UNIT IV

WATER ANALYSIS AND FUELS

 HARDNESS OF WATER
“Soap consuming capacity of water is known as hardness of water.”
OR “Property of water which prevents lather formation with soap”
The soap consuming capacity of water is mainly due to presence of calcium and magnesium ions. These
ions reacts with sodium salts of soap to form insoluble scum (= like syrup) of calcium and magnesium
which do not possess any detergent value.
2C17H35COONa + CaCl2  (C17H35COO)2Ca ↓ + 2NaCl
Sodium Stearate Hardness Calcium Stearate
(Soluble-Soap) in water (Scum)
Type of hardness
There are two types of hardness
(a) Temporary or Carbonate Hardness (b) Permanent or Non-Carbonate Hardness
(a) Temporary Hardness or Carbonate Hardness or Alkaline Hardness
Temporary harness is due to presence of bicarbonates of calcium and magnesium in water. It can be
removed by simple boiling.

Ca( HCO3 ) 2   CaCO3   H 2 O  CO2 
(b) Permanent Hardness or Non-Carbonate Hardness or Non-Alkaline Hardness
Permanent Hardness is due to presence of Chloride, Sulphate and Phosphates salts of calcium and
magnesium and salts of other heavy metals in water. This type of hardness cannot be removed by simple
boiling. This hardness is removed by some external methods such as zeolite process, ion exchange process
etc.
 Disadvantages of Hard Water
There are various disadvantages of hard water:
a. In Domestic purpose: Lots of water is used for domestic purpose as follows:
(i) Washing: It causes wastage of soaps and formation of sticky precipitates (insoluble Ca and
Mg soaps) which stick to the fabric/cloth giving spots.
(ii) Cooking: Due to hard water, boiling point elevates which results into wastage of fuel and
consumption of more time of cooking. Food like pulses, beans, vegetables etc. do not cook
properly in hard water.
(iii) Drinking: It causes harmful effects on digestive system and causes various health problems.
b. In Industrial purpose:
(i) Textile Industry: It causes wastage of soap (used in washing fabrics etc.) because of formation
of insoluble Ca and Mg soaps (ppt). These ppt of Ca and Mg soap adhere to the fabrics. Theses
fabrics when dyed later do not produce exact shade of the colour.
(ii) Sugar Industry: Water containing sulphates, nitrates, alkali carbonates etc if used in sugar
refining, causes difficulties in crystallization of sugar.
(iii) In Pharmaceutical Industry: It may produce undesirable products in them when hard water
is used and may harm human beings.
c. In Boilers: Boilers are used for steam generation in many industries. If hard water is used for steam
generation then it will leads to corrosion, Scales and sludge formation, priming and foaming etc.
 DEGREE OF HARDNESS
Degree of Hardness is expressed in terms of equivalents of CaCO3 because –
(a) CaCO3 is most insoluble salt in water.
(b) The equivalent weight of CaCO3 is 50(Mol. Wt. 100), which cause ease (= easy) in calculations.
Therefore the calculation of the degree of hardness is given by-
[ Mass or Strength of hardness producing subs tan ce in mg / l ]  50
Degree of hardness or CaCO3 equivalent 
Equivalent weight of hardness producing subs tan ce

Or Degree of hardness or CaCO3 equivalent  [ Mass or Strength of hardness producing subs tan ce ]  100
Molecular weight of hardness producing subs tan ce

1
  UNITS OF HARDNESS
Hardness can be calculated in terms of four units. These are –
(a) ppm (Part per million)
It is defined as the number of parts by weight of calcium carbonate per million (106) parts by weight
of water. (1 ppm = 1 part of CaCO3 per 10,00,000 parts of water)
(b) mg/lit (Miligram per litre)
(c) Degree French (oFr) (1o French = 1 part of CaCO3 per 1,00,000 (105) parts of water)
(d) Degree Clarke (oCl) (1o Clark = 1 part of CaCO3 per 70,000 parts of water)
Relation between these units is – 1ppm = 1 mg/liter = 0.1oFr = 0.07 oCl

 NUMERICAL PROBLEMS FOR DEGREE OF HARDNESS

Q.1 A water sample contains 408 mg of CaSO4 per liter. Calculate the hardness in terms of CaCO3
equivalent.
Ans:- [ Mass or Strength of hardness producing subs tan ce in mg / l ]  50
CaCO3 equivalent 
[ Equivalent weight of hardness producing subs tan ce]
408  50
  300mg / l
68
So, hardness = 300 mg/l or 300 ppm.
Q.2
[ Mass or Strength of hardness producing subs tan ce in mg / l ]  50
Degree of Hardness 
[ Equivalent weight of hardness producing subs tan ce]
50
70  ( Mass or Strength of CaSO4 ) 
68
70  68
Strength of CaSO4   95.2 mg / litre
50
How many grams of CaSo4 dissolved per liter gives 70ppm of hardness?
Ans:-

Q.3 A water sample was found to contain CaSO4 80 mg/litre and MgSO4 100 mg/litre. Calculate the
hardness of water in ppm, oFr and oCl.
Ans :- Hardness due to CaSO4
[ Mass or Strength of hardness producing subs tan ce]  50
Degree of Hardness 
[ Equivalent weight of hardness producing subs tan ce]
50
 80   58.82 ppm.
68
Hardness due to MgSO4
[ Mass or Strength of hardness producing subs tan ce]  50
Degree of Hardness 
[ Equivalent weight of hardness producing subs tan ce]
50
 100   83.33 ppm.
60
Total Hardness  58.82  83.33
 142.15 ppm.
In terms of 0 Fr  14.21 0 Fr
0
In terms of Cl  9.95 0Cl

BOILER FEED WATER

2
 “The water mainly used in boilers for steam generation is known as boiler feed water”. For such
water we need some specification-
(i) Hardness should be below 0.2ppm
(ii) Its caustic alkalinity (due to OH-) should be in range of 0.15 - 0.45ppm.
(iii) Its soda alkalinity (due to CO32-, HCO3-) should be in range of 0.45 - 1.0ppm.
Excess of above impurities cause the following problems-
(a) Formation of Scale & Sludge
Scale: Scales are hard deposits firmly sticking to the inner surface of the boiler. Scale may be formed
inside the boiler due to decomposition of calcium-bicarbonate [Ca(HCO3)2].

