) + 2H2SO4
discharging

Advantages of lead acid batteries:

1. It is made easily
2. It produces very high current
3. The self discharging rate is low
4. It also acts effectively at low temperature

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Disadvantages:
1. Recycling of this battery causes environmental hazards
2. Mechanical strain and normal bumping reduces battery capacity
Applications:
1) Used in automobiles.
2) Used in UPS Systems and research centres etc.
3) Used in marketing areas etc.
4) Used in security and alarm systems.
5) Used in telephones, mines, hospitals, power plants.

IMPORTANT SECONDARY BATTERY

LITHIUM-ION BATTERIES (OR) LITHIUM-ION CELLS
Lithium-ion battery is a secondary solid state battery. The movement of
Li ions are responsible for discharging or charging.
Construction:
Anode (Negative current collector) : Li metal – Layers of porous Carbon
Cathode (Positive current collector) : LiCoO2
Electrolyte : LiAsF6 or LiPF6
Separator : Polypropylene
Voltage : 3.0 V

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Lithium ion battery is made up of an anode, cathode, separator,

electrolyte, and two current collectors (positive and negative). The anode and
cathode store the lithium.
Working (On discharging the current):
Lithium is oxidized to Li+ ions with release of electrons. Li+
ions move from anode to cathode and electrons pass through the external
circuit connecting anode and cathode. The cathode receives both Li +
ions and electrons.
Cell reactions
At anode: Li → Li+ + e-
At cathode: Li+ + e- + LiCoO2 → LixCoO2
Overall reaction: Li + LiCoO2 → LixCoO2
Working (On charging the battery):
When plugging in the device, the opposite happens: Lithium ions are
released by the cathode and received by the anode.
Overall reaction: LixCoO2 → Li + LiCoO2
Advantages :
1) Lithium ion battery is a light weight battery and higher energy density.
2) It generates a higher voltage than other types of cells.
3) It has none of memory effect.
4) It produces three times the voltage of Ni-Cd batteries.
5) It can be made in variety of size and shapes.
Disadvantages:
More expensive than all other batteries.
Uses:
Used in cell phone, note PC, Portable LCD TV, Safety and Security
Devices, camera, memory batteries, transistors etc.

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MSAJCE-DEPARTMENT OF CHEMISTRY

FUEL CELLS
Fuel cell is a device which converts chemical energy of the fuel
directly into electrical energy without combustion.
Fuel + Oxygen → Oxidation products + Electricity
Examples: Hydrogen-Oxygen fuel cell,
Methanol-Oxygen fuel cell,
Propane-Oxygen fuel cell.
Fuel Battery:
When a large number of fuel cells are connected in series, it forms fuel
battery.
HYDROGEN - OXYGEN (H2 - O2) FUEL CELL
It is the simplest and most successful fuel cell. In this cell, fuel, oxidizer
and electrolyte are simultaneously passed through the cell.
Description:
Fuel = Hydrogen
Oxidizer = Oxygen
Electrolyte = 25% KOH or NaOH
Electrodes (anode & cathode) = Porous compressed carbon containing small
amount of catalyst (Pt, Pd, Ag and Ni)
Voltage = 1.0 V
Construction:

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Working (Discharging):
Pure Hydrogen is bubbled through the anodic compartment where it is
oxidized. The oxidizer (oxygen) is bubbled through the cathodic compartment,
where it is reduced.
Cell reactions
At anode: Hydrogen molecules are oxidized to form water.
2 H2 + 4 OH- → 4 H2O + 4e-
At cathode:
The electrons from anode are absorbed by oxygen and produces
hydroxide ions.
O2 + 2 H2O+ 4e- → 4 OH-
Overall reaction:
2 H2 + O2 → 2 H2O + Electricity
Applications:
1) It is used in space vehicles, submarines or other military-vehicles.
2) The product water is 100% pure.
Advantages:
1) No noise pollution and no thermal pollution
2) More efficiency and take less time for operation.
3) Highly reliable
4) Eco friendly
5) It produces 100% pure water
Disadvantages:
1. Fuel cells cannot store electric energy as other cells do
2. It is very expensive
3. Hydrogen gas is an explosive
4. It is difficult to compress the hydrogen gas into liquid form
5. Storage and handling of hydrogen gas is dangerous.

