General

Chemistry
Course Code : CHY1001
Course Type: LTP; Credits: 4

Dr. Harihara Padhy, Ph.D.

Phone: 9668780860
harihara.padhy@vitbhopal.ac.in
 OUR SYLLABUS
•  WATER TREATMENT

•  PHASE AND ALLOY

•  ELECTROCHEMISTRY

•  CORROSION SCIENCE

•  ENERGY AND ENERGY CONVERSION

•  FUELS

•  POLYMERS
NO
Module DescripTon
1 Types of impurities in water – Types of Hardness in boiler water. Alkalinity of water and its estimation; Estimation of hardness by
EDTA method-Numerical problems; Scale, Sludge, Reasons for the formation of scale and Removal. Boiler water purification by ion-
exchange resin method. Specifications for potable water – Drinking water treatment – Disinfection by chlorination, ozonisation and UV
treatment; Sea water to drinking water conversion -Reverse osmosis & its significance
2 Phase equilibria: Gibbs phase rule, definition of terms with examples, One Component Systems- water and carbon dioxide systems
– Reduced phase rule. Two Component eutectic System- lead-silver systems. Alloys: Introduction- Definition- Properties of alloys-
Significance of alloying- Ferrous alloys- Nichrome and Stainless steel –
3 Electrochemistry - Corrosion: Introduction to Electrochemical reactions; Redox-reactions; Nernst equation; Problem solving using
Nernst equation. Standard Reduction Potentials; Cell potentials and Free Energy, Types and Mechanism of corrosion Galvanic
Corrosion; Determination of spontaneity of Corrosion, Relationship between corrosion and entropy, enthalpy and free energy.
Corrosion prevention; Cathodic protection – sacrificial anodic and impressed current protection methods; Electrolysis-electroplating-
process and typical applications, metal cladding; Coating processes – PVD and CVD and applications –
4 Energy conversion and storage: Fuel cells – Electrochemistry of a H2–O2 fuel cell, Basics of solid oxide fuel cells-applications;
Limitations of Batteries. Batteries- Chemical change and Electrical Work; Electrochemical reactions; Primary cells: Lechlanche,
alkaline and Li-primary cells. Secondary cells - Lead – acid, Ni-Cd, Ni-MH cells; Rechargeable lithium cells – LiCoO2 and LiC6
chemistry and applications.
5 Energy sources: Fuels-Definition. Calorific value - Definition of LCV, HCV. Measurement of calorific value using bomb and Boy’s
calorimeter – problem solving. Coal analysis-proximate and ultimate analysis and significance. Stoichiometric combustion reactions of
C, CH4 etc. Calculation of minimum quantity of air by volume and by weight-Numerical problems. Knocking and chemical structure,
octane number and cetane number and their importance; Alternate fuels and Fuel additives. Biodiesel-synthesis, advantages and
commercial applications;
6 Industrial and Conducting polymers : Introduction to Polymers- Classification. Types of Polymerization (Chain & Step growth);
Properties and engineering applications of BS, PVC, PMMA, PET, Teflon and Bakelite. Compression, injection, extrusion, Transfer
moulding methods of plastics. Fiber reinforced composites - Properties and applications in automobiles and aerospace. Second Law
of thermodynamics and entropy in recycling of plastics like PMMA. Introduction to metallic conductors. Conducting polymers:
Polyacetylene and Polyaniline - Mechanism of Conduction, doping, Electrical characterization, applications of conducting polymers in
semiconductor field.
Text Books:

1. O. G. Palanna, Engineering Chemistry, Tata McGraw-Hill EducaDon, 2009.
2.
Jain P.C. and Monica Jain, “Engineering Chemistry”, Dhanpat Rai Publishing Company
(P) Ltd., New Delhi, 2010

Reference Books:

1. Dara S.S, Umare S.S, “Engineering Chemistry”, S. Chand & Company Ltd., New Delhi
2010
2. O.V. Roussak and H.D. Gesser, Applied Chemistry-A Text Book for Engineers and
Technologists, Springer Science Business Media, New York, 2nd EdiDon, 2013.
3 R. Gowarikar and N.V. Viswanathan and J. Sreedhar, Polymer Science, John Wiley &
Sons, 2007.
4 Peter Atkins and Julio De Paula, Atkins’ Physical Chemistry, Oxford University Press,
2011.
5 David Linden, Hand Book of ba]eries, McGraw Hill Publishers, 4th EdiDon, 2010.
6 Brown and Holme, Chemistry for Engineering Students, 3rd EdiDon, Cengage, 2015.
7
Dr. Eliezer Gileadi , Electro kineDcs for Chemist and chemical engineers , Wiley-VCH,
1993, ISBN-10: 0471188581 , ISBN-13: 978-0471188582
 Module 1
•  Types of impurities in water – Types of Hardness in boiler
water. Alkalinity of water and its estimation; Estimation of
hardness by EDTA method-Numerical problems;

•  Scale, Sludge, Reasons for the formation of scale and

Removal.

•  Boiler water purification by ion-exchange resin method.

•  Specifications for potable water – Drinking water treatment –

Disinfection by chlorination, ozonisation and UV treatment;

•  Sea water to drinking water conversion -Reverse osmosis & its

significance
 Water
Chemical formula
Molecular weight
ConducDvity???

•  Existance on Earth
1. Solid state-ice,
2. Gaseous state (water vapor or steam)
3. Liquid
Ice float on water?!!!