Ca( HCO3 ) 2   CaCO3   H 2 O  CO2 
Scale
Sludge: When water is continuously Loose precipitate (sludge)
evaporated to form steam, then the Suspense in water (sludge)
concentrations of dissolved salts increases
and they settled down in the form of
precipitates. The soft, loose and slimy
stage of precipitates is known as sludge.
Example- MgCO3, MgCl2, CaCl2 etc.
(b) Priming & Foaming
Priming: Due to extremely rapid boiling of water in boiler, the steam formed may be associated with
small droplets of water. These droplets of water are carried away along with the steam. “The
phenomenon of formation of wet steam is called priming.” This may be due to- (i) high steam
velocities, (ii) very high level of water in boiler, (iii) due to suspended and dissolved impurities

Foaming: “Formation of small persistent bubbles at the surface of water in boiler is called foaming.”

(c) Caustic Embrittlement: “Boiler corrosion which takes place due to presence of highly alkaline water in
boiler is known as caustic embrittlement”. In caustic embrittlement the material of a boiler get brittle
due to the accumulation of caustic substances. It is caused in the high pressure boiler due to the
presence of sodium carbonate (Sodium carbonate is used in softening of water by lime soda process).
On hydrolysis Na2CO3 forms sodium hydroxide.

When sodium hydroxide containing water enters in cracks, rivets or joints of the boiler, it attacks the
surrounding material and dissolves the iron of the boiler as sodium ferroate and causes embrittlement.

(d) Boiler corrosion

Boiler corrosion is the decay of boiler material due to the attack of certain chemicals on its surface,
resulting formation of rust.

 Internal Treatment
The treatment is accomplished by adding chemicals to boiler water.
(a) To precipitate the scale forming impurities in the form of sludges which can be removed by blowdown
operation.
(b) To convert them into compounds this will stay in dissolved form in water and hence do not cause any
harm.
(i) Colloidal conditioning: In low pressure boilers, scale formation can be avoided by adding organic
substances like kerosene, tannin, agar-agar etc. These substances get coated over the scale forming
precipitates, thereby yielding non-sticky and loose deposits similar to sludge which can be removed
by blow down operation.
3
 (ii) Carbonate conditioning: In low pressure boilers, scale formation can be avoided by addition of
Na2CO3 to boiler.
CaSO4 + Na2CO3 CaCO3 + Na2SO4
CaCO3 formed can be removed by blow operation.
(iii) Phosphate conditioning: In high pressure boilers, scale formation can be avoided by adding
sodium phosphate. The soft sludge of Ca3(PO4)2 and Mg3(PO4)2 can be removed by blow down
operation.
3CaCl2 + 2Na3PO4 Ca3(PO4)2 + 6NaCl
(iv) Calgon conditioning or Calgon process or Descaling of boilers: Calgon conditioning is a most
useful method to remove hardness products (i.e. scale & sludge) from boiler. In this process the
Graham’s salt is used. Graham’s Salt is also known as Calgon (sodium hexa metaphosphate).
Calgon (sodium hexa metaphosphate) is soluble in water and it converts the impurity like CaCO3,
CaSO4 into soluble complex compound, which will remain in dissolved form in water. This
property helps to remove the scale and sludge.
Na2 [ Na4 ( PO3 ) 6 ] 2 Na   [ Na4 ( PO3 ) 6 ]2
Sodium Hexametaphosphate
(Calgon)
2CaSO4  [ Na4 ( PO3 )6 ]2  [Ca2 ( PO3 )6 ]2  2Na2 SO4
(Soluble complex)
 External Treatment
 WATER SOFTENING
The removal or reducing the hardness (Temporary or Permanent) from water is known as softening of
water. The important methods are –
(A) Lime soda process
It is one of the most important methods of water softening. A calculated amount of Lime [Ca(OH)2] and
soda [Na2CO3] are used to precipitate the dissolved salts of Ca2+ and Mg2+ as CaCO3 and Mg(OH)2, which
are then filtered off. At room temperature precipitate form are very fine and they do not settle down easily,
hence a small amount of coagulants like alum, Al2(SO4)3 or NaAlO2 are added.
(a) Lime removes temporary hardness, permanent hardness of (Mg2+, Fe2+, Al3+), CO2, mineral
acids, bicarbonates of Na and K, and NaAlO2 or alums.
1. Removal of temporary hardness of Ca2+
Ca(HCO3)2 + Ca(OH)2  2CaCO3 + 2H2O
2. Removal of Temporary hardness of Mg2+
Mg(HCO3)2 + 2Ca(OH)2  Mg(OH)2 + 2CaCO3 + 2H2O
3. Removal of Permanent hardness of Mg2+
MgCl2 + Ca(OH)2  Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2  Mg(OH)2 + CaSO4
4. Removal of CO2
CO2 + Ca(OH)2  CaCO3 + H2O
5. Removal of acids
2HCl + Ca(OH)2  CaCl2 + 2H2O
H2SO4 + Ca(OH)2  CaSO4 + 2H2O
6. Removal of bicarbonates of Na+ and K+
2NaHCO3 + Ca(OH)2  CaCO3 + Na2CO3 + 2H2O
2KHCO3 + Ca(OH)2  CaCO3 + K2CO3 + 2H2O
7. Removal Fe+2 and Al+3 [These may be present in water as permanent hardness or may be added as
coagulants]
FeSO4 + Ca(OH)2  CaSO4 + Fe(OH)2
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 Al2(SO4)3 + 3Ca(OH)2  3CaSO4 + 2Al(OH)3
8. Reaction with NaAlO2 or Alum
NaAlO2 + 2H2O  Al(OH)3 + NaOH
2NaOH + Ca+2  Ca (OH)2 + 2Na+ [Where, NaOH is equivalent to ½ Ca(OH)2]

