INDERPRASTHA ENGINEERING COLLEGE , GHAZIABAD

B.Tech. (FIRST YEAR): ENGINEERING. CHEMISTRY

UNIT 4 (WATER ANALYSIS)- NOTES

Hardness of Water : The water which does not form lather easily with soap is known as
hard water. (Soaps are the sodium or potassium salts of higher fatty acids.)
Cause of hardness : Hardness of water is due to the presence of dissolved (salts of
calcium (Ca), magnesium (Mg) and other heavy metals. There react with soluble sodium
soap to form insoluble salts of Ca and Mg.
2C17 H 35COONa + CaSO 4 → (C17 H 35COO)2 Ca  + Na 2SO 4
Sodium stearate Calcium stearate
2C17 H 35COONa + MgCl 2 → (C17 H 35COO)2 Mg  +2NaCl
Sodium stearate Magnesium stearate
Thus the precipitate formed is the insoluble soap of calcium and magnesium. Hence, a
large quantity of soap is required to produce lather with hard water.

Types of Hardness : Hardness of water is of 2 types.

(1) Temporary Hardness or Carbonate Hardness
(2) Permanent Hardness or Non-Carbonate Hardness

(1) Temporary Hardness or Carbonate Hardness : It is due to the presence of

dissolved salts of bicarbonates of Ca, Mg and other heavy metals and the
carbonates of iron.
Removal : It can be removed by following two ways.
(a) By boiling of the water
Ca (HCO 3 )2 ⎯
⎯→
Δ
CaCO3  +CO 2  + H 2 O
Calcium bicarbonate Calcium Carbonate (insoluble)

Mg (HCO 3 )2 ⎯
⎯→
Δ
Mg(OH) 2  +CO2 
Mag. Bicarbonate Mag. Hydroxide (insoluble)
(b) By adding slaked lime : A precipitate of calcium carbonate is formed. This is called
lime softening.
Ca (HCO 3 )2 + Ca (OH)2  2CaCO3  +2H 2 O
Calcium Slaked lime Calcium carbonate
Bicarbonate

(2) Permanent hardness or Non-Carbonate hardness : It is due to the presence of

chlorides and sulphate of Calcium (Ca), Magnesium (Mg) and other heavy metals
like iron (Fe). It cannot be removed by boiling.
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Permanent hardness or Non-Carbonate hardness : It is due to the presence of chlorides
and sulphate of Calcium (Ca), Magnesium (Mg) and other heavy metals like iron (Fe). It
cannot be removed by boiling.

Equivalents of CaCO3
Hardness in expressed in terms of Equivalents of CaCO3 (also known as Degree of
hardness) because The reason for choosing CaCO 3 as the standard for reporting
hardness of water is the ease in calculations as its molecular weight is exactly 100.
It is the most insoluble salt that can be precipitated in water treatment

The equivalents of various salts are as :

100g of CaCO3  136g of CaSO4 111g of CaCl2 120g of
MgSO 4  95g of MgCl 2 162g of Ca(HCO3 )2 146g of Mg(HCO3 )2
The Equivalents of CaCO3
Mass of hardness producing substance  Eq.wt. of CaCO3
=
Eq.wt. of the substance
100
Mass of hardness producing substance 
= 2
Eq.wt. of the substance
= Mass of hardness producing substance  Multiplica tion factor

Units of hardness : Various units of hardness are:- (1)Part per Million (ppm) : It is the
parts of CaCO3 equivalent hardness per 10 6 parts of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 10 6 parts of water.
(2) Milligrams per litre (mg/L) : It is the number of milligrams of CaCO3 equivalent
hardness present per litre of water.
1 mg / L = 1 mg of CaCO3 equivalent hardness per litre of water.
= 1 mg of CaCO3 equivalent hardness per 10 6 mg of water
( 1 Litre of water wt. = 1 kg = 10 6 mg)
= 1 part of CaCO3 equivalent hardness per 10 6 parts mg of water
= 1 ppm.
 1 mg / L = 1 ppm
(3) ( )
Degree French  Fr : It is the parts of CaCO3 equivalent hardness per 10 5 parts of
water.
1 Fr = 1 part of CaCO3 equivalent hardness per 10 5 part of H 2O .
(4) Degree Clarke ( Cl) : It is the parts of CaCO

3 equivalent hardness per 70,000 parts
of water.
1 Cl = 1 parts of CaCO3 equivalent hardness per 70,000 parts of H 2O .

