Water Technology: Types of Impurities and Hardness

UNIT I
WATER TECHNOLOGY
1.1 INTRODUCTION
Water is one of the most abundant commodities in nature. Water is essential for
survival of all living organisms. About 80% of the earth surface is covered by water. The
main sources of water are
i) Rain
ii) River and lakes (surface water)
iii) Wells and springs(ground water)
Among the above (sources of water) rain water is the purest form of water whereas sea
water is the most impure form. For drinking and industrial purposes we need water free
from undesirable impurities. So first we should understand about the nature and types of
impurities present in water so that the water can be treated suitably to remove the
undesirable impurities.
1.2 TYPES OF IMPURITIES IN WATER

The impurities present in the water may be broadly classified into three types
(i) Physical impurities
(a) Suspended impurities
(b) Colloidal impurities
(ii) Chemical impurities
(a) Dissolved salts
(b) Dissolved gases
(iii) Bacteriological impurities due to pathogenic bacteria which spread diseases.
1
1.3 HARD AND SOFT WATER
Water which does not produce lather with soap solution but forms a white precipitate
is called hard water.
Water which lathers easily with soap solution is called soft water.
1.3.1 Hardness of water

Hardness is the characteristic property of water which does not lather with soap
solution due to the presence of Ca2+ and Mg2+ ions. .
Hardness can be detected by treating water with soap.
2C17H35COONa + CaCl2 C17H35COO)2 Ca + 2NaCl
Depending upon the types of dissolved salts present in water, hardness of water can be
classified into two types.
i. Temporary hardness or Carbonate hardness or Alkaline hardness: This is due to the

presence of bicarbonates of calcium and magnesium. It can be removed by boiling the
water or adding lime to the water.
Ca (HCO3)2 Δ CaCO3 + H2O + CO2
Mg (HCO3)2 + 2Ca (OH)2 Mg (OH)2 + 2CaCO3 + 2H2O
ii. Permanent hardness or Non-Carbonate hardness or Non - alkaline hardness: This is

due to the presence of chlorides and sulphates of calcium and magnesium. Permanent
hardness is removed by lime-soda process or zeolite process.
CaCl2 + Na2CO3 CaCO3 + 2NaCl
(soda)
CaSO4 + Na2Ze CaZe + Na2SO4

(soda. zeolite)
2
1.3.2 Expression of hardness as equivalents of CaCO3 (or) CaCO3 standard
The concentration of hardness causing ions are usually expressed in terms of an
equivalent amount of CaCO3. The choice of CaCO3 is standard because its molecular
weight is 100 (equivalent weight =50) and also it is the most insoluble salt that can be
precipitated in water treatment.
If the concentration of hardness producing constituent is x mg/lit., then
Equivalent amount of CaCO3 = x × 100
Molecular weight of hardness producing substance
i.e., Amount Equivalent to CaCO3 = Amount of hardness producing salt

× Molecular weight of CaCO3
Molecular weight of hardness producing salt
i.e., Amount Equivalent to CaCO3 = Amount of hardness producing salt

× Equivalent weight of CaCO3
Equivalent weight of hardness producing salt
1.4 UNITS OF HARDNESS

i) Parts per million (ppm)
It is defined as the number of parts of CaCO3 equivalent hardness per 106 parts of water.
ii) Milligrams per litre (mg / lit)
It is defined as the number of milligrams of CaCO3 equivalent hardness per 1 litre of
water.
Relationship between ppm and mg/litre
Since weight of1 litre of water = 1 kg
= 1000gms = 1000 × 1000 = 106 mgs
1 mg/lit = 1 mg of CaCO3 equivalent hardness in
106 mgs of water 3
= 1 part of CaCO3 equivalent hardness
in 106 parts of water
= ppm
Thus mathematically ppm and mg/lit unites are equal.
iii) Clarke’s degree (0Cl)
It is defined as the number of parts of CaCO3 equivalent hardness per 70,000 parts of
water.
iv) French degree (0Fr)
It is defined as the number of parts of CaCO3 equivalent hardness per 105 parts of water.
Problems based on Hardness

1. A sample of water contains 100 mgs of MgSO4 per litre. Calculate the hardness in
terms of CaCO3 equivalents.
Solution
Given: The amount of MgSO4 = 100 mgs/lit
The amount of hardness producing salt
Amount equivalent to CaCO3 = ---------------------------------------------------------- X 100
Molecular weight of hardness producing salt
We know that, the molecular weight of MgSO4 = 120
 Amount equivalent to CaCO3 =100 x 100/120 = 83.3 mgs/lit
2. A water sample contains 200 mgs of CaSO4 and 75 mgs of Mg (HCO3)2 per litre.
What is the total hardness interms of CaCO3 equivalent?
Solution:
Name of the hardness Amount in Molecular Amount equivalent
producing salts mgs/lit weight to CaCO3
CaSO4 200 136 200 X 100 / 136 =
147 mgs/lit
Mg(HCO3)2 75 146 75 x 100 / 146 =
51.4 mgs/lit 4
Temporary Hardness = Mg (HCO3)2 = 51.4 mgs/lit
Permanent hardness = CaSO4 =147 mgs/lit.
Total hardness = Mg (HCO3)2 + CaSO4
= 51.4 + 147
= 198.4mgs/lit
3. A sample of water contains 25mgs of Ca2+ ions per litre, Calculate its hardness
interms of CaCO3 equivalent?
Solution
Given:
The amount of Ca2+ ions = 25 mgs/lit
We know that, the atomic weight of calcium = 40
Amount of CaCO3 = 25 X 100 / 40
= 62.5 mgs/lit
4. Calculate the carbonate and non-carbonate hardness of a sample water containing

the dissolved salts as given below in mgs/lit Mg(HCO3)2 = 10;Ca(HCO3)2 = 40; MgCl2 =
21.; and NaCl = 20
Solution
Name of the Amount Molecular Amounts
hardness producing in mgs/lit weight equivalent to
salts CaCO3
Mg(HCO3)2 10 146 10 X 100 / 146 =
6.8 mgs/lit
Ca(HCO3)2 40 162 40X 100 / 162 =
24.7 mgs/lit
MgCl2 21 95 21 X 100 / 95 = 22.1
mgs/lit
NaCl 20 NaCl does not contribute any
hardness to water, hence it is
ignored. 5
Carbonate hardness = Mg(HCO3)2 + Ca(HCO3)2
= 6.8 + 24.7 = 31.5 mgs/lit
Non-carbonate hardness = MgCl2
= 22.1 mgs/lit
Total hardness = carbonate hardness + Non-carbonate hardness
= 31.5 + 22.1
= 53.6 mgs/lit
Exercises
5. A sample of water contains the following dissolved salts in mgs/lit. Mg (HCO3)2 =
73; CaCl2=111; Ca (HCO3)2=81 and MgSO4=40. Calculate the temporary and permanent
hardness of the water (Atomic weights of Ca, Mg, O, C, Cl, S, H are 40, 24, 16, 12, 35.5, 32
and respectively.
6. A sample of water is found to contain 16.8 mg/lit Mg(HCO3)2, 12 mg/lit MgCl2, 29.6
mg/lit MgSO4, and 5.0 mg/lit NaCl. Calculate the permanent and temporary hardness of
water and express it in ppm. (Atomic weight of Mg=24; H=1; C=12; O=16; Cl=35.5;
Na=23; S=32)
1.5ALKALINITY
Alkalinity in water is due to the presence of soluble (i) hydroxide (OH-) ions, (ii)
carbonate (CO32-) ions and (iii) bicarbonate (HCO3-) ions. These can be determined by
titrimetry using standard acid and phenolphthalein and methyl orange as indicators. The
determination is based on the following reactions.
(i) [OH-] + [H+]  H2O
(ii) [CO3]2- + [H+]  [HCO3-] P

M
(iii) [HCO3-] + [H+]  H2O + CO2
6
Depending upon the anion that is present in water alkalinity is classified into three types.
1. Hydroxide alkalinity - due to (OH-)
2. Carbonate alkalinity - due to (CO3 2-)
3. Bicarbonate alkalinity - due to (HCO3-)
1.5.1 Detection of various alkalinity:

Titration 1:
Known amount of water sample is titrated against a standard acid using
phenolphthalein indicator, the end point indicates the completion of the reaction (i) and
(ii) i.e. neutralization of OH- and CO32- ions. The amount of acid used corresponds to all
the hydroxide ions + one half of the carbonate ions present.
Titration 2:
Similarly the same amount of water sample is titrated against a standard acid using
methyl orange indicator, the end point indicates the completion of reaction (i), (ii) and (iii).
The amount of acid used after the phenolphthalein end point corresponds to one-half of
normal carbonate {+} all the bicarbonates.
i.e., neutralization of OH-, CO32-, and HCO3- ions.
The total amount of acid used (amount of acid upto phenolphthalein end point {+}
amount of acid upto methyl orange end point) represents the total alkalinity (due to
hydroxide, carbonate and bicarbonates).
Note:
OH- and HCO3- ions cannot exist together in water, because they combine
instantaneously to form CO32- ions.
i.e., OH- + HCO3-  CO32- + H2O
e.g. NaOH + NaHCO3  Na2CO3 + H2O
Thus in a water all the three ions (OH-, CO32-, HCO3-) cannot exist together.
7
1.5.2 Determination of various types of alkalinity
Various types involved in the determination of various types of alkalinity are as
follows.
Step I : Experimental procedure

Titration I : Determination of Phenolphthalein alkalinity
Pipette out 100 ml of the given water sample into a clean conical flask. Add 2 to 3
drops of a phenolphthalein indicator and titrate it against N/50 H2SO4 taken in the
burette. The end point is the disappearance of pink colour.
Let the volume of acid consumed be V1 ml.
Titration II: Determination of methyl orange alkalinity

After the completion of titration I, to the same solution, add 2 to 3 drops of methyl
orange indicator, and continue the titration against the same N/50 H2SO4. The end point is
the reappearance of pink color.
Let the volume be V2 ml.
Step II: Calculation
(i) Calculation of Phenolphthalein Alkalinity

The volume of acid used to phenolphthalein indicator V1 = ml
N
Normality of the acid N1 =
50
Volume of the water sample V2 = 100 ml

Normality of water sample N2 = ?
According to volumetric law V1N1 = V2N2
V1N 1
N2 =
V2
8
V1 1
N2 = 
100 50
Phenolphthalein alkalinity (P) (in terms of CaCO3 equivalent)
= N2 Eq.wt of CaCO3 1000 ppm
V1  50  100
= ppm
100  50
P = 10V1
(ii) Calculation of Methyl Orange Alkalinity

Extra volume of acid used to methyl orange end point = V2 ml
Total volume of acid used to methyl orange end point = (V1+V2) ml
The volume of acid used to methyl orange end point} V1 = (V1+V2) ml
N
Normality of the acid N1 =
50
Volume of water sample V2 = 100 ml

Normality of alkaline water sample N2 = ?
V1  V 2  1
According to Volumetric law N2 = 
100 50
Methyl orange alkalinity (M)
V1  V 2   50  1000
(interms of CaCO3 equivalent) = ppm
100  50
M = 10(V1 + V2)
Conclusions
(i) When P = 0, both OH- and CO32-are absent and alkalinity is only due to HCO3-.
(ii) When P = 1/2 M, only CO32- is present, half of the carbonate neutralization reaction
takes place (i.e CO32- + H+  HCO3-) with phenolphthalein indicator complete
carbonate neutralization reaction (i.e CO32- + H+  HCO3-. HCO3-+ H+  H2O + CO2)
occurs when methyl orange indicator is used. Thus alkalinity due to CO32- = 2P.
9
(iii) When P = M, only OH— is present, alkalinity due to OH-= P = M
(iv) When P > 1/2M, besides CO32-, OH- ions are also present. Now half of CO32-
(i.e,HCO3- + H+  CO2 + H2O) equal to (M-P) so, alkalinity is due to complete CO32- =
2(M-P) alkalinity due to OH- = M-2(M-P) = 2P-M
(v) When P < 1/2 M, Besides CO32-, HCO3- ions are also present.
Now alkalinity due to CO32- = 2P
Alkalinity due to HCO3- = (M- 2P)
The data of the above conclusions are tabulated as follows.
Table 1.2 Calculation of alkalinity of water

Result of P end point Nature of
OH- (ppm) CO32- (ppm) HCO3-(ppm)
and P M end point alkalinity
P=0 0 0 M Only bicarbonate
P=1/2 M 0 2P 0 Only carbonate
Bicarbonate and
P<1/2 M 0 2P (M-2P)
carbonate
Hydroxide and
p>1/2 M (2P-M) 2(M-P) 0
carbonate
P=M P=M 0 0 Only hydroxide
10
Problems based on Alkalinity
1. 100 ml of a raw water sample on titration with N/50 H2SO4 required 10.0 ml of the
acid to phenolphthalein end-point and 14.0 ml of the acid to methyl orange end-
point. Determine the type and extent of alkalinity present in the water sample.
Solution:
Strength of HCl = 0.02 N
phenolphthalein end-point =P = 10.0 ml
methyl orange end-point =M = 14.0 ml
Since P > M,
the water sample must contain only OH- and CO32- alkalinities and there cannot be any
HCO3- alkalinity.
i) Volume of std .HCl required for OH- alkalinity = 2P - M
= (2 x 10.0) ml - 14 ml
= 20 ml- 14.0 ml
= 6.0 ml
Volume of acid consumed to OH- alkalinity V1 = 6.0 ml
ii) Volume of std .HCl required for CO32- alkalinity = 2M – 2P
= 2 x 14.0 ml – 2 x 10.0 ml
= 24 – 20
Volume of acid consumed to CO32- alkalinity V1 = 4.0 ml
1. Calculate the OH- alkalinity

Volume of HCl V1 = 6.0 ml
Strength of HCl N1 = 0.02 N
11
Strength of water sample due to OH- alkalinity N2 = ?
V1 N1 = V2 N2
V1N 1
N2 =
V2
6  0.02
N2 =
100
Strength of water sample due to OH- alkalinity = 0.0012 N

Amount of OH- alkalinity present in
1 litre in terms Of CaCO3 equivalent = Strength of OH- alkalinity
Eq. wt of CaCO3
= 0.0012 N 50
= 0.06 gm x 1000
Amount of OH- alkalinity = 60 ppm
2. Calculate the CO32- alkalinity

Strength of water sample due to CO32- alkalinity N2 = ?
V1 N1 = V2 N2
V1N 1
N2 =
V2
4  0.02
N2 =
100
Strength of water sample due to CO32- alkalinity = 0.0008 N

Amount of CO32- alkalinity present in
1 litre in terms Of CaCO3 equivalent = Strength of of CO32- alkalinity
Eq. wt of CaCO3
12
= 0.0008 N 50
= 0.04 gm x1000
= 40 ppm
Amount of CO32- alkalinity = 40 ppm
Total Alkalinity
Total alkalinity = Alkalinity due to OH— +
Alkalinity due to CO32-
= 60 ppm + 40 ppm
= 100 ppm
2. A water sample is not alkaline to phenolphthalein but, 100 ml of the sample on
titration with N/10 HCl, required 15 ml to methyl orange end point. What are the types
and amounts of alkalinity present in the sample.
Solution:
phenolphthalein end point p = 0
methyl orange end point M = 15 ml
Since P = 0
The water sample contain only HCO3- alkalinity ,
Volume of HCl required to HCO3- alkalinity = M
M = 15 ml
1) Calculate the HCO3- alkalinity
13
Strength of water sample due to HCO3- alkalinity N2 = ?
V1 N1= V2 N2
V1N 1
N2 =
V2
15  0.1
N2 =
100
= 0.015 N
Strength of water sample due to HCO3- alkalinity = 0.015 N
Amount of HCO3- alkalinity present in
1 litre in terms Of CaCO3 equivalent = Strength of HCO3- alkalinity
Eq. wt of CaCO3
= 0.015 N 50
= 0.75 gm x1000
= 750 ppm
Amount of HCO3- alkalinity = 750 ppm
3. 100 ml of a water sample on titration with 0.02 N H2SO4 gave a titre value of 7.8 ml
to phenolphthalein end-point and 15.6m l to methyl orange end-point. Calculate the
alkalinity of the water sample interms of CaCO3 equivalent and comment the type of
alkalinity present.
Solution:
Given:
Volume of the water sample = 100 ml
phenolphthalein end point P = 7.8 ml
methyl orange end point M = 15.6 ml
Given data satisfy the condition P = 1/2 M, Therefore water sample contains only
CO 32  alkalinity not OH - and HCO3- alkalinity,
14
Volume of HCl required to CO32- alkalinity = 2P
= 2 7.8
= 15.6 ml
Calculation for CO32- Alkalinity.
Strength of water sample due to CO32- alkalinity N2 = ?
V1 N1 = V2 N2
V1N 1
N2 =
V2
15.6  0.02
N2 =
100
Strength of water sample due to CO32- alkalinity = 0.00312 N

1 litre in terms Of CaCO3 equivalent = Strength of CO32- alkalinity
Eq. wt of CaCO3
= 0.00312 N 50
= 0.156 gm x1000
= 156 ppm
Amount of CO32- alkalinity = 156 ppm
15
4. 100 ml of a raw water sample on titration with N/50 H2SO4 required 7.5 ml of the
acid to phenolphthalein end-point and 18.0 ml of the acid to methyl orange end-point.
Determine the type and extent of alkalinity present in the water sample.
Solution.
phenolphthalein end-point P = 7.5 ml
methyl orange end-point M = 18.0 ml
If the data satisfy the condition, P < M,
the water sample must contain both CO32- and HCO3- alkalinities and there cannot be any
OH- alkalinity.
i) Volume of std .HCl required for CO32- alkalinity = 2P
= 2 x 7.5 ml
= 15.0 ml
Volume of acid consumed to CO32- alkalinity V1 = 15.0 ml
ii) Volume of std .HCl required for HCO3- alkalinity = M – 2P
= 18.0 ml – 2 x 7.5.0 ml
= 3.0 ml
Volume of acid consumed to HCO3- alkalinity V1 = 3.0 ml
Calculate the CO32- alkalinity
Strength of water sample due to
CO32- alkalinity N2 = ?
16
V1 N1 = V2 N2
V1N 1
N2 =
V2
15  0.02
N2 =
100
= 0.003 N
Strength of water sample due to CO32- alkalinity = 0.003N
1 litre in terms Of CaCO3 equivalent = Strength of CO32- alkalinity
Eq. wt of CaCO3
= 0.003 N 50
= 0.15 gm x 1000
Amount of CO32- alkalinity = 150ppm
Calculate the HCO3- alkalinity
Strength of water sample due to HCO3- alkalinity N2 = ?
V1 N1 = V2 N2
V1N 1
N2 =
V2
3  0.02
N2 =
100
N2 = 0.0006 N
Strength of water sample due to HCO3- alkalinity = 0.0006 N
Amount of HCO3- alkalinity present in
1 litre in terms Of CaCO3 equivalent = Strength of of HCO3- alkalinity
Eq. wt of CaCO3
17
= 0.0006 N x 50
= 0.03 gm x1000
= 30 ppm
Amount of HCO3- alkalinity = 30 ppm
Total Alkalinity
Total alkalinity = Alkalinity due to CO32- +
Alkalinity due to HCO3-
= 160 ppm + 30 ppm
= 190 ppm
1.6 ESTIMATION OF HARDNESS BY EDTA METHOD

EDTA is Ethylene Diamine Tetra Acetic acid. The structure of EDTA is
HOOCH2C CH2COOH
N-CH2-CH2-N
HOOCH2C CH2COOH
Since, EDTA is insoluble in water, its disodium salt is used as a sequestering or
complexing agent.
Principle:
The amount of hardness causing ions (Ca2+and Mg2+) can be estimated by titrating the
water sample against EDTA using Eriochrome-Black-T indicator (EBT) at a pH of 8-10. In
order to maintain the pH, buffer solution (NH4Cl-NH4OH mixture) is added. Only at this
pH such a complexation is possible.
When the EBT indicator is added to the water sample, it forms wine red coloured
weak complex with Ca2+and Mg2+ ions.
18
[ Ca2+ & Mg2+] + EBT pH = 8-10 Ca
EBT complex
Mg
wine red coloured weak complex
When this solution is titrated against EDTA, it replaces the indicator and form stable
EDTA complex. When all the hardness causing ions are complexed by EDTA, the
indicator is set free. The colour of the free indicator is steel blue. Thus the end point is
change of colour from wine red to steel blue.
Ca
EBT complex + EDTA pH = 8-10 Ca
Mg EDTA + EBT
Mg
wine red coloured weak complex Stable complex Steel blue
1.6.1 Preparation of solutions:

a) EDTA Solution
It is prepared by dissolving 4 gms of EDTA in 1000 ml of distilled water.
b) Standard hard water
1 gm of pure CaCO3 is dissolved in minimum quantity of HCl and then made up to
1000 ml using distilled water.
1 ml of standard hard water 1 mg of CaCO3
c) EBT Indicator
0.5 gms of EBT is dissolved in 100 ml of alcohol.
d) Buffer solution
67.5 gms of NH4Cl and 570 ml of NH3 are dissolved and the solution is made upto
1000 ml using distilled water.
19
1.6.2 Experimental procedure:
(i) Standardisation of EDTA
Pipette out 50 ml of standard hard water into a clean conical flask. Add 10 ml of buffer
solution and 4-5 drops of EBT indicator and titrate it against EDTA solution taken in the
burette. The end point is the change of colour from wine red to steel blue
Let the volume of EDTA consumed be V1 ml
(ii) Estimation of total hardness of water sample

Pipette out 50 ml of the given hard water sample into a clean conical flask. Add 10 ml
of buffer solution and 4-5 drops of EBT indicator and titrate it against EDTA as before.
Let the volume of EDTA consumed be V2 ml
(iii) Estimation of permanent hardness of water sample

