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CY1104 – ENGINEERING CHEMISTRY

UNIT – 1 WATER AND ITS TREATMENT

LECTURE PLAN

1.1) Desalination of water by Reverse Osmosis method

1.2) Boiler troubles – (sludge and scale, priming and foaming, caustic
embrittlement, boiler corrosion)

1.3) External treatment methods

a) Zeolite softening
b) Ion exchange demineralization

1.4) Internal treatment using boiler compounds

(Carbonate, Phosphate, Calgon, sodium aluminate and colloidal
Conditioning)

1.5) Hardness of water – Types – Units

1.6) Estimation of hardness of water by EDTA method

1.7) Numerical problems based on hardness

1
 CY8151 – ENGINEERING CHEMISTRY

UNIT – 1 WATER AND ITS TREATMENT

1.1) Desalination of brackish water by Reverse Osmosis method:

1. Definition of Desalination:

Removal of common salt (NaCl) from water is called ‘Desalination’. The various
desalination methods are Electrodialysis, Reverse osmosis, Distillation and Freezing.

2. Based on dissolved solids, water can be classified into three types.

S.No Type of water Dissolved solids

1 Fresh water Less than 1000 ppm

2 Brackish water 1000 ppm – 35,000 ppm

3 Sea water More than 35,000 ppm

3. Reverse osmosis is used to convert sea and brackish water to fresh water.

4. Osmosis:

When two different concentrated solutions are separated by a semi permeable membrane,
due to osmotic pressure, low concentrated solvent flows to higher one. This is known as
osmosis.

5. Reverse Osmosis:

But when we apply an excess and opposite Hydrostatic pressure of 15 – 40 kg / cm2 to

overcome the osmotic pressure, then higher concentrated solvent will flow to the lower
one. This is known as reverse osmosis.

6. During this RO process , only the water flows across the membrane and it prevents the
salt migration. So, this method is also called as ‘Super filtration’.

7. The membrane is made up of cellulose acetate, cellulose butyrate, polymethacrylate

2
Advantages / Applications of Reverse Osmosis:

1. The life time of membrane is quite high. ( 2- 3 years)

2. Removes ionic, non-ionic and colloidal silica impurities , which cannot be removed by
demineralization method.

3. Low capital cost.

4. Simple operational procedure.

5. The membrane can be replaced within a few minutes, thereby providing uninterrupted
water supply.

6. This method is also used to remove bio-molecules, proteins, sugar etc.,

7. It provides potable water.

8. RO treated water is used in nuclear power plants.

Disadvantages:

1. Periodical cleaning of membrane is needed.

2. Pretreatment for bacterial removal is needed.

Diagram:

3
 1.2) Boiler Troubles

1 .Definition of boiler feed water:

The setup used to produce steam in industries is known as ‘Boiler’. Water is fed to the
boiler and heated to produce steam. The water fed into the boiler is known as “Boiler feed
water”.

2. Requirements for boiler water

S.No Requirements for boiler water Permissible limits If not, it will cause
1 Free from hardness causing salts less than 0.2 ppm Sludge and scale
2 Free from oil and greases 0 ppm Foaming
3 Free from dissolved salts and alkalinity 0.45 ppm Caustic embrittlement
4 Free from dissolved gases, suspended salts 0 ppm Boiler corrosion

3. Boiler troubles:
If the untreated water is fed directly to the boiler, it may cause sludge, scale, priming,
foaming, caustic embrittlement and boiler corrosion which are collectively known as
boiler troubles.

1.2 – A) Sludge and scale:

When the boiler feed water is continuously converted into steam, the concentration of the
dissolved salts in water increase progressively. When the concentration reaches a
saturation point, the salts are getting precipitated on the inner walls of the boiler.

Definition:
If the water contains hardness causing salts like MgSO4, MgCl2 ,CaSO4 , Ca (HCO3)2 . on
evaporation, the salts are precipitated .
If they form loose, slim , non-adherent precipitate, It is known as sludge.
If they form hard, thick , adherent precipitate, it is known as scale.

4
Reasons for sludge and scale:

Sludge: MgCl2 , MgSO4, CaCl2

Scale: CaCO3 , MgCO3. Ca(HCO3)2

Disadvantages of scales and sludges:

a) Wastage of fuel
b) Decrease in efficiency
c) Boiler explosion

a) Wastage of fuel:

Scales have low thermal conductivity. So, the heat transfer from boiler to inside water
may not be sufficient. In order to provide steady supply of heat to water, over heating is
to be done which causes wastage of fuel. The wastage of fuel depends on the thickness
and nature of the scale which is shown in the table.