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Relationship Between Various Units :
1 ppm = 1 mg / L = 0.1 Fr = 0.07  Cl

METHODS OF WATER SOFTENING :

(1 ) EXTERNAL TREATMENT OF WATER

LIME SODA METHOD

In this process, soluble hardness causing impurities are chemically converted into insoluble
precipitates which may be removed by setting and filtration.

For this purpose, hard water is treated with lime, , followed by soda ash .

Reactions are as follows :-

Lime removes the following hardness:
Ca (HCO 3 )2 + Ca (OH)2 → 2CaCO3  +2H 2 O
Mg (HCO 3 )2 + 2Ca (OH)2 → Mg (OH)2  +2CaCO3 + 2H 2 O
MgCl 2 + Ca (OH)2 → Mg (OH)2  +CaCl2
MgSO 4 + Ca (OH)2 → Mg (OH)2  +CaSO 4
FeSO4 + Ca (OH)2 → Fe(OH)2  +CaSO4
Al 2 (SO4 )3 +3 Ca(OH)2 → 2Al(OH)3 + 3 CaSO4
2HCl + Ca (OH)2 → CaCl2  +2H 2 O
H 2SO 4 + Ca (OH)2 → CaSO4  +2H 2 O
Ca (OH)2 + CO 2 → CaCO3  + H 2 O
Ca(OH)2 + H 2S → CaS + 2H 2O
Soda removes the following hardness:
CaCl2 + Na 2 CO3 → CaCO3  +2 NaCl
CaSO4 + Na 2 CO3 → CaCO3  + Na 2SO 4

The L-S process may be classified into two groups

(i) Cold lime - Soda process

(ii) Hot lime - Soda process

(i) Cold lime - Soda process

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The hard water is first analysed and then fed into the inner vertical circular chamber fitted
with a stirrer. Now, a calculated quantities of lime and soda ash are added into the tank. Also, a
small amount of coagulant, , is added, which entraps the fine precipitate of thereby causing easy
filtration. It also removes silica and oil, if present in water.

Na Al O 2 + 2H 2 O → NaOH + Al(OH)3 
Al 2 (SO 4 )3 + 3Ca (HCO 3 )2 → 2Al(OH)3  +3CaSO 4 + 6CO 2 
• Water becomes soft due to vigorous stirring and mixing.
• The heavy sludge settles down in the outer chamber and softened water reaches up.
• The softened water is then passed through filtration unit and finally filtered soft water
flows out through the outlet at the top.
• This process provides water containing residual hardness of 50-60 ppm.

(ii)Hot lime - Soda process

➢ In this process hard water and softening chemicals are heated near about the boiling
point of water.
➢ The reactions are much faster and the precipitation is almost complete.
➢ While in cold. L-S process, the reactions take place at room temperature due to
which partial softening of water takes place.
In hot L-S process, the precipitation occurs more quickly and also settles down rapidly. So
no coagulants are needed
❖ The apparatus used in this process contains a reaction cum settling tank and a filter.
❖ Reaction tank has three separate inlets for hard water, chemicals and steam. All the
three are thoroughly mixed in the reaction tank.

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 ❖ Now the reaction content from the reaction tank comes to the conical sedimentation
tank, in which sludge settle down.
❖ Filter has layers of fine and coarse sand which acts as filter and ensures complete
removal of sludge from the softened water.

Advantages of L-S process :-

(1) It is very cheap and economical.

(2) No amount of coagulants will be required, if this process is carried out at higher
temp.
(3) Fe & Mn (upto some extent) are also removed from water.
(4) It helps in reducing the total mineral content of water.
(5) It leads to an increase in the pH value of water, thus reducing the corrosion of
the distribution pipes.

Disadvantages of L-S process :-

(1) Carefull operation and skilled supervision is required to get good results.
(2) Formation of large amount of sludge creates its disposal problem.
(3) This process cannot produce water having zero hardness.
(4) Softened water from L-S softeners is not good for boilers.

Comparision between cold L-S process and hot L-S process:-

Cold L-S process Hot L-S process
1.Reactions take place at slower rate Reactions take place at faster rate
2.Coagulants are added to settle down Coagulants are not required.
the precipitate
3.Temporary hardness is removed by Temporary hardness in removed by
adding lime boiling and hence lime consumption
is less.
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4.No fuel consumption A steam is used, so there is fuel
consumption.
5. It takes longer time (few hours) It takes lesser time (few minutes)
6.The residual hardness is about The residual hardness is about
50-60 ppm 15-30 ppm.