Take a 100 ml of the same hard water sample in a 250 ml beaker. Boil it for 15 minutes.
During boiling temporary hardness gets removed. Cool and filter the solution and make
upto 100 ml in a standard flask by adding distilled water. Pipette out 50 ml of the made up
solution into a clean conical flask and titrate against EDTA as before.
Let the volume of EDTA consumed be V3 ml.
Calculation:
(i) Standardization of EDTA using standard hardwater
1 ml of std. hard water = 1 mg of CaCO3
50 ml of std. hard water = 50 mgs of CaCO3
50 ml of std. hard water consumes = V1 ml of EDTA
V1 ml of EDTA 50 mgs of CaCO3 equivalent of hardness
(Or)
50
1 ml of EDTA  mgs of CaCo3 equivalent of hardness
V1
20
(ii) Estimation of total hardness of water sample
50 ml of the given hard water sample consumes} = V2 ml of EDTA
50
= V2  mgs of CaCO3 equivalent of hardness
V1
50
[ 1 ml of EDTA = mgs of CaCO3]
V1
1000 ml of the given sample hard water sample
50 1000
= V2  
V1 50
V2
= 1000  {mgs of CaCO3 equivalent of hardness}
V1
V2
 Total Hardness = 1000  ppm
V1
(iii) Estimation of permanent hardness of water sample

50 ml of same hard water samples after boiling, filtering, etc, consumes}
= V3 ml of EDTA
50
= V3  mgs of CaCO3 equivalent of hardness
V1
 1000 ml of the given hard water sample}

50 1000
= V2  
V1 50
V3
= 1000  {mgs of CaCO3 equivalent of hardness}
V1
V3
 Permanent Hardness = 1000  ppm
V1
21
(iii) Temporary hardness
Temporary hardness = Total hardness - Permanent hardness
V2 V
= 1000   1000  3
V1 V1
1000
 Temporary hardness = V 2  V1  ppm
V1
Problems based on Hardness

1. 100 ml of a water sample requires 20 ml of EDTA solution for titration. 1 ml of EDTA
solution is equivalent to 1.1 mgs of CaCO3.Calculate the hardness of the water in ppm
unit.
Solution
Given:
1 ml of EDTA solution = 1.1 mgs of CaCO3
20 ml of EDTA solution = 20 x 1.1 mgs of CaCO3
= 22 mgs of CaCO3
100 ml of water sample requires = 20 ml of EDTA
= 22 mgs of CaCO3
1000
1000 ml of water sample, = 22  mgs of CaCO3
100
= 220 mgs/lit or 200 ppm
2. In an estimation of hardness of water by EDTA titration, 50 ml of a sample of water

required 15 ml of 0.02M EDTA solution to reach the end point. Calculate the hardness
of water.
Estimation of hardness
Volume of water sample V1 = 50ml
Strength of water sample M1 = ?
Volume of std EDTA V2 = 15 ml 22
Strength of b std EDTA M2 = 0.02 M
V1M1 = V2M2
V2 M 2
M1 =
V1
15  0.02
M1 =
50
M2 = 0.006 M
Strength of hard water sample = 0.006 M

Amount of hardness present in per liter in
terms of CaCO3 equivalent = Strength of hard water x M .W of CaCO3
= 0.006 M X 100
= 0.6 gm x1000
Amount of hardness = 600 ppm
3. 100 ml of a water sample of consumed 19.5 ml of 0.01 M EDTA for titration using
Erio-chrome Black-T indicator. In another experiment, 100 ml of the same water sample
was boiled to remove the carbonate hardness, the precipitate was discarded and then it
is allowed to reach the room temperature. The filtrate CaCO3 solution was then titrated
against 0.01 M EDTA which consumed 10 ml of EDTA, in the presence of EBT
indicator. Calculate (i) the total hardness (ii) permanent hardness of non carbonate
hardness (iii) carbonate hardness, in terms of mg/lit of CaCO3.
Titration: I
Strength of EDTA = 0.01M
Estimation of total hardness.
Volume of std EDTA V2 = 19.5 ml
23
V1M1 = V2M2
V2 M 2
M1 =
V1
19.5  0.01
M1 =
100
M1 = 0.00195 M

Amount of total hardness present in per
liter in terms of CaCO3 equivalent = Strength of hard water x M .W of CaCO3
= 0.00195 M X 100
= 0.195 gm x1000
Amount of total hardness = 195 ppm
Titration: II
Estimation of permanent hardness.
Volume of boiled water V1 = 100 ml
Strength of boiled water M1 = ?
Volume of std EDTA V2 = 10 ml
V1M1 = V2M2
V2 M 2
M1 =
V1
10  0.01
M1 =
100
M1 = 0.001 M
Strength of boiled water = 0.001 M

Amount of permanent hardness present in per liter in
24
Terms of CaCO3 equivalent = Strength of boiled water x M .W of CaCO3
= 0.001M X 100
= 0.1 gm x1000
Amount of permanent hardness = 100 ppm
Temporary hardness = 195 ppm - 100 ppm
Temporary hardness = 95 ppm
4. Calculate permanent and temporary hardness from the following. 250 ml of a water
sample is boiled for 1 hr. It is then cooled nd filtered. The filtrate is made upto 250 ml
again with the addition of distilled water. 20 ml of this solution requires 10 ml of 1/100
EDTA with EBT-indicator and NH4Cl - NH4OH buffer.
Titration: I
Strength of std EDTA M2 = 0.01 M
V1M1 = V2M2
V2 M 2
M1 =
V1
10  0.01
M1 =
20
M1 = 0.005 M
Strength of boiled water = 0.005 M
Terms of CaCO3 equivalent = Strength of boiled water x M .W of CaCO3
= 0.005 M X 100
= 0.5 gm x1000
Amount of permanent hardness = 500 ppm 25
5. 100 ml of a water sample consumed 25.0 ml of 0.01 M EDTA for the titration using
EriochromeBlack-T indicator. Calculate the total hardness.
Estimation of hardness.
Strength of std EDTA M2 = 0.01 M
V1M1 = V2M2
V2 M 2
M1 =
V1
25  0.01
M1 =
100
M1 = 0.0025 M

Terms of CaCO3 equivalent = Strength of hard water x M .W of CaCO3
= 0.0025 M X 100
= 0.25 gm x1000
26
6. 0.25 gm of CaCO3 was dissolved in HCl and the solution made upto one litre with
distilled water. 100 ml of the above solution consumed 25 ml of EDTA solution on
titration.100 ml of hard water sample required 30 ml of same EDTA solution on
titration. 100 ml of this water, after boiling cooling and filtering required 11 ml of
EDTA solution on titration. Calculate the temporary permanent and total hardness of
water.
Calculate the strength of given std water,
Amount / Lit
Strength of Std Water = _________________________
Molecular Weight
0.25 gm
Strength of std Water =
100
Strength of Std water = 0.0025 M
Titration: I
Standardization of EDTA :
Volume of std water V1 = 100 ml
Strength of std water M1 = 0.0025M
Volume of EDTA V2 = 25 ml
Strength of EDTA M2 = ?
V1M1 = V2M2
V2 M 2
M1 =
V1
100  0.0025
M1 =
25
M2 = 0.01 M
Strength of EDTA = 0.01 M
27
Titration: II
Estimation of total hardness.
V1M1 = V2M2
V2 M 2
M1 =
V1
30  0.01
M1 =
100
M2 = 0.003 M
Amount of total hardness present in per liter in
terms of CaCO3 equivalent = Strength of hard water x M .W OF CaCO3
= 0.003M X 100
= 0.3 gm x1000
Amount total hardness = 300 ppm
Titration: III
V1M1 = V2M2
V2 M 2
M1 =
V1
11  0.01
M1 =
100
M2 = 0.0011 M
Strength of boiled water = 0.0011 M 28
terms of CaCO3 equivalent = Strength of boiled water x M .W of CaCO3
= 0.0011M X 100
= 0.11 gm x1000
Amount of permanent hardness = 110 ppm
Temporary hardness = 300 ppm - 110 ppm
Temporary hardness = 190 ppm
7. 100 ml of a molecular water sample of requires 18.5 ml of EDTA solution for

titration. 20 ml of the same EDTA solution was required for the titration of 100 ml of
standard hard water containing 1 gm of CaCO3 per litre. Calculate the hardness of water
in ppm unit.
Calculate the strength of given std hard water.
Amount / Lit
Strength of Std Water = _________________________
Molecular Weight
1gm
Strength of std Water =
100
Strength of Std water = 0.01
Titration: I
Standardization of EDTA :
Volume of std water V1 = 100 ml
Strength of std water M1 = 0.01M
Volume of EDTA V2 = 20 ml
Strength of EDTA M2 = ?
V1M1 = V2M2
V1M 1
M2 =
V2 29
100  0.01
M2 =
20
M2 = 0.05 M
Strength of EDTA = 0.05 M
Titration : II
Estimation of hardness.
Volume of std EDTA V2 = 18.5 ml
V1 M1 = V2 M2
V1M1 = V2M2
V2 M 2
M1 =
V1
18.5  0.05
M2 =
100
M2 = 0.00925 M
terms of CaCO3 equivalent = Strength of hard water x M .W of CaCO3
= 0.00925 M X 100
= 0.925 gm x1000
30
1.7 BOILER FEED WATER
The water fed into the boiler for the production of steam is called boiler feed water. Water
used in steam making should be free from dissolved salts and gases, suspended
impurities, silica and oil. If it is used in boilers, these impurities lead to following
problems.
(i) Scale and sludge formation
(ii) Boiler Corrosion
(iii) Priming and foaming
(iv) Caustic embrittlement
1.7.1 Scale and sludge formation

When water is converted into steam in boilers, the concentration of dissolved salts in
water increases progressively. When the salts concentration reach their saturation point,
they are thrown out in the form precipitate, i.e., the least soluble one gets precipitated first.
If the precipitated matter is soft and slimy, it is called sludge and when the precipitate
forms an adherent coating on the inner walls of the boiler, it is called scale.
Figure 1.1 a) sludge b) scale

31
Table 1.1. Difference between Sludge and Scale
S.NO Sludge Scale
Sludge is a loose, slimy and non-adherent
1 Scale is a hard, adherent coating.
precipitate.
The main sludge forming substances are The main scale forming substances
2
MgCO3, MgCl2, MgSO4 and CaCl2 etc. are Ca (HCO3)2, CaSO4, Mg (OH)2.
Disadvantages: Scales act as
Disadvantages: Sludges are poor thermal insulators. It decreases the
3 conductors of heat. Excess of sludge efficiency of boiler. Any crack
formation decreases the efficiency of boiler. developed on the scale, leads to
explosion.
Prevention: Scale formation can be
Prevention: Sludge formation can be
4 prevented by dissolving using
prevented by using softened water.
acids like HCl, H2SO4.
(ii) Scale formation can be
(ii) Sludges can also be removed by “blow – removed by
5
down operation”. (a)External treatment
(b) Internal treatment
(iii) Blow down operation is a process of
(iii) They can also be removed by
removing a portion of concentrated water
6 applying thermal shocks, scrapers,
by fresh water frequently from the boiler
wire brush, etc.,
during steam production.
1.7.2 Boiler corrosion

Corrosion in boilers is due to the presence of
a) dissolved oxygen,
32
b) dissolved carbon dioxide
c) dissolved salts like MgCl2
a) Dissolved oxygen: The concentration of oxygen in water used in all types of boilers
should be minimum (0.01 ppm 0.05 ppm). Dissolved oxygen in water attacks the boiler
material at high temperature.
4Fe + 2H2O + O2 4Fe (OH)3
b) Dissolved carbon dioxide: Dissolved carbon dioxide in water produces carbonic
acidic, which is acidic and corrosive in nature.
Ca (HCO3)2 CaCO3 + H2O + CO2
CO2 + H2O H2CO3
c) Dissolved MgCl2: When water containing dissolved MgCl2 is used in the boiler, HCl is
produced which attacks boiler in a chain like reaction producing HCl again and again
which corrodes boiler severely.
MgCl2 + H2O Mg (OH)2 + 2HCl
Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe (OH)2 + 2HCl
1.7.2.1 Removal of dissolved oxygen and carbon dioxide
i) Chemical method
Sodium sulphite, hydrazine are some of the chemicals used for removing oxygen.
2Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2 + 2H2O
Hydrazine is found to be an ideal compound for removing dissolved oxygen in the
water, since the products are water and inert N2 gas.
Carbon dioxide can be removed from water by adding of calculated amount of
NH4OH in to water
2NH4OH + CO2 (NH4)2CO3 + H2O
Corrosion by acids can be avoided by the addition of alkali to the boiler water. 33
ii) Mechanical de-aeration method
Dissolved oxygen along with CO2 can be removed by mechanical deaeration.
Deaeration: It is a mechanical method of removal of dissolved gases such as O2 and CO2.

The solubility of a gas is directly proportional to pressure and inversely proportional to
temperature (Daltons law and henrys law). These two principles are made use in the
design of mechanical deaerator.
In this process, water is allowed to fall slowly on the perforated plates fitted inside the
tower. The sides of the tower are heated, and vacuum pump is also attached to it. The high
temperature and low pressure produced inside the tower reduce the dissolved oxygen
content of the water.
Figure 1.2 Mechanical deaeration of water
1.7.3. Priming and foaming (Carry over)

During the production of steam in the boiler, due to the rapid boiling, some droplets of
liquid water are carried along with steam. Steam containing droplets of liquid water is
34
called wet steam. These droplets of liuid water carry with them some dissolved salts and
suspended impurities. The phenomenon is called carry over. It occurs due to priming and
foaming.
Priming:
Priming is the process of formation of wet steam. It is caused by
(i) very high water level
(ii) high steam velocity
(iii) sudden steam demands leading to sudden boiling.
(iv) improper boiler design
Priming can be controlled by
(i) keeping the water level lower
(ii) good boiler design providing mechanical steam purifier
(iii) avoiding rapid changes in the steaming rate, caused by sudden steam
demands.
Foaming:
The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried along with steam leading to excessive priming.
It may be caused by presence of oil, grease in water and finely divided sludge
particles.
Foaming can be prevented by
(i) adding antifoaming agents like synthetic polyamides
(ii) finely divided sludge particles, oil and grease can be removed by the addition
of coagulants such as sodium aluminate, ferrous sulphate etc.
35
1.7.4 Caustic embrittlement (Inter-crystalline cracking)
As water evaporates in the boiler, the concentration of sodium carbonate increases in
the boiler. Sodium carbonate is used in softening of water by lime soda process, due to
this some sodium carbonate maybe left behind in the water. As the concentration of
sodium carbonate increases, it undergoes hydrolysis to form sodium hydroxide.
Na2CO3 + H2O → 2NaOH + CO2
This NaOH flows into the minute hair cracks and crevices usually present on the boiler
material by capillary action and dissolves the surrounding area of iron as sodium ferroate.
Fe + 2NaOH Na2FeO2 + H2
This causes brittlement of boiler parts, Particularly stressed parts like bends, joints,
rivets etc, causing even failure of the boiler.
Prevention :
Caustic embrittlement can be prevented by using sodium phosphate as softening
agent instead of sodium carbonate
By adding tanning lignin to the boiler water, which blocks the minute hair cracks
1.8 Softening (Or) Conditioning Methods

Water used for industrial purposes should be free from hardness producing
substances, suspended impurities and dissolved gases etc. The process of removing
hardness producing salts from water is known as softening (or) conditioning of water.
Softening of water can be done in two methods
i. External treatment
ii. Internal treatment
1.8.1 External treatment

It involves the removal of hardness producing salts from the water before feeding into
the boiler. The external treatment can be done by the following method demineralization
or ion-exchange process.
36
1.8.1.1 Ion exchange (or) demineralisation process:
This process removes almost all the ions (both anions and cations) present in the hard
water.
The Soft water, produced by lime-soda and zeolite processes, does not contain
hardness producing Ca2+ and Mg2+ ions, but it will contain other ions like Na+,K+,SO42-,Cl-
etc. On the other hand D.M.(Demineralised) water does not contain both anions and
cations.
Thus a soft water means it is not demineralized water whereas a demineralized water
means it is a soft water.
This process is carried out by using ions exchange resins, which are long chain, cross
linked, insoluble organic polymers with a micro porous structure. The functional groups
attached to the chains are responsible for the ion exchanging properties.
Figure 1.3 Demineralisation Process
37
Cation exchanger:
Resins containing acidic functional groups (-COOH,-SO3H) are capable of exchanging
their H+ ions with other cations of hard water. Cation exchange resin is represented as
RH2.
Examples
i. Sulphonated coals.
ii. Sulphonate polystyrene.
R-SO3H: R-COOH = RH2
Anion exchanger:
Resin containing basic functional groups (-NH2, -OH) are capable of exchanging their
anions with other anions of hard water. Anion exchange resin is represented as R (OH)2.
Examples
i) Cross-linked quaternary ammonium salts.
ii) Urea-formaldehyde resin
R-NR3OH; R-OH; R-NH2 = R (OH)2
Process
The hard water first passed through a cation exchange column,
Which absorbs all the cations like Ca2+,Mg2+,Na+,K+,etc.,present in the hard water.
RH2 + CaCl2  RCa + 2HCl
RH2 + MgSO4  RMg + H2SO4
RH + NaCl  RNa + HCl
The cation free water is then passed through a anion exchange column, which absorbs
all the anions like Cl-, SO42-, HCO3-, etc., Present in the water.
R’ (OH)2 + 2HCl  R’Cl2 + 2H2O
R’ (OH)2 + H2SO4  R’SO4 + 2H2O
38
The water coming out of the anion exchanger is completely free from cations and
anions. This water is known as determineralised or deionized water.
Regeneration
When the cation exchange resin is exhausted, it can be regenerated by passing a
solution of dil. HCl or H2SO4
RCa + 2HCl  RH2 + CaCl2
RNa + HCl  RH + NaCl
Similarly, when the anion exchange resin exhausted, it can be regenerated by passing a
solution of dil.NaOH.
R’Cl2 + 2NaOH  R’(OH)2 + 2NaCl.
Advantage of Ion-Exchange Process

i. Highly acidic or alkaline water can be treated by this process
ii. The water obtained by this process will have very low hardness
(nearly 2 ppm).
Disadvantage of ion exchange process

i. Water containing turbidity, Fe and Mn cannot be treated, because turbidity
reduces the output and Fe, Mn form stable compound with resin.
ii. The equipment is costly and more expensive chemicals are needed.
1.8.2 Internal conditioning

It involves the removal of scale forming substance, which were not completely
removed in the external treatment, by adding chemicals directly into the boiler. These
chemicals are also called boiler compounds.
39
1.8.2.1 Carbonate Conditioning
Scale formation can be avoided by adding Na2CO3 to the boiler water. It is used only
in low pressure boilers. The scale forming salt like CaSO4 is converted into CaCO3, which
can be removed easily.
CaSO4 + Na2CO3 CaCO3 + Na2SO4
1.8.2.2 Phosphate Conditioning

Scale formation can be avoided by adding sodium phosphate. It is used in high
pressure boilers. The phosphate reacts with Ca2+and Mg2+salts to give soft sludge’s of
calcium & magnesium phosphates.
3CaSO4 + 2Na3PO4 Ca3 (PO4)2 + 3Na2SO4
Generally 3 types of phosphates are employed.
(a) Trisodium phosphate – Na3PO4 (Too alkaline) – Used for too acidic water.
(b) Disodium hydrogen phosphate – Na2HPO4 (Weakly alkaline) – Used for
weakly acidic water.
(c) Sodium dihydrogen phosphate – NaH2PO4 (Acidic) – Used for alkaline water.
1.8.2.3 Calgon Conditioning

Calgon is sodium hexameta phosphate Na2 [Na4(PO3)6]. This substance interacts with
calcium ions forming a highly soluble complex and thus prevents the precipitation of scale
forming salt.
2CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2Na2SO4
The complex Na2 [Ca2(PO3)6] is soluble in water and there is no problem of sludge
disposal.
40
1.9 TREATMENT OF WATER FOR DOMESTIC SUPPLY
Rivers and lakes are the most common source of water used by municipalities. These
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 process.
Sources of water Screening Aeration
Filteration Coagulation Sedimentation
Sterilisation
(or)
Disinfection
i. Screening
It is a process of removing the floating materials like leaves, wood pieces, etc. from
water. The raw water is allowed to pass through a screen, having large no of holes, which
retains the floating materials and allow the water to pass.
ii. Aeration
The process of mixing water with air is known as aeration. The main purpose of
aeration is to remove gasses like CO2, H2S, and other volatile impurities causing bad taste
and odour to water and remove ferrous and manganous salts as insoluble ferric and
manganic salts.
41
iii. 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.
iv. Coagulation
Finely divided clay, silica, etc 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 hydrolyzed to form a gelatinous
precipitate of Al (OH)3. The gelatinous precipitate of Al (OH)3 entraps the finely divided
clay and colloidal impurities, settles to the bottom and can be removed easily.
v. Filtration
It is the process of removing bacteria, colour, taste, odour and suspend particles by
passing the water through filter beds containing fine sand, coarse sand and gravel.
The sand filter consists of a tank containing a thick top layer of fine sand followed by
coarse 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 clogging of filtration becomes very slow, the filtration is stopped and the thick top
layer of fine sand is scrapped off and replaced with clean sand. Bacteria are also partly
removed by this process.
42
Water
Fine sand
Coarse sand
Fine gravel
Coarse gravel
Water outlet
1.4 Sand filter
vi. Sterilization (Or) Disinfection

The process of destroying the harmful bacterias is known as sterilization or
disinfection. The chemical used for this purpose is called as disinfectants. This process can
be carried over by the following methods
1.By Boiling
When water is boiled for 10-15 minutes all the harmful bacteria are killed and water
becomes safe for use
Disadvantages
1. Boiling alters the taste of drinking water
2. It is impossible to employ it in municipal water works.
43
2. By Using Ozone
Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly
unstable and break down to give nascent oxygen.
O3  O2 + [O]
The nascent oxygen is a powerful oxidizing agent and kills the bacteria.
Disadvantages
1. This process is costly and cannot be used in large scale
2. Ozone is unstable and cannot be stored for long time
3. By Using Ultra Violet Radiations