Thickness of scale (mm) 0.325 0.625 1.25 2.5 12

Wastage of fuel (%) 10 15 50 80 150

b) Decrease in efficiency:

Scales sometimes deposit in the valves and condensers of the boilers and heat exchangers
and cause choking. This results in decrease in efficiency of the boiler and heat
exchangers.

c) Boiler explosion:

Sometimes due to overheating the thick scales may crack which causes the sudden
contact of high heated boiler material with water. This causes formation of a large
amount of steam and it develops high pressure. This leads to explosion.

Types of Sludge and Scale deposits:

CaCO3 Deposit, CaSO4 deposit, Mg(OH)2 deposit, SiO2 deposit, Fe deposit

5
 Prevention of Scales:

1. At earlier stage, scraper, wire brush, mechanical scrubber can be used to remove scales.

2. Thermal shocks are used to remove brittle scales.

3. By external treatment methods (eg) Ion exchange demineralization, zeolite softening

4. By using boiler compounds in internal treatment (eg) phosphate, calgon, EDTA

5. By acid treatment

Differences between sludge and scale:

N Sludge Scale
o
1 Loose, slim , non-adherent deposit on the Hard, thick , adherent precipitate
inner walls of boiler.

2 Due to salts like MgSO4 , MgCl2
3 Due to poor conductance, they decrease
the boiler efficiency to lesser extent and
causing chocking in the pipelines.
Due to salts like CaSO4 , Ca(HCO3)2
Due to poor conductance, they decrease
the boiler efficiency to maximum extent,
cause reduced fuel economy , improper
boiling, boiler explosion etc.,

4 It can be prevented by periodical It can be prevented by special methods like

replacement of concentrated hard water
by fresh water. This process is known as
“blow down” method.
i)external treatment of ion exchange ,
ii)Internal carbonate, phosphate, Calgon
conditioning
iii)Mechanical hard scrubbing methods.
iv) Thermal shocks

5 Diagram:

6
 1.2 – B) Priming and Foaming:

Priming:
Due to rapid boiling, the steam may carry some water droplets along with it. This is
called wet steam .The process of wet steam production is called Priming. It can reduce
the heat of the steam and cause corrosion in the pipelines.
S.No Reasons for Priming Control measures of priming
1 Improper design of boiler Proper boiler design
2 High water level Maintaining proper water level
3 High velocity of steam Regulating the velocity of steam
4 Uneven boiling Proper boiling

Foaming:
If oils and greases are present, they produce stable bubbles on the water surface.This will
increase the wet steam production. This is known as “Foaming”.
Prevention of foaming:
Foaming is prevented by adding
i) Anti foaming agents (e.g.) synthetic poly amides , castor oil, cotton seed oil
ii) Coagulants (e.g.) Aluminium hydroxide, sodium aluminate
iii) Oil can be removed by cataphoresis ( separation of colloidal charged particle by
electrical plates)

Foaming and priming are collectively known as ‘ Carry over”.

1.2- C) Caustic Embrittlement:

It is the intercrystalline cracking of boiler due to NaOH. NaOH content in water is

increased due to the dissolved salts like Na2CO3 which is added during internal
treatment.
Na2CO3 + H2O  2 NaOH + CO2

This NaOH occupies the hair line cracks of boiler metal and converts the insoluble Fe
into soluble Sodium Ferroate. Thus it makes the cracks bigger in bents, joints and
crevices.

Fe + 2 NaOH  Na2FeO2 + H2 ↑
( Insoluble) (Soluble) 7
Prevention of caustic embrittlement:
1. As softening agent, we can use sodium phosphate instead of sodium carbonate.
2. The hair line cracks can be sealed by waxy materials like Tannin and Lignin.
3. By adjusting the pH of the water around 6.5 – 8.5

1.2 - D) Boiler Corrosion

It may be due to three major reasons:
i) Dissolved Oxygen
ii) Dissolved CO2
iii) Dissolved salts like MgCl2

Corrosion Due to dissolved oxygen:

Dissolved oxygen in presence of water, causes corrosion.
4Fe + 6 H2O + 3O2  4 Fe (OH)3 (Rust)

Prevention from oxygen:

a) Chemical method -
i)Adding Sodium Sulphite:
2 Na2SO3 + O2  2 Na2SO4
This method results in other precipitates which can have some side effects. So this
method is less preferred.
ii)Adding Hydrazine:
N2 H4 + O2  N2 + 2 H 2 O
This method results in inert gas and pure water, and has no side effects. So it is preferred.

b) Mechanical deaeration method:

1. This is based on the Henry and Dalton’s law principle that at high temperature , low
pressure and high exposed area, the solubility of gases in water is decreased. So, the
gases can be expelled easily.