CALCULATION OF LIME-SODA REQUIREMENT:-

Final formula for calculating the amount of lime or soda

required is given as:

Lime = (74/100) {temp. Ca2+ + 2 temp. Mg2+ + perm

(Mg2+ + Fe2+ + Al3+ ) + CO2 + HCl + H2SO4 +
HCO–3 – NaAlO2} 100 / % purity volume of
water

Soda = (106/100) {perm (Ca2+ + Mg2+ + Fe2+, Al3+ )+

HCl + H2SO4 – HCO–3} 100 / % purity
volume of water.

ZEOLITE PROCESS OR PERMUTIT PROCESS

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Zeolites are the hydrated sodium alumino Silicate . The artificial zeolite is called permutit
having the formula Na2O. Al2O3. X SiO2 y H 2O
(X= 2-10, y = 2-6 )
Natural Zeolites:
1. Natrolite - Na2O. Al2O3 4SiO2 .2H 2O
2. Laumontite - CaO. Al2O3 4SiO2 .4H 2O
3. Harmotome - (BaO.K2O). Al2O3 5SiO2 .5H 2O
Zeolite is capable of exchanging its Na ions with hardness causing cations Ca2+, Mg2+.For
softening of water by zeolite process, hard water is percolated at a specified rate through a
bed of zeolite, kept in a cylinder. The hardness causing ions like Ca2+, Mg2+ are retained by
the zeolite as CaZe and MgZe; while the outgoing water contains sodium salts.

The various reactions taking place are as:

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3
Na2Ze + MgCl2 MgZe + 2NaCl
Na2Ze + CaCl2 CaZe + 2NaCl
Na2Ze + MgSO4 MgZe + 2Na2SO4
Na2Ze + CaSO4 CaZe + 2Na2SO4

Regeneration:
After some time, the Zeolite is completely converted into calcium and
magnesium zeolites and it ceases to soften water, i.e., it gets exhausted. At this stage, the
supply of hard water is stopped and the exhausted zeolite is reclaimed by treating the bed
with a concentrated Brine solution(10% NaCl).
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl Na2Ze + MgCl2
Advantages:
a. It removes the hardness completely and water of about 10 ppm hardness is produced.
b. The equipment used is compact, occupying a small space.

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c. No impurities are precipitated, so there is no danger of sludge formation in the treated
water at a later stage.
d. The process automatically adjusts itself for variation in hardness of incoming water.
e. It is quite clean
f. It requires less time for softening.
g. It requires less skill for maintenance as well as operation.

Disadvantages / Limitations:
a. The treated water contains more sodium salts than in lime-soda process,
So water softened by this method causes caustic embrittlement in boilers.
b. If the supply of water is turbid, the suspended matter must be removed, before the water
is admitted to the zeolite bed. Otherwise the turbidity will clog the pores of zeolite bed,
thereby making it inactive.
c. If water contains large quantities of coloured ions such as Mn+2 and Fe+2 they must be
removed first, because these ions produce magnesium and Ferrous zeolites. This cannot
be easily regenerated.
d. Mineral acids, if present in water, destroy the zeolite bed and therefore, they must be
neutralized with soda, before admitting the water to the zeolite softening plant.

ION EXCHANGE RESIN METHOD

Ion exchange process also known as demineralization or de-ionization process. Ion-

Exchange resins are insoluble cross linked long chain organic polymers with a micro
porous structure, and the “functional Groups” attached to the chains are responsible for the
ion-exchanging properties.
In De-ionization process all the ions present in water are eliminated by using ion-exchange
resins.
Basically resins with acidic functional group are capable of exchanging H+ ions with other
cations.
Resins with functional groups are capable of exchanging OH- ions with other anions.
Resins are classified as
1. Cation Exchange Resins
2. Anion Exchange Resins
1. Cation Exchange Resins: These are mainly styrene divinyl benzene co-polymers,which
on sulphonation or carboxylation. These are capable of exchanging their hydrogen ions
with cations in water.