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Cell reactions

At anode: Hydrogen molecules are oxidized to form water.

2 H2 + 4 OH- 4 H2O + 4e-

At cathode: The electrons from anode are absorbed by oxygen and

produces hydroxide ions.
O2 + 2 H2O+ 4e- 4 OH-
Overall reaction: 2 H2 + O2 2 H2O + Electricity

Applications:
1) It is used in space vehicles, submarines or other military-vehicles.

2) The product water is 100% pure.

Advantages:
1) No noise pollution and no thermal pollution

2) More efficiency and take less time for operation.

3) Highly reliable

4) Eco friendly

5) It produces 100% pure water

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Microbial Fuel Cells (MFCs)

Microbial fuel cell is a device that converts chemical energy to electrical

energy by the action of micro-organisms under anaerobic conditions.

Bioelectricity is generated by the oxidation of organic waste and renewable

biomass using bacteria.

Construction:

MFC are type of electrochemical cell constructed using either bio cathode or
bio anode. A membrane separates both cathode and anode compartments. The
electron produced during oxidation is transferred directly to the cathode. The
organic electron donor that is oxidized to produce CO2, proton and electron
are used in most MFC.

Cathode uses variety of electron acceptor mostly oxygen

Anode Compartment: Microbes suspended under anaerobic conditions in

the analyte

Cathode: Graphite, carbon paper

Membrane/ Separators: Separates Anode and Cathode
Limits the Oxygen diffusion from cathode to anode

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Working principle

 When both electrode connected active biocatalyst in the anode oxidizes

the organic substrates and produces electrons and protons.

 The protons are conducted to the cathode through membrane, and the
electrons are reached through the external circuit.

 Finally oxygen present at the cathode recombines with hydrogen and

electron to produce water.

Applications of Microbial Fuel Cell

 Microbial fuel cell (MFC) can generate electricity from bio waste and
organic matter
 MFCs, generate less sludge as compared to the aerobic waste water
treatment process
 MFCs used in river, deep-water environments and space (remotely
operated vehicles)
 MFCs are used to convert carbon rich wastewater into methane gas
 MFCs are used as convenient biosensor for wastewater streams
 MFCs play an important role in the field of microbiology, soil chemistry
and electrical engineering
 Many commercial soil based MFC kits are available as an education tool

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Super Capacitor

Super capacitor is an electronic device that store large amount of electric

energy. They store 10-100 times more energy per unit volume and deliver
much faster than batteries.
Ordinary capacitor uses conventional dielectric storage, but super capacitor
uses electrostatic double layer capacitance (EDLC) for storage

Principle

The basic principle of super capacitor is to store electrical energy through

the electric double layer capacitance formed by the charge separation on the
interface between the electrode and electrolyte.

Design & Working

Super capacitor consists of two electrodes made up of metal coated with

porous substance like activated carbon.
The electrodes are separated by ion permeable membrane (separator) and
dipped in electrolyte having positive and negative ions

Working

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When the electrodes are connected to the power source, ions in the electrolyte form
electric double layers (Helmholtz electrical double layer) of opposite polarity to the
electrodes polarity, creating an electric field between them.

 For example, positively polarized electrodes will have a layer of negative ions at the
electrode/electrolyte interface.
 Similarly negatively polarised electrodes will have a layer of positive ions at the
electrode/electrolyte interface.
 This electric field polarizes the dielectric that stores more electrical energy at an
electrode-electrolyte interface

Classified into 3 types:

 Double-layer capacitors
 Psuedo-capacitors
 Hybrid capacitors

1. Double layer capacitors

Charge Storage: Electrostatically (Helmholtz double layer)
2. Pseudo capacitors
Charge Storage: Electrochemically. This can be done by redox reaction.
3. Hybrid capacitors
Charge Storage: Electrostatically & Electrochemically

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Advantages
 Highly safe
 Long life time (10-20 years)
 It can be cycled millions of time.
 Provides high power density and high load currents
 Good performance even at low temperature
 It can be charged in seconds.
Disadvantages
 Cost per watt is high
 High self-discharge that batteries
 It cannot be used as source for continuous power supply

Applications:

Super capacitors are used in many power management applications like,

 Voltage stabilization in start/stop system

 Consumer electronics
 Utility meters
 Remote power for sensors, LEDs, switches.
 Energy harvesting.
 Kitchen appliances.
 Wind energy.