2. Here, the water is fed into the mechanical deaerator which is provided with vacuum
pump, heaters and perforated plates.

4. The out coming water will be free from dissolved gases.

8
 .
Corrosion due to Carbon – di – oxide:

Salts like Calcium bicarbonate on heating produces CO2 . CO2 dissolves in water to
form carbonic acid which corrodes the boiler metal.

Ca(HCO3)2 ∆ CaCO3 + H2O + CO2

H2O + CO2  H2CO3

Prevention from CO2

1. Chemical method: By adding calculated amount of ammonium hydroxide
2NH4OH + CO2  (NH4)2CO3 + H2O

2. Mechanical deaeration method ( similar to oxygen method)

Corrosion due to Dissolved salts like MgCl2

Dissolved salts like MgCl2 cause acid formation. This will be prevented by alkali
neutralisation.
MgCl2 + 2 H2O  Mg(OH)2 + 2 HCl (Corrosive acid)

Neutralisation:
Excess acidic nature is neutralized by adding alkalis and vice versa.
HCl + NaOH  NaCl + H2O
9
 1.3) EXTERNAL TREATMENT

Removal of impurities, salts from boiler feed water before feeding it to the boiler is
known as external treatment. (e.g) Zeolite process, ion exchange demineralisation
1.3) - A) ZEOLITE (PERMUTIT) SOFTENING PROCESS

i)Hydrated sodium alumino silicates available in nature are known as zeolite.

ii) These natural zeolites are green sand . They are non porous in nature.

iii) Zeolites are having the general formula Na2O . Al2O3. xSiO2 . yH2O
(x = 2 to 10; y = 2 to 6)
iv) The porous and gel structured synthetic zeolites are known as permutit.

v) These zeolites and permutits are used for water softening.

vi) Synthetic zeolite is represented as Na2Ze.

Principle

i) The sodium ions are loosely held in these zeolites. They are easily replaced by Calcium

and magnesium ions present in the water.

ii) When hard water is passed through a bed of sodium zeolite kept in a cylinder, it

exchanges its sodium ion with Ca2+ and Mg2+ ions present in the water to from Calcium

and Magnesium zeolites.

iii) Zeolite softeners may be of pressure type or gravity type.

Reactions:

CaSO4 + Na2Ze  CaZe + Na2SO4

MgSO4 + Na2Ze  MgZe + Na2SO4

CaCl2 + Na2Ze  CaZe + 2 NaCl

MgCl2 + Na2Ze  MgZe + 2 NaCl

The outcoming water is enriched with large amount of sodium salts which do not cause
any hardness. But in cannot be used in boiler.
10
Regeneration:
i) On prolonged use, all the zeolite sodium ions are exhausted.
ii) There will be no sodium ions to exchange the Calcium and magnesium ions. So, they
have to be regenerated.
iii) The exhausted zeolite is regenerated by treating with 10% solution of NaCl.

Regeneration reaction:
The regeneration step comprises of a) back washing b) salting c) rinsing before reuse

CaZe + 2 NaCl  Na2Ze + CaCl2

MgZe + 2 NaCl  Na2Ze + MgCl2

Advantages of zeolite process:

1. The outlet water will have least hardness around 1 – 2 ppm only.
2. As the zeolite can be regenerated, the method is cheap.
3. Operation is easy.
4. The space requirement for this setup is minimum .
5. No sludge is formed during this process.

Disadvantages of zeolite process:

1. Turbid water cannot be treated as it blocks the pores of the zeolite bed.
2. Acidic water cannot be treated as it decomposes the structure of zeolite.
3. Water containing Fe, Mn cannot be treated as the regeneration is difficult.
4. Brackish water cannot be treated because it contains Na+ ions. So, the ion exchange
reaction will not occur.
5. When the softened water contains more dissolved sodium salts, it may result in boiler
corrosion and caustic embrittlement. 11
 1.3) - B).Ion exchange method - ( Demineralisation)

Working:

1. Here all the cations and anions are completely removed. It uses two cylinders of cation
exchange cylinder and anion exchange cylinder filled with resins.