UV rays are produced by passing electric current through mercury vapour lamp. This
is particularly useful for sterilizing water in swimming pool.
Disadvantages
1. It is costly
2. Turbid water cannot be treated.
4. By Chlorination
The process of adding chlorine to water is called chlorination. Chlorination can be
done by the following methods.
a) By Adding Chlorine Gas

Chlorine gas can be bubbled in water and it is a very good disinfectant.
44
b) By Adding Chloramine
When chlorine and ammonia are mixed in the ratio 2:1, a compound chloramine is
formed.
Cl2 + NH3  ClNH2 + HCl
When chloramine is added to water it decomposes slowly to give chlorine. It is a better
disinfectant than chlorine.
c) By Adding Bleaching Powder

When bleaching powder is added to water, it produces hypochlorous acid (HOCl).
HOCl is a powerful germicide.
CaOCl2 + H2O  Ca (OH)2 + Cl2
Bleaching powder
Cl2 + H2O  HCl + HOCl
Hypochlorous acid
HOCl + Bacterias  Bacterias are killed
1.9.1Break Point Chlorination

Water contains the following impurities
i) Bacteria’s
ii) Organic impurities
iii) Reduction substances (Fe2+, H2S, etc.)
iv) Free ammonia
Chlorine may be added to water directly as a gas or in the form of bleaching powder.
When chlorine is a applied to water, the result obtained can be depicted graphically as
given below. The graph shows the relationship between the amount of the chlorine added
to water and the residual chlorine.
45
It is seen from the graph that initially the applied chlorine is used to kill the bacteria
and it oxidises all the reducing substances present in the water and there is no free
residual chlorine.
As the amount of applied chlorine increases, the amount of combined residual
chlorine also increases. This is due to the formation of chloramines and other
chlorocompounds.
At one point, on further chlorination the oxidation of chloramines and other impurities
starts and there is a fall in the combined chlorine content. Thus the combined residual
chlorine decreases to a minimum point at which oxidation of chloramines and other
impurities complete and free residual chlorine begins to appear, this minimum point is
known as ”break point chlorination”.
Formation of Destruction
chloramines& of Free residual
chloro chloramine chlorine
Kill the bacteria, and oxidation of
reducing compounds by chlorine
compounds &chloro
compounds
Residual chlorine
Applied chlorine
Figure 1.5 Break point chlorination
Thus the break point chlorination eliminates the bacterias, reducing substances, organic
substances responsible for the bad taste and odour, from the water. 46
1.10. 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. The driving force in this phenomenon is
called osmotic pressure.
Figure 1.6 Reverse Osmosis

If a hydrostatic pressure, in excess of osmotic pressure supplied on the higher
concentration side, the solvent flow is reversed i.e., solvent flows from higher
concentration side to lower concentration side. This process is called reverse osmosis.
Thus, in the process of reverse osmosis pure water is separated from salt water. This
process is also known as super – filtration. The membranes used are acetate, cellulose
butyrate, etc.
Advantages:
1. The life time of the membrane is high, and it can be replaced within few minutes.
2. It removes ionic as well as non – ionic, colloidal impurities.
3. Due to low capital cost, simplicity, low operating, this process is used for converting
sea water into drinking water.
47
IMPORTANT QUESTIONS
1. Explain how sterilization of water carried out using chlorine? Give the mechanism.
2. (i) What is meant by carbonate and non-carbonate hardness of water ?Explain with
example
(ii) What is break-point chlorination? State its significance
3. Write a detailed procedure for the determination of various forms of alkalinity.
4. (i) Define the term desalination with a neat diagram, describe desalination by
reserve osmosis’ method.
(ii) What are coagulants? Write the mechanism of coagulation process with suitable
example.
5. What are the boiler troubles? How are they caused? Suggest steps to minimize the
boiler troubles.
6. What is desalination? How is this achieved by reverse osmosis?
Explain break point chlorination, State its significant.
7. Compare the zeolite process with ion-exchange process in water softening. How will
you regenerate the used up reagents.
8. (i) How is the hardness of water determined by EDTA method
(ii) Describe briefly the different steps in the purification of water for drinking
purposes. What is the usage of breakpoint chlorination? (or) Out line the various
stages of domestic water treatment in sequence.
9. What is meant by sterilization of water? What are the chemicals that are normally
used for this purpose? Explain break-point chlorination.
(i) Distinguish between softwater and demineralized water.
(ii) How do you estate the total hardness of water by EDTA method? Explain.
10. Explain how sterilization of water carried out using chlorine? Give the mechanism.
48
11. Explain with a neat sketch the various steps in the treatment of water for municipal
supply.
12. What is the principle of EDTA method? Describe the estimation of hardness by
EDTA method.
(or)
Explain the principle and procedure involved in the determination of permanent and
temporary hardness by EDTA method.
13. Describe de-mineralisation process of water softening. Explain the reaction involved.
14. What is potable water? What are the steps taken to obtain pure drinking?
15. How is water disinfected by chlorine.
16. Describe the principle and method involved in the determination of different types
and amount of alkalinity of water.
17. 0.28 gm of CaCO3 was dissolved in HCl and the solution made upto one litre with
distilled water. 100 ml of the above solution required 28 ml of EDTA solution on
titration.100 ml of hardwater sample required 33 ml of same EDTA solution on
titration. 100 ml of this water, after boiling cooling and filtering required 10 ml of
EDTA solution on titration. Calculate the temporary and permanent hardness of
water.
18. Explain the various steps involved in the domestic water treatment.
19. How is the exhausted resin regenerated in an ion-exchanger? What are the merits
and demerits of ion-exchange method?
20. What are the requisites of water for municipal supply. How is raw water treated for
domestic purpose.
21. Discuss the causes and prevention of priming and foaming.
22. What is the principle of reverse osmosis. How is it used for desalination process.
23. Discuss desalination by reverse osmosis process.
24. Explain
(i) Phosphate conditioning. 49
(ii) Sedimentation with coagulation.
25. What is desalination. Name the different methods of desalination. Explain any one in
detail.
26. What is caustic embrittlement. How can it be prevented.
27. What are scales and sludges. Describe the disadvantages of scale and sludge
formation.
28. What are the problems one would face when hard water is used in boiler industries.
Question Bank
1. Define hard water and soft water.

Water, which does not produce lather with soap solution, but produce white
precipitate (scum), is called hard water.
Water which produce lather readily with soap solution is called soft water.
2. Define hardness of water.

Hardness is the property or characteristics of water which does not produce lather
with soap.
Hardness can be detected by treating water with soap.
2C17H35COONa + CaCl2  (C17H35COO)2 Ca + 2NaCl
Soap Hardness causing substance Hard soap
3. Distinguish between carbonate hardness (CH) and non-carbonate hardness (NCH).

S.NO Carbonate hardness (or) Non-carbonate hardness(or)
Temporary hardness permanent hardness
1 It is due to the presence of It is due to chlorides and
bicarbonates of calcium and sulphates of calcium and 50
magnesium. magnesium.
2 It can be removed by boiling It cannot be removed by
the water. boiling the water
3 It is also called as alkaline It is also called as non-alkaline
hardness. hardness.
4. How is the hardness of water expressed? (or) bring out the significance of calcium
carbonate equivalents?
The concentration of hardness producing salts are usually expressed interms of an
equivalent amount of CaCO3.
Significance: Its molecular weight is a whole number and it is the most insoluble
salt.of the concentration of hardness producing salt is X mgs/lit, then
Amount equivalent to
X x molecular weight of CaCO3
CaCO3 = --------------------------------------------------------------
Molecular weight of hardness producing substances
5. Write the units of hardness (or) bring out the relationship between ppm and mg/lit.
(i) parts per million (ppm) : it is defined as the no of parts of CaCO3 equivalent
hardness per 106 parts of water.
(ii) milligrams per litre(mg/lit) : it is defined as the no of milligrams of CaCO3
equivalent hardness per 1 litre of water.
(iii) clarke’s degree (°Cl) : it is defined as the no of parts of CaCO3 equivalent hardness
per 70,000 parts of water.
(iv) French Degree (°Fr) : It is defined as the number of parts of CaCO3 equivalent
hardness per 105 parts of water.
Relationship between ppm and mg/lit:
1 mg/lit= 1 mg of CaCO3 equivalent in 106 parts of water
= 1 part of CaCO3 equivalent hardness in 106 parts of water.
51
= 1 ppm.
6. A water sample contains 73 mg of Mg (HCO3)2 per litre. Calculate the hardness

interms of CaCO3 equivalents.
Given : Amount of Mg (HCO3)2 = 73 mg/lit
Mol. Wt. of Mg (HCO3)2 = 146
Amount equivalent to CaCO3 = = 50 mgs/lit
7. How does Eriochromo-Black-T indicator function as an indicator in EDTA titration?

Why NH4Cl-NH4OH buffer is used in EDTA titration.
This complexation is possible only at pH = 8-10, that can be maintained by this buffer.
8. What is meant by permanent hardness of water?mention the salts responsible for

the permanent hardness of water.
This is due to the presence of chloride and sulphates of calcium and magnesium.
CaCl2, CaSO4, MgCl2 and MgSO4 are responsible for permanent hardness of water.
9. Draw the structure of EDTA. What happens when EDTA is added to hard water ?
HOOCH2C CH2COOH
N - CH2 - CH2 - N
HOOCH2C CH2COOH
When EDTA is added to hardwater, it forms stable complex with hardness producing ions
like Ca and Mg the pH range = 8 -10
[Ca++, Mg++] + EDTA ------------ [ Ca, Mg EDTA] complex
10. Why is water softened before using in boiler ?
52
If hard water obtained from natural sources is fed directly to the boilers, the following
troubles may arise.
1. Scale and sludge formation
2. Priming and foaming (carry over)
3. Caustic embrittlement
4. Boiler corrosion.
11. What are scales and sludges ?

1. Scales
Scale forms hard and adherent coating on the inner walls of the boiler, it is called scale.
Scales are formed by the substances like Ca (HCO3)2, CaSO4 and MgCl2.
2. Sludge
If the precipitate is loose and slimy it is called sludge. Sludges are formed by
substances like MgCl2, MgCO3, MgSO4 and CaCl2. They have greater solubilities in hot
water than cold water.
12. What is meant by priming and foaming? How can they be prevented?
Priming is the process of production of wet steam. Priming can keep prevented by
controlling the velocity of steam and keeping the water level lower.
Foaming is the formation of stable bubbles above the surface of water. Foaming can be
prevented by adding coagulants like sodium aluminate and antifoaming agents like
synthetic polyamides.
13. What is meant by caustic embrittlement? How is it prevented?

Caustic embrittlement means intercrystalline cracking of boiler metal.
Prevention
Caustic embrittlement can be prevented by
53
(i) Using sodium phosphate as softening agent instead of sodium carbonate
(ii) By adding tannin, lignin to the boiler water, which blocks the hair cracks
14. How does boiler corrosion arise?
Boiler corrosion arise due to the presence of
(i) Dissolved oxygen
(ii) Dissolved carbon dioxide
(iii) Dissolved salts
15. What are the requirements of drinking and boiler feed water?
(i) Boiler feed water Must have zero hardness and free from dissolved gases like
O2, CO2.
(ii) Drinking water (i) pH of water should be in the range of 7.0 – 8.5.
(ii) Total hardness and dissolved solids of water should be
less than 500 ppm
16. What are the advantages of ion-exchange process.

(i) Highly acidic or alkaline water can be treated by this process.
(ii) The water obtained by this process will have very low hardness (nearly 2 ppm).
17. How is exhausted resin regenerated in ion-exchange process?

When the cation exchange resin is exhausted, it can be regenerated by passing a
solution of dil. HCl or H2SO4.
RCa + 2HCl --- RH2 + CaCl2
RNa + HCl --- RH + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated by
passing a solution of dil. NaOH.
R’Cl2 + 2NaOH --- R’(OH)2 + 2NaCl
18. Give some examples for cation exchange resins.

54
(i) Sulphonate coals
(ii) Sulphonate polystyrene
19. Give some example for anion exchange resin.

(i) Cross – linked quaternary ammonium salts
(ii) Urea – formaldehyde resin
20. How is water demineralized in an ion - exchanger?

The water containing ions (both anion and cations) are passed through ion exchange
columns, which absorb all the ions (anions and cations ) as shown below.
Cation exchanger : RH2 + CaCl2 ------ RCa + 2HCl.
Anion exchanger : R(OH)2 + 2HCl ---- R’Cl2 + 2H2O.
21. Write the structure of sand filter.

The sand filter contains a thick top layer of fine sand followed by coarse sand, fine
gravel and coarse gravel.
22. How is boiler corrosion, due to dissolved oxygen, removed? How?

Sodium sulphite, hydrazine are some of the chemicals used for removing
dissolved oxygen from water.
2Na2SO3 + O2 -- 2Na2SO4
N2H4 + O2 -- N2 + 2H2O
23. What is aeration of water? Mention its purpose.

The process of mixing water with air is known as aeration. The main purpose of
aeration is
(i) To remove gases like CO2, H2S and other volatile impurities causing bad taste and
odour to water.
55
(ii) To remove ferrous and manganous salts as insoluble salts as insoluble ferric and
manganic salts.
24. What is carbonate conditioning? For what type of boiler it is used?
Scale formation can be avoided by adding Na2CO3 to the boiler water. It is used only
in low pressure boilers. The scale forming salt like CaSO4 is converted into CaCO3, which
can be removed easily.
CaSO4 + Na2CO3 --- CaCO3 + Na2SO4.
25. Write briefly on disinfection of water by UV treatment.

When the water containing bacteria is irradiated by UV light, all the bacterias are
killed out. This process is known as disinfection. This is useful for sterilizing water in
swimming pool.
26. Write the principle involved in the desalination of water by reverse osmosis.
(Or)
What is meant by ‘reverse osmosis’? How is it applied in the desalination of water?
If the process 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 side. This process is called reverse osmosis.
Salt water is taken as higher concentration and water is taken as solvent of pressure is
applied on the salt water, the water flows from salt water to water side.
27. Define the term break point chlorination. (Or)

What is break point chlorination? Explain
Break point chlorination is the point at which all the impurities are removed and free
chlorine begins to appear.
28. What are the disadvantages of using ozone in disinfection of water?

56
(a) This process is costly and cannot be used in large scale.
(b) Ozone is unstable and cannot be stored for long time.
57
UNIT-II
ELECTROCHEMISTRY
Introduction
Electrochemistry deals with chemical changes produced by an electric current and
the production of electricity by chemical reactions. All electrochemical reactions involve
transfer of electrons and are redox reactions. Electrochemistry is a branch of physical
chemistry, which deals with the relationship between chemical energy and electrical
energy. Electrochemistry is the basis for batteries, cells, corrosion and its prevention,
metal coatings, etc. And holds a central position in the study of chemistry for a number of
reasons:
(i) It acts as a bridge between thermodynamics and the rest of the chemistry because
it provides techniques both for measuring the thermo dynamical state functions
and for predicting equilibrium concentrations of dissolving and reacting ions.
(ii) It is of enormous commercial importance because of the costly destruction caused
by corrosion and the exciting possibilities of fuel cells which generate electricity
directly from fuel.
From the above valid reasons, the subject electrochemistry consists of major
technological importance.
58
2.1. Basic Definitions:
2.1.1 Conductors
Conductors are the substances or materials, which allow electric current to pass through
them.
Examples: all metals, graphite, fused salts, aqueous solutions of acids, bases and salts.
2.1.2 Non-conductors or Insulator

Non-conductors or Insulators are substances, which do not conduct electric current
through them.
Examples: Wood, rubber.CCl4
2.1.3 Conductors are classified into two types namely:

(i) Metallic conductors
(ii) Electrolytic conductors.
Metallic conductors are the substances, which conduct electricity, but are not
decomposed by the process. Conduction takes place by the transference of electrons. No
chemical change takes place in the conductor during electrical conduction. As the
temperature increases, the conducting power of a conductor generally decreases.
Examples: All metals, graphite.
Electrolytic conductors are the substances, which conduct electricity, but

decomposition of electrolyte takes place during the process. Conduction takes place by the
movement of ions in solution or in fused electrolyte. Chemical change takes place in the
conductor/electrolytic solution during electrical conduction. As the temperature
increases, the conducting power of a conductor/electrolyte also generally increases.
Examples: Acids, bases and electrovalent salts.
59
Table 2.1 Differences between metallic conduction and electrolytic conduction
S.No Metallic conduction Electrolytic conduction
1 It involves the flow of electrons in It involves the movement of ions in a
a conductor solution.
2 It does not involve any transfer of It involves transfer of electrolyte in the
matter. form of ions.
3 Conduction decreases with Conduction increases with increase in
increase in temperature. temperature.
4 No change in chemical properties Chemical reactions occur at the two
of the conductor. electrodes.
2.1.4. Electrical Conductance

The unit of electrical current is ampere. The unit of quantity of electricity is
coulomb. When one ampere (I)of current is passed for one second(t), then the quantity of
current passed is one coulomb(Q).
(i.e.,) Q = I x t Coulomb
Ohm’s law:
This law can be stated as, at constant temperature, the strength of the current
flowing through a conductor is directly proportional to the potential difference and
inversely proportional to the resistance(R) of the conductor.
V
I  , V  RI , V = volt I  ampere , R = ohm
R
Specific resistance:
The resistance (R) ohms offered by the material of the conductor to the flow of
current through it is directly proportional to its length (l) and inversely proportional to the
area of cross section (a) of the conductor. Thus,
60
l
R 
a
ρ called the specific resistance and it is resistance in ohms which one meter cube of
material offers to the passage of electricity through it, Unit of specific resistance is ohm-
meter.
Specific conductance:
The reciprocal of specific resistance is called as specific conductance (or) specific
conductivity (k) [k is called ‘kappa’].k is defined as the conductance of one meter cube of
an electrolyte Solution
1 1 l 1 l
k   . k  .
 R a R a
Unit of specific conductance is ohm-1 m-1 (or) mho.m-1

Since ohm-1 = mho
1 cm
k = .
Ohm cm 2
k = Ohm-1.cm-1
Also, 1 siemen = 1 mho.
k is also expressed as S.m-1.
Equivalent conductance:
Equivalent conductance (  C) is defined as the conductance of an electrolyte
solution containing one gram equivalent of the electrolyte. It is equal to the product of
specific conductance (k) of the electrolytic solution and the volume (V) of the solution that
contains one gram equivalent of the electrolyte.
c  k  V
In general if an electrolyte solution contains C gram-equivalents in1, 000 cc of the

61
(C is concentration of solution in normality )solution the volume of the solution containing
1 gram equivalent will be
1000
c  k  mho.m2.(gram.equiv) -1
c
c values depend on the type of the electrolyte, concentration of the solution and
temperature.
2.2 Kohlraush’s Law

This law states that, ‘‘at infinite dilution wherein the ionisation of all electrolytes is
complete, each ion migrates independently and contributes a definite value to the total
equivalent conductance of the electrolyte’’. Consider an electrolyte AB in aqueous
solution. It dissociates as
Am Bn mAn+ + nBm-
     
 and  are the cationic and anionic equivalent conductance at infinite
dilutions and n+ and m– correspond the valency of cations and anions furnished by each
molecule of the electrolyte
  , NaCl =   Na+ +   Cl–
  , BaCl2 = 1/2   Ba2+ +   Cl–
  , AlCl3 = 1/3   Al3+ +   Cl–
For weak electrolytes,
  , CH3COOH =   H+ +   – CH3COO–
  , NH4OH =   NH4+ +   – OH–
62
Application of Kohlraush’s law:
The important use of Kohlraush’s law is to deduce the   values of weak
electrolytes correctly by arithmetically combining the   values of strong electrolytes in
appropriate manner.
For example
  of CH3COOH, which is a weak electrolyte, is deduced from   values of NaCl,
HCl, and CH3COONa in such a manner that   of CH3COOH is obtained. Sodium acetate
(CH3COONa) is a strong electrolyte and it ionises to acetate (CH3COO–) and sodium (Na+)
ions at all concentrations in water. Applying Kohlraush’s law,
  CH3COONa +   HCl –   NaCl =   CH3COOH
This method produces agreeable values of   for weak electrolytes. Similarly  
NH4OH can be deduced as,
  NH4OH =   NH4Cl +   NaOH –   NaCl
Example 1 :The equivalent conductances at infinite dilution of HCl, CH3 COONa and
NaCl are 426.16,91.0 and 126.45 ohm–1 cm2 gm.equiv-1 respectively. Calculate the   of
acetic acid.
  CH3COOH =   CH3COONa +   HCl -   NaCl

= 426.16 + 91.0 – 126.45
  CH3COOH = 391.16 ohm–1 cm2 gm.equiv-1
63
2.3 Conduct metric Titration
This method of estimation is applicable to any titration in which there is a sharp
change in conductance at the end point .The principle involved in these titrations is that
electrical conductance depends upon the number and mobility of the ions. In these
titrations it is a necessary to observe the following.
1. To keep the temperature constant throughout the experiment.
2. The titrant solution should be 10 times stronger than the solution to be titrated so
that the volume change is as little as possible.
Conductance is followed during the course of titration and the values are plotted
against volume of the titrant added. Conductrometric curves should be straight line or
nearly straight lines and only few readings on each sides of the end point are required
.The end point of titration is the point of intersection of the two straight lines.
2.3.1. Titration of a strong acid against a strong base (HCl Vs NaOH)

Consider the titration of a strong acid (say, HCl) with a strong base(NaOH). A
definite volume of the acid is pipetted out in to the conductivity cell or in to a beaker
where the conductivity cell is dipping and the alkali is taken in the burette.
At the beginning of the titration the conductance of the HCl acid solution is due to
the H+ and Cl - .As alkali is added gradually from the burette, fast moving H+ ions are
replaced by slow moving sodium ions and the reaction is.
H+ + Cl – + [Na++OH-] Na+ + Cl- + H2O
Hence on continuous addition of sodium hydroxide, the conductance goes on

decreasing till the neutralization of acid is completed. After the neutralization, further
addition of alkali results in the increase in conductance of the solution in the cell.The
64
points will lie on two straight lines as in figure (A).The point of intersection of these two
straight lines AB and CD gives the volume of alkali required for the neutralization
Conductance (ohm-1)
D
B
C
| l
Volume of NaOH
2.3.2. Titration of a weak acid against a strong base (CH3COOH Vs NaOH)