Amount of lime required for softening (L)

𝟕𝟒
= 𝟏𝟎𝟎 [Temporary hardness of Ca2+ + 2 x Temporary hardness of Mg2+ + permanent hardness of
Mg2+ + CO2 + ½ HCl + H2SO4 + ½ NaHCO3 + ½ KHCO3 + FeSO4 + 3 x Al2(SO4)3 – ½ NaAlO2] in
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓 𝟏𝟎𝟎
terms of CaCO3 equivalents x 𝟏𝟎𝟔
x % 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒍𝒊𝒎𝒆 kg

(b) Soda reacts with permanent hardness of Ca+2.

CaCl2 + Na2CO3 CaCO3 + 2NaCl
CaSO4 + Na2CO3 CaCO3 + Na2SO4
[It also reacts with CaCl2 and CaSO4 formed by removal of acid, Fe2+, Al3+ to form CaCO3.]

Amount of soda required for softening

𝟏𝟎𝟔
= 𝟏𝟎𝟎 [permanent hardness of Ca2+ + permanent hardness of Mg2+ + ½ HCl + H2SO4 + FeSO4
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
+ 3 x Al2 (SO4)3 – ½ NaHCO3 – ½ KHCO3] in terms of CaCO3 equivalents x 𝟏𝟎𝟔
x
𝟏𝟎𝟎
% 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒔𝒐𝒅𝒂
kg
[Note: the impurities such as NaCl, KCl, SiO2, Fe2O3, Na2SO4 etc should be ignored as they do
not consume Lime and Soda.]

Types of Lime Soda Process:

Lime Soda process is of two types:
(1) Cold Lime Soda Process (2) Hot lime soda process

(1) Cold Lime Soda Process: In this process,

chemicals are added to hard water at room
temperature. Raw water and calculated
amount of chemicals (Lime, soda and alum)
are continuously added from the top into a
vertical circular tank with continuous
stirring to remove hardness of water.
Raw water and chemicals are
properly mixed by continuous stirring and
hence softening reactions takes place.
Sludge formed settles down at the bottom of
outer chamber. This is removed time to time
through sludge outlet.
Then the softened water rises up and passes through wood fibre filter where traces of sludge
are removed.

5
 (2) Hot lime soda process: In this
process water is heated with
chemicals at temperature of 80-
150oC. Since the reaction takes place
at higher temperature, no or very less
amount of coagulant is needed in this
process and sludge formed settled
rapidly which is filtered off.
Three parts-
(a) Reaction tank: raw water,
chemicals and steam are added in
this tank through different inlets.
(b) Sedimentation tank: A conical sedimentation vessel in which sludge and ppt settle down.
(c) Sand filter: It ensures complete removal of sludge from softened water.

Advantage of Lime Soda process

(i) Economical, (ii) Less coagulants needed, (iii) Corrosion rate is decreased due to pH increase,
(iv) Iron and Manganese salts are removed
Disadvantage of Lime Soda process
(i) Careful calculations are required, (ii) Residual hardness is 15 - 60ppm (not suitable for boiler),
(ii) Large amount of sludge formed, (iv) Softened water contains more sodium salts.

COMPARISION BETWEEN HOT AND COLD LIME SODA PROCESSES

COLD LIME SODA PROCESSES HOT LIME SODA PROCESSES
1. It is carried out at room temperature (25 – 30 0C) 1. It is carried out at high temperature (95 – 100 0C)
2. It is a slow process 2. It is a rapid process
3. Use of coagulant is necessary 3. No coagulant required
4. Filtration is not easy 4. Filtration is easy as viscosity of water is low
5. Residual hardness is 60 ppm 5. Residual hardness is 15 – 30 ppm
6. Dissolved gases are not removed 6. Dissolved gases are removed
7. It has low softening capacity 7. It has high softening capacity

 SOLVED EXAMPLE FOR LIME SODA PROCESS

Q.1 Calculate the amount of lime and soda required for softening 15000 litres of water which analysed as
follows: temporary hardness of Ca2+ = 20ppm, permanent hardness of Ca2+ = 15ppm, and permanent
Magnesium hardness = 10ppm.
𝟕𝟒
Ans :- Lime Requirement (L) = [Temporary hardness of Ca2+ + permanent hardness of Mg2+] in
𝟏𝟎𝟎
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
terms of CaCO3 equivalents x 𝟏𝟎𝟔
kg
𝟏𝟓𝟎𝟎𝟎
= 0.74 [20 + 10] x kg
𝟏𝟎𝟔
= 0.74 x 30 x 0.015
= 0.333 kg or 333 gm
𝟏𝟎𝟔
Soda Requirement (S) = 𝟏𝟎𝟎 [Permanent hardness + permanent hardness of Mg2+] in
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
terms of CaCO3 equivalents x 𝟏𝟎𝟔
kg
𝟏𝟓𝟎𝟎𝟎
= 1.06 [15 + 10] x 𝟏𝟎𝟔
kg
= 1.06 x 25 x 0.015 = 0.3975 kg or 397.5 gm