2. Resins are long chain, insoluble, cross linked, organic polymers. There are 2 types.

i) Cation exchange resins – RH2

(e.g) Sulphonated coals , RSO3H, commercially available as Dowex-50

ii) Anion exchange resins . R’(OH)2

(e.g) Ureaformaldehyde, Amines R-NH2, commercial name is Dowex -3.

3. The resins are prepared by copolymerization of styrene and di vinyl benzene.

The resultant polymer is treated with acid, it forms cation exchange resin. If the polymer
is treated with bases and ammonium chloride, it forms anion exchange resin.

4. The water is fed into cylinder –I where all the cations are replaced by RH2 Resins.
RH2 + CaCl2  R Ca + 2 HCl
RH2 + MgCl2  R Mg + 2 HCl

5. The cation free water is fed to cylinder II, where all the anions are replaced.
R’(OH)2 + 2 HCl  R’Cl2 + 2H2O

6. So, the resultant water is free from all types of ions. 12

Regeneration:

On prolonged use, as all the resins are exhausted, there will be no H+ orOH – ions
to exchange the unwanted ions. So, they have to be regenerated. Cation resins are
regenerated by HCl and anion resins are regenerated by NaOH.

R Ca + 2 HCl  RH2 + CaCl2

R’Cl2 + 2NaOH  R’(OH)2 + 2NaCl

Advantages of Ion exchange method:

i) Can be used for high pressure boilers also.
ii) It can treat highly acidic or alkaline water.
iii) We can get pure water as hardness as low of 2 ppm.

Drawbacks of Ionexchange method:

i) Expensive
ii) Fe, Mn cannot be removed as they form complexes with resins
iii) Cannot be used for turbid water as they clog the resins.

Diagram:

13
 Differences between soft water and demineralized water.
S. Soft water
No
1 It does not contain hardness
producing calcium and magnesium
ions, but it may contain other ions
like K+, Na+, Cl- etc.
2 Softening involves removal of only
hardness causing ions.
Differences between Zeolite and ion exchange process:
No Zeolite process
1 It exchanges only cations.
2 The cylinder is filled with zeolite.
Na2O . Al2O3. xSiO2 . yH2O
3 NaCl is used for regeneration
4 Softening involves removal of only
hardness causing ions.
5 The treated water contains relatively
large amount of dissolved Na salts
which causes caustic embrittlement in
boilers.
6. The setup and operating cost is
relatively low.
7 Acidic water cannot be treated
because acid decomposes the zeolite.
Demineralized water
Demineralized water does not contain
any ions including hardness producing
ions.
Demineralization involves removal of
all the ions present in water.
Ion exchange process
It exchanges cations and anions
The cylinders are using
cationexchange resin - RH2
Anion exchange resin - R’(OH)2
HCl, NaOH are used for regeneration.
Demineralization involves removal of all
the ions present in water.
The treated water does not contain any
dissolved salts. They may not cause any
boiler troubles.
The setup and operating cost high.
Acidic water can be treated.
14
 1.4) INTERNAL TREATMENT METHODS

i) The residual salts that are not removed by external methods can be removed by adding
some chemicals directly into the boiler water.
ii) These chemicals are known as ‘Boiler compounds’. This method is known as
‘Internal treatment’ (or) sequesterisation.
iii)E.g) Carbonate conditioning, Phosphate conditioning , Calgon conditioning,
colloidal conditioning, Sodium aluminate conditioning
iv) In general, internal treatment methods are followed by blow down operation.

a) Carbonate conditioning:

i) Carbonate conditioning is used for low pressure boilers.

ii) Here the salts like CaSO4 are converted to easlity removable CaCO3.

iii) But in high pressure boilers, the excess Na2CO3 undergoes hydrolysis and is converted
to NaOH.

iv) It leads to caustic embrittlement and boiler corrosion. So it is less preferred.

