Department of Chemistry

School of Advanced Sciences

Vellore Institute of Technology
Vellore, 632014

SJT-504B
Module 1 Water Technology
Characteristics of hard water - hardness, DO, TDS in water and their determination –
numerical problems in hardness determination by EDTA; Modern techniques of water
analysis for industrial use - Disadvantages of hard water in industries
Module 2 Water Treatment
Water softening methods: - Lime-soda, Zeolite and ion exchange processes and their
applications. Specifications of water for domestic use (ICMR and WHO); Unit processes
involved in water treatment for municipal supply - Sedimentation with coagulant- Sand
Filtration - chlorination; Domestic water purification – Candle filtration- activated carbon
filtration; Disinfection methods- Ultrafiltration, UV treatment, Ozonolysis, Reverse Osmosis;
Electro dialysis
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art
forms, emphasizing Differential aeration, Pitting, Galvanic and Stress corrosion cracking;
Factors that enhance corrosion and choice of parameters to mitigate corrosion
Module 1 Water Technology
Characteristics of hard water - hardness, DO, TDS in water and their determination –
numerical problems in hardness determination by EDTA; Modern techniques of water
analysis for industrial use - Disadvantages of hard water in industries
Module 2 Water Treatment
Water softening methods: - Lime-soda, Zeolite and ion exchange processes and their
applications. Specifications of water for domestic use (ICMR and WHO); Unit processes
involved in water treatment for municipal supply - Sedimentation with coagulant- Sand
Filtration - chlorination; Domestic water purification – Candle filtration- activated carbon
filtration; Disinfection methods- Ultrafiltration, UV treatment, Ozonolysis, Reverse Osmosis;
Electro dialysis
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art
forms, emphasizing Differential aeration, Pitting, Galvanic and Stress corrosion cracking;
Factors that enhance corrosion and choice of parameters to mitigate corrosion
Module 4 Corrosion Control
Corrosion protection - cathodic protection – sacrificial anodic and impressed current
protection methods; Advanced protective coatings: electroplating and electroless plating,
PVD and CVD. Alloying for corrosion protection – Basic concepts of Eutectic composition and
Eutectic mixtures - Selected examples – Ferrous and non-ferrous alloys.
Module 5 Electrochemical Energy Systems
Brief introduction to conventional primary and secondary batteries; High energy
electrochemical energy systems: Lithium batteries – Primary and secondary, its Chemistry,
advantages and applications. Fuel cells – Polymer membrane fuel cells, Solid-oxide fuel cells-
working principles, advantages, applications. Solar cells – Types – Importance of silicon single
crystal, polycrystalline and amorphous silicon solar cells, dye sensitized solar cells - working
principles, characteristics and applications
Module 6 Fuels and Combustion
Calorific value - Definition of LCV, HCV. Measurement of calorific value using bomb
calorimeter and Boy’s calorimeter including numerical problems. Controlled combustion of
fuels - Air fuel ratio – minimum quantity of air by volume and by weight Numerical problems-
three way catalytic converter- selective catalytic reduction of NOX; Knocking in IC engines-
Octane and Cetane number - Antiknocking agents.
Module 7 Polymers
Difference between thermoplastics and thermosetting plastics; Engineering application of
plastics - ABS, PVC, PTFE and Bakelite; Compounding of plastics: moulding of plastics for Car
parts, bottle caps (Injection moulding), Pipes, Hoses (Extrusion moulding), Mobile Phone
Cases, Battery Trays, (Compression moulding), Fibre reinforced polymers, Composites
(Transfer moulding), PET bottles (blow moulding); Conducting polymers- Polyacetylene-
Mechanism of conduction – applications (polymers in sensors, self-cleaning windows)
 Course Objectives
• To impart technological aspects of applied chemistry
• To lay foundation for practical application of chemistry in
engineering aspects
Expected Course Outcome
Students will be familiar with the water treatment, corrosion and
its control, engineering applications of polymers, types of fuels
and their applications, basic aspects of
electrochemistry and electrochemical energy storage devices
 Water is nature’s most wonderful, abundant and useful
compound. “Without food, human can Survive for a number
of days, but water is such an essential that without it one
cannot survive”

Sources of Water:
o Surface water
• Rain water: It is probably the purest form of natural water,
since it obtained as a result of evaporation from the surface
water. However during the journey downwards through the
atmosphere, it dissolves a considerable amount of industrial
gases (like CO2, SO2, NO2, etc.) and suspended solid
particles, both of organic and inorganic origin.
• River water: Rivers are fed by rain and spring water. In general
the greater the contact that water has with the soil, or the more
soluble the minerals of the soils with which it has come in
contact, greater the amount of dissolved impurities in river
water
• Lake water: It has more constant chemical composition. It,
usually contains much lesser amounts of dissolved minerals
than even well water, but quantity of organic matter present in
it is quite high
• Sea water: It is the most impure form of natural water. Sea
water contains, on an average, about 3.5% of dissolved salts,
out of which about 2.6% is sodium chloride. Other salts
present are Na2SO4, KHCO3, Mg(HCO3)2, Ca(HCO3)2, KBr,
MgBr2 ect
o Underground water
• A part of rain, which reaches the surface of the earth,
percolates into the earth
• In general, is cleaner in appearance due to the filtering action
of the soil, but contains more of the dissolved salts. Thus,
water from these sources contains more hardness. Usually,
underground water is of high organic purity
 Suspended Impurities:
Particles in water give rise to turbidity
Debris
Colloids
 Dissolved Impurities:
Total Dissolved solids (TDS)
Inorganic salts
Organic Matter
Dissolved Gases
 Biological Impurities:
Microorganism
Pathogens
Natural water is contaminated mostly by three major types
of Impurities:
o Physical impurities
o Chemical impurities
o Biological impurities

Physical Chemical Biological

impurities impurities impurities

Color Acidity

Turbidity Gases Microorganisms

Taste Minerals

Odor
 Physical Impurities

 Color: Color in water is caused by metallic substance like salts

of iron, manganese, human materials, tannins, peat, algae,
weeds, protozoa, industrial effluents. Actually, color in water is
due to dissolved substances and substances present as fine
colloid. The change in color of water is not harmful, unless it is
associated with any chemical of toxic nature.
 Usually yellow tinge indicates the presence of chromium
 Usually Yellowish-red color indicated the presence of Organic
matter
 Usually Red-brown color indicates the presence of peaty
matter
 Turbidity
 It is due to the colloidal, extremely fine suspension such as
clay, slit, finely divided matters and micro-organism like
plankton etc.
 Turbidity depends not only on the quantity of the insoluble
substances, but also on their size, shape and refractive index.