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2. Anion Exchange Resins: Anion exchange resins are styrene-divinyl benzene or amine-
formaldehyde copolymers, which contains amino, quaternary ammonium or quaternary
phosphonium or tertiary sulphonium groups as an internal parts of the resin matrix. These
after treatment with dilute NaOH solution. Become capable of exchanging their OH- ions
with anions in water.

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. Thus by
passing hard water through cation hardness is observed by the following reactions.
Cation Exchange Resins
2RH+ + Ca+2 R2Ca + 2H+
+
2RH + Mg +2 R2Mg + 2H+ (RH+ = cation exchange resin)
After cation exchange resin , the water is passed through anion exchange column when all
the anions like Cl- , SO4-2 etc. are taken up by resin and equivalent amount of OH- ion is
released from this column to water.
Anion Exchange Resins
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R’OH + Cl- R’Cl + OH-
2R’OH + SO4-2 R2SO4+ 2OH-
2R’OH + CO3 -2 R’2 CO3 + 2OH- (R’OH = anion exchange resin)
H+ and OH- ions, thus released in water from respective cation and anion exchange
columns, get combined to produce water molecules.
H+ + OH- H2O
The water coming out from the exchanger is ion free i.e., free from anions and cations.
Thus water of zero hardness is obtained.

REGENERATION:
When cation exchanger losses capacity of producing H+ ions and exchanger losses
capacity of producing OH- ions, they are said to be exhausted. The exhausted cation
exchanger is regenerated by passing it through dilute sulphuric acid.
R2Ca+2 + 2H+ 2RH+ + Ca+2

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

R2SO4-2 + 2OH- 2R’OH- + SO4-2

Demineralization of water

Merits of Ion-exchange process:

a. The process can be used to soften highly acidic or alkaline water.
b. It produces water of very low hardness (2 ppm)
c. So it is very good for treating water for use in high-pressure boilers.

Demerits of Ion-exchange process:

a. The equipment is costly and more expensive chemicals are needed.
b. If water contains turbidity, the output of the process is reduced. The turbidity must be
below 10ppm; else it has to be removed by coagulation and filtration

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 REVERSE OSMOSIS:

The process of removing common salt from the water is known

as desalination. The water containing dissolved salts with a peculiar salty taste is called
brackish water. Sea water, containing on an average about 3.5% salts, comes under this
category. Brackish water is totally unfit for drinking purpose. Commonly used methods for
the desalination of
brackish water is: 1. Reverse Osmosis & 2. Electrodialysis

Reverse Osmosis:
Osmosis is the phenomenon by virtue of which flow of solvent takes place from a region of
low concentration to high concentration when two solutions of different concentrations are
separated by a semi permeable membrane.
The flow continues till the concentration is equal on both the sides. The driving force for
osmosis is osmotic pressure. However, if a hydrostatic pressure in excess of osmotic
pressure is applied on the concentrated side, the flow of solvent reverses as it is forced to
move from concentrated side to dilute side across the membrane. This is the basis of
reverse osmosis
forced to move from concentrated side to dilute side across the membrane.
.For practical purposes, semipermeable membrane based on thin films of cellulose
acetate,polymethyl acrylate and polyamide polymers are used. A pressure of the order of
15-40 kg/cm2 is applied for separating the water from its contaminants The process is also
known as super or hyper filtration.

Advantages:
1. Colloidal SiO2 can be removed by reverse osmosis which even cannot be removed
by demineralization.
2. It is simple and reliable process.
3. Capital and operating expenses are low.
4. The life of the semi permeable membrane is about 2 years and it can be easily
replaced within a few minutes, thereby nearly uninterrupted water supply can be p

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 NUMERICAL:

Q.1 A water sample contains 408 mg of CaSO4 per litre. Calculate the hardness in terms of
CaCO3 equivalents.

Q2. How many grams of MgCO3 dissolved per litre gives 84 ppm of hardness?
Ans.

Q.3 An exhausted zeolite softner was regenerated by passing 150 litres of NaCl solution, having strength
of 1.5 gm/l of NaCl . Find the total volume of water that can be softened by this zeolite softner , if the
hardness of water is 600ppm.
Ans. 150 L of NaCl solution contains
= 150 x1.5 gm/l NaCl
= 225 gm of NaCl
=225 x 100/117 CaCO3 eq.
=192.308 gm CaCO3 eq.
= 192.308 x 1000mg
= 192308 mg of CaCO3 eq.
Let V litres of water contain hardness = 600 ppm
600 ppm= 192308 mg of CaCO3 eq.l
Therefore the total volume of water that can be softened
= 192308
600
= 320.5 L

Q.4 The hardness of 50,000 litres of a sample was removed by passing it through a zeolite softner. The
softner then required 200 litres of NaCl solution containing 125g / L of NaCl for regeneration. Calculate
the hardness of the sample of water.