CaSO4 + Na2CO3  CaCO3 + Na2SO4

b)Phosphate conditioning:
i) Phosphate conditioning is used for high pressure boiler.

ii) It is superior than carbonate conditioning as there is no risk of CO2 liberation, caustic

embrittlement and boiler corrosion.

iv) For better results, a pH range of 9.5 – 10.5 is recommended.

v) Reaction: 3CaSO4 + 2 Na3PO4  Ca3(PO4)2 + 3 Na2SO4

Three types of Phosphate salts are used:

S.No Salt Name Used for treating

1 Na3PO4 Tri sodium Phosphate highly acidic water
2 Na2HPO4 Di sodium hydrogen Phosphate slightly acidic water
3 NaH2PO4 Sodium di hydrogen phosphate highly alkaline water
15
 b) Calgon conditioning:
i) Calgon is the trade name of sodium hexa meta phosphate- Na2 [ Na4 (PO3)6].
ii) With calcium ions it forms a soluble complex of Na2 [Ca2(PO3)6].
iii) So, there is no problem of sludge disposal.
iv) It is used for high and low pressure boilers.
v) Because of these reasons, calgon conditioning is better than phosphate conditioning.
vi) Reaction: 2CaSO4 + Na2[ Na4 (PO3)6]  Na2 [Ca2(PO3)6] + 2 Na2SO4

c) Colloidal conditioning:
i) Colloidal conditioning is used for low pressure boilers.
ii) Here, scale formation is avoided by adding organic substances like kerosene, tannin,
agar-agar etc., which get coated over the scale forming precipitates.
iii) This converts the scale into sludge and they are removed by blow down operation
methods.

d) Sodium aluminate (NaAlO2) conditioning:

i) Sodium aluminate (NaAlO2) undergoes hydrolysis in boiler water to give gelatinous
white precipitate of aluminium hydroxide and sodium hydroxide.
NaAlO2 + 2 H2O  Al(OH)3 ↓+ NaOH
ii) The Sodium hydroxide then precipitates magnesium salt as magnesium hydroxide.
NaOH + MgCl2  Mg(OH)2 ↓+ 2NaCl
iii) The gelatinous precipitates of aluminium hydroxide [Al(OH)3] and magnesium
hydroxide [Mg(OH)2] entrap the colloidal silica and finely divided solids.
iv) Finally the precipitates can be removed by blow down method.

Differences between internal treatment and external treatment

S.No External conditioning Internal conditioning
1 (Eg). Zeolite method, Ion exchange (Eg) Phosphate, calgon, colloidal, sodium
demineralization aluminate method
2 It is a preventive method It is a corrective method
3 Frequently used in high pressure boilers Frequently used in Low pressure boilers
4 It is carried out before the water entry It is carried ou in the boiler itself by using
in to the boiler boiler compounds.
16
 1.5 ) HARDNESS OF WATER – TYPES - UNITS
1. Definition:

If the water produces lather with soap, it is soft water.

If the water does not produce lather with soap, it is called as Hard water. The property
is known as hardness. But it will produce a scummy white precipitate. The hardness is due
to Ca2+ , Mg2+ and SO42- , Cl- , CO32-, HCO3- ions and their salts.
.
2.Test for hardness:

a) Eriochrome Black – T indicator gives red colour in hard water.

b) With soap, hard water gives a scummy precipitate.
2C17H35COONa + CaCl2  (C17H35COO)2Ca + 2NaCl
(Sodium stearate) (Scummy precipitate)

3. Types of Hardness:
a) Temporary Carbonate hardness : The hardness due to carbonates and
bicarbonates can be removed by simple boiling. So, they are known as temporary or
carbonate or alkaline hardness.
Ca(HCO3)2 (On heating)  CaCO3 + H2O + CO2

b) Permanent hardness ( Non-carbonate): The hardness due to chlorides and

sulphates cannot be removed by simple boiling. They need special methods like lime soda
process and zeolite process. This hardness is called as “Permanent hardness or Non-
carbonate or non alkaline hardness.
CaCl2 + Na2CO3  CaCO3 + 2NaCl ( Lime soda process)
CaSO4 + Na2Ze (Zeolite)  CaZe + Na2SO4 (Zeolite process)

4. Units of hardness:
i) ppm ii) mg/L iii) degree Clarkes iv) Degree French
S.No Unit Parts of CaCO3 equivalence Parts of water
1 Ppm (parts per million) 1 106
2 Degree French (0F) 1 105
3 degree Clarkes (0Cl) 1 70,000
4 mg/L 1 mg 1 litre
0 0
Therefore , 1ppm = 1mg/L = 0.07 Cl = 0.1 F
5.CaCO3 equivalence:
Hardness is expressed in CaCO3 equivalence. Because,
i) It is the most insoluble and easily precipitatable salt.
ii) Its molecular weight is 100 and equivalent weight is 50. As these are whole numbers, it
is very easy to use them in calculations. 17
 1.6) ESTIMATION OF HARDNESS OF WATER BY EDTA METHOD