Consider the titration of a weak acid acetic acid against a strong alkali, sodium
hydroxide. At the beginning of the titration the conductance of the solution will be very
low because acetic acid is a weak electrolytes and is feebly ionized. When a small quantity
of NaOH is added from the burette to acetic acid, the conductance will increases due to
the formation of highly ionized sodium acetate.
A
CH3COOH + [Na++OH-] CH3COO-+ Na+ + H2O
After the completion of neutralization of the acid, any further addition of alkali will
show a sharp increase in conductance due to the sodium and the fast moving hydroxide
ions. The plot of conductivity against volume of alkali added is shown in the figure (B).the
point of intersection straight lines gives the end point
65
D
Conductance (ohm-1)
C
l
B
l
A
l
Volume of NaOH
Fig 2.2
2.3.3 Titration of a mixture of acids (CH3COOH + HCl) against a strong base (NaOH)
(CH3COOH + HCl ) Vs NaOH
When a mixture of acetic acid and hydrochloric acid is titrated against sodium
hydroxide, usually a combination of figures (2.1 &2.2) will be obtained. It is as shown in
the figure 2.3. In these titrations the strong acid (HCl) will get titrated first and the titration
of the weak acid (CH3COOH) will commence only after the complete neutralization of the
strong acid. It is evident from the figure 2.3 , that the first end point corresponds to the
neutralization of HCI, the second end point corresponds to the neutralization of acetic
acid.
Conductance (ohm-1)
A
D
C l
l l
l l
Volume of NaOH
Fig 2.3 66
2.3.4 Precipitation titration (BaCl2 Vs Na2SO4)
Let us now see how the conductance varies during the course of titration of barium
chloride against sodium sulphate. Here BaSO4 gets precipitated; while chloride ions
remain unchanged.
[Ba2++2Cl-]+[2 Na+ + SO42-] BaSO4 +2 Na+ +2Cl-
As a result of addition of Na2SO4 Solution to BaCl2 solution, Ba2+ ions in solution

are replaced by free Na+ ions. Since the mobility of Na+ ions is less than that of Ba2+ ions,
so the conductance of resulting solution falls. However, if the addition of Na2SO4 Solution
is continued beyond the equivalence point, the conductance value starts increasing, due to
the rise in total concentration of free ions in solution,i.e., there will now be increase in free
Na+ and SO42- ions, in addition to the Na+ and Cl-ions already present. This is shown in
fig.2.4
A D
Conductance (mho-1)
Volume of Na2SO4
Fig 2.4
Advantages of conductometirc titration

1) No special care is necessary near the end point it is ascertained graphically.
2) Colored solution which cannot be titrated by ordinary volumetric methods with the
help of indicators can be titrated.
67
3) The titrations of weak bases can be performed conductometrically .These are not
possible in conventional volumetric titrations because they do not produce sharp
change in the colour of indicator
4) Very dilute solutions can be titrated
5) It gives more accurate end point
6) No indicator is required
2.4 Cell Terminology

i) Current
Current is the flow of electrons through a wire or any conductor.
ii) Electrode
Electrode is a material or metallic rod/bar/strip which conducts electrons.
iii) Anode
Electrode where oxidation occurs.
iv) Cathode
Electrode where reduction occurs.
v) Electrolyte
Electrolyte is a water soluble substance forming ions in solution and conduct an
electric current
vi) Anode Compartment
Anode Compartment is the compartment of the cell in which oxidation half-
reaction occurs. It contains the anode.
vii) Cathode Compartment
Cathode Compartment is the compartment of the cell in which reduction half-
reaction occurs. It contains the cathode.
68
viii) Half-cell
Half-cell is a part of cell, containing an electrode dipped in an electrolyte solution.
If oxidation occurs at the electrode that is called oxidation half cell. If reduction occurs at
the electrode, that is called reduction half cell.
ix) The salt bridge
It allows charge transfer through the solutions but prevents mixing of the
solutions.
Single Electrode Potential (E)

It is the measure of tendency of a metallic electrode to lose electrons or gain
electrons when it is in contact with a solution of its own salt.
Standard Electrode Potential (E0)

It is the measure of tendency of a metallic electrode to lose or gain electrons when
it is in contact with a solution of its own salt at standard conditions (solution
concentration:1 M, Temp: 25 0C and Pressure:1 atm)
2.5 Nernst equation – Expression for electrode potential

Consider a general redox reaction,
Mn+ + ne- M
An electrode potential forms between the metal and the solution of its own ions of
valency ‘n’.The electrical energy required to transfer 1g equivalent of metal ion from the
metal to the solution would be ‘nFE’, where F is 1 Faraday and E is the electrode potential.
The decrease in free energy namely
-G would be equal to the electrical energy released namely nFE.
-G = nFE ---------- (1)
According to Van’t Hoff reaction isotherm, at equilibrium this free energy change
in terms of concentrations is given by, 69
[Pr oduct ]
G = G 0  2.303 RT log ---------- (2)
[Re ac tan t ]
Substituting equation (1) in equation (2), we get,
[M ]
 nFE =  nFE 0  2.303 RT log ---------- (3)
[ Mn  ]
Dividing Equation (3) both sides by – nF,
E = E0 
2.302 RT
log
M 
nF [ Mn  ]
2.302 RT 1
E = E0  log
nF [ Mn  ]
(as activity or concentration of metal=1 at all temperatures) [M]= 1
E = E0 
2.302 RT
nF
log Mn   
This expression is known as Nernst’s equation for electrode potential. Since R=8.314
J/K/mole; F= 96,500 Coulombs; T= 25 0 C+273 = 298K ; then, Nernst equation at 250C is
E = E0 
0.0591
n

log Mn  
Nernst equation for reversible electrochemical cell.
E = E0 
0.0591
log
Pr oduct 
nF [Re ac tan t ]
Where E0 is standard electrode potential and

n is number of electrons transferred
70
Problems based on Nernst equation.
1) Calculate the reduction potential of the Cu/Cu2+(0.5M) at 25 0C . E0 Cu2+ / Cu =
0.34V
Given:
E 0  0.34V ; [Cu2+] =0.5M; n =2;
Solution
Electrode reaction Cu2+ +2e Cu
E red = E0 
0.0591
log
Pr oduct 
n Re ac tan t 
E0 
0.0591 Cu 
E red =
n
log

Cu 2  
E red = 0.34 
0.0591
log
1
n 0.5 
0.0591
E red = 0.34  log 2
n
0.0591  0.3010
E red = 0.34 
2
E red = 0.34  0.0089
E red = 0.3311V
2) Find the oxidation potential of Zn/Zn2+ = 0.2 M electrode at 25 0C .Standard

oxidation potential of of Zn/Zn2+ is 0.76V.
Given:
E 0  0.76V ; [Zn2+] =0.2M; n =2;
Solution
Electrode reaction: Zn Zn2 +2e
E oxd = E0 
0.0591
log
Pr oduct 
0.0591 0.2
E oxd = 0.76  log
n 1 71
0.0591 0. 2
E oxd = 0.76  log
2 1
0.0591 1
E oxd = 0.76  log
2 0.2
0.0591
E oxd = 0.76  log 5
2
E oxd = 0.76  0.02955  0.6990V
E oxd = 0.76  0.0206V
E oxd = 0.7806V
3) Calculate the electrode potential of Zinc electrode dipped in 0.1 M ZnSO4 solution
at 250C .
Given:
Concentration of ZnSO4 = 0.1M ; n = 2 ; E 0Zn / Zn2+ = - 0.76V
Solution
Electrode reaction: Zn2+ + 2e Zn
E = E0 
0.0591
log
Pr oduct 
0.0591 Zn 
E =  0.76 
n
log

Zn 2  
0.0591 1
E =  0.76  log
n 0.1
0.0591
E =  0.76  log 0.1
2
E = 0.76  0.02955 1
E = 0.76  0.02955 V
E = 0.7896V
72
4) Calculate the standard e.m.f. of the cell : Cd, Cd2+||Cu2+,Cu and determine the
cell reaction. The standard reduction potentials ofCu2+, Cu and Cd2+, Cd are
0.34V and –0.40 volts respectively. Write the cell reaction and predict the
feasibility of the cell reaction.
Solution.
0
E Cell = E0right – E0 left
0
E Cell = [Std. reduction potential of Cu2+, Cu]
– [Std. reduction potentials of Cd2+, Cd]

0
E Cell = E0Cu2+,Cu – E0Cd2+,Cd
0
E Cell = 0.34 V – (– 0.4 V)
0
E Cell = + 0.74 Volts.
Left hand electrode (oxidation half cell) reaction is

Cd(s) Cd2+ + 2e
Right hand electrode (reduction half cell) reaction is
Cu2+ + 2e Cu(s)
The cell reaction is
Cd(s) + Cu2+ (aq) Cd2+(aq) + Cu(s)
E0cell is positive.  The cell reaction is feasible.
5) Calculate the standard free energy of the cell reaction is the following cell at
250C Zn, Zn2+ Ni2+, Ni. The standard reduction potentials of Zn2+, Zn and
Ni2+, Ni half cells are – 0.76 V and – 0.25 V respectively.

Solution
0
E Cell = E0Right – E0Left = – 0.25 – (– 0.76)
0
E Cell = + 0.51 V
0
E Cell is + ve. G 0 = – ve
73
G 0 = – nFE0cell
n = 2 electrons
G 0 = –2 x 96495 x 0.51
= –97460 Joules
G 0 = – 97.46 kJ.
6) What is the potential of a half-cell consisting of zinc electrode in 0.01 M ZnSO4

solution 25 0C. E0 = 0.763 V.
7) Calculate the emf of the cell.
Zn | Zn2+ (0.001 M) || Ag+ (0.1 M) | Ag
The standard potential of Ag/Ag+ half-cell is + 0.80 V and Zn/Zn2+ is – 0.76 V.
8) Calculate the equilibrium constant for the reaction between silver nitrate and
metallic zinc.
Solution:
Cell construction: Zn /Zn2+ / / Ag+ / Ag
Step 1 : Write the equation for the reaction
2Ag+ + Zn → Zn2+ + 2Ag E0cell = 1.56 V
Step 2 : Substitute values in the Nernst equation at equilibrium
0.0591
E Cell = E0  log K
n
At the Eqm, E Cell =0, Where K = Equilibrium Constant
0 0.0591
0 = E Cell  log K
n
0.0591 0
 log K = E Cell
n
0
nE Cell
log K =
0.0591
2  1.56
log K =
0.0591
74
log K = 53
K = 1053
9. Calculate the E.M.F. of the zinc - silver cell Z n Zn 2  Ag  Ag at 25oC when
[Zn2+] = 0.10 M and [Ag+] = 10 M. (E0cell at 25 oC = 1.56 volt]

Solution:
LHSE : oxdn Zn → Zn 2  + 2e-
RHSE : redn 2 Ag   2e  → 2 Ag
__________________________________
Overall Cell reaction 2Ag+ + Zn → 2Ag + Zn2+

__________________________________
n=2
0.0591
E Cell = E0  log K
n
E Cell = E0 
0.0591
log
Ag 2 Zn 2   [Zn]=1, [Ag]=1
n Ag 2 Zn 
E Cell = 1.56 
0.0591
log
1 0.1
2
2 10 2 1
0.0591 0. 1
E Cell = 1.56  log
2 [ 10 ] 2
E Cell = 1.56  0.02955 log 10 3
E Cell = 1.56  0.02955   3 
E Cell = 1.56  0.08865
E Cell = 1.6487V
75
10) Calculate the potential of the following cell at 298 K Zn/Zn2+ (a = 0.1) // Cu2+ (a
= 0.01) / Cu, E 0Zn 2  Zn
0
= – 0.762 V E Cu 2
Cu
= + 0.337 V Compare the free energy
change for this cell with the free energy of the cell in the standard state.
Solution:
The overall cell reaction is
Zn + Cu2+ (a = 0.01) Zn2+ (a = 0.1) + Cu
E0cell = ERight - ELeft
E0cell = 0.337 – (- 0.76)
E0cell = 1.099 V
The cell potential given by nernst equation
Ecell = E0 
0.0591 
Cu  Zn 2  
n
log

Cu 2  Zn  
0.0591 1  0.1
Ecell = 1.099  log
2 0.01  1
0.0591 0.1
Ecell = 1.099  log
2 0.01
Ecell = 1.099  0.02955
Ecell = 1.0694V
The free energy change  G is given by  G = – nFE

G = – 2 x 1.0694 x 96495
G = – 206.4 kJ mol-1
The standard free energy change :
 G0 = – 2 x 1.099 x 96495
 G0 = –212.1 kJ mol-1.
76
2.6 Types of Electrodes:
Some common types of reversible electrodes
1) Metal-Metal ion electrodes
An electrode of this type consist of a metal rod dipping in a solution containing its
own ions, Example, zinc rod dipping in zinc sulphate solution.
Representation: Zn/Zn2+
Reaction: Zn2+ + 2e- Zn
2) Gas electrodes: (Hydrogen electrode)

Hydrogen gas bubbling in a solution of an acid (say HCl) forms an electrode of this
type.
Representation: Pt, H2(gas)/H+(aq)
Reaction: H+(aq) +e- 1/2 H2(gas)
3) Metal-Insoluble metal salt Electrodes

These electrodes consist of a metal and a sparingly salt of the same metal dipping
in a solution of a soluble salt having the same anion. an important electrode of this
type is the calomel electrode.
Representation: Hg, Hg2Cl2(s); KCl
Reaction: Hg2Cl2 + 2e- 2Hg(l) + Cl-(aq)
4) Oxidation – reduction electrodes

A typical example of re-dox electrode is platinum wire immersed in an aqueous
solution containing a mixture of ferrous and ferric ions,
Representation: Pt /Fe2+,Fe3+
Reaction: Fe3+ + e- Fe2+
77
2.6.1 Metal –metal ion electrodes
A metal (in the form of a rod ,strip or wire) in contact with it own ions in an
aqueous salt solution constitutes a metal –metal ion electrode represented M / Mn+ .
Reactivity of metal should be intermediate otherwise the reactive metal will reactive with
water and cannot function as electrodes.
Example of metal-metal ion electrodes : Cu/Cu2+ and Zn/Zn2+
2.7. Reference electrodes or Standard electrodes:

It is the electrode of standard potential with which we can compare the potential of
other electrodes. Standard Hydrogen Electrode (SHE) is the best reference electrode,
whose electrode potential at all temperature is taken as zero
2.7.1 Primary reference electrode :( Standard Hydrogen Electrode)

Cell representation:
Pt|H2( 1 atm)|H+(1M); (E° = 0 V)
Cell construction:
Hydrogen electrode consists of a small platinum foil(0.5cm x 0.5cm) .that is
connected to a platinum wire and sealed in a glass tube. Hydrogen gas passed through the
side arm of the glass tube. This electrode, when dipped in a1N HCl and hydrogen gas at 1
atmoshspheric pressure is maintained ,forms a normal or standard hydrogen electrode.
0
( SHE) . The emf of this cell has been arbitrarily fixed at zero. (i.e. E SHE  E 0HE  0 )
0 0
 E oxd HE   E oxd HE   0
78
Fig 2.4
Electrode act as anode 1/2 H2(g) → H+(aq) + e 

Electrode act as cathode H+(aq) + e  → 1/2H2(g)
E oxd = E0 
0.0591
log
H  
n H 2 12
0 0.0591 H 
log 2 
1
2
E red = E 
1 H  
H2  2
1
= - 0.0591 log
H  
1
 H 2 
1
2 1 2 1
1
= - 0.0591 log
H  
= 0.0591 log H  
E HE =  0.0591 p H  p H   log( H  )
79
Limitations
i) The potential of the electrode can be altered by changing the barometric pressure.
ii) It requires considerable volume of test solution.
iii) It requires hydrogen gas and is difficult to set up and transport.
2.7.2 Secondary reference electrode :( Insoluble salt anion electrode)

Calomel Electrode
Calomel electrode is an example for secondary reference electrode.
Cell representation:
Hg, Hg2Cl2(s) , KCl (saturated solution)
Fig 2.5
It is a mercury-mercurous chloride electrode. It is made up of a glass tube containing
mercury at the bottom above which mercurous chloride is placed. The rest of the vessel is
filled with KCl solution. The glass tube consists of two side-tubes, one is used to fill the
tube with solutions and the other side-tube is used for making electrical contact with a salt
bridge. The electrode potential depending upon the concentration of KCl solution, the
80
potential of calomel electrode varies. The activity of Cl  ion is inversely proportional to
electrode potential The reduction potentials for different KCl solution concentrations at
25 0C are given below:
Concentration Electrode Potential

of KCl (in Volts)
0.1N 0.3335v
1.0N 0.2810v
Saturated 0.2422v
If the concentration of KCl solution are 0.1N, 1N and saturated, They are called as
decinormal, normal (NCE) and saturated calomel electrodes (SCE).
The reaction taking place in this electrode:
If the electrode acts as anode, the reaction is,
2 Hg(l) + 2 Cl  Hg2 Cl 2 ( s ) +2 e 
If the electrode acts as cathode, the reaction is,

Hg2Cl2 + 2 e  2 Hg(l) + 2 Cl 
The potentiol of the saturated calomel electrode is represented as
E = E0 
0.0591
log
Pr oduct 
E = 0.2422 
0.0591
2
 
log Cl 
2
2.7.3 Measurement of single electrode potential of Zn using saturated calomel

electrode
The saturated calomel electrode is coupled another Zn electrode, the potential of
which is to be determined.
81
The cell constructed is : Zn Zn 2  SCE
E Cell = E SCE  E Zn , Zn 2 
Zn electrode Calomel electrode

Fig 2.6
E Zn , Zn 2  = E Cell  E SCE
Since E SCE is known, measuring the Emf of the cell & Ecell, We can calculate the potential of the
Zn electrode.
2.7.4 Glass Electrode or Internal reference electrode:

Construction
A glass electrode is the ion selective electrode and also an internal reference
electrode. It will be respond only H+ ion in a solution. It consists of thin- walled glass bulb.
The glass is made up of a special type of glass having low melting point and high
electrical conductivity. It contains Ag wire coated with AgCl or a Pt wire in 0.1M HCl.
82
Cell representation: Pt, HCl (0.1M) / Glass
Fig 2.7 Glass electrode
Glass electrode is used as the internal reference electrode, to determine the pH of

solution, especially colored solution containing oxidation or reducing reagent. When two
solutions having different pH value are separated by a thin glass membrane, there
develops a difference of potential between the surface of the membrane .the potential
difference developed is proportional to the difference in pH values. The glass membrane
functions as ion exchange resin and equilibrium is set up between the Na+ ion of glass and
H+ ions in solution. The potential difference varies with the H+ ion concentration, and is
given by the expression, and an
EG = E0G + 0.0591 pH
2.7.5 Determination of pH of a solution using glass electrode:
The glass electrode is placed in the solution under test and coupled with saturated
calomel electrode
The emf of the cell is measured. From the emf, the pH of the solution is calculated
as follows,
83
Fig 2.8
E Cell = E SCE  E GE
E Cell = 
E SCE  E G0  0.0591 pH 
E Cell = 0.2422  E a0  0.0591 pH
0.0591pH = 0.2422  E a0  E cell
0.2422  E a0  E cell
pH =
0.0591
Advantages of glass electrode

1. It can be easily constructed and readily used.
2. The results are accurate.
3. It is not easily poisoned.
4. Equilibrium is readily achieved.
Limitations
Since the resistance is quite high, special electronic potentiometer is employed for
measurement
84
The glass electrode can be used in solutions only with pH range of 0-10. However
above pH 12 (high alkalinity), cations of the solution affect the glass and make the
electrode useless.
2.8 Electrochemical series:

It is a serial arrangement of metallic elements or ions according to their standard
electrode potentials. Electrochemical series is built up by arranging species either in the
decreasing or in the increasing order of their standard electrode potentials.
Standard Reduction Potentials in Aqueous Solution at 250C
1) Li+(aq) + e-  Li(s) - 3.045

2) k+(aq) + e-  k(s) - 2.925
Increasing strength of reducing agents

3) Al3+(aq) + 3e-  Al(s) - 1.66
Increasing strength of oxidizing agents
4) Zn2+(aq) +2 e-  Zn(s) - 0.763

5) Fe2+(aq) +2 e-  Fe(s) - 0.44
6) Cd2+(aq) +2 e-  Cd(s) - 0.40
7) Ni2+(aq) +2 e-  Ni(s) - 0.25
8) sn2+(aq) +2 e-  sn(s) - 0.14
9) 2H+(aq) +2 e-  H2(g) 0.00
10) sn4+(aq) +2 e-  sn2+(s) + 0.15
11) Cu2+(aq) +2 e-  Cu(s) + 0.34
12) Fe3+(aq) + e-  Fe2+(aq) + 0.77
13) Hg2 2+(aq) +2 e-  2Hg(l) +0.78
14) Ag+(aq) + e-  Ag(s) +0.80
15) Au3+ (aq)+ 3e-  Au(s) +1.50
16) MnO4-(aq) + 8 H+(aq) +5 e-  Mn2+(aq)+4H2O(l) +1.52
17) PbO2(s) +SO42-(aq) + 4 H+(aq) +2 e-  PbSO4(s)+2H2O(l) +1.685
18) F2(g) + 2e  2F- (aq) +2.87
85
2.8.1 Application of electro chemical series
1. Calculation of standard emf of a cell
The standard emf of a cell (E°) can be calculated if the standard electrode potential
values are known using the following reaction
E°cell = E°R.H.E – E°L.H.E
2. Relative ease of oxidation or reduction

Higher the value of standard reduction potential (+ve value) greater is the
tendency to get reduced. i.e. elements on the top are more easily reduced
a) Fluorine has higher positive value of standard reduction potential (+2.87 V),
and shows higher tendency towards reduction.
b) Lithium has highest negative value (-3.01 V) and shows higher tendency
towards oxidation
3. Displacement of one element by the other