The holes/cages
Hydrogen Bonding in Ice
DistribuDon of Earth’s Water
 Sources of Water

A.  Surface Waters:
1. Rain Water
2. River Water
3. Lake Water
4. Sea water

B. Underground Water:
1. Spring
2. Well water




Types of ImpuriDes
1. Dissolved ImpuriTes:
a) Inorganic salts e.g salts of calcium, Magnesium, Iron, Aluminium, Mn,
b) gases like carbon dioxide, nitrogen , oxygen, hydrogen sulphides
c) organic salts

2. Suspended ImpuriTes:
a) Clay
b) mud
c) Vegetable and animal ma]ers

3. Colloidal ImpuriTes:
Fine size parDcles like silica and alumina, organic wastes etc.

4. Bacterial ImpuriTes:
Bacteria, Germs, Pathogens, Microbes, Viruses, Parasites

 Types of impuriDes in Water
Natural Water may contain physical, chemical and biological impurities
such as

Physical impurities Chemical Impurities

1.  Conductivity
1.  Colour -Can be measured by 2.  pH
Tintometer (Fe, Mn) 3.  Alkalinity
2.  Taste 4.  TDS – Total dissolved salts
3.  Turbidity-Total Suspended solids 5.  Hardness-hardness causing ions
4.  Odor (Ca2+ and Mg2+)

Biological impurities
1.  Microorganism, Bacteria, Viruses
(BOD, COD, DO)

Impurity varies with season???

 Effects of ImpuriDes:
ü Colour of surface water- dissolved organic ma]ers

ü Taste and Odour- formaDon of compounds

ü Turbidity- suspended ImpuriDes

ü Pathogenicity- micro organisms

 Water Analysis
•  pH
•  Hardness
•  Alkalinity
•  Chlorides
•  Nitrates
•  Sulphate
•  Fluoride
•  TDS
•  Dissolved Gases
 Hardness of Water
•  CharacterisDcs of water which prevent the Leather FormaDon.
•  due to presence of:- salts like bicarbonates, sulphates,
chlorides of Ca, Mg and other metals


•  PracDcally speaking, measurement of:
> Calcium (Ca) ions
> Magnesium (Mg) ions

 Hardness
Why hard-water prevents lathering of Soap?

2C17H35COONa + (H.W)CaCl2) (C17H35COO)2Ca + 2NaCl

Sodium stearate Hardness Calcium stearate
(sodium soap) (Insoluble)

2C17H35COONa + (H.W) MgSO4 (C17H35COO)2Mg + Na2SO4

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)

Without Hardness
C17H35COONa + H2O C17H35COOH + NaOH
Soap Stearic acid

C17H35COOH + C17H35COONa Lather

Stearic acid Soap
15
 Types of Hardness
Temporary Hardness
•  Caused by the presence of dissolved bicarbonate of calcium, magnesium and
other heavy metals and the carbonate of iron.

•  It is mostly destroyed by more boiling of water, when bicarbonates are decomposed

yielding insoluble carbonates.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Mg(HCO3)2 Heat MgCO3 + H2O + CO2

Permanent Hardness
Contains chlorides or sulphates of calcium or magnesium or of both
Can not be removed by boiling
CaCl2 → Ca+2 + 2Cl-1
MgSO → Mg+2 + SO -2
4 4
 Disadvantages of Hard Water
(A) DomesTc Uses:
1.  Washing
2.  Bathing
3.  Drinking
4.  Cooking

(B) Industrial Uses:
1. Boiler Feed: should not contain nitrates- scale and sludges
2. Paper Mill: should not contain iron and lime- destroy resin of soap
3. Sugar industries: Sulphates and Alkaline carbonates- Deliquescent
4. Dyeing Industries: should not contain iron and hardness
5. Laundries: should be sok

 Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO3 eq Hardness in 106 parts of water

• Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 eq Hardness in one liter of water

• Clarke's Degree(oCl)
1o Clarke= 1grain of CaCO3 eq Hardness per gallon of water (GPG)
1 grain = 64.8 mg
• Degrees French ( Fr)
o

1oFr = 1 part of CaCO3 eq per 105 parts of water 1 gallon = 3.78 L

1mg/L=? ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water
= 1 ppm

04/08/18
1o Clarke=? ppm 18
 Hardness Table
Hardness as calcium carbonate
mg/L (ppm)
Soft 0 -20
Moderately soft 20-40
Moderately hard (Medium) 60 -120
Hard 120 -180
Very hard 180 & above

TDS
mg/L (ppm)

Drinking Water 25 -250

Distilled Water 0.5-1.5
Ground water 500 -2000
River and Lakes 50 -200
Rain water 10-50
CalculaTon of CaCO3 equivalent hardness of water

Mass of hardness Chemical equivalent

producing substance X of CaCO3
Calcium carbonate equivalent =
Chemical equivalent of hardness
producing substances
Problem 1
Calculate the calcium carbonate equivalent hardness of a water sample
containing 204mg of CaSO4 per litre

Solution:
204 X 100
Calcium carbonate equivalent hardness = = 150 mg of CaCO3/L
136
= 150 ppm

Note : Mol. Weight of CaCO3 = 100

Mol. Weight of CaSO4 = 136

20
Calcium carbonate equivalence calculaTon
Why calcium carbonate is chosen as standard?

Hardness Molecular Chemical Multiplication factor

producing weight equivalent
substance
Ca(HCO3)2 162 81 100/162 or 50/81
Mg(HCO3)2 146 73 100/146 or 50/73
CaSO4 136 68 100/136 or 50/68
CaCl2 111 55.5 100/111 or 50/55.5
MgSO4 120 60 100/120 or 50/60
MgCl2 95 47.5 100/95 or 50/47.5
CaCO3 100 50 100/100 or 50/50
MgCO3 84 42 100/84 or 50/42
 Problems
1. A water sample from VIT Bhopal tap water had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, CaCO3 = 20 ppm, MgSO4 =24.0mg/L
and Calculate the temporary, permanent and total hardness of the water
sample.
NB: Mol. Wts of Mg(HCO3)2= 146, MgCl2= 95, CaCO3 =100 and MgSO4 = 120