Q.2 Water sample was found to contains following salts:

CaCl2 = 55.5 mg/l, SiO2 = 20.0 ppm, NaHCO3 = 12.6 mg/l, KCl = 250 mg/l, MgSO4 = 48 mg/l, CO2
= 2.2 ppm, Fe2+ = 2.0 ppm, Al2(SO4)3 = 10.0 ppm and Mg(HCO3)2 = 43.8 mg/l
Calculate the quantity of lime (85% pure) and soda (95% pure) for softening 50,000 litres of water.
Ans. Calculation of CaCO3 equivalents for impurities

6
 S.No. Salt Quantity Mol. CaCO3 equivalent Requirement of
(mg/l) wt. Lime (L) & /or Soda
(S)
1. CaCl2 55.5 111 100 Add only in S
55.5 x 50.0
111
2. SiO2 20.0 60 Does not react with L/S -
3. NaHCO3 12.6 84 100 Add in L & subtract in
12.6 x 15.0
84 S
4. KCl 250 74.5 Does not react with L/S -
5. MgSO4 48 120 100 Add in L & also add in
48 x 40.0
120 S
6. CO2 2.2 44 100 Add only in L
2.2 x 5.0
44
7. Fe2+ 2.0 55.8 100 Add in L & also add in
2.0 x 3.58
55.8 S
8. Al2(SO4)3 10.0 342 100 Add in L & also add in
10.0 x 2.92
342 S
9. Mg(HCO3)2 43.8 146 100 Add only in L
43.8 x 30.0
146
Amount of lime required for softening (L)
𝟕𝟒
= 𝟏𝟎𝟎 [Temporary hardness of Ca2+ + 2 x Temporary hardness of Mg2+ + permanent hardness of
Mg2+ + CO2 + ½ HCl + H2SO4 + ½ NaHCO3 + ½ KHCO3 + FeSO4 + 3 x Al2(SO4)3 – ½ NaAlO2] in
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓 𝟏𝟎𝟎
terms of CaCO3 equivalents x 𝟏𝟎𝟔
x % 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒍𝒊𝒎𝒆 kg
74 50000 100
= 100 [2 x 30 + 40 + 5 + ½ x 15 + 3.58 + 3 x 2.92] x 106
x 85
kg
5
= 0.74 [60 + 40 + 5 + 7.5 + 3.58 + 8.76] x kg
85
= 0.74 x 124.84 x 0.059 = 5.4505 kg of Lime
Amount of soda required for softening (S)
𝟏𝟎𝟔
= 𝟏𝟎𝟎 [permanent hardness of Ca2+ + permanent hardness of Mg2+ + ½ HCl + H2SO4 + FeSO4 +
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
3 x Al2 (SO4)3 – ½ NaHCO3 – ½ KHCO3] in terms of CaCO3 equivalents x x
𝟏𝟎𝟔
𝟏𝟎𝟎
% 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒔𝒐𝒅𝒂
kg
106 50000 100
= 100 [50 + 40 + 3.58 + 3 x 2.92 – ½ x 15.0] x 106
x 95
kg
106 5
= [93.58 + 8.76 – 7.5] x kg
100 95
= 1.06 x 94.84 x 0.053 kg
= 5.328 kg of Soda
So, Lime Required = 5.4505 kg and Soda Required = 5.328 kg

Q.3 A water sample was found to contains the salts in mg/l CaSO4 = 20.4, MgCl2 = 9.5 and HCl = 7.3.
Calculate the quantity of lime (85% pure) and soda (80% pure) required for softening 80,000 litres of
water. What would be the total cost of chemicals if lime and soda are Rs. 9 and Rs. 35 per Kg.?
Ans. Calculation of CaCO3 equivalents for impurities
S.No. Salt Quantity Mol. CaCO3 equivalent Requirement of Lime
(mg/l) wt. (L) & /or Soda (S)
1. CaSO4 20.4 136 100 Add only in S
20.4 x 15.0
136
2. MgCl2 9.5 95 100 Add in L & also add in
9.5 x 10.0
95 S
3. HCl 7.3 36.5 100 Add in L & also add in
7.3 x 20.0
36.5 S

7
 Amount of lime required for softening (L)
𝟕𝟒 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
= 𝟏𝟎𝟎 [Permanent hardness of Mg2+ + ½ HCl] in terms of CaCO3 equivalents x 𝟏𝟎𝟔
𝟏𝟎𝟎
x % 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒍𝒊𝒎𝒆 kg
74 80000 100
= [10+ ½ x 20] x x kg
100 106 85
8
= 0.74 x 20 x kg
85
= 1.392 kg of Lime
Cost of Lime (L) = 1.392 x Rs. 9 = Rs. 12.53

Amount of soda required for softening (S)

𝟏𝟎𝟔
= 𝟏𝟎𝟎 [Permanent hardness of Ca2+ + permanent hardness of Mg2+ + ½ HCl] in terms of
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓 𝟏𝟎𝟎
CaCO3 equivalents x 𝟏𝟎𝟔
x % 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝒔𝒐𝒅𝒂 kg
106 80000 100
= 100 [15 + 10 + ½ x 20] x x kg
106 80
106 8
= 100 x 35 x kg
80
= 3.71 kg of Soda
Cost of Soda (S) = 3.71 x Rs. 35 = Rs. 129.85
So, Lime Required = 1.392 kg and Soda Required = 3.71 kg
Cost of Lime (L) = Rs. 12.53 and Cost of Soda (S) = Rs. 129.85