Element which have higher reduction potentials can be displaced by those
elements which have lower reduction potential,
For example, we may know whether Cu will displace Zn from the solution
or vice-versa. We know that standard reduction potential of Cu & Zn Zn
E°Cu²+|Cu = +0.34 V and E°Zn²+|Zn = -0.76 V.
 Cu will be displaced from it’s salt solution by Zn.
 E Cu  E zn
Zn + CuSO4 ZnSO4 + Cu
Cu + ZnSO4 No reaction
i.e. Cu²+ has a greater tendency to acquire Cu form, than Zn2+ has for
acquiring Zn form.
86
4. Determination of equilibrium constant for the reaction
Standard electrode potential can also be used to determine the equilibrium constant
(K) for an equal reaction. We know that,
 G 0 = RT ln K
 G 0 = 2.303 RT log K
G 0
log K = 
2.303 RT
nFE 0
log K =
2.303 RT
From the value of E°, the equilibrium constant for the cell reaction can be
calculated.
5) Hydrogen displacement behavior

Metals with negative reduction potential will displace the hydrogen from an acid
solution.
Example: Zinc reacts with dil. H2SO4 to give H2 but Ag does not, why?
Zn+H2SO4 ZnSO4 +H2 E°Zn = -0.76 volt
The metal with positive reduction potential will not displace the hydrogen from
an acid solution
Ag+H2SO4 No reaction E°Ag = +0.80 volt
6) Predicting spontaneity of redox reactions

Spontaneity of redox reaction can be predicted from the emf (E°) value of the
complete cell reaction
i) If the E° of the cell is positive, the reaction is spontaneous.
ii) If the E° of the cell is negative, the reaction is not feasible
87
In general, an element having lower reduction potential can displace another metal
having higher potential from its salt solution spontaneously.
Galvanic series:
Oxidation potential of various metals and alloys are measured by immersing them
in sea water using standard calomel electrode as the reference electrode. These values are
arranged in decreasing order of activity and this series is known as the galvanic series.
2.8.2 Significance of galvanic series

This series provides more practical information on the relative corrosion tendency
of different metals and alloys. The speed and severity of corrosion depends on the
difference in potential between the anodic and cathodic metals in contact
88
Difference between Electrochemical series and Galvanic series:
S.No Electrochemical series Galvanic series

1 It gives no information regarding Since alloys are included in this series,
position of alloys. their corrosion can also be studied from
this series.
2 The position of metal in this series is The position of a metal, when present in
permanently fixed. the form of an alloy is different from that
of pure metal.
3 This series comprises of metal and This series comprises of metals and alloys.
non metals.
It predicts the relative displacement It predicts the relative corrosion
4 tendencies. tendencies.
2.9 Types of Cells

1. Electrolytic cell
2. Electrochemical cell
Electrolytic Cell
Electrolytic cells are cells in which electrical energy is used to bring about the
chemical change. Electrolysis is very good example for the electrolytic cell . An electrolytic
cell is an electrochemical cell in which the energy from an applied voltage is used to drive
an otherwise nonspontaneous reaction. Such a cell could be produced by applying a
reverse voltage to a voltaic cell like the Daniell cell.
89
Fig 2.9
If a voltage greater than 1.10 volts is applied as illustrated to a cell under standard
conditions, then the reaction
Cu(s) + Zn2+(aq) Zn(s) + Cu2+(aq)
will be driven by removing Cu from the copper electrode and plating zinc on the zinc
electrode. Electrolytic processes are very important for the preparation of pure substances
like aluminum and chlorine.
2.10 Electrochemical Cell

Electrochemical cell is used to get electrical energy by the expense of redox
reaction. An electrochemical cell is commonly known as Galvanic cell. The electrode
where oxidation takes place is called anode, while the electrode where reduction takes
place is called cathode.
90
2.11.1 Galvanic cell
Galvanic cell is used to convert chemical energy released in a redox reaction into
electrical energy. The electrons transferred in the redox reaction (oxidation and reduction)
are utilized as a source of producing electrical energy.
Construction of Daniel cell

In this cell, a zinc rod is partially immersed in ZnSO4 solution and copper rod is
partially immersed in CuSO4 solution. A salt bridge, to eliminate liquid junction potential,
interconnects the two solutions. The salt bridge provides electrical contact between the
two half-cells. It also helps to maintain electrical neutrality by allowing the migration of
ions. If Zn and Cu rods are connected from outside, electrons flow from zinc to copper,
since zinc atoms are oxidized and copper atoms are reduced. An ammeter is placed in the
circuit. As soon as the connection is made, current starts flowing as indicated by the
ammeter due to flow of electrons.
Galvanic cell or Daniel cell

Fig 2.10
91
The electrode reactions in the cell are
At anode (oxidation) : Zn Zn2+ + 2e-

At cathode (reduction): Cu2+ + 2e- Cu
Net Cell reaction : Zn + Cu2+ Zn2+ + Cu
Thus the number of electrons liberated in one half-reaction is equal to the number
of electrons consumed in the other half-reaction. The overall cell reaction is called as redox
reaction.
Applying the rules for the representation of a cell, the Daniel cell can be
represented as follows;
Zn | ZnSO4 || CuSO4 | Cu
Or
Zn | Zn2+ || Cu2+ | Cu
2.11.2 Representation of a cell: IUPAC Convention:

1) Usually, a cell consists of two electrodes namely, anode and cathode.
2) The anode half-cell is written on the left side while the cathode half-cell is written
on the right side.
3) The anode half-cell is written by writing metal first and the electrolyte. The two are
separated by a vertical line (|) or a semicolon (;).
Example: M | Mn+ or M ; Mn+
4) But the cathode half-cell is written by writing electrolyte first and then the metal.
The two are separated by a vertical line or a semicolon.
Example: Mn+ | M or Mn+ ; M
5) The electrolyte may be represented by whole formula (e.g. ZnSO4) or its ionic
species (e.g. Zn2+). The concentration of the electrolyte may also be represented in
bracket (e.g 1 M).
92
6) A salt bridge is indicated by double vertical lines ( ) separating the two half-cells.
7) The symbol for an inert electrode, like the platinum electrode is often enclosed in a
bracket. For example,
Mg | Mg2+ H+ | H2(Pt)
(8) The value of emf of a cell is written on the right of the cell diagram.
Thus a zinc-copper cell has emf 1.1 V and is represented as
Zn | ZnSO4 CuSO4 | Cu E = + 1.1 V
Direction of electron flow
If the emf acts in the opposite direction through the cell circuit,it is denoted as a
negative value.
Cu | CuSO4 ZnSO4 | Zn E = – 1.1 V
Direction of electron flow
The negative sign also indicates that the cell is not feasible
2.11.3 Differentiate between electrochemical cell and electrolytic cell.

No Electro chemical cell Electrolytic cell
1 It is the cell which the chemical energy is It is the cell which the electrical
used to produce electrical energy. energy is used to bring about
chemical reaction at the electrode
2 Anode is negatively charged electrode An external source of electrical
and oxidation reaction occurs on it. Due voltage is supplied into this cell.
to this electrons will be released from Anode is positively charged with
the electrode. respect to cathode. Negatively
charged anions migrate to this
electrode and get oxidized
3 Cathode is positively charged with Cathode is negatively charged with
respect to anode respect to anode
4 The electron move from anode to Electron flow towards cathode and
cathode in the external circuit come out through anode.
93
5 The emf of the cell depends on the The extent of chemical reaction
concentration of the electrolytes and taking place at the electrodes is the
chemical nature of electrodes governed by Faradays law of
electrolysis.
6 The emf produced by the cell is Amount of electricity passed during
measured using potentiometer electrolysis is measured by
coulometer
7 In ordinary galvanic cell, two different In this type of cell ,only one type of
electrods and two different electrolytes electrolyte and two electrodes of the
are employed usually same element are employed mostly
8 Eg .Zn/Zn //Cu /Cu
2+ 2+ Eg. Zn/ZnSO4 /Zn
2.12 Concentration Cell

If two plates of the same metal are dipped separately into two solutions of the
same electrolyte and are connected with a salt bridge, the whole arrangement is found to
act as a galvanic cell. In general, there are two types of concentration cells:
2.12.1 (i) Electrode concentration cells:

In these type, two identical electrodes of different concentrations are dipped in the
same electrolytic solution of the electrode metal.
Example: Amalgam concentration cell
Amalgam electrodes are produced by mixing various proportions of metals and mercury.
Heave the concentration of the metal differ in the two electrodes.
Example : Zinc amalgam conc. cell
Zn (Hg) (C1) /ZnSO4 / Zn (Hg) (C2)
0.0591 C
E Cell = log 2 at 25° C
2 C1
2.12.2 (ii) Electrolyte concentration cells:

In this type , two identical electrodes are dipped in the electrolytic solutions of
different concentrations. Example: Zinc ion concentration cell
Zn / ZnSO4 (C1) Zn / ZnSO4(C1)
CONSTRUCTION: 94
The zinc electrode dipped in diluted ZnSO4 solution is the anode. The zinc
electrode dipped in concentrated ZnSO4 solution is the cathode. These two solutions are
connected through a salt bridge. The chemical reaction taking at anode and cathode can be
written as follows:
At anode (left hand electrode) oxidation takes place
Zn Zn2+(C1) + 2e-
At cathode (Right hand electrode) reduction occurs
Zn2+ (C2) + 2e- Zn
The net reaction is the sum of these two electrode reactions.
Zn2+ (C2) Zn2+ (C1)
From this, it is clear that there is no net chemical reaction and this involves only the
transfer of Zn2+ ions from a solution of higher concentration (C2) to a solution of lower
concentration (C1).
We can write the Nernst equation at 25˚c obtain the emf of the concentration cell
as follows
0.0591
At anode: ER = E0  log C1
n
0.0591
At cathode: ER = E0  log C 2
n
E0 , Value for any concentration cell = 0

Ecell = ER–EL
0.0591 C
Ecell =  log 2
n C1
For the process to be feasible, emf should be positive. Hence, C2>C1.

Silver ion concentration cell
Ag/AgNO3 (C1) AgNO3 (C2) /Ag (C2 >C1)
2.12.3 Determination of emf of concentration cell

95
Consider silver ion concentration cell. The Ag electrode dipped in AgNO3 solution
of lower concentration is anode .and the Ag electrode dipped in AgNO3 solution of higher
concentration is cathode. The two solutions are connected together by a salt bridge. The
chemical reaction occur at anode and cathode are given blew.
At anode (LHE)
Ag Ag+ (C1) + e-
At cathode (RHE)
Ag+ (C2) + e- Ag
The net cell reaction is
Ag+ (C2) Ag+ (C1)
From the net cell reaction it is very clear that, there is no net chemical reaction and
this process merely involves transfer of Ag+ ions from a solution of higher concentration
(C2) to a solution of lower concentration (C1)
Concentration cell
Fig 2.11
96
From the Nernst equation, the electrode potential of the cell is given as follows. We
can write the Nernst equation at 25˚c and obtain the emf of the concentration as follows
0.0591
At anode : E L = E0  log C1
n
0.0591
At cathode: ER = E0  log C 2
n
E0 Value for any concentration cell = 0

Ecell = ER–EL
0.0591 C
Ecell =  log 2
n C1
For the process to be feasible, emf should be positive. Hence, C2 > C1.
2.12.4 Application of concentration cells:

1. Determination of the solubility of sparingly soluble salts:
The solubility of a sparingly soluble salt like AgCl can be calculated by measuring
the emf of the cell.
Ag | AgCl, 0.01 N KCl 0.01 N AgNO3 | Ag
[Ag+] = C1 [Ag+] = 0.01 = C2

The cell can be constructed by placing one of the Ag electrodes in contact with 0.01
N solutions of Ag NO3 and the other in contact with 0.01 N solution of KCl. The two
solutions are connected by a salt bridge. A drop of AgNO3 solution is added to the KCl
solution. A small amount of AgCl formed is sufficient to give its saturated solution.
The emf of the above cell is given by the relation
0.0591 C
E Cell =  log 2
n C1
Here n = 1 and C2 = 0.01 N

0.0591 0.01
E Cell =  log
n C1
97
Where, C1 is the concentration of Ag+ ions furnished by AgCl in KCl solution.
By measuring emf of the cell, the concentration of AgCl is calculated. Multiplying this by
143.5, the equivalent weight of AgCl , we can get the solubility of AgCl in grams/litre
Solubility = C1×143.5 (Eq.wt of AgCl)
2. Determination of the valency of an ion.

By substituting the measured values of emf of a concentration cell and the values
of C1 and C2 in the equation.
0.0591 C
E Cell =  log 2
n C1
The value of n, the number of electrons involved in the cell reaction, (Called the
valency of ions) can be calculated.
Problem based on concentration cell.

1) Calculate the emf of the following concentration cell at 250C.
Zn Zn 2  ( 0.01M ) Zn 2  ( 0.10 M ) Zn
Solution
0.0592 C
E Cell = log 2
n C1
0.0592 0.1
E Cell = log
2 0.01
0.0592
E Cell = log 10
2
E Cell = 0.0295 V
98
2) Calculate the emf of a Daniel cell at 250 C, when the concentration of ZnSO4 and
CuSO4 are 0.001 and 0.1 M respectively .The standard emf of the cell 1.1 volt
Concentration of the cell
Zn / ZnSO4 (0.001M) // CuSO4(0.1M) / Cu
Solution
Emf = Eright - Eleft
 0 0.0591   0.0591 
E = E Cu  log 0.1  E 0Zn  log 0.001
 2   2 
E = E 0
Cu 
 E 0Zn 
0.0591
2
log
0.1
0.001
E = 1.1  0.02955  2
E = 1.1591 V
3) The emf of the cell consisting of a hydrogen electrode and the normal calomel
electrode is 0.664V at 250C .the emf of normal calomel electrode is 0.2802V.
Calculate the pH of the solution.
Given:
E Cell = 0.664V;
EHydrogen = -0.0591 pH;

ECalomel = 0.2802V
Solution
ECell = ECalomel - EHydrogen
0.664 = 0.2802 – 0.0591 pH
0.664  0.2802
pH =
0.0591
pH = 6.5
99
Excises :
1) Calculate the potential of the following concentration cell at 250C
/ Cu2+ (0.012M) // Cu2+(0.032M)/ Cu
2) Calculate the emf of the following concentration cell at 250C .

/ Cu2+ (0.2M ) // Cu2+(2M)/ Cu
3) Calculate the emf of the following cell at 250 C.

Zn/Zn2+(0.1M)//Ag+(0.1M)/Ag : E0 Cell = 1.56 V
4) Calculate the emf of the following cell.
Mg/Mg2+ (0.1M)//Ag+ (0.01M)/Ag : EAg = 0.8V; EMg = -2.4V
5) Calculate the emf of the cell Zn/Zn2+(0.1M)//Ag+(10.0M)/Ag.Writ down the
cell reaction ,
E0 Zn /Zn2+ = -0.76V and E0Ag+/Ag = + 0.80 V.
6) Calculate the concentration of H+ in following cell.
Pt. H2 1atm / H+ (1X10-6M)//H+( C=?) / H2 1atm .Pt ; Ecell = 0.118V at 25oC
2.13 Reversible and Irreversible Cells
Daniel cell has the emf value 1.10 volt. If an opposing emf exactly equal to 1.10 volt
is applied to the cell, the cell reaction, stops
Zn + Cu2+ Zn2+ + Cu
but if it is increased infinitesimally beyond 1.10 volt, the cell reaction is reversed.
Cu + Zn2+ Cu2+ + Zn
Such a cell is termed a reversible cell. Thus, the following are the two main
conditions of reversibility:
(i) The chemical reaction of the cell stops when an exactly equal opposing emf
is applied.
(ii) The chemical reaction of the cell is reversed and the current flows in
opposite direction when the opposing emf is slightly greater than that of
the cell.
100
Any other cell which does not obey the above two conditions is termed as
irreversible. A cell consisting of zinc and copper electrodes dipped in a solution of
sulphuric acid is irreversible.
Zn |H2S04 (aq) | Cu
is also irreversible because when the external emf is greater than the emf of the cell, the
cell reaction,
Because the normal cell reaction is
Zn + 2H+ Zn2+ + H2
But when an opposing emf greater then the emf of the cell is applied the cell reaction is
Cu + 2H+ Cu2+ + H2
Thus the cell reaction is not exactly reversed.
Hence the cell is irreversible
Thus the cell reaction is not exactly reversed. Hence

Electromotive force (EMF) of a cell
It is defined as the algebraic sum of single electrode potentials, provided proper
signs are given according to the actual reaction taking place on the electrodes. In other
words, emf of a cell is the difference of potential which causes the flow of current from an
electrode having higher potential to another having lower potential. Generally, cell is
written with the negative electrode to the left.
EMF of a cell, Ecell can be calculated by

E cell = E right – E left
E cell = E cathode – Eanode
(where, E right = Reduction potential of right-hand side electrode
E left = Reduction potential of left-hand side electrode)
101
If the value of Ecell is positive, it indicates that the cell reaction is feasible and if it
is negative then the reaction is not feasible. Every galvanic or voltaic cell is made up of
two half-cells, the oxidation half-cell (anode) and the reduction half-cell (cathode). The
potentials of these half-cells are always different. On account of this difference in electrode
potentials, the electric current moves from the electrode at higher potential to the electrode
at lower potential, i.e., from cathode to anode. The direction of the flow of electrons is
from anode to cathode.
Flow of electrons
Anode Cathode
Flow of current
The difference in potentials of the two half-cells is known as the electromotive

force (emf) of the cell or cell potential.
The emf of the cell or cell potential can be calculated from the values of electrode
potentials of the two half-cells constituting the cell. The following two methods are in use:
(i) When reduction potentials of both electrodes are taken into account:
E0Cell = Reduction potential of cathode - Reduction potential of anode
E0Cell = ECathode - EAnode
E0Cell = Eright - Eleft
(ii) When oxidation potentials of both electrodes are taken into account:
E0Cell = Oxidation potential of anode - Oxidation potential of cathode
E0Cell = Eoxi (anode) - Ered (cathode)
E0Cell = Eoxi (Left) - Ered (right)
102
Measurement of emf of a cell
The potential difference or emf of a cell can be measured on the basis of
Poggendorff’s compensation principle. Here the emf of the cell is just opposed or balanced
by an emf of a standard cell so that no current flows in the circuit.
The potentiometer consists of a uniform wire AB . A storage battery (K) is
connected to the ends A and B of the wire through a rheostat (R) .The cell of unknown
emf (x) is connected in the circuit by connecting its positive pole to A and the negative
pole to a sliding contact (D) through a galvanometer G. The sliding contact is freely
moved along the wire AB till no current flows through the galvanometer. Then the
distance AD is measured. The emf of unknown cell is directly proportional to the distance
AD.
Fig 2.12
Ex α AD
Then the unknown cell (x) is replaced by a standard cell (s) in the circuit. The
sliding contact is again moved till there is null deflection in the galvanometer. Then the
distance AD’ is measured.
The emf of unknown cell can be calculated from the following equation.
103
Emf of the unknown Cell x Length AD
=
Emf of the s tan dard cell s Length AD 
EX AD
=
ES AD 
AD
Emf of the unknown cell Ex =  Es
AD 
Factors affecting emf of a cell
1. Nature of the electrolyte and electrodes
2. Concentration and composition of the electrolytes
3. pH and temperature of the solution
Applications of EMF measurements

1. Determination of solubility of a sparingly soluble salt
The solubility of a sparingly soluble salt like AgCl can be calculated by measuring the
emf of the cell
Ag | AgCl, 0.01 N KCl || 0.01 N AgNO3 | Ag
[Ag+] = C1 [Ag+] = 0.01 = C2
The cell can be constructed by placing one of the Ag electrode in contact with 0.01 N
solution of Ag NO 3 and the other in contact with 0.01 N solution of KCl. The two solution
are connected by a salt bridge. A drop of AgNO 3 solution is added to the KCl solution.
A small amount of AgCl formed is sufficient to give its saturated solution.
The emf of the above cell is given by the relation
0.0591 C
E = log 2
n C1
Here n = 1 and C2 = 0.01 N

0.0591 0.01
E = log
n C1
104
Where, C1 is the concentration of Ag+ ions furnished by AgCl in KCl solution. By
measuring emf of the cell, the concentration of AgCl is calculated. Multiplying this by
143.5, the equivalent weight of AgCl , we can get the solubility of AgCl in grams/litre
Solubility = C1×143.5(Eq.wt of AgCl)
2. Determination of the valency of an ion

By substituting the measured values of emf of a concentration cell and the values of C1
and C2 in the equation.
0.0591 C
E = log 2
n C1
The value of n, the number of electrons involved in the cell reaction, (called the
valency of ions) can be calculated.
3. Determination of standard free energy change and equilibrium Constant .

i) The standard free energy change of a reaction can be calculated as
follow - G° = nFE°
where, n = Number of electrons involved ; F = 96,500 coulombs ;
E° = standard emf of the cell
ii) The equilibrium constant of reaction can be calculated as follows.
0.0591
E0 = log K
n
4. Potentiometric titration can be carried out.

5. Hydrolysis constant can be determined.
6. Determination of pH by using a standard hydrogen electrode.
A hydrogen electrode is introduced into the solution, pH of which is to be
determined it is connected to a standard hydrogen electrode and thus a cell is constructed.
the emf of the cell is measured. If E is the emf of the cell.
105
E = 
2.303
F
 
log H 
2.303
=  pH  pH   log[ H  ]
F
i.e at 250C
E = 0.0591 pH
From the above equation the hydrogen ion concentration or the pH of the solution
can be calculated
Two mark questions and answers

1) What is a cell?
A cell is a device consisting of two half cells. Each half cell contain an electrode
dipped in an electrolytic solution. The two half cell are connected through one wire
2) What are electrolytic cells?

Electrolytic cell in which electrical energy is converted into chemical energy. (eg)
Electrolysis, Electroplating.ect
3) Define single electrode potential

It is the measure of the tendency an electrode lose or gain of electrons. When it is in
contacts with a solution of its own salt
4) Define electrochemical cell.