Solution Step 1 conversion in to CaCO3 equivalent

Constituent present quantity Conversion factor CaCO3 eq hardness

Mg(HCO3)2 16.8 mg/L 100/146 16.8 *100/146 = 11.5ppm

MgCl2 19.0 mg/L 100/95 19.0*100/95 = 20ppm
CaCO3 20 ppm 100/100 20.0*100/100 = 20 ppm
MgSO4 24.0 mg/L 100/120 24.0*100/120 = 20 ppm

Calculation

Temp. Hardness = 31.5 ppm P. Hardness = 40 ppm

Tot. Hardness =71.5 ppm

 Problem
How many grams of FeSO4 dissolved per liter gives
300 ppm hardness
NB: MW FeSO4= 152 Ans: 456 mg

A sample was found to contain 15 gm of KNO3, 2 gm

of silica, 5.1 gm of sodium chloride and 3 gm of
CaCO3 per liter. Find the hardness.
Ans: 3000 ppm
Problem 2:
A water sample has the following analytical data on analysis , MgCO3
= 84ppm, CaCO3= 40ppm, CaCl2 = 55.5ppm, Mg(NO3)2 = 37ppm and
KCl = 20ppm. Calculate the temporary, permanent and total
hardness of the water sample. Ans: 215 ppm

Problem 3:
A water sample found to have the following analytical data on analysis ,
MgCl2 = 95ppm, Mg(HCO3)2 = 14.6 ppm, CaSO4= 68ppm, MgSO4 =
120ppm, H2SO4 = 49 ppm, Ca(HCO3)2 = 81 ppm and SiO2 = 4ppm.
Calculate the temporary, permanent and total hardness of the water
sample.
Ans: 60, 250, 310 ppm
 ESTIMATION OF WATER HARDNESS
Titrimetric Method

v Primary standard?

v Secondary Standard?

v Indicator

v Titration Types?

v Complexometric Titration

v Chelating Ligand

04/08/18 25

•  Ethylenediaminetetracetic acid (EDTA)
 Structure of EBT
Sodium 4-[(1-hydroxynaphthalen-2-yl-hydrazinylidene]-7-nitro-3-oxo-Y-
naphthalene-1-sulfonate

EBT

Blue to wine red colour

 Steps for the Titration
•  Preparation of Std. Hard Water
‘X’ gm of CaCO3 in 1L of Water
•  Standardization of EDTA
‘M’ mL of standard HW+ 2-3 mL buffer + few drops of
EBT indicator and Titrate against EDTA
V1 ml of EDTA consumed

•  Determination of Total Hardness

‘N’ mL of sample hard water + 2-3 mL buffer + few
drops of EBT indicator and Titrate against EDTA
V2 ml of EDTA consumed
•  DeterminaDon of Permanent Hardness
‘O’ mL of Boiled sample hard water + 2-3 mL buffer + few drops
of EBT indicator and let the volume of EDTA consumed = V3 mL
•  V3 ml of EDTA consumed

•  DeterminaDon of Temporary Hardness

Estimation of hardness of water by EDTA

Step I : Preparation of standard Hard water

1g of pure dry CaCO3 is dissolved in 1L of distilled water.
1000 mg of CaCO3 is present in 1000 mL of water
Or 1mL of standard hard water contains 1 mg of CaCO3

Step 2: Standardization of EDTA solution

20mL of standard HW+ 2-3 mL buffer + few drops of EBT indicator and let the
volume of EDTA consumed = V1mL

Therefore, V1mL of EDTA consumed by = 20mL Std. HW ≅ 20 mg of CaCO3

1mL EDTA will be consumed by = 20/V1 mg CaCO3 eq
Step 3: Estimation of Total Hardness using Standardized EDTA solution
20mL of sample hard water + 2-3 mL buffer + few drops of EBT indicator and
let the volume of EDTA consumed = V2 mL

Therefore, 20mL Sample. H W = V2 mL of EDTA = (20/V1)*V2 mg CaCO3 eq

20 * V2
And 1L sample HW contains = * 1000 mg/L CaCO3
V1 *20

Total Hardness = (V2/V1)*1000 ppm

04/08/18 30
Step 4: Estimation of Permanent Hardness
20mL of Boiled sample hard water + 2-3 mL buffer + few drops of EBT indicator and let
the volume of EDTA consumed = V3 mL

Therefore, 20mL Boiled sample. H W = V3mL of EDTA = (20/V1)*V3 mg CaCO3 eq

20 * V3
And 1L sample HW contains = * 1000 mg/L CaCO3
V1 *20

Permanent Hardness = (V3/V1)*1000 ppm

Temporary Hardness = (Total – Permanent )

04/08/18 31
 Problem
A standard hard water contains 15g of CaCO3 per liter. 20 mL of this required
25 ml of EDTA soluDon.
100 ml of sample water required 18 ml of EDTA soluDon.
The same sample aker boiling required 12 ml of EDTA soluDon.
Calculate the temporary hardness of the given sample of water in ppm.