(B) ZEOLITE PROCESS OR PERMUTIT PROCESS

Zeolites are hydrated sodium alumino silicates capable of exchanging its sodium ions reversibly with
the hardness producing substances or cations in water. The chemical formula of Zeolite is –
Na2O.Al2O3.xSiO2.yH2O, Where x = 2 to 10 and y = 2 to 6
Water softening process or working
Zeolites can be simply represented as Na2Ze. When
hard water is passed through Zeolite Ca++ and Mg++ ions are
retained by Zeolites as CaZe and MgZe respectively. The
reactions are –
Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3
CaSO4 + Na2Ze CaZe + Na2SO4
Regeneration of Zeolite
After some times the zeolite bed gets exhausted. At this stage
the supply of hard water is stopped and regeneration is carried
out with a strong solution of NaCl (10% brine solution). The
regenerated zeolites are again used for softening.
CaZe + 2NaCl Na2Ze + CaCl2
Exhausted Brine Regenerated Washing
Zeolite Solution Zeolite
Advantage of Zeolite process
i. Hardness of produced water is about 10 ppm.
ii. The equipment used is compact and occupies less space.
iii. It requires less time for softening.
Disadvantage of Zeolite process
i. Only contains (Ca2+, Mg2+) are replaced by sodium ions and not the anions.
ii. The process cannot be used for highly alkaline or acidic water.

 SOLVED EXAMPLE FOR ZEOLITE PROCESS

8
Q.1 A Zeolite softener was 80% exhausted, when 10,000L of hard water was passed through it. The softer
required 200L of NaCl solution of strength 50 gm NaCl / L of solution. What is the hardness of water?
Ans :-
10 ,000 L of hard water  200 L of NaCl Solution
200 L  (50 gm / L) of NaCl
 10000 gm of NaCl
100
 10000 gm  CaCO3 equivent
117
 8,547 gm of CaCO3 equivalent
1 L of hard water  8,547 gm of CaCO3 equivalent / 10 ,000
 0.8547 gm of CaCO3 equivalent
 854 .7 mg of CaCO3 equivalent
Hence, Hardness of water = 854.7 mg/L or ppm.

Q.2 The hardness of 50,000 liters of a sample of water was removed by passing it through a Zeolite softener. The
softener was than required 200 liters of NaCl Solution containing 125 gm/liter of NaCl for regeneration.
Calculate the hardness of sample of water.
Ans :- 50,000 L of hard water  200 L of NaCl Solution
200 L  (125 gm / L) of NaCl
 25,000 gm of NaCl
 100 
 25,000 gm    of CaCO3 equivent
 117 
 21367.52 gm of CaCO3 equivalent
1 L of hard water  21367.52 gm of CaCO3 equivalent / 50,000
 0.42735 gm of CaCO3 equivalent
 427.35 mg of CaCO3 equivalent

Hence, Hardness of water = 427.35 mg/L or ppm.

Q.3 An exhausted Zeolite softener was regenerated by passing 150 L of NaCl solution, having a strength of
150gm/L of NaCl. If the hardness of water is 600 ppm. Calculate the total volume of water that is softened
by this softener.
Ans:- 150 L of NaCl Contains  150 L  (150 gm / L) of NaCl
 22,500 gm of NaCl
 100 
 22,500 gm    CaCO3 equivent
 117 
 1.923  10 4 gm CaCO3 equivalent
 1.923  10 7 mg CaCO3 equivalent
1.923  10 7
The number of liters of hard water 
600
 3.2050  10 3  10 7 liters
 3.2050  10 4 liters

Q.4 A zeolite bed, on softening 7000 litres of hard water, required 60 litres of NaCl solution having a strength of
100gm/L of for regeneration. Calculate the hardness of water in ppm.
Ans.
One litre solution containing = 100 gms NaCl
So, 60 litres solution containing = 6000 gms NaCl
100
= 6000 × 117 of CaCO3 equivalent
= 5128.20 gms of CaCO3 equivalent

9
 Now for 7000 litres Hard water requires
So, for 1 litres Hard water requires
= 5128.20 gms of CaCO3 equivalent
5128.20
= gms of CaCO3 equivalent
7000
= 0.7326 gms of CaCO3 equivalent per litre
= 732.60 mgs of CaCO3 equivalent per litre

Hence, Hardness of given water sample = 732.60 mg/litre or ppm

(C) ION EXCHANGE PROCESS OR DEIONIZATION OR DEMINERALIZATION PROCESS

CH2 CH CH2 CH CH2 CH CH2

Ion Exchange Resins These types of resins are insoluble,

cross linked, long chain polymers with high molecular
weight containing functional groups which are responsible
for the ion exchange properties.
These are of two types- SO3 H+ SO3 H+
(a) Cation Exchange Resin
(b) Anion Exchange Resin CH2 CH CH2 CH CH2 CH CH2

(a) Cation Exchange Resin :-

These resins containing acidic functional groups (-
COOH, -SO3H etc.) are capable of exchanging their H+
ions with other cations, which comes in their contact.
These are denoted by R– H+. Examples are Zeocarb, SO3 H+ SO3 H+