 Taste: It is directly interlinked with odor of the water

 Bitter: Due to presence of sulphate of Fe, Al, Mn
 Soapy: Due to presence of large amount of NaHCO3
 Brackish: Due to the presence unusual amount of salts
Major Impurities of water

Cationic Anionic Gases Biological Nonionic and

undissolved
Calcium Bicarbonate CO2 Microorganis Turbidity, silt, mud, dirt
Magnesium Carbonate H2S ms such as and other suspended
Sodium Hydroxide NH3 algae, fungi, matter Color, Plankton,
Potassium Sulfate CH4 bacteria Organic matter,
Ammonium Chloride O2 Microorganisms,
Iron Nitrate Bacteria
Manganese Phosphate
 Total
Dissolved
pH dissolved
oxygen
solids

Chemical Biological
oxygen oxygen
demand demand
 pH, a measure of hydrogen ion activity, is used to express the
intensity of acidic or alkaline condition of a solution. It is also an
important factor in water analysis since it enters into the calculation
of acidity, alkalinity and processes like coagulation, disinfection and
corrosion. The pH of a sample can be determined electrometrically or
colorimetrically
 When an acid or base is dissolved in water, the pH will be less or
greater than pure water. pH will be 0 to 14
• Water that has been exposed to air is mildly acidic as it absorbs
carbon dioxide and converted into bicarbonate and hydrogen ions
(essentially creating carbonic acid)
• The pH of seawater plays an important role in the ocean's carbon
cycle, ocean acidification caused by carbon dioxide
emissions
• High pH causes a bitter taste, water pipes and water-using
appliances become encrusted with deposits, Low-pH water will
corrode or dissolve metals and other substances
Based on pH values, following
conclusions can be drawn:
 Waters having pH above 8 contains
carbonates or hydroxide. It may be
with or without bicarbonates
 Water with pH value in the range of 4.5
to 8 contain no carbonates but contain 10.2- more OH‒ + CO32‒
bicarbonates and carbonic acid. 8.3-10.2 HCO3‒ + CO32‒
Natural waters falls this category
 Water having pH value below 4.5 4.3-8.3 HCO3‒ + CO2
contains carbonic acid but not 4.3 or less No Alkalinity
carbonates or bicarbonates
 The desirable pH range for drinking
waters is 7.0 to 8.5
 pH in conjunction with total salinity,
total alkalinity and temperature is used
to determine whether a water is
corrosive in nature or having scale
forming tendencies
 Dissolved oxygen (DO) is the amount of oxygen dissolved in a
given quantity of water at a particular temperature and
atmospheric pressure

 DO: Amount
of oxygen
dissolved in
one liter of
water-
expressed as
mg/L (ppm)
• Aeration
• Water temperature: Temperature of the water body
• Organic wastes
• Aquatic plant populations
• Photosynthetic activity of the water
• Respiration of animals and plants
• Speed of water flow
• Roughness of surface over which water flows
• Altitude(atmospheric pressure)
• Human activities
• Salt concentration: The solubility of oxygen decreases with increase in
concentration of the salt under a pressure of one atmosphere, the
solubility is less in saline water.
• Other dissolved gases concentrations: Dissolved N2, CO2 etc reduces DO
 Henry's Law: Henry's law states that at a constant temperature, the amount
of a gas that dissolves in a liquid is directly proportional to the partial
pressure of that gas in equilibrium with that liquid. It was formulated by
William Henry in 1803
 Temperature-Oxygen relationship
Temperature (0 ⁰C) Oxygen Solubility (mg/L)
0 14.6
5 12.8
10 11.3
15 10.2
20 9.2
25 8.6
100 0
 Most life
supporting water
systems: 4-6 mg/L
of DO
 It is one of the most useful titrations involving iodine was originally
developed by Winkler to determine the amount of oxygen in sample
of water
 The dissolved oxygen content is not only important with respect to
the species of aquatic life which can survive in the water, but is also
measure of its ability to oxidize organic impurities in water
 DO test is used to control the amount of oxygen in boiler feed water
by mechanical, physical and chemical methods
 DO test is helps to assess the raw water quality and to keep a check
on stream pollution
 DO test is the basis of BOD ( Biological oxygen demand) which is an
important parameter in evaluating the pollution potential of domestic
and industrial wastes
 In order to avoid loss of oxygen from the water sample, it is fixed by
MnSO4
 The principle involved in this methods of determination of DO is to
bring about the oxidation of potassium iodide (KI) to iodine with
dissolved oxygen present in water sample after adding MnSO4, KI
and KOH
 The reaction with manganese(II) hydroxide which is converted rapidly
and quantitatively to manganese(III) hydroxide. Here MnSO4 acts
oxygen carrier to enable the dissolved oxygen in molecular form to
take part into the reaction
 The DO present water sample oxidises the Mn(II) to Mn(III) which
precipitates as a brown hydrated hydroxide after the addition of KI
and KOH
 On acidification, the manganese reverts back to the divalent state and
an equivalent amount of iodine is liberated form the KI present
 The liberated I2 is titrated against standard sodium thiosulfate (hypo)
solution, using starch as indicator
 This means that 4 mol thiosulphate correspond to 1 mol dissolved
oxygen
 MnSO4 + 2KOH Mn(OH)2 + K2SO4

Mn(OH)2 + O2 + 2H2O Mn(OH)3 (Brown compound)

Mn(OH)3 + I‒ + 3H+ Mn2+ + I/2 I2 + 3H2O

2Na2S2O3 + I2 Na2S4O6 + 2NaI

Sodium thiosulfate Sodium tetrathionate
 What is the interference of Winkler’s method and how to overcome
it?
The main interference in this process is due to the presence of nitrites.
This is overcome by treating the original water sample with sodium
azide which destroys any nitrite when the sample is acidified

HNO2 + HN3 N2 + N2O + H2O

 Theory
• The secondary standard solution of sodium thiosulphate is
standardized by titrating with a primary standard potassium
dichromate (K2Cr2O7) using starch as indicator

Cr2O72‒ + 14H+ + 6I‒ 2Cr3+ + 3I2 + 7H2O

2S2O32‒ + I2 S4O62‒ + 2I‒
Which part of starch gives blue coloration with iodine?
 Starch can be separated into two major components, amylose
and amylopectin which exist in different proportions in in
various plants. Amylose, which is a straight-chain compound
and is abundant in potato starch, gives a blue color with iodine
and assumes a spiral form. Amylopectine, which has a
branched-chain structure, forms a red product, probably by
adsorption.

Amylose Amylopectine
 What is the mechanism of starch as indicator in iodometry
titration?
 Starch reacts with iodine in presence of iodide to form an
intensely blue-colored complex, which is visible at low
concentration of iodine. The sensitivity of the color reaction is
such that a blue color is visible when the iodine concentration is
2×10‒5 M and the iodide concentration is greater than 4×10‒4 M
at 20 ⁰C.