Ans: Total hardness= 2160 ppm
Permanent hardness = 1440 ppm
Temporary hardness= 720 ppm
1)  Problem: 1.0 gm of CaCO3 was dissolved in dil. HCl and diluted to 1000 ml. 25 ml of
this solution required 25 ml of EDTA solution for titration. 50 ml of sample hard water
required 45 ml of EDTA solution. In another titration 50 ml of same hard water on
boiling, cooling and filtering etc. required 20 ml of EDTA solution using eriochrome
blact-T as indicator, calculate total, temporary and permanent hardness of water
sample in different units.
2)  Problem: 0.5 gm of CaCO3 was dissolved in dil. HCl and diluted to 500 ml. 50 ml of
this solution required 48 ml of EDTA solution for titration. 50 ml of sample hard water
required 15 ml of EDTA solution for titration. Calculate total hardness of water
sample.
3)  Problem: 0.28 gm of CaCO3 was dissolved in dil. HCl and the solution diluted to one
litre. 100 ml of this solution required 28 ml of EDTA solution, while 100 ml of sample
hard water required 33 ml of EDTA. On the other hand 100 ml of the boiled water
sample when titrated consumed 10 ml EDTA of . Calculate total, temporary and
permanent hardness of water sample in different units.
4)  Problem: A standard hard water contains 1000 mg of CaCO3 per liter. 50 ml of this
required 50 ml of EDTA solution, 50 ml of sample water required 40 ml of EDTA
solution. The sample after boiling required 20 ml EDTA solution. Calculate the
temporary and permanent hardness of the given sample of water, in different units.
 Problem
50 mL of sample of hard water obtained from a bore well in Patencheru
near Hyderabad consumed 16 mL of EDTA. However the same water
sample when boiled and subjected to titration consumed only 5 mL of
EDTA.
Comment on why only 5 mL volume of EDTA is consumed after boiling
the sample water. At the same time, 50 mL of a standard hard water
containing 1 mg CaCO3 per mL consumed 24 mL of EDTA for titration.
In addition to this, calculate the total hardness of water in ppm units,
giving the temporary & permanent hardness.
 Alkalinity in Water
Alkalinity is the acid neutralizing capacity of a water sample

It is due to OH-, CO3-2 and HCO3-

Also from borates, phosphates, silicates or other bases (if any)

ü  OH-
CausDc Alkalinity
ü  CO32-
ü  HCO3- Temporary Hardness
ü  OH- and CO32-
ü  HCO3- and CO32-

OH- and HCO3- ions can exist together?

 Alkalinity in Water

ü  The possibility of OH- and HCO3- together is ruled out

because they combine to form CO32-ions.

OH- + HCO3- CO32- + H2O

Ø  Thus OH- and HCO3- ions can not exist together in water.
NaOH vs. HCl Carbonate vs. HCl

Bicarbonate vs. HCl

 Method

1.  20 ml sample water in conical flask

2.  Add 2-3 drops of phenolphthalein indicator
3.  Titrate against N/50 HCl
4.  ConDnue Dll pink colour disappear (Phenolphthalein alkalinity P)
5.  To the same soluDon add 2-3 drops of methyl orange
6.  Titrate Dll yellow colour changes to red (Total alkalinity T)

 OH-+H+ → H2O
-2 +
CO3 + H → HCO3-

HCO3-+H+ → H2O+ CO2

T
P
 Volume of p and T Alkalinity due to

(mL) OH- CO32- HCO3-

[p] = 0 0 0 [T]

[p] = [T] [T] 0 0

[p] = ½ [T] 0 [T] 0

[p] > ½[T] 2[P] - [T] 2[T - P] 0

[p] < ½[T] 0 2[P] [T] – 2[P]

T
P
 CalculaDon
•  Phenolphthalein alkalinity
Acid Water

N1V1 = N2V2
N2 = N1V1
P
CaCO3 Equivalent of Ph alkalinity = N2 x 50 x 1000 ppm
•  Total alkalinity
Acid Water

N1V1 = N3V3
N3 = N1V1
T
CaCO3 Equivalent of Total alkalinity= N3 x 50 x 1000 ppm
•  From the value of total and Ph. Alkalinity find the case and
amount of each ions


 Problem
•  100 mL of a water required 20ml of 0.02 N H2SO4 for
neutralizaDon to phenolphthalein end point. Aker this methyl
orange indicator was added to this and further acid required
was again 20 mL. Calculate the alkalinity of water as CaCO3in
ppm.
Problem-1: 200 ml of water sample on titration with N/50 HCl required 9.4
ml of acid to phenolphthalein end point. When a few drops methyl orange
are added to the same solution and titration further continued, the yellow
colour of the solution just turned red after addition of another 21 ml of the
acid solution. Elucidate on the type and extend of alkalinity present in the
water. [P<1/2T]

Problem-2: 500 ml of water sample require 29 ml of N/50 H2SO4 for

phenolphthalein end point and another 29 ml of the acid to methyl orange
end point on separate titration. Determine the type and extend of alkalinity
present in the water. [P=1/2T]

Problem-3: 50 ml of a sample of water requied 5 ml of N/50 H2SO4 using

methyl orange as indicator but did not give any colouration with
phenolphthalein. What type of alkalinity is present? Express the same in
ppm. [P=0]
Problem-4: 200 ml of water sample on titration with N/50 H2SO4 using
phenolphthalein as indicator, gave the end point when 10 ml of acid were
run down. After that, when methyl orange added the colour of the solution
becomes red (no yellow color). What type of alkalinity is present and what
is its magnitude? [P=T]

Problem-5: A sample of water was alkaline to both phenolphthalein and

methyl orange. 100 ml of this water sample required 12 ml of N/50 HCl
for phenolphthalein end point and another 5 ml of the acid to methyl
orange end point. Determine the type and extent of alkalinity present.
[P>1/2M]

Problem-6: 100 ml of a water sample required 20 ml of N/50 H2SO4 for

neutralization to phenolphthalein end point. After this, methyl orange
indicator was added to this and further acid required was 15 ml.
Calculation the type and the extent of alkalinity.
Boilers and troubles

https://www.youtube.com/watch?
v=is5wdVgPOkI

Boiler feed water

 Boiler troubles
I. Scale and Sludge

II. Caustic embitterment

III. Priming and Foaming

IV. Boiler corrosion

 Sludge and Scale
•  ConcentraDon of the dissolved salts increases when water
evaporates conDnuously insides the boiler.

•  When the soluDon is saturated with respect to salt concentraTon,

the salts starts precipitaDng out on the inner walls of the boilers.