ELECTRIC VEHICLE

 An electric vehicle (EV) is a vehicle that uses one or more electric motors for
propulsion
 It can be powered by a power system with electricity from external source or by
battery

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 They have electric motor instead of Internal Combustion Engine (ICE)

Working Principle

Electric vehicles work by plugging into a charge point and taking electricity
from the grid. They store electricity in rechargeable battery that power on
electric motor, which rotates the wheels. Electric vehicles accelerate faster than
the traditional fuel engines. So they feel lighter to drive.

Various steps of working

Step I: Controller takes and regulates electrical energy from battery to inverter.

Step II: The inverter then sends a certain amount of electrical energy to the motor.

Step III: The motor converts electrical energy into mechanical energy (rotation).

Step IV: Rotation of the motor rotor rotates the transmission, so the wheels turn
and then the vehicle moves.

Step V: When the brakes are pressed, the motor becomes an alternator and
produces power, which is sent back to the battery

Components

1. Battery: It provides electricity to power the vehicles.

2. Charge port: It allows the vehicle to connect to an external power supply

to recharge the battery.

3. DC/DC converter: It converts higher voltage DC power from battery to

lower voltage DC power.

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4. Electric motor: It drives the vehicle's wheels.

5. Onboard charger: It converts AC electricity to DC power for charging

the battery.

6. Power electronics controller: It controls the flow of electrical energy

from battery to motor and controls the speed.

7. Thermal system (cooling): It maintains the proper operating temperature

range of the engine, motor etc.

8. Transmission: It transfers mechanical power from the motor to drive the

wheels.
Types of Electric Vehicles

 Battery Electric Vehicle (BEV

 Hybrid Electric Vehicle (HEV)
 Plug-in Hybrid Electric Vehicle (PHEV)
 Fuel Cell Electric Vehicle (FCEV)

Battery Electric Vehicle (BEV)

• It runs entirely on a battery do not have an ICE.

• Energy stored in a large battery pack that is charged by plugging into the
electricity grid.
• The battery pack provides power to one or more electric motors to run the
electric car.
• Its typical driving ranges from 150-300 miles

Example Volkswagen e-Golf, Tesla Model 3, BMW i3

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Hybrid Electric Vehicle (HEV)

 HEVs have both an Internal Combustion Engine ICE and an electric motor.
 The engine gets energy from fuel, and the motor gets electricity from batteries.
 Both the engine and electric motor can turn the transmission at the same time,
which drives the wheels.

 The batteries in HEV can only charged by the ICE, motion of the wheels or
combination of both.

 The battery cannot be recharged from outside of the system.

Examples of HEV:
Honda Civic Hybrid, Toyota Prius Hybrid, Toyota Camry Hybrid.

Plug-in Hybrid Electric Vehicle (PHEV)

 PHEVs are powered by gasoline or bio-diesel and by a rechargeable battery pack.

 The battery can be charged up with electricity by plugging into an electrical outlet
or electric vehicle charging station (EVCS).

 It operates on electricity until the battery is depleted.

 Then the engine takes over and the vehicle operates as a conventional gasoline
vehicle PHEVs can run in at least 2 modes:
(i) All-electric Mode (ii) Hybrid Mode

Examples of PHEV:

Mercedes GLE550e, Mini Cooper SE Countryman, Audi A3 E-Tron

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Fuel Cell Electric Vehicle (FCEV)

 FCEVs employ ‘fuel cell technology’ to generate the electricity to run the vehicle.
 The chemical energy of the fuel is converted directly into electric energy.
 The FCEV generates the electricity required to run this vehicle on the vehicle itself.
 FCEVs are also known as Zero-Emission Vehicles.

Examples

Toyota Mirai, River simple Rasa, Hyundai Tucson FCEV, Honda Clarity Fuel Cell,
Hyundai Nexo.

Advantages Disadvantages
 Electric vehicles are energy  Electric vehicles cannot travel as far
efficient  Fueling takes longer
 It reduces emissions  Electric vehicles are expensive
 Batteries need rare materials
 It requires less maintenance
 There aren’t enough charging points
 Environmental friendly
 Saving lots of money on fueling
the car than gasoline vehicles

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