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Q.5 100 mL of water sample has a hardness equivalent to 12.5 mL of 0.08 N MgSO4. Find the hardness
in degree ppm.
Ans. N1V1 of water sample = N2V2 of MgSO4
N1 X 100 = 0.08 x 12.5
N1= 0.08 x 12.5
100
= 0.01 N
Now, Hardness of water sample = N1 x Eq. wt. of CaCO3 in gm/L
= 0.01 x 50 = 0.5 gm/l
= 0.5 x 1000 mg/l
= 500 ppm
Q.5

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Q 6. Calculate the amount of lime and soda required for softening 5,000 litres of hard
water containing 72 ppm of MgSO4 .
Ans: Step 1 List out the given data

Given data : Hardness 72 ppm due to MgSO4; water qty = 5000 litres; mol. wt. MgSO4 120
Step 2 calculate the CaCO3 equivalent

Step 3 calculation of lime requirement

Lime required = 74/100 (hardness due to MgSO4) x vol. of water

= 74/100 (60 mg/L) x 5000 L

= 222,000 mg

= 222 g

Soda required = 106/100 (hardness due to MgSO4) x vol. of water

= 106/100 (60mg/L) x 5000L

= 318,000 mg

= 318 gm

Q 7.Calculate the amount of lime and soda required for softening 50,000 litres of hard water
containing: MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 =
25ppm and Na2SO4 = 15ppmStep 1 List out the given data

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 Given data : MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 =
25ppm and Na2SO4 = 15ppm

Step 2 calculate the CaCO3 equivalent

Hardness Quantity (ppm) Multiplication factor CaCO3

producing equivalent
substance hardness (ppm
or mg/L)
MgCO3 144 100/84 144 x(100/84) =
CaCO3 025 100/100 171.4
095 100/95 25 x (100/100) =
MgCl2 25.0
111 100/111
CaCl2 95 x (100/95) =
025 (does not cause hardness)
Fe2O3 100.0
015 (does not cause hardness)
111 x (100/111)
Na2SO4
= 100.0

Step 3 calculation of lime requirement

Lime required = 74/100 ( {2 x MgHCO3} + CaCO3 + MgCl2 in terms of CaCO3 eq) x vol. of water