Dowex-50 etc.
Cation Exchanger
(b) Anion Exchange Resin :-
These resins containing basic functional groups (- CH2 CH CH2 CH CH2 CH CH2
NH2, = NH as hydrochloride) are capable of exchanging
their anions with other anions, which comes in their
contact. These are denoted by R+ OH–.
Example- Dowex – 3, Amberlite – 400 etc.
CH2N(CH3)3+OH CH2N(CH3)3+OH

Water Softening process :-

The hard water is passed first through cation exchange CH CH2
CH2 CH CH2 CH CH2
column, which removes all the cations (like Ca2+, Mg2+
etc.) from it and equivalent amount of H+ ions are released
from this column to water.
2 R  H   Ca 2  R2Ca 2  2 H 
CH2N(CH3)3+OH CH2N(CH3)3+OH
2 R  H   Mg 2  R2 Mg 2  2 H 
Anion Exchanger

After passing through the cation exchange column, the hard water is passed through anion exchange
column, where all the anions like SO42 , Cl  etc. are removed from water and equivalent amount of OH-
ions are released from this column to water.
R OH   Cl   R Cl   OH 
2 R OH   SO42  R2 SO42  2OH 

10
 H+ and OH– ions (released from cation and anion exchange columns) get combined to produce water
molecule.

H   OH   H 2 O
Regeneration of Cation and Anion resins:-
When cation and anion exchange resins are exhausted completely then cation exchange resin is treated
with acids (dil HCl or dil H2SO4) and anion exchange resin is treated with a base (NaOH) solutions to
regenerate these resins then regenerated ion exchange resins are then used again.
R2 Mg 2  2 H   2 R  H   Mg 2
Advantage:- R2 SO42  2OH   2 R  OH   SO42
(i) It produces water of very low hardness (say 2ppm)
(ii) The process can be used for softening of highly acidic or alkaline waters.
(iii) It removes both types (cationic & anionic) of hardness impurities.
Disadvantage:-
(i) The equipment is costly and more expensive chemicals are used or needed.
(ii) It requires more time for water softening.

(D) REVERSE OSMOSIS (RO METHOD)-

When two solutions having different concentration
are separated by a semi permeable membrane, flow of
solvent molecules from the lower concentration to higher
concentration takes place, until the concentration
becomes equal on both sides. This phenomenon is called
Osmosis.
In reverse osmosis by applying hydrostatic pressure
on solution side flow of solvent molecules from the
higher concentration to lower concentration takes place. This process is the reverse of osmosis. During
reverse osmosis, water is separated from the dissolved salts through membrane separation.
Advantage of Reverse Osmosis (RO) process :-
a) It is simple and reliable process.
b) Purification through RO removes all impurities of water.
c) The semi-permeable membrane has a lifetime of about 2years & it can be easily replaced within a few
minutes.
Disadvantage of of Reverse Osmosis (RO) process:-
A major problem with RO process is to find membrane strong enough to withstand the high pressure
applied on it.
Applications: (i) Treatment of waste water (ii) Desalination
(iii) In pharma industry (iv) In regeneration of minerals

11
 Fuel
Fuel may be defined as “A substance which on combustion provide adequate amount of heat for a limited
period of time.”
Or
“Any combustible substance containing carbon as the main constituent which during combustion gives a
large amount of industrially and/or domestically useful heat.”

 Characteristics of a good fuel-

1. Moderate ignition point 2. High calorific value 3. Cost should be low (cheap)
4. Low moisture content 5. Moderate speed of combustion
6. Ease to handle, transport and store.

 Calorific Value-
“The total amount of heat liberated by complete combustion of a unit mass of fuel.”

Units for calorific value-

Calorie- The amount of heat required to raise the temperature of one gram of water by 1oC (15-16oC).
1Cal = 4.185 Joule
British Thermal Unit (B.Th.U.)- The amount of heat required to raise the temperature of one pound of water by 1oF
(60-61oF). 1B.Th.U. = 252Cal = 0.252 Kcal
1 Kcal = 3.968 B.Th.U.
Centigrade Heat Unit (C.H.U.)- The amount of heat required to raise temperature of one pound of water by 1oC (15-
16oC). 1 C.H.U. = 1.8 B.Th.U. = 453.6 Cal
1 Kcal = 3.968 B.Th.U. = 2.2 C.H.U.

Gross Calorific Value (G.C.V) or High Calorific Value (H.C.V.)

The amount of heat liberated, when a unit mass or unit volume of fuel has been burnt completely and the
combustion product are cooled down to room temperature.

Net Calorific Value (N.C.V) or Low Calorific Value (L.C.V.)

The amount of heat liberated, when a unit mass or volume of fuel is burnt completely and combustion product
are allowed to escape.
N.C.V or L.C.V. = H.C.V. – 0.09H x latent heat of steam
N.C.V or L.C.V. = (H.C.V. – 0.09H x 587) cal/gm (Latent heat of steam = 587 cal/gm)

Dulong’s Formula If the % of C, H, O, S are known then the HCV can be calculated by-
1   O 
HCV  8080C  34500   H    2240S  Kcal / kg
100   8  
 Determination of Calorific Value by Bomb Calorimeter-
Bomb calorimeter is used for the determination of calorific value
of solid or liquid fuel.
Description-
Bomb: It consists of a strong cylindrical bomb made of stainless
steel, resistant to acids & corrosion.
It is of 250-300 ml capacity, and provided with a gas tight screw
cap, with a couple of electrodes.
The fuel is kept in crucible inside the bomb.
Calorimeter:

12
The bomb is then placed in a copper calorimeter. It can contain two liters of water. The calorimeter consists of a motor
driven stirrer and Beckmann’s thermometer.
Procedure-
A known amount of fuel (0.5 to 1.0 gm) is kept in crucible. (Fuel)
Fine Mg-wire touching the sample fuel is stretched across the electrodes. (Mg-wire)
The bomb lid is tightly screwed and O2 is filled at about 25atm pressure. (O2 at 25atm)
Now bomb is places in calorimeter containing (w) gm of water. (Bomb in calorimeter)
Now the electrodes are connected to battery & circuit is complete. (Attach battery)
Thus combustion of fuel takes place & heat is liberated. (Burning of fuel)
Calculations:-
(𝐖+𝐰)
GCV = cal/gm (Formula without corrections)
𝐱

(𝐖+𝐰)(𝐭 𝟐 −𝐭 𝟏 +𝐭 𝐜 )−(𝐂𝐀 +𝐂𝐅 +𝐂𝐓 )

GCV = cal/gm (Formula with corrections)
𝐱

W = water taken in calorimeter,

w = water equivalent of calorimeter/stirrer/thermometer,
x = weight of fuel taken in crucible (in gm),
t1 = initial temp.,
t2 = final temp.,
tC = Cooling correction, CA = Acid correction, CF = Fuse Wire correction, CT = Cotton thread correction.

N.C.V or L.C.V. = (H.C.V. – 0.09H x 587) cal/gm

Corrections-
Cooling Correction-
It is the time taken to cool the water in bomb calorimeter from maximum temperature to room temperature.
Fuse wire correction-
The heat liberated, as measured above, include the heat given out by ignition of fuse wire. Hence it must be subtracted
from the total value.
Cotton Thread Correction-
The heat liberated, as measured above, include the heat given out by burning of cotton thread. Hence it must be
subtracted from the total value.
Acid correction-
Fuel contains S & N are also oxidized (under high pressure & temperature of ignition) to H2SO4 & HNO3 respectively.
S + 2H + 2O2  H2SO4 + Heat
2N + 2H + 3O2  2HNO3 + Heat
Formation of HNO3 & H2SO4 is exothermic reaction. So measured heat also contains it, Hence it is subtracted to the
total value.

 COAL
Coal is one of the major fossil fuel. It formed over millions of years ago from decomposition of plants. Coal is
a complex mixture of C, H, O. Small amount of N and S also occurs in coal.
(i) Anthracite (Hard coal):- Contains maximum carbon percentage (above 90%)
(ii) Bituminous (Soft coal):- Contains 80% carbon (Bituminous ≡ Wood Coal)
(iii) Lignite (Brown coal):- Contains 70% carbon.
(iv) Peat: - Contains less than 60% carbon (Peat ≡ decomposed vegetable matter or dried turf used as
fuel) (turf ≡ surface of earth with grass roots)

13
 ANALYSIS OF COAL
There are two ways for the analysis of coal.
A. Proximate analysis B. Ultimate analysis
(A) Proximate Analysis: - In this analysis the percent of fixed carbon is determined and is useful when the coal
contain the following impurities. These are:
(i) Moisture content (ii) Volatile matter (iii) Ash
(i) Determination of Moisture content: - The Moisture content in a coal is the loss of weight of coal when heated
at about 150oC in a crucible. After getting a constant weight the loss in weight of a coal is reported as moisture.
Loss in weight
% of moisture  100
Weight of coal sample taken
(ii) Determination of Volatile matter: - The volatile matters present in coal are hydrogen, methane, CO2 & N2.
The moisture free coal (dry coal) is taken in a silica crucible & heated up to 950 0C for 5-10 minutes. After getting
constant weight, the loss in weight is reported as volatile matter.
Loss in weight
% of volatile matter   100
Weight of Coal sample
(iii) Determination of Ash: - The presence of ash reduces the calorific value of coal. The dry coal is burned
in presence of oxygen in a crucible at temperature 7000C in a furnace for half an hour. The crucible is taken out, cooled
& weighed. After getting a constant weight the ash value is determined.
Weight of Ash
% of Ash  100
Weight of dry Coal
(iv) Determination of fixed carbon: - The fixed carbon is determined by following formula.
% of fixed carbon = 100 – % of (moisture + volatile matter + Ash)

(B) Ultimate Analysis: - In this type of analysis the percentage of carbon, hydrogen, nitrogen, sulphur & oxygen
is determined in the coal sample.
(i) Determination of Carbon & Hydrogen: - Known weight of coal (0.5gm approx) is burnt in a presence
of oxygen. The C and H of coal are converted into CO2 and H2O which are absorbed in KOH and CaCl2 absorption
tubes of known weights. Increase in weight of KOH tube 12
% C  100
Weight of Coal taken 44
Increase in weight of CaCl2 tube 2
% H  100
Weight of Coal taken 18

(ii) Determination of Nitrogen: - It is determined by Kjeldahl’s method which consists heating the coal sample
with concentrated H2SO4 and K2SO4 in Kjeldahl’s flask. The liberated ammonia is titrated against standard solution of
HCl or H2SO4.
Volume of acid used  Normality 1.4
% N
Weight of Coal taken
(iii) Determination of Sulphur: - The washings of bomb calorimeter are treated with BaCl2 to convert ‘S’ into
BaSO4. The precipitate is filtered and dried to constant weight.
Weight of BaSO4 obtained 32
% S  100
Weight of Coal taken 233
(iv) Determination of Oxygen: - % of oxygen is determined as follows.
% of oxygen = 100 – % (C+ H + N + S + Ash)
Numerical Problems

Q.1 The following data is obtained in a Bomb Calorimeter experiment:-

Weight of Crucible = 3.649 gm
Weight of crucible + Fuel = 4.687 gm
Water equivalent of calorimeter = 570 gm
Water taken in calorimeter = 2200 gm