It is device which converts chemical energy in to electrical energy. (eg. Daniel cell)
5) Mention the function of salt bridge.

i) It eliminates liquid junction potential.
ii) It provide the electrical continuity between two half cell.
106
iii) It allows the movement of ion from one solution to other.
6) Define emf of a cell.

Emf of a cell is the difference of potential which causes the flow of current from an
electrode having higher potential to the lower potential.
7) What are the factors affecting emf of cell?

i) Temperature ii) pH of solution iii) concentration of electrolyte
iv) Nature of electrode and electrolyte
8) Zinc react with dil.H2SO4 to give hydrogen but Ag does not react with dil.H2SO4
Why?
Zn react with dil.H2SO4 And librates hydrogen but Ag does not react with
dil.H2SO4 because Zn more oxidation potential value than Ag
E0Zn/Zn2+ = 0.76V
E0 Ag/Ag+ = -0.80V
Zn + dil.H2SO4 → ZnSO4 + H2 
Ag + dil.H2SO4 → No reaction
9) Mention the applications of Nernst equation.

i) It is used to calculate electrode potential of the unknown metals.
ii) The corrosion tendency of metals can be predicted.
10) Why can glass electrode not be used for a solution of high alkalinity?
The glass electrode can be used in solution only with pH range of 0 to 10.
However when the pH is above 12(high alkalinity) ,cations of the solution will affect the
glass and make the electrode useless.
107
11) Define a reference electrode. Give any example.
Reference electrode is the one ,the potential of which is known or arbitrarily fixed as
zero. It is measure the electrode potential of another unknown electrode by combining
with it. Example: Std hydrogen electrode; Calomel electrode
12) Differentiate between Reversible cell and Irreversible cell.

S.No Reversible cell Irreversible cell
1 Cell reaction reversed when
external potential grater than cell cell reaction completely reversed
potential, is applied.
2 Example: Zn/Zn2+//Cu2+/Cu Example: Zn/H2SO4/Ag
13) Define terms (i) single electrode potential (ii) electrode chemical cells
(i) Single electrode potential(E)
It is the measure of the tendency of an electrode to lose or gain electrons, when it is
in contact with a solution of its own salt
(ii) Electro chemical cells
It is a device which converts chemical energy in to electrical energy or electrical
energy into chemical energy
14) What are galvanic cells?

Galvanic cell is a device in which a redox reaction is utilized to get electrical
energy. It consists of two electrodes immersed in one or more suitable electrolytes. When
the electrodes are connected externally, chemical reaction occurs in the cell involving
oxidation at electrode (anode) and reduction at another electrode (cathode)
108
15) Define emf of a cell?
Electromotive force is defined as,” the difference in potential which causes flow of
electrons from one electrode of higher potential to the other electrode of lower potential’.
Thus, the emf of an electrochemical cell can readily be calculated using the following
relationship.
E0cell = E0right – E0left
16) What are factors that affect electrode potential?

(i) Temperature
(ii) Nature if the metal
(iii) Concentration of metal ion in solution
17) What is electrode potential? How is it developed?

It is the measure of the tendency of an electrode to lose or gain electrons, when it is
in contact with a solution of its own salt. It is developed when the metal dipped in a
solution of its own salt.
18) Write Nernst equation.

Write Nernst equation at 250C
E = E0 
0.0591
log
Pr oduct 
nF Re ac tan t 
19) Explain oxidation and reduction potentials of an electrode.

The tendency of an electrode to lose the electrons is called the oxidation potential,
and the tendency of an electrode to gain the electrons is called the reduction potential
109
20) Zinc reacts with dil. H2SO4 to give hydrogen but Cu does not react with dil.
H2SO4 Why Explain
Zn reacts with dil H2SO4 and liberates hydrogen due to it possess negative
reduction potential (E0 Zn = - 0.76 V) and also it is placed higher in the emf series.Cu
does not react with dil. H2SO4 due to it’s possess positive reduction potential (E0 Zn = -0.76
V) and also it is placed higher in the emf series. Cu does not react with dil. H2SO4 due to it
possess positive reduction potential (E0Cu = + 0.34V) and also it is placed lower in the emf
series.
21) Suggest a method to determine the electrode potential of Zinc.

The saturated calomel electrode is coupled with another Zn electrode, the potential
of which is to be determined. Since the reduction potential of the coupled Zn electrode is
less than E ̊ value of calomel electrode (+ 0.2422 V), the calomel electrode will act as
cathode and the reaction is
E cell = E0calomel – E0Zn
E0Zn = E0calomel - E cell = + 0.2422 – 3.0025 = - 0.7603 volt
Where, E cell = 3.0025 V
22) Define a reference electrode. Give one example.

The electrode (standard potential), with we can compare the potentials of other
electrodes, is called reference electrodes. The electrode potential is found out by coupling
the electrode with the reference electrode, the potential of which is known or arbitrarily
fixed as Zero. (e.g.) std. hydrogen electrode, sat. Calomel electrode.
110
23) Write the construction of saturated calomel electrode.
Calomel electrode consists of a glass tube containing mercury at the bottom over
which mercurous chloride is placed. The remaining portion of the tube is filled with a
saturated solution of KCL. The bottom of the tube is sealed with a platinum wire. The side
tube is used for making electrical contact with a salt bridge. The electrode potential of the
calomel electrode is + 0.2422 V
24) What is emf series? What is its significance?

When the various metallic electrodes are arranged in the order of their increasing
values of standard reduction potential on the hydrogen scale, then the arrangement is
called electrochemical series.
(i) The standard electrode potential can be calculated
(ii) The equilibrium constant can be calculated
25) Describe the construction of a glass electrode. How is it significant in its

application?
A glass electrode consists of thin- walled glass bulb. The glass is made up of a
special type glass having low melting point and high electrical conductivity. It contains
AgCl coated Ag wire or a pt wire in 0.1 M HCl. The pH of solutions, especially coloured
solutions containing oxidizing or reducing agents can be determined.
26) What are the advantages and limitations of glass electrode?

Advantages of glass electrode.
(i) It is simple and can be easily constructed and readily used.
(ii) It is not easily poisoned.
(iii) Equilibrium is rapidly achieved
(iv) The results are more accurate.
111
Limitations of Glass Electrode.
(i) Although glass membrane of electrode is very thin, yet its resistance is
extremely high, which cannot be measured by ordinary potentiometers it is,
therefore, necessary to use special electronic potentiometers for
measurement.
(ii) The glass electrode can be used in solutions only with pH range of 0 to 10.
However when the pH is above12 (high alkalinity), cations of the solution
will affect the glass and make the electrode useless.
27) What are the advantages of conductometric titrations?

(i) The end point more accurate
(ii) Dilute solutions and weak acids can be used for analysis by this method.
(iii) It can be used in the case of “coloured solutions”, where colour change of
the indicator is not clearly observed.
(iv) Since the end point is determined graphically, no keen observation is
necessary near the end point.
28) What is the basic principle of potentiometric titrations?

The potentiometric titrations involve the measurement of electrode potential (emf)
between reference electrode and an indicator electrode, with the addition of the titrant.
29) Mention any three advantages of potentiometric titrations.

(i) Very dilute solutions can be titrated accurately.
(ii) The necessary equipment required is cheap and easily available.
(iii) Several components may be titrated in the same solution.
(iv) This method can be used for coloured solution.
112
30) Give any two limitations of H2 electrode.
(i) The potential of the electrode is altered by changing in barometric pressure
(ii) It requires considerable volume of test solution.
31) Calculate the EMF of the cell

Zn(s) | Zn2+ (0.024 M) || Zn2+ (2.4 M) | Zn(s)
Solution
Zn2+ (2.4 M) + 2 e Zn Reduction
Zn Zn2+ (0.024 M) + 2 e Oxidation
--------------------------------------------
Zn2+ (2.4 M) Zn2+ (0.024 M), E° = 0 - - - Net reaction
Using the Nernst equation

0.0591 C
ECell = log 2
n C1
0.0591 0.024
ECell = log
2 2.4
0.0591
ECell = log 0.01
2
0.0591
ECell = log 1  10 2
2
ECell = 0.0591V
IMPORTANT QUESTIONS
1. i) How is emf of an voltaic cell (or) galvanic cell measured.
ii) Calculate the reduction potential of Cu/Cu2+ 0.5Mat 25oC;EoCu/Cu2+= -0.337 V.
2. Describe the construction and working of calomel electrode and hydrogen
electrode.
3. Define electromotive force. How is it measured by potentiometric method? 113
4. i) How is the emf of a galvanic cell measured by poggendorff’s compensation
method
ii) How is pH Of a solution determined from emf measurement?
5. Derive Nernest equation for emf of a cell.
6. Give the construction and uses of a saturated calomel electrode. Write its electrode
reaction.
7. What is emf ? How is it measured potentiometrically?
8. How is calomel electrode constructed? Discuss how this electrode may be used for
the determination of pH of a solution.
9. Describe the following electrodes giving the diagram, electrode notations and
electrode reaction. Standard hydrogen electrode and calomel electrode.
10. Calculate the emf of the cell
Zn /Zn2+ (0.1M)//Ag(10.0M) / Ag.
Write down the cell reaction given that Eo Zn2+/Zn=-0.76V and EoAg+/Ag= +0.80V
11. Calculate the potential of the following concentration cell at 25oC.
Cu(s) / Cu2+ (0.012M) // Cu2+ (0.032M) / Cu(s)
12. Writ schematic curves explain the principle involved in the different conductmetric
Acid base titrations.
13. Bring out the application of emf series.
14. Dscribe the construction and working of a galvanic cell.
16. Describe a glass electrode. How can it be used for determining the pH of a
solution?
17. Discuss the titration curves in the conductometric titration of
i) A strong acid with a strong base.
ii) A weak acid with a strong base.
18. Derive the Nernest equation for emf of a cell .write Nernest equation for emf of
Daniel cell.
114
19. Consider the cell reaction
Zn(s)+ Fe2+(0.005M) Zn2+ (0.01M) + Fe(s)
Given the std emf of the cell at298K is 0.323V
i) Construct the cell.
ii) Calculate the emf of the cell.
20. What is the principle underlying conductometric titration? Discuss the titration
Curve obtained in the case of a mixture of acid with a strong base.
21. Define single electrode potential. What is the value of electrode potential of SHE?
22. Explain acid-base titrations conductomtrically.
115
UNIT - III
CORROSION AND ENERGY STORAGE DEVICES
3.1 INTRODUCTION
Metals and alloys are generally used as fabrication or construction materials in
engineering. If the metal or alloy structures are not properly maintained, they deteriorate
slowly by the action of atmospheric gases, moisture and other chemicals. This
phenomenon of deterioration or destruction of metals and alloys is known as corrosion.
Definition
Corrosion is the deterioration of materials by chemical interaction with their
environment. The term corrosion is sometimes also applied to the degradation of plastics,
concrete and wood, but generally refers to metals.
3.11 Causes of Corrosion

Generally metals exist in nature in the form of oxides, sulphides, sulphates and
carbonates. They are thermodynamically more favourable state of metals. A considerable
amount of energy is required for the extraction of metals from its ore.
The extracted metal in the pure form has high energy, which is thermodynamically
unstable state. It is the natural tendency of the metal to go back to the thermodynamically
stable state. Metals do this by interacting chemically with their environment to form
surface compound and undergo corrosion.
116
Extraction environment
Ore of the Metal + Pure Metal Corroded Metal

Energy
(Thermodynamically (Thermodynamically (More stable state
stable state) unstable state) than pure metal)
Metal
Corrosion
Ore
products
Although corroded metal is thermodynamically more stable than pure metal but
due to corrosion, useful properties of a metal like malleability, ductility, hardness, lustre
and electrical conductivity are lost.
3.1.2 The Consequences of Corrosion

The consequences of corrosion are many and varied and the effects of corrosion on
the safe, reliable and efficient operation of equipments or structures are often more serious
than the simple loss of a mass of metal. Failures of various kinds and the need for
expensive replacements may occur even though the amount of metal destroyed is small.
Some of the major harmful effects of corrosion are:
1. Reduction of metal thickness leading to loss of mechanical strength and structural
failure or breakdown. When the metal is lost in localised zones so as to give a crack
like structure, very considerable weakening may result from a small amount of
metal loss.
117
2. Hazards or injuries to people arising from structural failure or breakdown
(e.g. bridges, cars, aircraft).
3. Loss of time in the availability of profit-making industrial equipment.
4. Reduced value of goods due to deterioration of appearance.
5. Contamination of fluids in vessels and pipes
6. Perforation of vessels and pipes allowing escape of their contents and possible
harm to the surroundings. For example a leaky domestic radiator can cause
expensive damage to carpets and decorations, while corrosive sea water may enter
the boilers of a power station if the condenser tubes perforate.
7. Loss of technically important surface properties of metallic component. These
could include frictional and bearing properties, ease of fluid flow over a pipe
surface, electrical conductivity of contacts, surface reflectivity or heat transfer
across a surface.
8. Mechanical damage to valves, pumps, etc, or blockage of pipes by solid corrosion
products.
9. Added complexity and expense of equipment which needs to be designed to
withstand a certain amount of corrosion, and to allow corroded components to be
conveniently replaced.
3.2 CLASSIFICATION OF CORROSION

Corrosion is classified into the following two types based on environment
1) Dry or Chemical corrosion
2) Wet or Electrochemical corrosion
Chemical corrosion is the direct attack of metals by the gases such as oxygen,
carbon dioxide, hydrogen sulphide etc.
Examples
i. Tarnishing of silver articles in hydrogen sulphide gas.
ii. Action of dry hydrogen chloride on iron surface. 118
There are three main types of chemical corrosion.
i. Oxidation corrosion or corrosion by oxygen.
ii. Corrosion by hydrogen.
iii. Liquid metal corrosion.
3.2.1 Oxidation Corrosion

This type of corrosion is brought about by the attack of oxygen gas on a clean free
metal surface. Alkali metal and alkaline earth metals are rapidly oxidized at low
temperature. Almost all metals, except Ag, Au and Pt are oxidized at high temperature.
Mechanism
Oxidation takes place at the surface of the metal forming metal ions, (M2+)
M M2+ +2e‾
Oxygen is converted to oxide ion (O2- ) due to the transfer of electrons from the
metal.
1/2O2 + 2e- O2-
Oxide ion reacts with the metal ions to form metal oxide film
M2++O2- M2+O2- = MO (film)
Once the metal surface is converted with mono-layer of oxide, the oxide film
grows perpendicular to the metal surface which causes the formation of thick oxide film.
The nature of the oxide film formed on the metal surface plays a significant role.
Different types of oxide films are explained below:

(i) Porous and non-porous oxide film (Pilling- Bedworth rule)
In the case of alkali and alkaline earth metals, the volume of oxide film formed on
the surface is less than the volume of the metal consumed. Hence, the oxide layer formed
is non- protective and porous. If
119
Volume of oxide film < volume of metal → non protective
In the case of heavy metals such as Sn and Pb, the volume of oxide film formed on
the surface is more than the volume of the metal consumed. Hence, the oxide layer formed
is protective and non-porous.
Volume of oxide film > volume of metal → protective
ii) Stable oxide layer

A stable oxide layer gets adsorbed tightly on the metal surface. This layer is
impervious in nature. It stops further oxygen attack through diffusion. As it acts as a
protective coating, no further corrosion can develop.
Eg. Al, Sn, Pb and Cu form stable oxide layer.
iii) Unstable oxide layer

This is formed on the surface of noble metals such as Ag, Au, Pt. As the metallic
state is more stable than the oxide, it decomposes back into the metal and oxygen. Hence,
oxidation corrosion is not possible with noble metals.
iv) Volatile oxide layer

This type of oxide film volatiles as soon as it is formed. Hence, always a metal
surface is available for further attack. This causes continuous corrosion. Molybdenum
oxide, MoO3, is volatile in nature.
3.2.1.1 Corrosion by Hydrogen

a) Hydrogen embrittlement
Definition: Loss in ductility of a material in the presence of hydrogen is known as
hydrogen embrittlement.
120
Mechanism
This type of corrosion occurs when a metal is exposed to hydrogen environment.
Iron liberates atomic hydrogen with hydrogen sulphide as follows.
Fe + H2S FeS + 2H
Hydrogen diffuses into the metal matrix in the atomic form and gets collected in
the voids present inside the metal. Further diffusion of atomic hydrogen makes them
combine with each other and form hydrogen gas.
H+H H2(g)
Collection of these gases in the voids develops high pressure, causing cracking or
blistering of metal.
b) Decarburization
We know that the presence of carbon in steel gives sufficient strength to it. But
when steel is exposed to hydrogen environment at high temperature, atomic hydrogen is
formed.
H2 ∆ 2H
Atomic hydrogen reacts with the carbon of the steel and produces methane gas.
C + 4H CH4
Hence, the carbon content in steel is decreased. The process of decrease in carbon
content in steel is known as decarburization.
Collection of methane gas in the voids of steel develops high pressure which
causes cracking. Thus, steel loses its strength.
121
3.2.1.2 Liquid Metal Corrosion
This is due to the chemical action of flowing liquid metal at high temperature. This
may involve either dissolution of solid metal by a liquid or maybe due to the penetration
of a liquid metal into the solid metal.
This type of corrosion has been found to occur in devices used for nuclear power.
3.2.2 Wet or Electrochemical Corrosion

Electrochemical corrosion takes place under the following two conditions.
1. When two dissimilar metals are in contact with each other in the presence of
aqueous solution or moisture.
2. When a metal is exposed to an electrolyte with varying amount of oxygen.
According to electrochemical theory of corrosion, wet corrosion involves the following
two steps.
1) Oxidation or metal dissolution.
2) Reduction.
Mechanism
i. Corrosion or metal dissolution (or oxidation) always occurs at anode.
M Mn+ + ne-
ii. Reduction reaction occurs at the cathode which depends on the corrosive
environment are;
a) When the corrosive environment is acidic, hydrogen gas is evolved at the
cathode
2H++ 2e- H2
b) When the corrosive environment is neutral or slightly alkaline, hydroxide ion is
formed
1/2O2 + 2e- + H2O 2OH-
122
3.2.2.1 Hydrogen evolution type corrosion
All metals placed above hydrogen in electrochemical series have a tendency to get
dissolved in acid solution with simultaneous evolution of hydrogen gas.
This process is explained by considering the corrosion of iron metal by industrial
wastes containing non oxidizing acids like HCl.
At Anode
Iron undergoes dissolution (oxidation) to form Fe2+ with the liberation of electrons.
Fe Fe2+ + 2e-
At Cathode
The liberated electrons go from anode to cathode where H+ ions are reduced to
hydrogen gas.
2H+ +2e- H2(g)
3.2.2.2 Adsorption of oxygen or hydroxide ion type corrosion

Example: Rusting of iron in neutral solution of an electrolyte in the presence of oxygen.
123
Mechanism
The surface of iron is usually coated with a thin film of oxide. However, while the
rest of the metal part acts as cathode.
At Anode
Iron dissolves as Fe2+ with the liberation of electrons.
Fe Fe2+ + 2e- (oxidation)
At Cathode
The liberated electrons flow from anodic to cathodic part of the metal, where the
electrons are taken up by the dissolved oxygen to form hydroxide ions, OH-.
½ O2 + H2O + 2e- 2OH-
The resulting ions Fe2+ and OH- combine together to form ferrous hydroxide as a
precipitate.
Fe2++ 2OH- Fe(OH)2 (ppt)
If enough oxygen is present, Fe(OH)2 is easily oxidized to ferric hydroxide
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3 (Rust)
The differences between (dry) chemical corrosion and (wet) electrochemical

corrosion are given below in the following table.
Table 3.1 Difference between chemical corrosion and electrochemical corrosion

S.No Chemical corrosion Electrochemical corrosion
It occurs in the presence of moisture or
1. It occurs in dry condition.
electrolyte.
It is due to the direct chemical attack It is due to the formation of a large number
2.
of the metal by the environment. of anodic and cathodic areas.
Even a homogenous metal surface Heterogeneous (bimetallic) surface alone
3.
gets corroded. gets corroded.
124
Corrosion products accumulate at Corrosion occurs at the anode while the
4.
the place of corrosion. products are formed elsewhere.
5. It is a self controlled process. It is a continuous process.
6. It adopts adsorption mechanism. It follows electrochemical reaction.
Example: Formation of mild scale on Example: Rusting of iron in the moist
7.
the iron surface. atmosphere.
3.3 TYPES OF ELECTROCHEMICAL CORROSION

The electrochemical corrosion is classified into the following two types.
1. Galvanic corrosion
2. Differential aeration or concentration cell corrosion
3.3.1. Galvanic Corrosion

This type of corrosion occurs when two different metals are in contact with each
other in the presence of an aqueous solution or moisture. Here, the more active metal acts
as anode while the less active metal acts as cathode. This reaction is explained in the
following figure.
Zinc dissolves in preference to iron. In other words, zinc acts as anode and
undergoes corrosion. Iron acts as cathode.
125
-------------------------------------------------- -----------------------------------------
-------------------------------------------------
Electrolyt ----------------------------------------
Electrolyt
--------------------------------------------------- ---------------------------------------
Zn Fe Fe Cu
Less active More active
More active Less active (anode) (cathode)
(anode) (cathode) Fe → Fe2+ + 2e- E0 = 0.34
Zn→Zn2+ + 2e- E0 = -0.44V
E0= -0.76V E0= -0.44
Fig. 3.3 (a) Zn-Fe Bimetallic couple Fig. 3.3 (b) Fe-Cu Bimetallic couple
But in the case of Fe and Cu iron dissolves in preference to copper. Iron acts as
anode and undergoes corrosion. Copper acts as cathode.
Example: steel screw in a brass marine hardware.

Prevention
Galvanic corrosion can be minimized by providing an insulating material between
the two metals.
3.3.2. Differential Aeration or Concentration Cell Corrosion.