= 74/100 (2 x 171.4 + 25.0 +100.0) mg/L x 50,000 L

= 74/100 (467.8) mg x 50,000

= 17, 309,000 mg

Answer = 17. 31 kg

Step 4 calculation of soda requirement

soda required = 106/100 ( MgCl2 + CaCl2 in terms of CaCO3 eq) x vol. of water

= 106/100 (100 +100.0) mg/L x 50,000 L

= 106/100 (200) mg x 50,000

= 10, 6,00,000 mg

Answer = 10. 6 kg

15
Q 8.

16
 FUELS
Fuel is a combustible substance which during combustion gives large amount of heat that
can be used economically for domestic and industrial purpose. In general fuels contain
carbon as the main constituent. There are chemical fuels, nuclear fuels and fossil fuels.
For e.g. Coke, charcoal, petroleum, diesel, kerosene oil etc.
During combustion carbon, hydrogen etc. present in fuel react with O 2 to form products like
CO2, H2O etc. and release heat.
Classification of Fuels:
These can be classified on the basis of their (i) Occurrence and (ii) Physical state
(i) On the basis of occurrence they are of two types:
(a) Primary Fuels: Fuels which occur in nature as such are called primary fuels or natural
fuels. For e.g., wood, peat, coal, petroleum, and natural gas.
(b) Secondary Fuels: The fuels which are derived from the primary fuels by further chemical
processing are called secondary fuels or artificial fuels. For e.g., coke, charcoal, kerosene,
coal gas, producer gas etc.
(ii) On the basis of physical state these may be classified as:
Solid Fuels: For e.g., Wood, coke, charcoal etc.
Liquid Fuels: For e.g. Crude oil, petrol, diesel etc.
Gaseous Fuels: For e.g., Natural gas, LPG, coal gas, biogas, CNG etc.
Calorific value: It is defined as the total quantity of heat liberated when a unit mass of a fuel
is burnt completely in excess supply of oxygen. For a good fuel calorific value should be high.
Calorific value of carbon is 32.83 KJ
Units of Heat: The quantity of heat can be measured in the following units:
(i) Calorie: It is defined as the amount of heat required to raise the temperature of 1g of
water by 1oC (14.5 – 15.50C).
1 calorie = 4.184 Joules
(ii) Kilo Calorie: It is defined as the amount of heat required to raise the temperature of 1Kg
of water by 1oC (14.5 – 15.50C).
1 K cal = 1000 cal
(iii) British Thermal Unit: (B. T. U.) It is defined as the amount of heat required to raise the
temperature of 1 pound of water through 1oF.
(IV) Centigrade Heat Unit (C.H.U): It is defined as the amount of heat required to raise the
temperature of 1 pound of water through 1oC.
1Kcal = 1000 Calorie = 3.968 B.T.U. = 2.2 C.H.U.
Characteristics of a Good Fuel:
(i) High Calorific value
(ii) Ignition Temperature: A good fuel should have moderate ignition temperature.
(iii) Moisture content: Should be low.
(iv) Ash content: Should be low.
(v) Rate of combustion: It should be moderate.
(vi) Cheap and readily available.
(vii) Suitability: The fuel selected should be most suitable for the process. For e.g., coke
made out of bituminous coal is most suitable for blast furnace.
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(viii) Free from objectionable substances: Like smoke, H2S, CO, SO2 etc.
(ix) Low storage cost and conveniently transportable.

Gross and net calorific Value

Depending upon the fact weather the products of combustion are allowed to cool down at
room temperature or they are allowed to escape, there are two types of calorific values:
Gross Calorific Value or Higher Calorific Value: It is the total amount of heat generated
when a unit quantity of fuel is completely burnt in excess of oxygen and the products of
combustion are cooled down to the room temperature.
As the products of combustion are cooled down to room temperature, the steam gets
condensed into water and latent heat is evolved. Thus, in the determination of gross calorific
value, the latent heat also gets included in the measured heat. Therefore, gross calorific
value is also called the higher calorific value.
Net Calorific Value or Lower Calorific Value: It is defined as the net heat produced when
a unit quantity of fuel is completely burnt and the products of combustion are allowed to
escape.
The water vapor does not condense and escape with hot combustion gases. Hence, lesser
amount of heat than gross calorific value is available. It is also known as lower calorific value
(LCV). Thus,
LCV = HCV - Latent heat of water vapors formed during burning
Latent heat of steam is 587 cal/g.
We know, H2 + ½ O2 H2O (v)
2 g or 1 part by wt. 18 g or 9 part by wt.
Therefore,
LCV = HCV-Weight of hydrogen present per unit mass of fuel x 9 x latent heat of steam
If % of H present in fuel is H%;
H
LCV = HCV - x 9 x 587 Cal/g or Kcal/Kg
100

Determination of Calorific value

18
Determination of calorific value of solid
and non volatile liquid fuels: It is
determined by Bomb Calorimeter.

Principle: A known amount of the fuel is

burnt in excess of oxygen and heat liberated
is transferred to a known amount of water.
The calorific value of the fuel is then
determined by applying the principle of
calorimetery i.e. Heat gained = Heat lost

Calculations:
Let weight of the fuel sample taken = m g;
Bomb Calorimeter
Weight of water in the calorimeter = W g
Water equivalent of the apparatus (calorimeter, stirrer, bomb, thermometer etc.) = w g
Initial temperature of water = t10C; Final temperature of water = t20C
Higher or gross calorific value = HCV; Heat liberated by m g fuel = m x HCV
Heat gained by water and apparatus = (W + w) x Δt x Specific heat of water
= (W + w) x (t2-t1) x 1 cal/g/0C
Heat liberated by the fuel = Heat gained by water and apparatus
m x HCV = (W+w) (t2-t1)
(W+w)(t2−t1)
HCV = Cal/g or Kcal/Kg
m
Let percentage of hydrogen in the fuel = H
Weight of water vapor (steam) produced from 1 gm of the fuel = 9H/100 g
Heat liberated during condensation of steam = 0.09H x 587 cal/gm
LCV = HCV – 0.09 H x 587 Cal/g or Kcal/Kg
Corrections: For getting accurate results the following corrections are also incorporated:

(a) Fuse wire correction: As Mg fuse wire is used for ignition, the heat generated by burning
of Mg fuse wire is also included in gross calorific value. Hence this amount of heat has to be
subtracted from the total value.