I2 + I‒ I3‒
Total dissolved solids (TDS):
 Total dissolved solids (TDS) is the amount of particles dissolved
in water
 It is a measure of the combined content of all inorganic and
organic substances contained in a liquid in molecular, ionized
or micro-granular (colloidal sol) suspended form.
 It is expressed in units of mg per unit volume of water (mg/L) or
as parts per million (ppm).
 TDS is directly related to the purity and the quality of water
purification systems
 Sources:
 Organic sources:
Silt, plankton, and industrial waste and sewage
Inorganic sources:
Weathering and dissolution of rocks and soils and
air that may contain calcium bicarbonate, nitrogen, iron
phosphorous, sulfur, and other minerals
Other sources:
• Runoff from urban areas, agricultural and residential
• Runoff road salts used on street during the winter
• Fertilizers and pesticides used on lawns and farms
• Discharge from industrial or sewage treatment plants
• Lead or copper as they travel through pipes used to
distribute water to consumers
• Industrial waste and sewage as well as runoff from urban
sources
• Recommended TDS for drinking water is 25-250 mg/L
• At any cost drinking water TDS should not exceed 500 mg/L.
• TDS for distilled water will be 0.5-1.5 mg/L
• TDS ranges from 100-20,000 mg/L in river water and will be
generally higher in ground water
• Sea water will have 3500 mg/L of TDS.
• Lakes and streams will have a TDS of 20-250 mg/L

 Measurement of TDS

The two principal methods of measuring total dissolved solids are

Gravimetry
Conductivity
 Hardness of water is the characteristic of preventing lather
formation of water with soap
• This is due to presence of certain salts of Calcium,
magnesium and other heavy metals dissolved in it
• A sample of hard water, when treated with soap (sodium or
potassium salt of higher fatty acid like oleic, palmitic acid or
stearic acid) does not produce lather, but on the other hand
forms a white scum or precipitate
• This precipitate is formed, due to the formation of insoluble
soaps of calcium and magnesium

2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl

2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

 Domestic Use Industrial Use
Washing Textile industry
• Does not lather freely • Wastage of soap
• Produces sticky precipitates • Precipitates of Ca & Mg soap
• Wastages of soap adhered to the fabric which don’t
• Sticky scup adhere to cloth leading to produce the exact shades of color
spot
Bathing Pharmaceutical Industry
• Washing quality of soap decreased • May produce undesirable substance
Cooking Sugar Industry
• The boiling point of water elevated • water containing sulphates, nitrates,
• More fuel and time are required alkali carbonates etc. causes
• Unpleasant taste of tea and coffee difficulties in sugar crystallization
• Dissolved salts deposited as on inner
walls of
Drinking Paper industry
• Bad effect in digestive system • Ca and Mg salts tends to react with
• Possibility of forming calcium oxalate chemical employed to provide
crystals in urinary tracks smooth and glossy finish
 Hardness of water is due to dissolved salts of mainly calcium and
magnesium as well as iron and other heavy metals
 Hardness is two types:
a) Temporary :
• Due to dissolved bicarbonates of calcium and magnesium and carbonates of
iron and other heavy metals. Hence it is also called as carbonate or alkaline
hardness.
• Can be easily removed by boiling where CO2 gas gets expelled removing
the hardness. The bicarbonates decompose on boiling giving rise to
carbonates and hydroxides which are insoluble and deposit at the bottom of
the vessel.
Ca(HCO3)2 CaCO3 + H2O + CO2
Mg(HCO3)2 Mg(OH)2 + CO2
b) Permanent:
• Due to dissolved chlorides and sulphates of calcium and magnesium. Also
called as non-carbonate hardness.
• Can be removed through zeolite, Lime-soda, ion-exchange processes
c) Pseudo hardness
Sea, brackish, and other waters that contain appreciable
amounts of Na+ interfere with the normal behavior of soap
because of the common ion effect. Soap may not lather.
Sodium(Na+) is not a hardness-causing cation, and so this
action which it exhibits when present in water in high
concentration is termed pseudo-hardness
 The common ion effect is responsible for the reduction in the
solubility of an ionic precipitate when a soluble compound
containing one of the ions of the precipitate is added to the
solution in equilibrium with the precipitate

 When there is high concentration of Na+ or K+ in water. It

interfere with normal behavior of soap
 Parts per million (ppm):
Parts of CaCO3 equivalent hardness per 106 parts of water
1 ppm= (1 part of hardness)/(106 parts of water)
 Milligrams per liter (mg/L):
No. of milligrams of CaCO3 equivalent hardness present per liter
of water
 Degree Clarke (ºCl):
It is defined as the parts of CaCO3 equivalent hardness per
70000 parts of water
So ºC = 1 part of CaCO3 per 70000 parts of water
 Degree French (⁰ Fr):
Parts of CaCO3 equivalent hardness per 105 parts of water.
1 French Degree of hardness=(1 part of hardness)/(105 parts of
water)
 Milliequivalent per litre (meq/L):
Milli equivalents of hardness per liter
1 meq/L = 1 meq of CaCO3 per liter
 Parts per million (ppm):
Parts of CaCO3 equivalent hardness per 106 parts of water
1 ppm= (1 part of hardness)/(106 parts of water)
 Milligrams per liter (mg/L):
No. of milligrams of CaCO3 equivalent hardness present per liter
of water
 Degree Clarke (ºCl):
It is defined as the parts of CaCO3 equivalent hardness per
70000 parts of water
So ºC = 1 part of CaCO3 per 70000 parts of water
 Degree French (⁰ Fr):
Parts of CaCO3 equivalent hardness per 105 parts of water.
1 French Degree of hardness=(1 part of hardness)/(105 parts of
water)
 Milliequivalent per litre (meq/L):
Milli equivalents of hardness per liter
1 meq/L = 1 meq of CaCO3 per liter
 ppm mg/L ⁰Fr ⁰Cl
ppm 1 1 0.1 0.07
mg/L 1 1 0.1 0.07
⁰Fr 10 10 1 0.7
⁰Cl 1/0.07 1/0.07 1/0.7 1

Numerical Problem:
If the hardness of water is 210.5 ppm Calculate its hardness in ⁰Cl

Solution: 1 ppm = 0.07 ⁰Cl

210.5 ppm = 0. 07 × 210.5 = 14.735 ºCl
Although the hardness of water is never present in the form of
calcium carbonate because it is insoluble in water, hardness of
water is conveniently expressed in term of equivalent amount
(equivalents) of CaCO3