•  These precipitates are called scale or sludge depending upon their

characterisDcs.
 Sludge
v  Sludge is a soft, loose and slimy
precipitate formed within the boiler.
sludge
v  It can be easily scrapped off with a wire
brush.
water
v  It is formed at comparatively colder
portions of the boiler.
Boiler wall
v  It is formed by substances which have
greater solubility's in hot water than in
cold water, e.g. MgCO3, MgCl2, CaCl2,
MgSO4 etc.,
 Scale
v  Scales are hard substances which sticks very firmly to the inner surfaces
of the boiler wall.
v  Scales are difficult to remove even with the help of a hammer and chisel.
v  These are formed mainly due to
1.  Decomposition of Calcium Bicarbonate
Ca(HCO3)2 → CaCO3 + H2O + CO2
Scale

2.  Formation of Ca(OH)2

CaCO3 + H2O → Ca(OH)2
water
3.  Deposition of CaSO4
Boiler wall
4.  Formation of Mg(OH)2
MgCl2 + H2O → Mg(OH)2

5.  Presence of SiO2

Forms MgSiO3 and/or CaSiO3
 Disadvantages of scale formaDon
1.  Fuel wastage – scales have low thermal conductivity
2.  Degradation of boiler material and increases the risk of accident
3.  Reduces the efficiency of the boiler and- deposit on the valves and
condensers
4.  The boiler may explode – if crack occurs in scale

Heating Heating Scale

H2Ovap H2Ovap

Heating Heating

A boiler without scale A boiler with scale

 Caustic embrittlement
Boiler materials becomes brittle due to accumulation of
excess alkali

This also causes embrittlement of boiler parts like rivets,

bends and joints.

These are also called stress corrosion

Na2CO3 + H2O → 2 NaOH + CO2

Fe + 2 NaOH → Na2FeO2+ H2
Na2CO3
3Na2FeO2 + 4H2O → Fe3O4+ H2+ ????

BFW
We are rivets

Crack NaOH
 Priming and foaming
Foaming
It is the production of continuous foam or
bubbles in boilers.
It is due to the presence of substance like oil
in boiler feed water.
Foaming
Normal bubble Priming
It is the process in which some particles of
liquid water are carried along with the steam.
It is then called as wet steam and the process
of formation of wet steam in boilers is called
priming.
Priming
Carry over bubble Priming is due to the
Presence of dissolved salts
High velocity steam due to sudden boiling
Improper boiler design
52
 Boiler corrosion
Degradation or destruction of boiler materials (Fe) due to the
chemical or electrochemical attack of dissolved gases or salts is
called boiler corrosion.

1. Corrosion due to dissolved O2

Fe + 2H2O +O2 →2 Fe(OH)2

4 Fe(OH)2+O2 → 2Fe2O3 +4H2O

2. Corrosion due to dissolved CO2

Mg(HCO3)2 →MgCO3 + H2O + CO2
CO2 + H2O →H2CO3

3. Corrosion due to dissolved salts

MgCl2 + 2 H2O → Mg(OH)2 + 2HCl

How to remove dissolved O2 and

CO2 from boiler feed water??
 Boiler Water Treatment
Water can be purified by two types of methods
1.  Internal conditioning (or) Internal Treatment
2.  External conditioning (or) External treatment

Internal conditioning methods

1. Carbonate conditioning – addition of carbonate compound

2. Phosphate conditioning – addition of phosphate compound
3. Calgon conditioning – addition of calgon Na2[Na4(PO3)6]
4.  Physical methods- Radioactive, Electrical or Colloidal Conditioning

 Chemical conditioning
1. Carbonate conditioning (Low Pressure Boilers)
CaSO4 + Na2CO3→ CaCO3 + Na2SO4

2. Phosphate conditioning (Low and High Pressure Boilers)

3CaCl2 + 2 Na3PO4 →Ca3(PO4)2 + 6NaCl
Calcium can not be precipitated below a pH = 9.5-10.5, hence the selection of
phosphate has to be based on the pH of the boiler feed water.
NaH2PO4 (acidic in nature) ,
Na2HPO4(weakly alkaline in nature),
Na3PO4 (Alkaline in nature)

3. Calgon conditioning (Low and High Pressure Boilers)

Na2[Na4(PO3)6 ] → 2Na+ + [Na4P6O18]2-
2CaSO4 + [Na4P6O18]2-→ [Ca2P6O18]2- + 2Na2SO4
Soluble complex
 Physical Methods
v Radioactive conditioning:
Energy radiation prevents aggregation of the scale
forming particles.

v Electrical Conditioning:
Mercury lamps emits discharges which prevent the
scale aggregation.

v  Colloidal conditioning:
Tannin, agar-agar gel, kerosene like oily substance
make a coating on the scale which prevent aggregation
 External treatment of water
1.  Lime soda process
Addition of Lime [Ca(OH)2 ] or Soda [Na2CO3]

2.  Zeolite methods

Passed through Zeolite Bed

3.  Ion exchange resin method

Passed through Ion-exchange resin
 Lime soda process
q It is a process in which calculated quanTty of Lime (Ca(OH)2) and
soda (Na2CO3) are added to the hard water to convert the soluble
calcium and magnesium salts to insoluble compounds by a
chemical reacDon.
q The CaCO3, Mg(OH)2 and/or CaS precipitated can be removed by
sedimentaDon or filtraDon.
q It can remove the hardness, impuriDes, mineral acids and also
gases present in the hard water.
q The precipitate formed are very fine and do not se]le easily
causing difficulty in filtraDon. Therefore small amount of coagulant
like alum (K2SO4. Al2(SO4)3.24H2O or FeSO4 or NaAlO2 are added.
q These coagulant entraps the fine precipitates of CaCO3 and
Mg(OH)2
NaAlO2 + 2H2O → NaOH + Al(OH)3
Coagulant Flocculent- Gelatinous precipitate
 Lime soda process
Cold Lime Soda Process Hot Lime Soda Process