(b) Acid correction: During combustion, sulphur and nitrogen present in the fuel are oxidized
to their corresponding acids under high pressure and temperature.

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 S + O2 SO2

2SO2 + O2 + 2H2O 2H2SO4

2N2 + 5O2 + 2H2O 4HNO3

The corrections must be made for the heat liberated in the bomb by the formation of H2SO4
and HNO3. The amount of H2SO4 and HNO3 is analyzed by washings of the calorimeter. For
each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted. For each ml of 0.1 HNO3
formed, 1.43 calories must be subtracted.

(c) Cooling correction: As the temperature rises above the room temperature, the loss of
heat does occur due to radiation during cooling down of water in calorimeter. If the time taken
for the water in the calorimeter to cool down from the maximum temperature attained to the
room temperature is x minutes and the rate of cooling is dt/min, then the cooling correction
= x  dt. This should be added to the observed rise in temperature.

Therefore, Gross calorific value

(W+w)(t2−t1)− (Ca+Cf+Cct)
HCV = Cal/g or Kcal/Kg
m

Dulong’s Formula: If C, H, O and S are the percentage of carbon, hydrogen, oxygen and
sulphur in a fuel then the higher calorific value is given by:

1
HCV = [8080 C + 34500 (H – O/8) + 2240 S] Kcal/Kg or cal/g
100

Coal: Coal is regarded as a fossil fuel produced from the vegetable debris (cellulosic matter)
under conditions of high temperature and pressure over millions of years. It is mainly
composed of C,H, N, O and non-combustible inorganic matter. It consists of layers of fused
aromatic nuclei stacked one another. The transformation of the vegetable debris to coal takes
place in two stages:

(a) Biochemical or peat stage: During this stage, the plant materials were attacked by
various micro organisms.
(b) Chemical stage or metamorphism: In this stage, the peat deposits buried under
sedimentary deposits lose moisture and volatile components under the effect of high
temperature and pressure. The peat gets enriched in carbon whereas its oxygen content
decreases. The spongy peat transforms into hard brittle coal gradually. This process
involved evolution of CO2 & CH4, loss of water, increase in hardness and transition from
vegetation to anthracite coal which is the best quality coal.

Classification of Coal: Coals are mainly classified on the basis of their degree of
coalification from the parent material wood. When wood is converted into coal, there is
gradual increase in the concentration of corbon and decrease in the percentage of oxygen &
nitrogen.

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Coal is given ranking depending upon the corbon content of the coal from wood to anthracite.

S.No. Type of Coal Percentage Calorific Value

Carbon (Kcal/Kg)
1. Wood 50 4000-4500
2. Peat 57 4125-5400
3. Lignite 67 6500-7100
4. Bituminous 83 8000-8500
5. Anthracite 93 8650-8700

Analysis of Coal

The quality of coal is analyzed in two ways: 1. Proximate analysis 2. Ultimate analysis

Proximate Analysis

It is the simplest type of analysis of coal which includes the determination of moisture, ash,
volatile matter and fixed carbon in coal. This analysis is assay rather than true analysis. The
data varies with the procedure adopted and hence it is called proximate analysis. However,
it gives valuable information for assessing the application of a fuel for a particular domestic
and industrial purpose.

1. Determination of Moisture Content: Air dried moisture is determined by heating a known

amount of coal to 105-110 oC in an electric hot air oven for about one hour. After one hour,
it is taken out from the oven and cooled in a dessicator and weighed.

Loss in weight
Percentage of moisture = x 100
weight of coal sample

Significance: Excees of moisture is undesirable in coal. It reduces the calorific value of the
coal. It also increases transportation cost and some amount of heat is wasted for its
evaporation from coal during combustion.

2. Determination of volatile matter: Volatile matter consists of a complex mixture of

gaseous and liquid product resulting from the thermal decomposition of the coal. It is
determined by heating a known weight of moisture free coal sample in a covered platinum
crucible at 950 ± 20oC for 7 minutes in a muffle furnace.

loss of weight due to volatile matter

Percentage of volatile matter = x 100
Weight of coal sample

Significance: A high percent of volatile matter reduces the calorific value of fuel. Such coal
burns with lonf flame and high smoke. It gets converted into gas and tar during heating.