 The main reason for choosing CaCO3 as the standard for

reporting hardness of water is the ease in calculations as its
molecular weight is exactly 100
 It is the most insoluble salt that can be precipitated in water
treatment
Hardness as well as non-hardness constituting ions are generally
expressed in terms of equivalent amount of CaCO3. Temporary
and permanent hardness are expressed in ppm as CaCO3
equivalent. The choice of CaCO3 is due to the fact that its
molecular weight is 100 and equivalent weight is 50 and it is the
most insoluble salt in water
Hardness = [Strength of hardness producing salt (in mg/L)] ×
[Multiplication factor]

100
factor =
2×
Multiplication Chemical equivalents of hardness
producing substances
 Disodium dihydrogenethylenediaminetetra-acetate of analytical
reagent quality is available commercially but this may contain a
trace of moisture. After drying the reagent at 80 ⁰C its
composition agrees with the formula Na2H2C10H12O8N2·2H2O
(relative molar mass 372.24)

 The structure of EDTA disodium salt is

O
O OH
N O Na
HO N
O O

O Na
 Complexometry involves the estimation of metal ions titrimetrically though
complex formation with a strong multidentate chelating ligand. These are
also called Chelometric or Chelatometric titration. Ligands having more than
one co-ordination centers are known as chelating ligands. They give extra
stability to a metal complex due to chelate effect – the stability with the
number of points of attachment of the ligand to metal ion
 A feasible complexometric titration should fulfil
the following conditions:
1. The ligands must react with metal ion to satisfy
all points of attachment i.e. co-ordination O
number at a time in a single step to form a H4 Y
O OH
soluble complex, without any precipitation N OH
HO N
2. The rate of reaction should be fast
O O
3. The stability constant of the complex should be
high OH
4. Suitable indicator must be available in
detecting the end pint sharply
Commercially EDTA is available as its disodium salt-
Na2H2Y·2H2O. This salt ionises in water to give H2Y2‒, which can
form complex with all metal ions in the mole ratio 1:1 with
simultaneous release of H+ ions
2
Na2H2Y H2 Y + 2Na
n 2 (n-4)
M + H2Y M
[ Y] + 2H

It is evident that complex formation depends upon the pH of the

medium, each metal ion forms a stable complex with EDTA at a
definite pH at which the titration with EDTA is possible. So pH of
the solution being titrated is kept constant or within a certain limit
by adding buffer solution
 Metal ion Log K
Mg(II) 8.70
Ca(II) 10.70
Mn(II) 13.79
Fe(II) 14.33
Co(II) 16.31
Zn(II) 16.50
Ni(II) 18.60
Cu(II) 18.80
Fe(III) 25.30
K = Stability Constant
 The end point of complexometric titrations are detected by
metal indicators. Organic dye ligands, which indicates the end
points of the complexometric titrations by changing color of
metal dye complex to that of the free dye ion are called metal
indicators.
HO SO3Na
OH
N
N

NO2

Eriochrome-Black-T (EBT)

1-(1-hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulphonate
 Metal-indicators are weak acids and form metal-indicator
colored complex at the pH where metal-EDTA complex is
formed
 The color reaction must be such that before the end point, when
nearly all the metal ion is complexed with EDTA, the solution is
strongly colored
 The metal-indicator complex must possess sufficient stability
else, because of dissociation, a sharp color change is not
observed. But Metal-Indicator complex must be less stable than
Metal-EDTA complex.
 The color contrast between the free indicator and the Metal-
Indicator should be readily observable
 The indicator must be very sensitive to metal ions, so that color
change occurs as near to the equivalence point as possible
• Discussion will be confined to the more common 1 : 1-complexes. The use
of a metal ion indicator in an EDTA titration may be written as:
M-In + EDTA→M-EDTA + In
• This reaction will proceed if the metal-indicator complex M-In is less stable
than the metal-EDTA complex M-EDTA. The former dissociates to a limited
extent, and during the titration the free metal ions are progressively
complexed by the EDTA until ultimately the metal is displaced from the
complex M-In to leave the free indicator (In), indicated by the formation of a
steel blue colored complex
• The indicator color change is affected by the hydrogen ion concentration of
the solution, and no account of this has been taken in the above expression
for the formation constant. Thus solochrome black, which may be written as
H21n-, exhibits the following acid-base behavior:

• In the pH range 7-11, in which the dye itself exhibits a blue color, Mg(II) ions
(in presence of NH4OH+NH4Cl buffer) give a distinct red color with the
indicator
Brief procedure of hardness measurement
• First EDTA Solution is standardized using standard hard water (1 mg/ml of
CaCO3 equivalents is prepared as standard hard water).
• For this, first known aliquot of Standard hard water is taken and 10-15 mL of
ammonia buffer is added to bring the pH between 9-10.
• Then a few drops of EBT solution is added to form the unstable complex
giving wine red color.
• This solution is titrated with the EDTA solution till the solution turns to steel
blue indicating the formation of stable EDTA-Metal ion complex.
• This volume of EDTA is noted as V1.
• The above procedure is repeated with sample hard water of unknown
hardness
• Volume of EDTA is noted as V2
• Then sample hard water of 250 mL is taken and evaporated to a volume of
50mL when the temporary hard salts settle down.
• The solution is filtered and washed thoroughly and made up again to 250mL.
• From this solution, 50 mL is pipetted out and titrated in similar manner as
done with standard hard water.
• Volume of EDTA is noted as V3
 Why in determination of total hardness of water, pH should
maintain between 7 -11?
a) Eriochrome black T is a dye, tend to polymerize to a red-brown product, and
consequently the indicator is rarely applied in titrations of solutions more acidic
than pH = 6.5
b) Complex formation with EDTA release equivalent amount of H+, reaction being
reversible increase in H+ concentration will decrease the stability of the
complex and excess EDTA will be consumed to give erroneous result
(n-4) + 2H
Mn + H2Y2 [MY]
c) In basic condition Mg(II) present in hard water get precipitated as Mg(OH)2
d) The sulphonic acid group gives up its proton long before the pH range of 7-12,
which is of immediate interest for metal-ion indicator use. Only the dissociation
of the two hydrogen atoms of the phenolic groups need therefore be
considered, and so the dyestuff may be represented by the formula H2D‒. The
two pK values for these hydrogen atoms are 6.3 and 11.5 respectively. Below
pH = 5.5, the solution of solochrome black is red (due to H2D‒), between pH 7
and 11 it is blue (due to HD2‒), and above pH = 11.5 it is yellowish-orange (due
to D3‒). In the pH range 7-11 the addition of metallic salts produces a brilliant
change in color from blue to red
 Importance of Water Analysis:
• Water analysis is essential to ensure its quality or to detect pollutants
that should be removed by water treatment. However, water quality
does not mean making the water suitable for human consumption; it
depends on its end use. For example, completely different quality
standards are applied in case of industrial water compared to those
applied to drink water, i.e., drinking water must be fit for human
consumption, while industrial water should be free from any
contaminants that may corrode or damage equipment.
 Limitations of Traditional Methods of Water Analysis:
• The traditional analysis includes chemical analysis, colorimetry,
spectrometry, chromatography, and atomic absorption. Although
these techniques differ in sensitivity and accuracy, most of them are
highly accurate. Nevertheless, they require sampling, expensive
devices, and manpower; besides, they are time-consuming and
difficult to conduct onsite
A lab-on-a-chip (LOC) is a device that integrates one or several laboratory
functions on a single integrated circuit (commonly called a "chip") of only
millimeters to a few square centimeters to achieve automation and high-
throughput screening
● Lab-on-a-chip devices are a subset of microelectromechanical systems
(MEMS) devices and sometimes called "micro total analysis systems" (μTAS)
● LOCs may provide advantages, which are specific to their application. Typical
advantages are:
a) Low fluid volumes consumption (less waste, lower reagents costs, and fewer
sample volumes)
b) Faster analysis and response time due to short diffusion distance & high
surface to volume ratio
c) Better process control because of a faster response of the system
compactness of the systems due to the integration of much functionality and
small volumes
d) Lower fabrication costs, allowing cost-effective disposable chips, fabricated in
mass production
e) Safer platform for chemical, radioactive or biological studies because of
integration of functionality, smaller fluid volumes, and stored energies Modern
methods of water
 Main components: The main components of a lab-on-a-chip system
for water analysis are; a liquid delivery system (injector and fluidic
transporter), mixer, reactor, separator, and power supply