This type of corrosion occurs when a metal is exposed to varying amount of
oxygen or any electrolyte on the surface of the metal.
Examples
1) The metal part immersed in water or in a conducting liquid is called water line
corrosion.
2) The metal part partially buried in soil.
126
Explanation: If a metal is partially immersed in a conducting solution, the metal part
inside the solution is less aerated and becomes anodic and suffers corrosion. The metal
part above the solution is more aerated and becomes cathodic.
At anode: Corrosion occurs (less aerated)
M M2+ + 2e -
At cathode: OH- ions are produced (more aerated)
1/2O2 + H2O +2e- 2OH-
More aerated (cathode)
Less aerated (anode)
Zn2+
Fig. 3.4 Differential

aeration corrosion
Examples for this type of corrosion are
1) Pitting or localized corrosion
2) Crevice corrosion
3) Pipeline corrosion
4) Corrosion on wire fence
(i) Pitting Corrosion

Pitting is a localized attack, which results in the formation of a hole, around which
the metal is relatively unattacked.
127
Example
Metal area covered by a drop of water, san, dust, scale, etc. Let us consider a drop
of water or aqueous NaCl resting on a metal surface. The area covered by the drop of
water acts as an anode due to less oxygen concentration and suffers corrosion. The
uncovered area (freely exposed to air) acts as a cathode due to high oxygen concentration.
The rate of corrosion will be more, when the area of cathode is larger and the area
of anode is smaller. Therefore, more and more material is removed from the spot. Thus a
small hole or pit is formed on the surface of the metal.
(ii) Crevice Corrosion

If a crevice between metallic and non-metallic is in contact with a liquid, the
crevice becomes anodic region and undergoes corrosion. Hence, oxygen supply to the
crevice is less. The exposed area has high oxygen supply and acts as cathode.
Bolts, nuts, rivets, joints are example for this type of corrosion.
128
More aerated
(cathode)
Fig. 3.6 Crevice corrosion
Prevention of crevice corrosion

a) Use welded butt joints instead of riveted or bolted joints in new equipment
b) Eliminate crevices in existing lap joints by continuous welding or soldering
c) Use of solid, non-absorbent gaskets such as Teflon.
d) Use of higher alloys for increased resistance to crevice corrosion.
(iii) Pipeline Corrosion

Differential aeration corrosion may also occur in different parts of pipeline. Buried
pipelines or cables passing from one type of soil to another say, from clay (less aerated) to
sand (more aerated) may get corroded due to differential aeration.
Clay Sand
Fig. 3.7 Pipeline corrosion
129
(iv) Corrosion on Wire Fence
The figure 3.8 shows a wire fence in which the areas where the wire cross are less
aerated than the rest of the fence and hence corrosion occurs at the wire crossings which
are anodic.
Fig. 3.8 Corrosion on wire
3.4 FACTORS INFLUENCING THE RATE OF CORROSION

There are two factors that affect rate the corrosion. Knowledge of these factors and the
mechanism with which they affect the corrosion rate is essential because the rate of
corrosion is different in different atmosphere.
1. Nature of the metal
2. Nature of the environment
3.4.1 Nature of the metal

a) Purity of the metal
The cent percent (100%) pure metal will not undergo any type of corrosion. But
even a trace amount of impurity in a metal causes galvanic corrosion. When it is exposed
to the corrosive medium, due to this heterogeneity, the anodic part gets oxidised and gets
corroded.
130
It has been found that the higher the percentage of impurity, faster the rate of
corrosion. For example, the rate of corrosion of aluminum in hydrochloric acid with
increase in the percentage impurity is given below:
% purity of Aluminum 99.99 99.97 99.20

Relative rate of Corrosion 1 1000 3000
b) Relative areas of electrodes

We know that corrosion always takes place at anodic areas due to the oxidation of
metal. The rate of corrosion will be more when the cathodic area is larger. The larger
cathodic area demands more electrons for reduction from the smaller anodic area which
results in the increase rate of corrosion. So, we may conclude that when the anodic area is
small and the cathodic area is large, the rate of corrosion will be more.
c) Position in the galvanic (emf, electrochemical) series

It has been found that the extent of corrosion depends on the position of the metal
in the galvanic series. Metals above hydrogen in the electrochemical series get corroded
vigorously. i.e., lower the reduction potential, greater is the rate of corrosion. When two
metals are in contact with other in presence of an electrolyte, the more active metal (with
high negative reduction potential) undergoes corrosion. The rate of corrosion depends on
the difference in their position in the electrochemical series. Greater the difference, faster is
the rate of corrosion.
d) Over voltage
The over voltage of a metal in a corrosive environment is inversely proportional to
corrosion rate. For example, the over voltage of hydrogen is 0.7 V, when zinc metal is
placed in 1 M sulphuric acid and the rate of corrosion is low. When we add small amount
131
of copper sulphate to the dilute sulphuric acid, the hydrogen over voltages is reduced to
0.33 V. This results in the decreased rate of corrosion of zinc metal.
e) Nature of the surface film

As seen earlier, the nature of the film formed on the metal surface decides the extent
of corrosion.
 In the case of alkali and alkaline on the earth metals, the oxide film formed is non
protective and porous. Hence, the rate of corrosion is higher and continuous.
 In the case of heavy metals, the oxide film formed is non protective and acts as a
protective layer.
 If the corrosive product formed on the metal surface is soluble in the environment,
corrosion can take place at a faster rate.
f) Nature of the corrosion product

If the corrosion product is soluble in the corroding medium, the corrosion rate will
be faster. Similarly, if the corrosion product is volatile (like MoO3), the rate of corrosion
will be faster.
3.4.2 Nature of the Environment

a) Temperature
The rate of corrosion is directly proportional to temperature i.e., rise in
temperature increase the rate of corrosion. This is because the rate of diffusion of ions
increases with rise in temperature.
b) Humidity
The rate of corrosion will be more when the relative humidity of the environment
is high. The moisture acts as a solvent for O2, CO2, SO2 etc. in the air to produce the
electrolyte which is required for setting up a corrosion cell.
132
c) Impurities in the environment
Impurities in the atmosphere from industrial exhaust gases like SO2 ,SO3 ,NO2 ,CO2
H2S,CO etc and fumes of HCl,H2SO4 etc, produce electrolytes and increase the rate of the
corrosion.
d) Presence of suspended particles

Solid pollutants present in air like
i) chemically active substances(like NaCl,(NH4)2 SO4 )
ii) chemically neutral substances
iii) chemically inactive substances are increase the rate of corrosion by setting up
concentration cell.
e) pH of the corrosion environment

The rate of corrosion is maximum when the corrosion environment is acidic (i.e.
pH is less than seven). In general, acidic environment is more corrosive than alkaline
medium. However, metals such as Al, Zn dissolve in alkaline medium.
Corrosion
P
Corrosion
Fig.3.9 Pourbiax diagram for Fe- H2O system
133
This figure3.9 clearly indicates the zones of passivity, immunity and corrosion. In
this diagram, P is the point whose pH is 7(neutral condition) and the corresponding
electrode potential is -0.4 V. Evidently this point is present in the corrosion zone. Under
this condition iron undergoes corrosion or rusting.
The rate of corrosion of iron can be changed by shifting point P into the immunity
or passivity zones. This can be achieved by changing the electrode potential as follows.
i. If the potential is changed to -0.8 V, by applying external current, iron will be
immune to corrosion.
ii. By applying positive potential, the corrosion rate can be reduces as become
passive.
iii. This diagram clearly indicates that rate of corrosion will be maximum when
the pH is less than 7 i.e., the corrosive environment is acidic. The rate of
corrosion can be reduced by increasing the pH of the solution by adding
alkalies.
3.5 CORROSION CONTROL

The rate of corrosion can be controlled by either modifying the metal or the
environment.
3.5.1 Control of Corrosion by Modifying the Metal

1. Choice of metals and alloys
i. The first choice is to use noble metals such as gold and platinum. They are most
resistant to corrosion. As they are precious, they cannot be used for general
purposes.
ii. The next choice is to use purest possible metal. But in many cases, it is not possible
to produce a metal a high chemical purity. Hence, even a trace amount of impurity
leads to corrosion.
134
iii. Thus, the next choice is the use of corrosion resistant alloys. Several corrosion
resistant alloys have been developed for specific purposes and environment. For
example
a. Stainless steel containing chromium produces an exceptionally coherent oxide film
which protects the steel from further attack.
b. Cupro-Nickel (70%+30% Ni) alloys are now used for condenser tubes and for
bubble trays used in fractionating column in oil refineries.
c. Highly stressed nimonic alloys (Ni-Cr-Mo alloys) used in gas turbines are very
resistant to hot gases.
2. By proper design
Some of the important rules for designing, which must be observed, are given
below.
a) Galvanic corrosion is prevented by
i. Selecting the metals as close as possible in the electrochemical series.
ii. Providing smaller area for cathode and larger area for anode.
iii. Inserting insulating material between the two metals
Insulation
Fig 3.10
135
b) Drainage affects corrosion
Tanks and other containers must be designed in such a way that, the whole of the
liquid should be draining out completely.
-------------------
-------------------
-------------------
-------------------
------------
Fig.3.11.a.Poor design of
drainage corrosion Fig.3.11.b.Good design
of drainage corrosion
Sharp corners or edges should always be avoided. Corrosion can be avoided by

smooth corners or curved pipe bends.
Fig.312.a.Poor Design Fig.3.12.b.Good Design
136
c) Avoid crevices
Crevices allow moisture and dirt, which results in increased electrochemical
corrosion. This can be prevented by filling the crevices with filler
Filler
Fig.3.13.a.Crevice corrosion Fig.3.13.a. Prevention of Crevice
Example
Riveted joints produce crevice corrosion, so welded joints preferred to avoid
corrosion.
3. By cathodic protection
The principle involved in the cathodic protection is to force the metal to behave
like a cathode.The important cathodic protections are (i) sacrificial anodic protection.
(ii)Impressed current cathodic protection .
(i) Sacrificial anodic protection method

In this method, the metallic structure to be protected is made cathode by
connecting it with more active metal (anodic metal). Hence, all the corrosion will
concentrate only on the active metal. The artificially made anode thus gradually gets
corroded protecting the original metallic structure. Hence this process is otherwise
137
known as sacrificial anodic protection. Aluminium, Zinc, Magnesium are used as
sacrificial anodes.
Zn/Mg
Anode
Pipeline to be protected - Cathode
Fig.3.14. Sacrificial anodic protection
Applications of sacrificial anodic protection

i) This method is used for the protection of ships and boats. Sheets of Mg or Zn are
hung around the hull of the ship. Zn or Mg will act as anode, so corrosion concentrates on
Zn or Mg. Since they are sacrificed in the process of saving iron, they are called sacrificial
anodes.
138
Zn
Zn
Fig. 3.15.a. Sacrificial anodic protection-Ship
Zn
Zn
Fig.3.15.b. Sacrificial anodic

Fig.3.15.c. Sacrificial anodic
protection-boiler
Protection in pipeline
ii) Protection of underground pipelines, cables from soil corrosion.

iii) Insertion of Mg sheets into the domestic water boilers to prevent formation
of rust.
(ii) Impressed current cathodic protection method

In this method, an impressed current is applied in the opposite direction of the
corrosion current to nullify the corrosion current and the corroding metal is converted
from anode to cathode.
139
Graphite anode
Backfill
Underground pipeline
Fig.3.16. Impressed current cathodic protection
This can be done by connecting negative terminal of the battery to the metallic
structure to be protected, and positive terminal of the battery is connected to an inert
anode. Inert anodes used for this purpose are graphite and platinised titanium. The
anode is buried in a “back fill” (containing mixture of gypsum, coke, breeze, sodium
sulphate). The “back fill” provides good electrical contact to anode.
Structures like tanks, pipelines, transmission line towers, underground water pipe
lines, oil pipe lines, ships, etc., can be protected by this method.
140
Table3.2 Comparison of Sacrificial anodic method and impressed current method
S. No Sacrificial anodic method Impressed current method
It requires periodical replacement of Here anodes are stable and do not
1.
sacrificial anode. disintegrate.
2 Investment low. Investment is more.
Soil and microbiological corrosion Soil and microbiological corrosion effects
3.
effects are not taken into account. are taken into account.
This is most economical method
This method is well suited for large
4. especially when short-term
structures and long term operations.
protection is required.
This method is suitable when the
But this method can be practiced even if
current requirement and the
5. the current requirement and the
resistivity of the electrolytes are
resistivity of the electrolytes are high.
relatively low.
3.5.2 Corrosion Control by Modifying the Environment

The environment around the metal plays a major role in the corrosion of metals.
Hence, we can prevent corrosion to a great extent by modifying the environment. Few
methods have been discussed here.
a) Deaeration
Fresh water contains dissolved oxygen. The presence of increase amount of oxygen
is harmful and increases the corrosion rate. Deaeration involves the removal of dissolved
oxygen by increase of temperatue together with mechanical agitation. It also removes
dissolved carbon dioxide from the water.
141
b) Deactivation
It is the process of removing dissolved oxygen by adding some chemicals (known
as scavenger) in aqueous solution.
Examples: sodium sulphite (Na2SO3), hydrazine (N2H4) remove the dissolved oxygen in
the following way.
N2H4 N2 + 2H2O
2Na2SO3 +O2 2Na2SO4
c) Dehumidification
In this method, moisture from air is removed by lowering the relative humidity of
the surrounding air. This is achieved by adding silica gel or alumina which adsorbs
moisture preferentially on its surface.
d) By Neutralizing the Environment

If the corrosion is found to occur in an acidic environment due to the presence of
HCl, H2S, CO2, SO2 etc, it is neutralized by spraying alkaline neutralizers like NH3, NaOH,
lime etc.
e) By Using Inhibitors
Inhibitors are organic or inorganic substances which decrease the rate of corrosion.
Usually, the inhibitors are added in small quantities to the corrosive medium.
Inhibitors are classified as
i) Anodic inhibitors(chemical passivators )
ii) Cathodic inhibitors(adsorption inhibitors)
iii) Vapour phase inhibitors(volatile corrosion inhibitors)
142
i) Anodic Inhibitors
These inhibitors retard the corrosion of metals by forming a sparingly soluble
compound with newly produced metal cations. This compound will then adsorb on the
corroding metal surface forming a passive film or barrier.
Examples: chromate, phosphate, tungstate, nitrate, molybdate etc.
ii) Cathodic inhibitors

These are two types, depending on the nature of the cathodic reaction in an
electrochemical corrosion as below…
a)In an acidic solution
In acidic solution, the main cathodic reaction is the liberation of hydrogen gas. The
corrosion can be controlled by slowing down the diffusion of H+ ions through the
cathode.
Examples: Amines, Mercaptans, Thiourea etc.,
b)In a neutral solution
In a neutral solution, the cathodic reaction is the adsorption of oxygen or formation
of hydroxyl ions. The corrosion is therefore controlled either by eliminating oxygen from
the corroding medium or by retarding its diffusion to the cathodic area. The dissolved
oxygen can be eliminated by adding reducing agents are Na2SO3.The diffusion of oxygen
can be controlled by adding inhibitors like Mg, Zn, or Ni salts.
Examples: Na2SO3, N2H4, salts of Mg, Zn, or Ni
c) vapour phase inhibitors
These are organic inhibitors which are readily vapourised and form a protective
layer on the metal surface.These are conveniently used to prevent corrosion in closed
spaces, storage containers, packing materials, sophisticated equipments etc.
Examples: Dicyclohexylammoniumnitrate, dicyclohexyl ammoniumchromate,
benzotriazole, phenylthiourea etc.
143
3.6 PRE-TREATMENT OF THE MATERIAL SURFACES(OR) PREPARATION OF
MATERIALS FOR COATING
Generally metal surface are covered with impurities like rust, scale, oil, grease, etc.
These substances, if present at the time of coating, will produce porous and discontinuous
coating. So, in order to get a uniform, smooth, cohesive and adherent coating, these
substances are removed by the following methods.
1. Solvent Cleaning
Organic solvents such as toluene, xylene, acetone, carbon tetrachloride, etc., are
used to remove oils, grease, and fatty substances present on the metal surfaces.
2. Alkali Cleaning
This method is particularly used for the removal of old paint coating from metal
surfaces. Solution of caustic soda, disodium phosphate with some detergents, emulsifying
and wetting agents are used for the alkali cleaning. After the alkali treatment, the metal
surface is rinsed with water and then with 0.1% solution of chromic acid.
3. Acid Cleaning or Pickling

Acid cleaning is applicable for the removable of oxide coating and other corrosion
product. Acid like HCl, H2SO4, HNO3, and H3PO4 are used for this process.
4. Mechanical Cleaning
Oxide scales, rust and corrosion products are removed by the mechanical cleaning
such as grinding, wire brushing, polishing, etc.,
144
5. Flame Cleaning
This process is done by passing high velocity hot flame over the metal surface. It is
applied to remove moisture and loosely adhering scales.
6. Sand Cleaning
This process consists of introducing sand into an air steam under the pressure of 25
to 100 atmospheres. It is used for removing oxide scale present especially on steel surface.
3.7 ELECTROPLATING (OR) ELECTRO-DEPOSITION

Principle
Electroplating is the process by which the coating metal is deposited on the base
metal by passing a direct current through the electrolytic solution containing the soluble
salt of the coating metal.
The base metal to be plated is made cathode of an electrolytic cell, whereas the
anode is either made of the coating metal itself or inert material of good electrical
conductivity.
Objectives of Electroplating
On Metals
1. To increase the resistance to corrosion of the coated metal
2. To improve the hardness and physical appearance of the article
3. To increase the decorative and commercial value of the article
4. To improve the properties of the surface of the article
5. To increase resistance to chemical attacks
On Non-Metals
1. To increase strength
2. To preserve and decorate the surfaces like plastics, wood, glass, etc.,
145
3. To introduce the surface conductivity by utilization of light weight, non-metallic
materials.
Theory
Suppose the anode is made of coating metal itself in the electrolytic cell. During
electrolysis, the concentration of electrolytic bath remains unaltered. This is because the
metal the metal ions deposited from the solution on cathode are replenished continuously
by the reaction of free ions with the anode metal. Thus, for example, If CuSO4 solution is
used as an electrolyte, it ionises as
CuSO4 Cu2+ + SO42-
Fig.3.17. Electroplating
On passing current, Cu2+ ions go to the cathode and get deposited there
Cu2+ + 2e- Cu (at cathode)
The free sulphate ions migrate to the copper anode and dissolve an equivalent amount of
copper to form CuSO4
SO42- + Cu CuSO4+2e- (at anode)
146
The copper sulphate formed gets dissolved in the electrolyte. Thus there is a continuous
replenishment of electrolytic salt during electrolysis.
Procedure
The article to be plated is first treated with dil.HCl or dil.H2SO4 to clean the
surface. The cleaned article is then made cathode of an electrolytic cell. The anode is either
the coating metal itself or an inert material of good electrical conductivity.
When direct current is passed from a battery, coating metal ions migrate to the
cathode and get deposited there. Thus a thin layer of coating-metal is obtained on the
article (at cathode)
In order to get strong, adherent and smooth deposit certain additives (glue, gelatin,
etc.,) are added to the electrolytic bath. In order to improve the brightness of deposit,
brightening agents are added in the electrolytic bath. They are at optimum temperature,
optimum current density and low metal ion concentrations.
3.8 ELECTROLESS PLATING

Principle
Electroless plating is a technique of depositing a noble metal (from its salt solution)
on a catalytically active surface of a metal to be protected, by using a suitable reducing
agent, without using electrical energy.
The reducing agent reduces the metallic ions to metal, which gets plated over the
catalytically activated surface giving a uniform thin coating.
Metal ion + reducing agent metal( Deposited) + oxidized product(s)
Various steps of electroless plating

Step 1 Preparation of active surfaces of the object to be plated
This is achieved by using any one of the following methods.
147
(a). Etching: Removal of unwanted particles by acid treatment.
(b). Electroplating: A thin layer of the metal to be plated or any other suitable metal is
coated on the surface of the object.
(c). Treating with stannous chloride, followed by dipping in palladium chloride
solution.
This treatment yields a thin layer of Pd on the treated surface. This method is
applied only for plastics and printed circuit board.
Step 2: Preparation of plating bath

The plating bath is composed of
a) Coating metal: Soluble salt of the metal (like chloride or sulphate) to be plated.
b) Reducing agent: formaldehyde, hypophosphite etc.,
c) Exaltant: succinate, fluoride, etc., which enhances the plating rate.
d) Complexing agent: tartarate, citrate, succinate, etc., which improves the quality of the
deposit
e) Stabilizer: like cations of Pb,Ca, etc., which prevent the decomposition of the plating
bath solution.
f) Buffer solution: Sodium hydroxide + Rochelle salt, sodium acetate etc., is added to
maintain the pH of the bath.
Step 3: Procedure
The object to be plated is immersed in the bath containing the salt of the metal and
reducing agent. The metal ions from the solution are reduced to the corresponding metal
and get plated over the surface of the object.
Various reactions
148
At cathode: M2+ + 2e- M
At anode: 2HCOH+4OH- 2HCOO-+2H2O+H2+2e-
Net reaction: M2+ + 2HCHO +4OH- M + 2HCOO- +2H2O + H2
3.8.1 Some Electroless Plating

1. Electroless Nickel Plating
Step 1.Pretreatment and activation of the surface
The surface to be plated is first degreased by using organic solvents or alkali,
followed by acid treatment.
Example
The surface of the stainless steel is activated by dipping in hot solution of 50% dil.
H2SO4. The surface of Mg alloy is activated by thin coating of Zn and Cu over it. Metals
and alloys like Al, Cu, Fe, brass, etc., can be directly Ni-plated without activation Non
metallic articles (like plastics, glass, etc., ) are activated by dipping them in the solution
containing SnCl2 + HCl followed by dipping palladium chloride solution. On drying a
thin layer of Pd is formed on the surfaces.
Step 2: Plating bath