Chemicals(soda+lime
Hard water feed
+ coagulant) feed

Sedimented sludge (CaCO3,

Mg(OH)2
 Hot vs Cold lime soda sokener

q  Rate of reaction increases

q  Accelerates the chemical reaction

q  No coagulant needed

q  Dissolved gases are expelled out.

q  Residual hardness is 15-20 ppm vs 50-60 ppm in

cold lime-soda process
 Advantages and Disadvantages
² Economical
² pH >7, alkaline, less corrosion
² pH >7, prevents the growth of Bacteria
²  Mineral content decreases
² Residual hardness is 15-20 ppm

v Required careful and skill supervision

v More sludge formed: disposal problem
v Residual hardness is 15-20 ppm. Not sufficient for boilers

QuanDficaDon of Lime and Soda
1.  React with Lime, Soda or both to get
]inal product as CaCO3, Mg(OH)2 and/
or CaS
2.  When the impurities are given as CaCO3
and MgCO3 present in water it should be
considered as due to bicarbonates of
calcium and magnesium respectively. So
Considered as temp. hardness
3.  Substances like NaCl, KCl, Na2SO4, SiO2,
Fe2O3 etc do not contribute to hardness

q  Temp Ca or CaCO3 L
q  Temp Mg or MgCO3 2L
q  Perm Ca except CaCO3 S
q  Perm Mg except MgCO3 L+S
q  NaHCO3 or KHCO3 L-S
QuanDficaDon of Lime and Soda

q  Temp Ca or CaCO3 L
q  Temp Mg or MgCO3 2L
q  Perm Ca except CaCO3 S
q  Perm Mg except MgCO3 L+S
q  NaHCO3 or KHCO3 L-S
q  Any gas L
q  Any Acid L+S
q  Coagulants L+S
q  NaAlO3 -L
 QuanDficaDon of Lime and Soda
Lime requirement for softening 1L
= 74 ( Impurity in CaCO3 equivalent which requires Lime)
100

Soda requirement for softening 1L

= 106 ( Impurity in CaCO3 equivalent which requires Soda)
100
 Problem
Calculate the amount of lime or soda required for softening
5,00 litres of hard water containing 60 ppm of MgSO4 (mol wt
= 120) Ans = 22.2g

Impurity Amount CaCO3 equivalent Lime or Soda

MgSO4 60 60*100/120 = 50 ppm L+S

Lime required per liter = 74/100(50) = 36 mg

Lime required for 500 L= 36mgx500= 18000 mg=18 g

Soda required per liter = 106/100 (50) = 53 mg

Soda required for 500 L= 36mgx500= 26500 mg=26.5 g
 Problem
Calculate the amount of lime and soda required for softening 5,000 litres of hard
water containing: MgCO3 = 126 ppm, CaCO3 = 50 ppm, MgCl2 = 95ppm, CaCl2 =
111ppm, Fe2O3 = 25ppm and Na2SO4 = 15ppm

Impurity Amount CaCO3 equivalent Lime or Soda

MgCO3 126 126 x(100/84) = 150 2L
CaCO3 50 50 x (100/100) = 50 L
MgCl2 95 95 x (100/95) = 100.0 L+S
S
CaCl2 111 111 x (100/111) = 100.0
Fe2O3 25
Na2SO4 15

Lime required per liter = 74/100(2x150+50+100) = 333 mg

Lime required for 5000 L= 314.5mgx5000= 1.665kg

Soda required per liter = 106/100 (100+100) = 212 mg

Soda required for 5000 L= 212mgx5000= 1.060kg
Calculate the lime and Soda required if Lime is 90 % pure and Soda is 85 % pure
 Problems
Problem-1: Calculate the amount of lime (84% pure) and soda (92% pure)
required for treatment of 20,000 litres of water, whose analysis is as follows:
Ca(HCO3)2 = 40.5 ppm, Mg(HCO3)2 = 36.5 ppm, MgSO4 = 30 ppm, CaSO4 = 34
ppm, CaCl2 = 27.75 ppm and NaCl = 10 ppm. Also calculate the temporary and
permanent hardness of water sample.
Temporary Hardness = 50 ppm, Permanent Hardness = 75 ppm, Lime
Requirement = 1.762 Kg, Soda Requirement = 1.728 Kg

Problem-2: A sample of hard water contains the following dissolved salts: MgSO4
= 10 ppm, CaCl2 = 85 ppm, Ca(HCO3)2 = 162 ppm, Mg(HCO3)2 = 73 ppm, CaSO4 =
68 ppm. Find out the temporary and permanent hardness of water in ppm.
Temporary Hardness = 150 ppm, Permanent Hardness = 134.84 ppm

Problem-3: When a sample of water was analyzed it is observed to have the

following minerals contaminants they are CaCO3 = 50 mg/l, MgCO3 = 100 mg/l,
CaCl2 = 111 mg/l, MgCl2 = 47.6 mg/l, NaCl = 5.86 mg/l. If this hard water is to be
softened by lime soda process, calculate the amount of lime and soda needed for
20,000 liters of water.
Temporary Hardness = 5002400 ppm, Permanent Hardness = 5702800 ppm
 Problems
Problem-4: Calculate the amount of lime and soda required for softening 75000
Liters of hard water. The analytical data obtained is as obtained is as followed: Ca2+ =
20 ppm, Mg2+ = 45 ppm, HCO3- = 30 ppm.
Lime Requirement = 8.96 Kg, Soda Requirement = 11.65 Kg

Problem-5: Calculate the amount of lime and soda required for softening one million
liters of water containing: H+ = 1.5 ppm, HCO3- = 396.5 ppm, Mg2+ = 42 ppm, Ca2+ =
90 ppm, FeSO4.7H2O = 14 ppm. The purity of lime is 91% and that of soda is 97.2%.
Lime Requirement = 471.67 Kg, Soda Requirement = 169.07 Kg