14
 Observed rise in temperature = 2.30C
Cooling Correction = 0.0470C
Acid correction = 62.6 calories
Fuse wire correction = 3.8 calories
Cotton thread correction = 1.6 calories
Calculate the gross calorific value of the fuel sample. If the fuel contains 6.5% hydrogen then, determine
the net colorific value.
Solution :- (W  w) (t 2  t1  CC )  (C A  CF  CCT )
HCV 
x
(2200  570) (2.3  0.047)  (62.6  3.8  1.6)
HCV 
(4.687  3.649)
(2770  2.347)  68.0
HCV 
1.038
HCV  6197.67 Cal / gm
Then,
Since the fuel contain 6.5% hydrogen,
LCV  ( HCV  0.09  H  587) cal / gm
LCV  6197.67  0.09  6.5  587
LCV  6197.67  343.4
LCV  5854.27 Cal / gm

Q.2 A sample of Coal containing 80% C, 15% H and 5% Ash is tested in bomb calorimeter. The
following insults were obtained.
Weight of Coal burnt = 0.98 gm
Weight of water taken = 1000 gm
Water equivalent of calorimeter = 2500 gm
Rise in temperature = 2.50C
Cooling Correction = 0.020C
Acid correction = 50.0 calories
Fuse wire correction = 8.0 calories
Assuming the latent heat of condensation of steam as 580 coal/gm, calculate the (i) higher (ii) Lower
calorific value of the fuel.
Solution :- (W  w) (t  t  C )  (C  C )
HCV  2 1 C A F
m
(1000  2500) (2.5  0.02)  (50  8)
HCV 
0.98
3500  2.52  58
HCV 
0.98
HCV  8940.82 cal / gm
LCV  ( HCV  0.09  H  580) cal / gm
LCV  8940.82  0.09 15  580
LCV  8940.82  783
LCV  8157.82 cal / gm

Q.3 0.85 gm of a fuel is burnt completely in excess supply of oxygen. The increase in temperature of
water in the calorimeter containing 1800 gm of water was found to be 30C. Calculate the higher

15
 calorific value of the fuel. Given that the water equivalent of calorimeter is 180 gm.
(W  w) (t 2  t1 )
Solution :- HCV 
m
(1800  180)  3
HCV 
0.85
1980  3
HCV 
0.85
HCV  6988.23 cal / gm

Q.4 A sample of Coal containing 90% C, 8% H and 2% Ash. When this coal sample was burnt in
bomb calorimeter, the following results were obtained.
Weight of Coal burnt = 0.90 gm
Weight of water taken = 800 gm
Water equivalent of calorimeter = 2000 gm
Rise in temperature = 2.400C
Cooling Correction = 0.020C
Acid correction = 60.0 calories
Fuse wire correction = 10.0 calories
Calculate the net and gross calorific values of the coal in cal/gm. Assume the latent heat of condensation of steam
as 580 cal/gm. (W  w) (t 2  t1  CC )  (C A  C F )
Solution :- HCV 
m
(800  2000) (2.40  0.02)  (60  10)
HCV 
0.90
2800  2.42  70
HCV 
0.90
HCV  7451.11cal / gm
LCV  ( HCV  0.09  H  580) cal / gm
LCV  7451.11  0.09  8  580
LCV  7451.11  417.60
LCV  7033.51 cal / gm

Q.5 A sample of coal was analysed as follows : Exactly 1.40gm was weighed into a silica crucible.
After heating for one hour at 105 at 1100C the residue weighed 1.10gm. The crucible next was
conved with a vented lid and strongly heated for exactly 7 minute at 950 + 200C. The residue was
weighed 1.00 gm. The crucible was then heated without cover, until a constant weight was
obtained. The last residu was found to weight 0.21gm. calculate the ash content, moisture content,
volatile matter and % of fixed carbon.
Solution :- Weight of moisture in Coal = 1.40 – 1.10 = 0.30gm
Weight of volatile matter = 1.10 – 1.00 = 0.10gm
Weight of Ash = 0.21gm
% of moisture = 0.30 x 100
= 21.4%
1.40

% of volatile matter = 0.10 x 100 = 7.14%

1.40
0.21 x 100
% of Ash = = 15%
1.40
% of fixed carbon = 100 – (21.4 + 7.14 + 15)
= 100 – 43.54 = 56.46%
Q.6 3.00 gm of a coal sample was kjeldahlised and NH3 gas thus evolved was absorbed in 40 ml of
N/10 H2SO4. After absorption, the excess (residual) acid required 10ml of N/10 NaOH for exact
neutralization. Calculate the percentage of Nitrogen in the coal sample.

16
Solution :- Vol. of Acid used byNH3 = Acid used – acid neutralized by NaOH = (40-10) = 30ml
Volume of acid used by ammonia x N x 1.4
% Nitrogen =
Wt. of coal sample taken
30  0.1  1.4
= = 1.4%
3
Q.7 0.8gm of a sample of coal was burnt in excess supply of oxygen in a bomb calorimeter. The
washing was then heated with BaCl2 and a precipitate of BaSO4 was obtained. The precipitate
was filtered, dried and weight and was found to be 0.08 gm. Calculate the percentage of sulphur
in coal sample.
Weight of BaSO4 32
% of Sulphur   100
Solution :- Weight of Coal takenin bomb 233
0.08 32
% of Sulphur   100
0.8 233
320
% of Sulphur  1.373%
233
% of Sulphur 1.373 %

17