 The Injector is used to deliver precise volumes into the chip. The
most common types of the injectors are syringe pumps and robotic
pipets.
 Transporters: control all aspects of the flow. They can be active,
which need an energy source, or passive, which are achieved by
manipulating the geometries of the channels and do not require any
energy source. The choice between the active and passive types is
based on the application. There are multiple types of active
transporters, but the most preferred is electrochemical pumping
systems, such as microsyringe pumps, because they eliminate the
design complexity.
.
 Mixers are used to mix different fluids into the channels. Similar
to the transporters, the types of mixers are divided into passive,
which are achieved by design manipulation, and active, which
require power.
 The reactor is where the reaction takes place. There are three
types of reactors used in lab-on-a-chip systems: gas phase,
liquid phase, and packed-bed reactors.
 Controllers are used for controlling all types of activities in the
chip as well as data acquisition and signal processing.
 Power supplies such as batteries, are essential to run the lab-
on-a-chip systems. Many research studies focus on finding
more advanced power supplies because some types of lab-on-
a-chip systems require high voltage
Lab-on-a-chip technology is rapidly developing and being used
in different industrial and research fields
Most biological lab-on-a-chip devices are commercialized, while
those for water analysis are still developing
However, some lab-on-a-chip applications in water analysis are
already established, such as pH testing and detection of various
chemicals (e.g., nitrates and nitrites, manganese, phosphates,
and silicates)
For example, the microfluidic pH analysis uses sulfonephthalein
as the main indicator
It includes the absorption cell, a static mixer, as well as a
syringe pump and four valves attached to the chip to regulate
the flow
References:
1. J. Cleary, C. Slater, D. Diamond,
Analysis of phosphate in
wastewater using an autonomous
microfluidics-based analyser,
World Acad. Sci. Eng. Technol. 52
(2009) 196–199

2. R. Paul Payel, “Lab on a Chip”

Systems for Environmental
Analysis, University of Stavanger,
2014
a) Washing:
 Hard water, when used for washing purposes, does not lather freely
with soap.
 It produces sticky precipitates of calcium and magnesium soaps.
 Similar problem exists in bathing.
b) Cooking:
 Due to the presence of dissolved hardness producing salts the boiling
point of water is elevated.
 Consequently more fuel is and time are required for cooking.
c) Drinking:
 Hard water causes bad effect on our digestive system.
 The possibility of forming calcium oxalate crystals in urinary tracks is
increased (Kidney stones)
 Paper Industry:
The presence of calcium and magnesium has impact on the properties
and quality of paper and their products
 Textile industry:
Hard water cause much of the soap to go as waste.
During dyeing process, calcium and magnesium salts present in water
make the quality of the shades very poor.
 Sugar industry:
If nitrates, sulphates of calcium and magnesium are present, they
cause hindrance to crystallization of sugar
 Concrete making:
Water containing chlorides and sulphates, if used for concrete making,
affects the hydration of the cement and the final strength of the
hardened concrete.
 In steam generation in boilers:
If the hard water is fed directly to the boilers, which led to the many
problems such as formation of scales which corrodes the boiler,
wastage of fuel etc
Boiler:
It is the closed vessel, in which water under pressure is
transformed into steam by the application of Heat in industries is
known as ‘Boiler’
Steam Utilization: Uses of steam generated from the boiler
are:
(1) Turbine drive for electric generating equipment, blowers and
pumps
(2) Heating and air electric generating equipment and comfort

 In most of the industries, water is used for production of steam.

This water should be free from dissolved Ca and Mg salts.
Such water is called BOILER FEED WATER
 Boiler troubles: If boiler water contains impurities beyond
prescribed limit, they lead to following problems.
Sludge, scale, caustic embrittlement, boiler corrosion, priming
and foaming are collectively known as boiler troubles