Table 3.3
Nature of compound Name of compound Quantity ( g/l)
Coating solution NiCl2 20
Reducing agent Sodium hypophosphite 20
Complexing agent cum
Sodium succinate 15
exhaltant
Buffer Sodium acetate 10
Optimum temperature 93°C -
Optimum pH 4.5 - 149
Step 3: Procedure
The pre-treated object is immersed in the plating bath for the required time.
During which the following reduction reaction will occur and Ni gets coated over the
object.
Various reactions
At cathode: Ni2+ + 2e- Ni
At anode: H2PO2- + H2O H2PO3-+2H++2e-
Net Reaction:Ni2+ +H2PO2- + H2O Ni+H2PO3-+2H+
Applications Electroless Ni - plating

i. It is extensively used in electronic appliances.
ii. It is used in domestic as well as automobile fields (eg. Jewelry, tops of perfume
bottles)
iii. Its polymers are used in decorative and functional works
iv. Electroless Cu & Ni coated plastic cabinets are used in digital as well as electronic
instruments
3.8.2 Advantages of Electroless Plating Over Electroplating

i. No electricity is required
ii. Electroless plating on insulators (like plastic, glass) and semiconductors can be
easily carried out
iii. Complicated parts can also be plated uniformly
iv. Electroless coating posses good mechanical, chemical and magnetic properties
150
Differences between electroplating and electroless Plating
Table 3.4
S.No. Electroplating Electroless plating
It is carried out by auto catalytic redox

1 It is carried out by passing current
reaction
The base metal to be plated can be either The base metal should be non-ferrous.
2
a pure metal or an alloy.
The base metal on which oxide coating
The base metal to be plated is made
3 produced is made anode in the
cathode in the electrolytic cell.
electrolytic cell.
ENERGY STORAGE DEVICES

3.9 BATTERIES
A battery is a device that converts chemical energy directly into electrical energy.
Batteries are made up of two or more electrochemical cells that convert stored chemical
energy into electrical energy. Since the invention of the first battery (or "voltaic pile") in
1800 by Alessandro Volta, batteries have become a common power source for many
household and industrial applications.
The cell potential is related to free energy change (G) of the system. In an
electrochemical cell, the system does work by transferring electrical energy through an
electric circuit. Thus G for a reaction is a measure of the maximum useful work, that can
be obtained from a chemical reaction.
Ie., G = maximum useful work (W)
But we know that
Maximum work W = nFE
When a cell operates, work is done on the surroundings (flow of electricity).
-G = nFE
G < 0
Decrease in free energy is indicated by (-)ve sign.
151
3.9.1 Definition
A battery is an arrangement of several electrochemical cells connected in series, that can
be used as a source of direct electric current.
A Cell: Contains only one anode and cathode.
A Battery: contains several anodes and cathodes.
3.9.2 Requirements of a battery

A useful battery should fulfill the following requirements
i. Safe
ii. High Power
iii. High Capacity
iv. Small and Light
v. Large Format
vi. Long Life
vii. Low Overall Cost
3.10 Types of Battery

1. Primary Battery (Disposable batteries)
In these cells, the electrodes and the electrode reactions cannot be reversed by
passing external electrical energy. The cell reactions occur only once. Primary batteries
have to be discarded after the exhaustion of their reactants. They are not rechargeable.
Generally primary batteries have a higher capacity and initial voltage than rechargeable
batteries.
Examples: Dry cell, Mercury cell
2. Secondary Battery (Rechargeable Batteries)
These batteries are rechargeable and can be used like the primary batteries. In
these cells, the electrode reactions can be reversed by passing an external electrical energy.
152
Hence, they can be recharged by passing electric current and used again and again. These
are called storage cells (or) accumulators.
Examples: lead acid storage cell, Nickel –cadmium cell
3. Flow Battery (or) Fuel cell
In these cells, the reactants, products and electrolytes are continuously passing
through the cell. In this chemical energy gets converted to electrical energy.
Examples: Hydrogen-Oxygen fuel cell.
IMPORTANT PRIMARY BATTERIES
3.11 DRY CELL (or) LECLANCHE’S CELL
It is a primary cell, which works without fluid component.
Description
A dry cell consists of a Zinc cylinder, which acts as anode. This Zinc cylinder is
filled with an electrolyte consisting of NH4Cl,ZnCl2 and MnO2 in the form of paste using
starch and water. A carbon rod (graphite), acts as cathode, is inserted in the electrolyte in
the centre of the cell. The zinc cylinder has an outer insulation of cardboard case. During
use, the zinc cylinder gets consumed and at the end, it will develop holes which are
responsible for leakages.
Mixture of
ZnCl2,MnO2, and
Fig.3.18 Dry cell Or Lechlanche’s cell
153
Cell Reactions
Anode: Zn(s) Zn+2(aq) + 2e-
Cathode: 2NH4+(aq) + 2MnO2(s) + 2e- Mn2O3(s) + 2NH3(aq) + H2O(l)
Overall Reaction: Zn + 2NH4+( aq)+ 2MnO2(s) Zn+2(aq) Mn2O3(s) + 2NH3(aq) + H2O(l)
Half reactions: E°Cell = 1.5 V

In cathode reaction, Mn is reduced from +4 oxidation state to +3 oxidation state.
The liberation of NH3 gas, which disrupts the current flow is prevented by a reaction of
NH3(g) with Zn2+ ( from ZnCl2).
ZnCl2+ 2NH3 [Zn(NH3)2]Cl2(s) .
Example for dry cell: Silver cell, Lithium cell
Advantage: Inexpensive, safe, many sizes

Disadvantages:
1. This dry cell does not have an indefinite life because NH4Cl being acidic corrodes
the zinc container, even if it is not used.
2. When current is drawn rapidly from it, products buildup on the electrodes, so
voltage drop occurs.
Uses:
It is used in transistor radios, calculators, flash lights, torches etc.,
3.12 ALKALINE BATTERY

Description
The alkaline battery is an improved form of dry cell, in which the half-reactions are
similar, but the electrolyte is a basic KOH paste, which eliminates the buildup of gases and
maintains the Zn electrode.
154
Fig.3.19 Alkaline battery
Cell Reactions
Ecell = 1.5 V
Anode (oxidation) : Zn(s) + 2OH- (aq) Zn(OH)2(s) + 2e-
Cathode (reduction): 2MnO2 (s) + H2O (l) + 2e- Mn2O3 (s) + 2OH-(aq)
Overall Cell reaction: Zn(s)+ 2MnO2 (s) + H2O (l)) Zn(OH)2(s) + Mn2O3 (s)
3.11.1 Advantages of alkaline battery over dry battery

1. Zinc does not dissolve readily in a basic medium.
2. The life of alkaline battery is longer than the dry battery, because there is no
corrosion on Zn.
3. Alkaline battery maintains its voltage, as the current is drawn from it.
Disadvantages:
More expensive than common dry cell.
Uses:
It is used in calculators, watches etc 155
IMPORTANT SECONDARY BATTERIES
3.12 LEAD STORAGE CELL (or) LEAD ACCUMULATOR OR ACID STORAGE
CELL
Storage cell
A storage cell is the one, which can operate both as a voltaic cell and as an
electrolytic cell. When it acts as a voltaic cell, it supplies electrical energy and becomes
“run down”. When it is recharged, the cell operates as an electrolytic cell.
Description
A typical 12-V lead-acid battery has six cells connected in series. Each cell contains
two lead grids packed with the electrode material. The anode is spongy Pb, and the
cathode is powered PbO2. The grids are immersed in an electrolyte solution of H2SO4
(38% by mass) having a density of 1.30 gm/ml. Fiberglass sheets between the grids
prevent shorting by accidental physical contact.
The cell may be represented as Pb/ PbSO4 //H2SO4(aq) / PbO2//Pb
Anode
-
+ Cathod
PbO2 plates
Pb Plates
Aqueous
H2SO4
Fig.3.20 Lead storage cell

156
Working (Discharging)
When the lead-acid storage battery operates, at the anode lead is oxidized to Pb2+
ions and insoluble PbSO4 is formed. At the cathode PbO2 is reduced to Pb2+ ions and PbSO4
is formed.
Cell Reactions
At Anode: Pb(s) Pb2+ +2 e-
Pb2+ (aq) + SO42-(aq) PbSO4 (s)
Overall anode Reaction:

Pb2+ (aq) + SO42-(aq) PbSO4 (s) +2 e-
At Cathode:
PbO2 gains electrons ie., Pb undergoes reduction at the cathode from +4 to +2 ions
then combines with SO42- forms insoluble PbSO4.
PbO2 (s) + 4H+ + 2e- Pb2+(aq) + 2 H2O
Pb2+(aq) + SO42- PbSO4 (s)
Overall cathode Reaction:

PbO2 (s) +4H+ + SO42- + 2e- PbSO4 (s) + 2 H2O
Overall cell reaction during use (Discharging)

At Anode: Pb(s) + SO42- PbSO4 (s) +2 e-
At Cathode: PbO2 (s) + SO42- + 4H+ + 2e- PbSO4 (s) + 2 H2O
Net: PbO2 (s) + Pb(s) + 2H2SO4 2PbSO4 (s) + 2 H2O
157
From the above cell reactions it is clear that, PbSO4 is precipitated at both
electrodes and H2SO4 is used up. As a result, the concentration of H2SO4 decreases and
hence the density of H2SO4 falls below 1.2 gm/ml. So the battery needs recharging.
Recharging the Battery

The Cell can be charged by passing electric current in the opposite direction. The
electrode reaction gets reversed. As a result, Pb is deposited on anode and PbO2 on the
cathode. The density of H2SO4 also increases.
The net reaction during charging is
2PbSO + 2 H O + Energy charging Pb(s) + PbO2
4 (s) 2 (s) +4H+ + SO42-
discharging
Uses:
1. This cell is used to supply current mainly in automobiles such as cars, buses,
trucks, etc.,
2. It is used in gas engine ignition, telephone exchanges, hospitals, power stations,
etc.,
3.13 NICKEL-CADMIUM BATTERY (or) NICAD BATTERY

This is also a rechargeable battery.
Description
Nickel-Cadmium cell consists of a cadmium anode and a metal grid containing a
paste of NiO2 acting as a cathode. The electrolyte in the cell is KOH.
It is represented as: Cd /Cd(OH)2// KOH(aq) / NiO2 /Ni
Working (Discharging)
When the Nicad battery operates, at the anode cadmium is oxidized to Cd2+ ions
and insoluble Cd(OH)2 is formed. It produces about 1.4V
158
Cell reactions
At Anode: Cadmium is oxidised to Cd2+ and further it combines with OH- ions to form
Cd(OH)2.
disChargin
Anode: Cd(s) + 2OH-(aq) Cd(OH)2 (s) + 2e-
charging
At cathode: NiO2 gains electrons, ie., Ni undergoes reduction at the cathode from +4 to +2.
The Ni2+ ions then combine with OH- ions to form Ni(OH)2 .
dischargin
Cathode: NiO2 (s) + 2H2O(l) + 2e- Ni(OH)2 (s) + 2 OH-(aq)
charging
Overall reaction
dischargin
Cd(s) + NiO2 (s) + 2H2O(l) Cd(OH)2 (s) + Ni(OH)2 (s) +
charging
Energy
From the above cell reactions it is clear that, there is no formation of gaseous
products, the products Cd(OH)2 adhere well to the surfaces. This can be reconverted by
charging the cell.
Recharging the Battery

The process is similar to lead storage battery. When the current is passed in the
opposite direction, the electrode reaction gets reversed. As a result, Cd gets deposited on
anode and NiO2 on the cathode.
The net reaction during charging is
charging
Cd(OH)2 (s) + Ni(OH)2 (s) + Energy Cd(s) + NiO2 (s) + 2H2O(l)
discharging
Advantage
1. It is smaller and lighter.
2. It has longer life than lead storage cell.
3. Like a Dry cell, it can be packed in a sealed container.
159
Disadvantage
It is more expensive than Lead storage cell.
Uses
Used in calculators, electronic flash unites transistors and cordless appliances.
3.14 LITHIUM BATTERY

Lithium battery is a solid state battery because instead of liquid or a paste
electrolyte, solid electrolyte is used.
Construction
The lithium battery consists of a lithium anode and a TiS2 cathode. A solid
electrolyte, generally a polymer, is packed in between the electrodes. The electrolyte
(polymer) permits the passage of ions but not that of electrons.
Anode (-) Cathode (+)
Solid electrolyte
Li TiS2
Li+
Fig.3.21 Lithium- Battery
160
At Anode: Li(s) Li+ + e-
At Cathode: TiS2(s) + e- TiS22-
Overall reaction
Li(s) + TiS2(s) Li+ + TiS22-
Li+ + Tis2- LiTiS2
This cell is rechargeable and produces a cell voltage of 3.0V.
3.14.1 Other types of secondary lithium Batteries

i) Li/MnO2
ii) Li/ V2O5
iii) Li/ MoO2
iv)Li/Cr3O8
Advantages of lithium battery

It is the cell of future – Why?
i) Its cell voltage ifs high, 3V.
ii) Since Li is a light weight metal, only 7g (1 mole) material is required to produce 1
mole of electrons.
iii) Since Li has the most negative E0 value, it generates a higher voltage than the other
types of cells.
iv) All the constituents of the battery are solids and hence there is no risk of leakage
from the battery.
v) It can be made variety of sizes and shapes.
161
3.14.2 Lithium – Sulphur Battery
Lithium-sulphur battery is a rechargeable battery. Its anode is made of Li. Sulphur
is the electron acceptor, the electron from LI is conducted to S by a graphite cathode. ß-
alumina (NaAl11O17) is used as the solid electrolyte.
This solid electrolyte allows the Li+ ions to migrate to equalize the charge, but will
not allow the big poly sulphide product ions.
This battery is operated at high temperatures as Li and S should be in their molten

states.
+ -
Cathode Anode
Li
ß- alumina
S (l)
Fig.3.22 Solid state lithium

battery
Cell Reactions
At Anode: 2Li 2Li+ + 2e-
At Cathode: S + 2e- S2-
Ov Net reaction: 2Li + S 2Li+ + S2-
162
The S2-ions formed, react with elemental sulphur to form the polysulphide ion.
S2-+ nS [Sn+1]2-
The direct reaction between Li and S is prevented by the alumina present in the
cell.
Advantages of Li-S battery

1. Li-S battery has light weight unlike the lead acid battery.
2. It possesses high energy density.
3. It is used in electric cars.
3.15 PHOTOGALVANIC CELL (or) SOLAR CELL

Definition
Photogalvanic cell is the one, which converts the solar energy (energy obtained by
the sun ) directly into electrical energy.
Solar cells consist of a p-type semiconductor (such as Si doped with B) and n-type
semiconductor (such as Si doped with P). They are in close contact with each other. When
the 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. There by potential difference between two layers is created. This causes
flow of electrons (ie., an electric current)
163
Fig 3.23 Solar cell
Solar battery: When a large number of solar cells are connected in series it form a solar
battery. It produces more electricity which is enough to run water pump, to run street
light,etc
Fig 3.24 Solar pump run by solar battery
164
Applications
1. Solar cells are used in boilers to produce hot water for domestic and industrial
uses.
2. Solar cells, if properly designed, can be used for lighting purposes.
3. These are superior to other types of cells as they are non polluting and eco-
friendly.
4. It can be used to derive vehicles.
5. The solar cells made of silicon have been used as a source of power in space craft
and satellites.
6. Solar cells can be used to produce hydrogen by electrolysis of water. The liberated
hydrogen can be used in H2-O2 fuel cells.
7. They are used in remote areas where conventional electricity supply is a problem.
The huge capital cost is the major limitations for the large scale use of solar cells.
3.16 FUEL CELLS (Flow Batteries)

Fuel cells also an electrochemical device for converting chemical energy into
electricity. In contrast to storage battery, fuel cell does not need to involve a reversible
reaction since the reactants are supplied to the cell as needed from an external source.
This technology has been used in the Gemini, Apollo and Space Shuttle program.
In fuel cells, the combustion reactions produce electricity. As with other batteries,
the reactants undergo separated half cell reactions (the fuel does not burn) and the
electrons are transferred through an external circuit. One fuel cell that oxidizes H2 has
carbon electrodes impregnated with metal catalysts and a molten Na2CO3 electrolyte.
165
Fig 3.25 Fuel Cells
Anode (Oxidation):
H2(g) + CO32-(l) H2O+ CO2(g) +2e-
Cathode (Reduction):
1/2O2(g) + CO2(g) +2e- CO32-(l)
Overall reaction
H2(g) + 1/2O2(g) H2O(l)
Uses
Provides electricity and pure water during space lights.
Advantage
1. Clean, portable and product is water. Many fuel cells produce no pollutants.
2. Fuel cells are very efficient, converting about 75% of fuel’s bond energy into
electricity. In contrast, an electric power plant converts about 35% to 40% of bond
energy into electricity, and a car engine converts about 25% of gaseous bond
energy into moving the car.
166
Disadvantage
1. It cannot store electrical energy, needs continuous flow of reactant.
2. Electrodes are short lived and expensive.
Important Questions
1. What is corrosion?
2. Define Hydrogen embrittlement.
3. State Pilling- Bedworth rule
4. What is meant by decarburization?
5. What is meant by liquid metal corrosion?
6. Mention the conditions for wet corrosion to take place.
7. Distinguish between dry corrosion and wet corrosion.
8. What is pitting corrosion?
9. How steel screws in brass marine hardware corrode?
10. Why Zinc is more readily corroded when coupled with copper than with lead?
11. Mention the various factors influencing the rate of corrosion.
12. What are corrosion inhibitors? Give examples.
13. What are vapour phase inhibitors?
14. An iron pipe does not rust when connected to Zinc but corrodes rapidly when it is
in contact with copper – Why?
15. Stainless steel is a corrosion resistant alloy – Why?
16. Write the difference between electro plating and electroless plating.
17. What are the advantages of electroless plating over electroplating?
18. Explain oxygen adsorption type corrosion.
19. How is galvanic corrosion occur?
20. Explain the nature of the metal influence the rate of corrosion.
21. Substantiate the statement that nature of the environment affects corrosion.
22. Write an essay on corrosion control methods. 167
23. Mention few guidelines for proper designing of metallic structures.
24. Explain the types of electro chemical corrosion with examples.
25. What is sacrificial anode? Mention its role in prevention of corrosion.
26. Write short notes on corrosion control by impressed current method.
27. Explain anodic protection.
28. How will you control corrosion by modifying the environment?
29. What are corrosion inhibitors? How do they function?
30. How is corrosion prevented by cathodic protection method.
31. Explain electroplating with an example.
32. Explain electroless platting with an example.
Energy storage devices

1. What are batteries? Mention the basis for their functioning.
2. What are primary cells? Give examples.
3. Explain secondary cells.
4. Explain alkaline battery. What is a storage cell?
5. Describe lead acid battery.
6. How is lead acid battery recharged?
7. Write the uses of lead storage battery.
8. Write in brief on NICAD battery.
9. Mention the advantages of NICAD battery.
10. Why lithium battery is regarded as the cell of future?
11. Describe lithium battery.
12. Write few applications of solar cells.
13. Explain the construction and working of lead acid battery.
14. Explain fuel cells.
168

Water Technology: Types of Impurities and Hardness

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Water Technology: Types of Impurities and Hardness

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UNIT I

1.2 TYPES OF IMPURITIES IN WATER

1.3.1 Hardness of water

i. Temporary hardness or Carbonate hardness or Alkaline hardness: This is due to the

ii. Permanent hardness or Non-Carbonate hardness or Non - alkaline hardness: This is

CaSO4 + Na2Ze CaZe + Na2SO4

i.e., Amount Equivalent to CaCO3 = Amount of hardness producing salt

Molecular weight of hardness producing salt

i.e., Amount Equivalent to CaCO3 = Amount of hardness producing salt

Equivalent weight of hardness producing salt

1.4 UNITS OF HARDNESS

Problems based on Hardness

4. Calculate the carbonate and non-carbonate hardness of a sample water containing

(i) [OH-] + [H+]  H2O

(ii) [CO3]2- + [H+]  [HCO3-] P

1.5.1 Detection of various alkalinity:

Step I : Experimental procedure

Titration II: Determination of methyl orange alkalinity

(i) Calculation of Phenolphthalein Alkalinity

Volume of the water sample V2 = 100 ml

Phenolphthalein alkalinity (P) (in terms of CaCO3 equivalent)

= N2 Eq.wt of CaCO3 1000 ppm

(ii) Calculation of Methyl Orange Alkalinity

Volume of water sample V2 = 100 ml

Table 1.2 Calculation of alkalinity of water

P=M P=M 0 0 Only hydroxide

1. Calculate the OH- alkalinity

Strength of water sample due to OH- alkalinity = 0.0012 N

2. Calculate the CO32- alkalinity

Strength of water sample due to CO32- alkalinity = 0.0008 N

Strength of water sample due to CO32- alkalinity = 0.00312 N

If the data satisfy the condition, P < M,

1.6 ESTIMATION OF HARDNESS BY EDTA METHOD

wine red coloured weak complex

wine red coloured weak complex Stable complex Steel blue

1.6.1 Preparation of solutions:

(ii) Estimation of total hardness of water sample

(iii) Estimation of permanent hardness of water sample

1000 ml of the given sample hard water sample

(iii) Estimation of permanent hardness of water sample

 1000 ml of the given hard water sample}

Problems based on Hardness

= 220 mgs/lit or 200 ppm

2. In an estimation of hardness of water by EDTA titration, 50 ml of a sample of water

Strength of hard water sample = 0.006 M

Strength of hard water sample = 0.00195 M

Strength of boiled water = 0.001 M

Strength of hard water sample = 0.0025 M

Strength of Std water = 0.0025 M

7. 100 ml of a molecular water sample of requires 18.5 ml of EDTA solution for

Strength of Std water = 0.01

1.7.1 Scale and sludge formation

Figure 1.1 a) sludge b) scale

1.7.2 Boiler corrosion

Deaeration: It is a mechanical method of removal of dissolved gases such as O2 and CO2.

Figure 1.2 Mechanical deaeration of water

1.7.3. Priming and foaming (Carry over)

1.8 Softening (Or) Conditioning Methods

1.8.1 External treatment

Figure 1.3 Demineralisation Process

Advantage of Ion-Exchange Process

Disadvantage of ion exchange process

1.8.2 Internal conditioning