Problem-6: Calculate the quantities of lime and soda required for softening 300,000
liters of water, using 32.8 ppm of Sodium aluminate as a coagulant. Impurities in
water are as follows:
Ca2+ = 240 ppm, Mg2+ = 96 ppm, HCO3- = 732 ppm, dissolved CO2 = 44 ppm, NaCl =
60 ppm, Fe2O3 = 160 ppm.
Lime Requirement = 239.76 Kg, Soda Requirement = 127.2 Kg
 Zeolite (Permutit) method
q  Zeolite = Boiling stone (Greek)
q  Zeolite is a Hydrated Sodium Alumino Silicate (HSAS).
q  Natural zeolites form where volcanic rocks and ash layers react with alkaline
groundwater.
q  Synthetic: Na2CO3 , Al2O3 and SiO2 mix at high temperature
q  The general chemical formula
Na2O.Al2O3.xSiO2.yH2O (x = 2-10 and y = 2-6)
Natural: x=4, y=2
q  It is capable of exchanging reversibly its sodium ions with other divalent
ions

Porous Structure
 Zeolite sokener

Hard water
in

Hard water
Ca Cl2
spray

NaCl
NaZe Zeolite bed Na Ze
Gravel

Injector

CaCl2
Softened
To sink water
NaCl storage
 Process of sokening by Zeolite method
To remove temporary hardness
Na2Ze + Ca(HCO3)2 → CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2 → MgZe + 2NaHCO3

To remove permanent hardness

Na2Ze + CaCl2 → CaZe + 2NaCl
Ca2+

Na2Ze + MgSO4 → MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl → Na2Ze + CaCl2 (MgCl2)

Used 10% brine Regenerated Washings
Zeolite solution Zeolite drained
Advantages
q  Soft water of 10 ppm can be produced by this method
q  The equipment occupies less space
q  No impurities are precipitated, hence no danger of sludge formation in the treated
water
q  It does not require more time and more skill

Disadvantages
1.  If the water is turbid ---- then the turbidity causing particles clogs the pores of the Zeolite
and makes it inactive
2.  It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3- and CO32-
in the softened water (then it may form NaHCO3 and Na2CO3 which releases CO2 when
the water is boiled and causes corrosion)
3.  It also causes caustic embrittlement when sodium carbonate hydrolyses to give NaOH
4.  The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can not be
regenerated that easily
Ion-Exchange or demineralizaDon process
Ion exchange resins are porous, insoluble,
cross linked, long chain organic polymers
with a microporous structure.
Functional groups attached to the chain is
responsible for the “ion-exchange”
properties.

1. Cation exchange resin (RH+)

Amberlite IR-120, Dowex-50

2. Anion Exchange resin (ROH-)

Amberlite 400, Dowex-3
 CaDon exchange resin (RH+)
v  These are mainly phenol-sulfonic acid-formaldehyde resin, styrene-
divinyl benzene copolymers. exp: Amberlite IR-120, Dowex-50
v  sulfonic acid exchanges their H+ ions with the caDons present in the
water i.e., Ca2+ and Mg2+
v  In general the resins containing acidic functional groups (-COOH, -
SO3H etc) are capable of exchanging their H+ ions with other
cations, which comes in their contact
 Anion Exchange resin
The styrene divinyl benzene or amine formaldehyde copolymer
contain quaternary ammonium, terDary sulphonium or amino
group in the resin. Example: Amberlite 400, Dowex-3
The resin on treatment with NaOH soluDon is capable of
exchanging the OH- with different anion of water i.e. Cl-, SO42- etc

sulphonium
quaternary ammonium
 CaDon and Anion exchange resin
Cation exchange resin Anion exchange resin

- CH – CH2 – CH – CH2 – CH – CH2 - - CH – CH2 – CH – CH2 – CH – CH2 -

SO-3H+ SO-3H+ CH2NR+3OH- CH2NR+3OH-

-CH – CH – CH- -CH – CH – CH-
-CH2 - CH CH – CH2- -CH2 - CH CH – CH2-

SO-3H+ SO-3H+ CH2NR+3OH-

CH2NR+3OH-
 Ion exchange purifier (or) softener
Hard
water

Gravel
2Cl- 4H+ SO 2-
bed
Cation exchange Resin Anion exchange Resin
4
Ca2+ 2Cl- Mg 2+
SO42-
Injector
4H+
Injector
4OH-

Acid solution for Wastages to

regeneration of sink
Alkaline solution
resin Wastages to
for regeneration
sink of resin
pump

04/08/18 Soft water 77

 Process

At Cation exchange resin

2 RH+ + Ca2+ → R2Ca2+ + 2 H+
2 RH+ + Mg2+ →R2Mg2+ + 2 H+

At Anion exchange resin

2 ROH- + SO42- →R2SO42- + 2 OH-
2 ROH- + Cl- →R2Cl- + 2 OH-

H+ + OH- → H2O
RegeneraDon of ion exchange resins
Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) → 2 RH+ + Ca2+ (CaCl2, washings)

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH) → 2 ROH- + SO42- (Na2SO4, washings)

 Advantage and LimitaDons
Advantages
1.  The process can be used to soften highly acidic or alkaline waters
2.  It produces water of very low hardness of 2ppm. So the treated waters
by this method can be used in high pressure boilers

Disadvantages
1.  The setup is costly and it uses costly chemicals
2.  Ion exchange should not be used when the concentration
of Fe, Mn, or the combination exceeds 0.3 mg/L
3.  Best applied for additional softening following lime-soda softening
4.  The water should not be turbid and the turbidity level should not
be more than 10ppm

04/08/18 80
 Portable water SpecificaDon
1.  The water should be clear, colorless and odorless
2.  It should be free form dissolved gases such as CO2, H2S etc
3.  Water should be free from pathogenic microorganisms
4.  The hardness should not be high ( not more than 125ppm)
5.  The turbidity in drinking water should not exceed 25 ppm
6.  The pH of the drinking water must be 7.0 – 8.5
7.  The total dissolved salts (TDS) should be 500ppm
Indian Standard DRINKING WATER — SPECIFICATION
IS 10500 : 2012
Indian Standard DRINKING WATER
Indian Standard DRINKING WATER
Indian Standard DRINKING WATER
 Municipal water treatment
Municipal water treatment
Purification steps
1.  Screening
2.  Aeration
3.  Sedimentation and coagulation
4.  Filtration
5.  Sterilization and disinfection
6.  Storage and distribution
 Municipal water treatment
1.  Screening
Removal of suspended impurities, the raw water is passed through the screens
having large number of holes, and the floating matters are retained by them.