No. Requirements for boiler water If not, it will cause

1 The hardness should be below 0.2 ppm Sludge and scale
2 Free from oil and greases Foaming
3 Free from dissolved salts, suspended impurities Caustic embrittlement
4 Free from dissolved gases, suspended salts Boiler corrosion
 Scale & Sludge Formation in Boilers
o In a boiler, water is continuously evaporated to form steam. This
increases the concentration of dissolved salts. Finally, a stage is
reached when the ionic product of these salts exceeds their solubility
product and hence, they are thrown out precipitates
o Sludge
o Soft, loose, slimy precipitates are sludge
o Can be easily scrapped off with a wire brush
o Forms in comparatively colder portions of the boiler such
as bends etc.
o Formed because of MgCO3, MgCl2, CaCl2, MgSO4,
Mg(OH)2 (more soluble in hot water)
o Scale
o Dissolved salts deposit because of continuous
evaporation of water concentration of salts increases
o These are hard and stick strongly to the walls
o Difficult to be removed even with a hammer and chisel.
o Formed because of CaCO3, CaSO4, CaSiO3, MgSiO3
 sludge scale
Loose, slimy , non-adherent Hard, thick , strong adherent
precipitate precipitate
Due to salts like MgSO4 , MgCl2 Due to salts like CaSO4 , Ca(HCO3)2
Due to poor conductance, they Due to poor conductance, they
decrease the boiler efficiency to lesser decrease the boiler efficiency to
extent and causing chocking in the maximum extent, cause reduced fuel
pipelines economy , improper boiling, boiler
explosion etc.
It can be prevented by periodical It can be prevented by special
replacement of concentrated hard methods
water by fresh water. This process is Like:
known as “blow down” method. i) External treatment of ion exchange ,
ii) Internal carbonate, phosphate,
Calgon conditioning
iii) Mechanical hard scrubbing
methods
 Sludges are formed by substances, which have greater solubilities
in hot water than in cold water, e.g. MgCO3, MgCl2, CaCl2 and
MgSO4. They are formed at formed at comparatively colder portions
of the boiler and get collected at places where the flow rate is slow.
They can be easily removed (scrapped off) with wire brush
 Disadvantages of Sludge Formation:
• Chocking of pipes
• Low supply of heat
• Poor conductor of heat, wastage of fuel
• If sludge formed along with the scale, sludge get entrapped within
scale and both gets deposited as scale.
• Excessive sludge formation disturbs the working condition of the
boiler.
 Removal of Sludges:
• By brushing
• Frequent blow down process: Withdrawing portion of sludge
containing water and replacing with fresh water
 Scale are hard deposits firmly sticking to the inner surfaces of
the boiler
 Formation of Scales
 Decomposition of calcium bicarbonate:
o Scales are the main source of boiler troubles. Scale composed
chiefly of calcium carbonate is soft and is the main cause of
scale formation in low-pressure boilers
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑
(Scale)
 But in high-pressure boilers, CaCO3 is soluble
CaCO3 + H2O → Ca(OH)2 + CO2↑
 Precipitation of calcium sulphate: This type of scale causes
trouble mainly in high-pressure boilers. Calcium sulphate scale
is quite adherent and difficult to remove, even with the help of
hammer and chisel
 Hydrolysis of Magnesium salts: Dissolved magnesium salts
undergo hydrolysis forming magnesium hydroxide precipitate
which forms a soft type of scale

MgCl2 + 2H2O → Mg(OH)2 ↓ + 2HCl ↑

Presence of Silica: Presence of silica (SiO2) in small quantities

deposits as calcium silicate (CaSiO3) or magnesium silicate
(MgSiO3).
These deposits stick very firmly on the inner side of the boiler
surface and are very difficult to remove.
 Wastage of fuel: Scale has a low thermal conductivity, so the
rate of heat transfer from boiler to inside water is greatly
decreased. In order to provide a steady supply of heat to water,
excessive or over-heating is done and this causes increase in
fuel consumption. The wastage of fuel depends upon the
thickness and the nature of scale
Thickness of 0.325 0.625 1.25 2.5 12.0
scale in (mm)
Wastage of 10% 15% 50% 80% 150%
fuel

 Decreases in Efficiency: Scales may sometimes deposit in

the valves and condensers of the boiler and choke them
partially. This results in decrease in efficiency of the boiler
 Lowering of boiler safety: Due to scale formation, over-
heating of boiler is to be done in order to maintain a constant
supply of steam. The over-heating of the boiler tube makes the
boiler material softer and weaker and this causes distortion of
boiler tube and makes the boiler unsafe to bear the pressure of
the steam, especially in high-pressure boilers
 Danger of Explosion: When thick scales crack, due to uneven
expansion, the water comes suddenly in contact with over-
heated iron plates. This causes in formation of a large amount
of steam suddenly. So sudden high-pressure is developed.,
which may even cause explosion of the boiler
 Clogging: Boiler tubes may clog due to scale formation
 Corrosion
 By scrapping: With the help of scraper or piece of wood or
wire brush, if the scales are loosely adhering.
 Giving thermal shocks (heating the boiler and then suddenly
cooling with cold water) if the scales are brittle.
 If the scales are adherent and hard dissolving them by using
chemicals.
 Calcium carbonate (CaCO3) scales can be removed by 5-10%
HCl
 Adding complexing agents: Calcium sulphate(CaSO4) scales
can be dissolved by adding EDTA (ethylene diamine tetra acetic
acid) with which they form soluble complex.
 Frequent blow down process if the scales are loosely
adhering : Withdrawing portion of water and replacing with
fresh water
 Prevention of scale formation

Internal
External
treatment:
treatment
(Sequestration)

 Conditioning  Lime soda process

methods  Zeolite or ion exchange
process
 Sequestration:
 The process where suitable chemicals are added to the boiler
containing hard water with which scales are either precipitated
or converted in to soluble complexes.
 The chemical used is called Sequestrating agent.
 Internal treatment (Conditioning)
• Colloidal Conditioning
• Phosphate Conditioning
• Carbonate Conditioning
• Calgon Conditioning
• Treatment with sodium meta aluminate
• Electrical conditioning
• Radioactive conditioning
• Complexometric method
 Colloidal Conditioning

 In low-pressure boilers, scale formation can be avoided by

adding organic substances.
 Adding kerosene, tannin, agar-agar (a gel). These organic
substances get covered over the scale forming precipitates to
yield non-sticky and loose deposits which can be removed by
pre-determined blow-down operations.
 Phosphate Conditioning
• Used for high pressure boiler. No risk of CO2 liberation. Three types
of phosphate salts are used.
 Prevention of scale formation
• Sodium phosphate reacts with Ca2+ and Mg2+ ions in water forming
non adherent and easily removable soft sludge of Ca and Mg
phosphates. The commonly used phosphates are NaH2PO4,
Na2HPO4 and Na3PO4.
• The choice of salt depends upon the alkalinity of the boiler-feed
water. Calcium cannot be precipitated properly below a pH of 9.5, so
select a phosphate that adjusts pH to optimum value (9.5‒10.5).
Trisodium phosphate is most suitable for treatment, when alkalinity of
boiler water is low, as it is most alkaline in nature. If boil water's
alkalinity is sufficient, then disodium phosphate is more preferred. But
if the alkalinity of boil water is too high and requires to be reduced,
then monosodium phosphate, being acidic in nature, is preferred.
S. No. Salt Name Used for treating
1 Na3PO4 Tri sodium Phosphate highly acidic water
2 Na2HPO4 Di sodium hydrogen slightly acidic or
Phosphate weakly alkaline water
3 NaH2PO4 Sodium di hydrogen highly alkaline water
phosphate

3CaSO4 + Na3PO4 → Ca3(PO4)3↓ + Na2SO4

3CaCl2 + Na3PO4 → Ca3(PO4)3↓ + NaCl

 Carbonate Conditioning: Low-Pressure boilers
In low pressure boilers, scale formation can be prevented by
adding Na2CO3 to boiler feed water. Ca salts are precipitated as
loose sludge of CaCO3 which can be removed by blow down
operation. But some times it produces NaOH, CO2 and hence
carbonic acid. So it is less preferred