3. Determination of Ash content: Coal contains inorganic mineral substances which are
converted into ash by chemical reactions during the combustion of coal. Ash usually consists

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of silica, alumina, iron oxide and small quantities of lime, magnesia etc. Ash content is
determined by heating the residue left after the removal of volatile matter at 700  50oC for
½ an hour without covering

Weight of the residue left

Percentage of ash = × 100
Weight of the coal

Significance: The high percentage of ash is undesirable. It reduces the calorific value of
coal. The ash may restrict the passage of air and lower the rate of combustion. High ash
leads to large heat losses and leads to formation of ash lumps. Apart from loss of efficiency
of coal, clinker formation also leads to loss of fuel because some coal particles also get
embedded in the clinkers.

4. Determination of Fixed Carbon: Fixed carbon content increases from lignite to

anthracite. Higher the percentage of fixed carbon greater is its calorific value and better is
the quality of coal. The percentage of fixed carbon is given by:

Percentage of fixed carbon = 100 - [% of moisture + volatile matter + ash content]

Significance: Higher the percentage of fixed carbon, greater its calorific value and hence
better is the quality of coal.

Ultimate analysis

It is carried out to ascertain the composition of coal. Ultimate analysis includes the exact
estimation of carbon, hydrogen, sulphur, nitrogen and oxygen in the fuel.

1. Determination of Carbon and Hydrogen: A known amount of coal is taken in a

combustion tube and is burnt in excess of pure oxygen. The products of combustion CO2 and
H2O from C and H are absorbed in KOH and CaCl2 tubes of known weights respectively. The
increase in weights of these tubes are then determined as:

1.corbon and hydrogen:a known amont of coal is taken in a combustion tube and is burnt in
excess of pure oxygen.

C + O2 CO2
12 g 44 g
H2 + 1/2 O2 H2O
2g 18 g

2KOH + CO2 K2CO3 + H2O

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 CaCl2 + 7H2O CaCl2.7H2O

Increase in wt.of KOH tube x 12

% of Carbon = x 100
Wt.of Coal sample x 44

Increase in wt. of CaCl2 x 2

% of Hydrogen = x 100
Wt.of Coal sample x 18

Significance: High percentage of carbon and hydrogen increase the calorific value of coal.
The content of hydrogen in coals varies between 4.5 to 6.5 present from peat to bituminous
stage.

2. Determination of Nitrogen: Nitrogen present in coal sample can be estimated by

Kjeldahl’s method. 1 g coal sample is heated with conc. H2SO4 & K2SO4 (catalyst) in
Kjeldahl’s flask. The liberated NH3 is absorbed in standard solution of H2SO4. The unused
acid is then determined by back titration with standard NaOH.
NaOH (excess)
N2 + H2SO4 (NH4)2SO4 Na2SO4 + NH3 + H2O
2NH3 + H2SO4 (NH4)2SO4

1.4 x N V
% of Nitrogen =
Wt.of Coal sample

Significance: Nitrogen is an inert and non-combustible material. It has no calorific value. Its
presence is undesirable.

3. Determination of Sulphur: A known weight of coal sample is burnt completely in Bomb

Calorimeter in a current of oxygen where sulphur converts to sulphates. The percentage of
sulphur is then determined by the washings of bomb calorimeter. The washings are treated
with BaCl2 solution which makes BaSO4 precipitate. It is now filtered washed and heated to
constant weight.
S + O2 SO4—
32 g
SO42— + BaCl2 BaSO4 + 2Cl-
233 g
Wt.of BaSO4 x 32
% of Sulphur = x 100
Wt.of Coal Sample x 233
Significance: Sulphur has its calorific value and hence, it contributes to the calorific value of
the fuel. However, the combustion products of sulphur i.e. SO 2 and SO3 etc. cause air
pollution and corrosion of equipments.
4. Determination of Ash: Ash is determined by proximate analysis.

5. Determination of Oxygen: % of Oxygen = 100 - % of [C + H + N + S + Ash]

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Significance: A good quality of coal should contain low percentage of oxygen as it lower the
calorific value of coal. A coal having high percentage of oxygen is characterized by high
moisture content and low calorific value.

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