Modern Plants: Comminutors

2. Aeration
It is the process of adding air to the water, this promotes taste by the exchange
of gases between atmosphere and water.

3. Sedimentation
It is a process of allowing water to stand undisturbed in a big tank of about 5 m
deep for 2 – 6 hours. When the most of the suspended particles settle down
the clear water is pumped out and the treated with coagulants such as
Al2(SO4)3, NaAlO2 etc., (to remove fine clay and colloidal particles).

4. Filtration
It is the process of removing most of the colloidal matter by passing water
through the bed of fine sand and other proper sized granular materials.
 FiltraDon tank

Fine sand

Coarse sand
Water
feed Gravel

Filtered
Water
 SterilizaTon and disinfecTon
q UV Treatment
q Ozonisation (O3) O3 O2 + [O]

q Bleaching powder (CaOCl2)

q Chlorination by passing Cl2
UV Treatment

² Oxidized (or) destroyed by UV

² Mercury vapour lamps emi|ng radiaDon in the range of
250-260nm are bactericidal & to a lesser extent sporicidal.
I am a Bacteria
 OzonizaTon
Ozone and raw water are allowed to come in contact with each other
-  10 – 15 min. in 2-8 ppm
3O2 → 2O3 (Highly Unstable)
O3 → O2 + [O]
[O] + Germs → Germs Killed
Advantage: 1. Leaves no residue. Because of unstability
2. Removes odour, colour, Taste.
Disadvantage: Very Expensive
SterilizaDon of water by Bleaching powder (CaOCl2)

CaOCl2 + H2O →Ca(OH)2 + Cl2

Cl2 + H2O → HOCl+ HCl
HOCl + Water → OCl-

q  Economical: 1kg per 100 kilo liter

q  Introduces calcium in water
q  Excess give bad taste
 Break Point ChlorinaDon
It is seen that when liquid chlorine is added to water, the consumption of
chlorine makes the available chlorine less and after some time the
available chlorine increase???
Residual Chlorine à
I II III IV

Oxidation Formation of Destruction of

of reducing chloro-organic chloro-organic and Free residual
compounds and chloramines chloramines chlorine

e
c

d
a b Cl dose added à
Break Point ChlorinaDon
Desalination methods: Reverse Osmosis
Osmosis
Diffusion of solvent through a semipermeable membrane from a dilute
solution to concentrated side is called osmosis which happens until an equal
concentration of ]luid on both sides of the membrane is achieved

Reverse Osmosis
Diffusion of solvent through a semipermeable membrane from a
concentrated Solution to dilute side due to external pressure is called
reverse osmosis

Reverse Osmosis and Water Puri]ication

Osmosis

Sea water Soft Water

Solvent< Solute Solvent > Solute
concentration concentration

Reverse Osmosis
 Reverse Osmosis Process
Direction of Osmosis

Direction of Reverse Osmosis

Salt Water
Pure water

H2O Na+ Cl-

Piston H2O
H2O Na+ Cl-
H2O H2O
Na+ Cl- Na+ Cl-
H2O
H2O H2O
H2O
Na+ Cl-

Semi permeable
membrane

Figure: Puridication of water by RO Method

Pure H2O
04/08/18 96
© S. Arockiasamy, VITC
 REVERSE OSMOSIS MEMBRANE AND MODULES

HOLLOW Hollow Fiber

FIBER module

Spiral wound
module
According to
Geometric
Shape,
FLAT SHEET
membranes
can be Plate and Frame
classified in module

TUBULAR Tu b u l a r
module
 ADVANTAGES AND DISADVANTAGES OF MEMBRANE

ADVANTAGES DISADVANTAGES

•  Low manufacturing cost •  It can not be used on highly turbid feed

•  Relatively easy to clean by both waters without extensive pretreatment.
SPIRAL-WOUND chemical and hydraulic methods. •  Susceptible to plugging by particulates
•  Has a very broad range of applications
•  High packing density

•  Extremely susceptible to fouling due to

HOLLOW FIBER •  Relatively low manufacturing cost.
very small spacing between fibers.
•  Compact
•  Difficult to clean.
•  High packing density
•  Requires extensive pretreatment.
•  Modes energy requirement
•  Limited range of applications.

TUBULAR •  Can be operated on extremely turbid •  High capital cost.

feed waters. •  Relative high volume required per unit
•  Relatively easy to clean either membrane area.
mechanically or hydraulically.
•  Can process high suspended solid
feed with minimal pretreatment.

PLATE AND •  Moderate membrane surface. •  Expensive to operate for large scale.
•  Well-developed equipment. •  Susceptible to plugging by particulates
FRAME at flow stagnation points.
•  Potentially difficult to clean.
Reverse osmosis can reduce:

Semipermeable membranes
ü  Arsenic
are fragile:
ü  Asbestos

ü  Fluoride
ü Hard water can clog membrane
ü  Herbicides
ü Chlorine can destroy membrane
ü  Lead
ü Membrane must be rinsed
ü  Mercury
regularly to prevent scaling
ü  Nitrate
ü Prediltration usually required
ü  Pesticides

ü  Radium
ü  Salt
ü  Colloidal silica