CaSO4 + Na2CO3 → CaCO3 + Na2SO4

 Calgon Conditioning
Calgon conditioning involves in adding Calgon (sodium
hexameta phosphate) to boiler water. It prevents the scale and
sludge formation by forming soluble complex compound with
CaSO4
Calgon: Sodium hexa meta phosphate: Na2[Na4(PO3)6]

Na2[Na4(PO3)6] → 2Na+ + [Na4(PO3)6]2‒

2CaSO4+ [Na4(PO3)6]2‒ → Ca2(PO3)6]2‒ + 2Na2SO4

Calgon is a brand registered trademark of water softener, and

bath and beauty products. Its name was a portmanteau derived
from the phrase "calcium gone". Today, the brand is owned by
Reckitt Benckiser for use in Europe as a water softener
Boiler water is treated with sodium meta aluminate when NaOH and
gelatinous precipitate of Al(OH)3 are formed. NaOH precipitates Mg salt
as Mg(OH)2. Both Al(OH)3 and Mg(OH)2 precipitates formed entraps all
the scale forming materials. These loose precipitates formed can be
removed by blow down operation.

NaAlO2 +2H2O → NaOH+Al[OH]3

MgCl2 +2NaOH → 2NaCl + Mg(OH)2

The flocculent precipitates of Mg(OH)2 plus Al(OH)3, produced inside the

boiler, entraps finely suspended and colloidal impurities, including oil
drops and silica. The loose precipitate can be removed by pre-
determined blow-down operation.
Sodium aluminate in thick solution form is available in plenty and at a
cheap rate from bauxite refining units and this can be used as such for
boiler- water treatment.
 Electrical conditioning:
Sealed glass bulbs, containing mercury connected to a battery, are set
rotating in the boiler. When water boils, mercury bulbs emit electrical
discharges, which prevents scale forming particles to adhere/stick
together to form scale
Prevention of scale formation
 Radioactive conditioning:
Tablets containing radioactive salts are placed inside the boiler water at
a few points. The energy radiations emitted by these salts prevent scale
formation
 Complexometric method:
It involves adding 1.5% alkaline (pH = 8.5) solution of EDTA to
feed-water. The EDTA binds the scale-forming cations to form
stable and soluble complex. As a result, the sludge and scale
formation in boiler is prevented.
Moreover, this treatment:
(i) prevents the deposition of iron oxides in the boiler,
(ii) reduces the carry over of oxides with steam, and
(iii) protects the boiler units from corrosion by wet steam (steam
containing liquid water).
 Caustic embrittlement: It is a type of boiler corrosion, caused by
using alkaline water in the boiler. During softening process by lime-
soda process, free Na2CO3 is usually present in small proportion in
the softened water. In high pressure boiler, Na2CO3 decomposes to
give sodium hydroxide and CO2
Na2CO3 + H2O → 2NaOH +CO2
 This NaOH flows into and occupies the minute hairline cracks present
on the boiler material by capillary action. Here water evaporates and
the concentration of NaOH increases progressively which attacks the
surrounding area. NaOH dissolves the surrounding area of iron as
sodium ferrate, Na2FeO2.
Fe + 2NaOH → Na2FeO2 + H2
Thus it makes the cracks bigger.

3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2

6Na2FeO2 + 6H2O + O2 → 12NaOH + 2Fe3O4
So NaOH is regenerated in the process and its concentration is keep on
increasing maintaining a required environment. Thus corrosion process
develops cracks and making the metal brittle by the deposition of the
product. This makes the boiler parts brittle (embrittlement).
 Causes of caustic embrittlement
 This type of electrochemical corrosion occurs when the concentration
of NaOH is above 100ppm. This causes brittlement of boiler parts,
particularly the stressed parts like bends, joints, rivets etc.

 Concentration cell formation inside the boiler.

 Iron surrounded by dilute NaOH becomes the cathodic side(cathode).
 Iron in contact with concentrated NaOH becomes anodic part(anode).
The anodic part slowly corrodes and dissolves.
 Concentration cell formation inside the boiler

Minute hairline cracks Caustic stress corrosion

crack in carbon steel
 By using sodium phosphate as softening reagent instead of
sodium carbonate. (phosphate conditioning)
 By adding tannin or lignin to the boiler water which block the
hair line cracks and pits. These prevent the infilteration of
NaOH through hair line cracks
 By adding sodium sulphate to boiler water, which also blocks
the hair line cracks and pits

[Na2SO4] 1:1 2:1 3:1

=
[NaOH]
Boiler pressure 10 atm 20 atm >20 atm

 Neutralization of excess alkali by suitable technique

It’s a decay of boiler material by chemical or electro-chemical
attack by its surrounding environment

Reasons for boiler corrosion are:

 Dissolved oxygen
 Dissolved carbon dioxide
 Acids from dissolved salts
 Presence of free acids
 Dissolved oxygen
Dissolved oxygen in water at high temperature attack boiler
material.
Fe + 2H2O + O2 → Fe(OH)2↓
2Fe(OH)2 + O2 → Fe2O3.2H2O↓
 Dissolved oxygen can be removed:
 By adding calculated quantity of sodium sulphite (Na2SO3),
hydrazine(N2H4) or sodium sulphide(Na2S)
2Na2SO3 + O2 → 2Na2SO4
N2H4 + O2 → N2+ 2H2O
Na2S + 2O2 → Na2SO4
 Hydrazine removes O2 without increasing the concentration of
dissolved solids. The products (N2 and H2O) are also harmless.
Hence, hydrazine is the most efficient internal treatment
chemical for the removal of dissolved oxygen
 Deaeration (Mechanical and Chemical):
Mechanical and chemical deaeration is an integral part of
modern boiler water protection and control. Deaeration,
coupled with other aspects of external treatment, provides the
best and highest quality feed water for boiler use.
Simply speaking, the purposes of deaeration are:
 To remove oxygen, carbon dioxide and other non-condensable
gases from feed water.
 To heat the incoming makeup water and return condensate to
an optimum temperature for:
 Minimizing solubility of the undesirable gases.
 Providing the highest temperature water for injection to the
boiler.
Removal of dissolved oxygen by
mechanical de-aeration
DO can be removed by mechanical
de-aeration also. Water spraying in a
perforated plate-fitted tower, heated
from sides and connected to Vacuum
pump. High temperature, low
pressure and large exposed surface
reduces dissolved oxygen in water.
Dissolved gases like CO2 and O2 can
be removed by this method. Water
undergoes deaeration at high
temperature and low pressure
because: Solubility of gases in
water α P /T.
 Dissolved CO2:
• Dissolved CO2 from the below reaction is hydrolyzed to form
carbonic acid (H2CO3) which corrodes the boiler.

Mg(HCO3)2 → Mg(OH)2 + 2CO2

CO2 + H2O → H2CO3

 Removal of CO2:
 CO2 is removed by adding calculated quantity of aqueous
ammonia
2NH4OH + CO2 → (NH4)2CO3 + H2O

 It is also removed by mechanical de-aeration along with oxygen

 Acids from dissolved salts:
 Dissolved magnesium salts hydrolyze to form acids:
MgCl2 + 2H2O → Mg(OH)2 + 2HCl
 This acid reacts with boiler in chain-like reactions producing
HCl
Fe + 2HCl → FeCl2 + H2
FeCl2 + 2H2O → Fe(OH)2 + 2HCl

 Even a small quantity of magnesium salts will cause large

amount of boiler corrosion.
 Neutralization:
Excess acidic nature is neutralized by adding alkalis and vice
versa
HCl + NaOH → NaCl + H2O
 Priming
• When a boiler is steaming rapidly some particles of the liquid water are
carried along with the steam. Its called priming.
o Presence of large amount of dissolved solids
o Sudden boiling
o Improper boiler design

 Foaming
• It is the production of persistent foam or bubbles in boilers, which do not
break easily. It is due to the presence of oil.
• Priming and foaming occur together

 Priming can be avoided by

• Fitting mechanical steam purifier
• avoid rapid change in steaming rate
 Foaming can be avoided by
• adding anti-foaming agent like castor oil
• Removing oil from boiler water by adding compounds like sodium aluminate
 Priming
• When a boiler is steaming rapidly some particles of the liquid water are
carried along with the steam. Its called priming.
o Presence of large amount of dissolved solids
o Sudden boiling
o Improper boiler design

 Foaming
• It is the production of persistent foam or bubbles in boilers, which do not
break easily. It is due to the presence of oil.
• Priming and foaming occur together

 Priming can be avoided by

• Fitting mechanical steam purifier
• avoid rapid change in steaming rate
 Foaming can be avoided by
• adding anti-foaming agent like castor oil
• Removing oil from boiler water by adding compounds like sodium aluminate
 Step-1: Calculation of Molarity of Standard hard Water (MSWH)
• Let weight of CaCO3 (in gms) =w
• Molecular weight of CaCO3 = 100
• Volume of solution in liters =V
• Number of moles of CaCO3 =n

Weight of CaCO3 (in gms)

• Number of moles of CaCO3 (n) =
Molecular weight of CaCO3

• Molarity of standard hard water = MSWH So, MSWH = n/V

= w/100V
 Step-2: Standard hard water vs EDTA solution
Molarity of EDTA solution (MEDTA)
M 1 V1 = M 2 V2
is determined in this step
Hard water EDTA solution
 Step-3: Given Hard water versus EDTA solution

By using the earlier equation, molarity of given hard water for total
hardness (MTH) is calculated
Total Hardness = (MTH × 100 × 1000)

 Step-4: Boiled, Cooled, filtered hard water for permanent hardness

(MPH) is calculated
Permanent Hardness = (MPH × 100 × 1000)

 Step-5:
Total Hardness = Temporary hardness + Permanent hardness
Example 1:
0.5 g of CaCO3 was dissolved in dilute HCl and diluted to 500 mL. 50
mL of this solution required 48 mL of EDTA solution for titration. 50 mL
of given hard water sample required 15 mL of EDTA solution for titration.
Calculate total hardness of water sample in ppm
 Solution:
(1) MSHW = w/100V
= 0.5/100 × 0.5
= 0.01 M
(2) Strength of EDTA solution is MEDTA
50 × 0.01 = 48 × MEDTA
So, MEDTA = 0.0104 M
(3) MTH × 50 = 0.0104 × 15
MTH = 3.12 × 10‒3 M
So Total hardness = MTH × 1000 × 100
= 3.12 × 10‒3 × 1000 × 100
= 312 ppm
`
Example 2:
One gm of CaCO3 was dissolved in dilute HCl and the solution was
made to one litre by dilution. 50 mL of this solution required 40 mL of
EDTA solution for titration while 50 mL of sample water sample required
20 mL of EDTA solution for titration. Calculate total hardness of water
sample in ppm
 Solution:
(1) MSHW = w/100V
= 1/100 × 1
= 0.01 M
(2) Strength of EDTA solution is MEDTA
50 × 0.01 = 40 × MEDTA
So, MEDTA = 0.0125 M
(3) MTH × 50 = 0.0125 × 20
MTH = 5 × 10‒3 M
So Total hardness = MTH × 1000 × 100
= 5 × 10‒3 × 1000 × 100
= 500 ppm
`
Example 3:
1.0 g of CaCO3 was dissolved in dilute HCl and the solution was made to one litre by
dilution. 25 mL of this solution required 25 mL of EDTA solution for titration. 50 mL of this
solution required 45 mL of EDTA solution. In another titration, 50 mL of same hard water
sample on boiling, cooling and filtering etc. required 20 mL of EDTA solution using EBT
as indicator. Calculate total, temporary and permanent hardness of water sample in
different units
Solution:
(1) MSHW = w/100V (4) MPH × 50 = 0.01 × 20
= 1/100 × 1 MPH = 4 × 10‒3 M
= 0.01 M Permanent hardness = MPH × 1000 × 100
(2) Strength of EDTA solution is MEDTA = 4 × 10‒3 × 1000 × 100
25 × 0.01 = 25 × MEDTA = 400 ppm
So, MEDTA = 0.01 M (a) 400 × 0.1 = 40 ºFr
(3) MTH × 50 = 0.01 × 45 (b) 400 × 0.07 = 28 ⁰Cl
MTH = 9 × 10‒3 M
So Total hardness = MTH × 1000 × 100 Temporary Hardness = Total
‒3
= 9 × 10 × 1000 × 100 hardness ‒ Permanent hardness
= 900 ppm
(a) 900 × 0.1 = 90 ºFr 900 ‒ 400 = 500 ppm
(b) 900 × 0.07 = 63 ⁰Cl (a) 400 × 0.1 = 50 ºFr
` (b) 500 × 0.07 = 35 ⁰Cl
Example 4:
A water sample contains 410 mg of CaSO4 per litre. Calculate the
hardness in terms of CaCO3 equivalents

Solution:
Hardness = [Strength of hardness producing salt (in mg/L)] ×
[Multiplication factor]
Hardness = [Strength of CaSO4 salt (in mg/L)] × [Multiplication factor]

Chemical equivalents of CaCO3

Multiplication factor =
Chemical equivalents of CaSO4

So Hardness = 410 × 50/68

= 301.47 ppm