The tendency of water not to lather with soap is known as hardness. The hardness
due to carbonates and bicarbonates can be removed by simple boiling. So, they are known
as temporary or carbonate or alkaline hardness. The hardness due to chlorides and sulphates
cannot be removed by simple boiling. They need special methods like lime soda process
and zeolite process. This hardness is called as Permanent hardness or Non-carbonate or
non alkaline hardness.

1. Aim:
To estimate the amount of hardness present in the given water sample.

2. Chemicals required:
a) Standard hard water – 1g CaCO3 + dil. HCl – made up to 1 Lr.
b) EDTA solution – 4 gms of EDTA sodium salt / 1 Lr of water
c) EBT Indicator – 0.5g EBT / 100 ml alcohol
d) Ammonia buffer - 67.5g Ammoniumchloride +570ml Ammonia-- made up to 1Lr

3. Principle:
EDTA stands for Ethylene Diamine Tetra Aceticacid. As it is insoluble in water, we use
its disodium salt.
Structure of EDTA:

By nature, Eriochrome Black T indicator is blue in colour. When EBT indicator is

added to water sample, it formsa wine red coloured unstable Ca-Mg-EBT complex.

This reaction is carried out under a basic PH of 8- 10 using ammonia buffer.

Ca2+ / Mg2+ in water + EBT  [Ca / Mg –EBT] unstable wine red complex

When EDTA is titrated against the complex, EDTA replaces all the EBT and forms a
stable Ca / Mg –EDTA complex. The liberated EBT indicates the end point as steel
blue.
[Ca / Mg –EBT] + EDTA  [Ca / Mg –EDTA] + EBT
(Wine red/unstable) Stable) (Steel blue)
So, the end point is the colour change from wine red to steel blue. 18
 4. Short Procedure:
S.No Content Titration-I Titration-II Titration-III
Standardisation Total Hardness permanent
of EDTA Hardness
1 Burette EDTA StandardEDTA StandardEDTA

2 Pipette(20 Std. Hardwater Sample water Boiled water

ml)
3 Additional 5 ml of NH3 5 ml of NH3 5 ml of NH3
solution buffer buffer buffer
4 Indicator EBT EBT EBT

5 Endpoint Wine red to Wine red to Wine red to

steel blue steel blue steel blue
6 Volume V1 V2 V3

5. Calculation:

Step1 – Standardisation of EDTA

1 ml of Std. Hard water = 1 mg of CaCO3 (Given)

So, 20 ml of Std. Hard water = 20 mg of CaCO3

V1 ml of EDTA is required for = 20 mg of CaCO3

Therefore, 1ml of EDTA = 20 / V1 mg of CaCO3

Step 2: Finding Total hardness:

20ml of sample water required = V2 ml of EDTA

= V2 X 20 mg of CaCO3
V1

Therefore, 1000ml of sample requires = V2 X 20 X 1000 mg of CaCO3

V1 20

Hence, total hardness = V2 X 1000 ppm

V1
19
Step 3: Finding Permanent hardness:

20ml of boiled water required = V3 ml of EDTA

= V3 X 20 mg of CaCO3
V1

Therefore, 1000ml of boiled sample requires = V3 X 20 X 1000 mg of CaCO3

V1 20

Hence, permanent hardness = V3 X 1000 ppm

V1

Step 4 : Temporary hardness = Total hardness – permanent hardness

1.7) NUMERICAL PROBLEMS BASED ON HARDNESS OF WATER

1. Calculate temporary hardness and total hardness of a sample of water containing

Mg(HCO3)2 = 7.3 mg/l; Ca(HCO3)2 = 16.2 mg/l; MgCl2 = 9.5 mg/l; CaSO4 = 13.6 mg/l.
Temporary hardness=[7.3x100/146+16.2x100/162]mg/l = (5+10) mg/l = 15mg/l
Permanent hardness=[9.5x100/95+13.6x100/136]mg/l = (10+10) mg/l = 20mg/l
2. What is hardness of a solution containing 0.585 grams of NaC1 and 0.6 grams of
MgSO4 per litre? (Jan 2009)
NaCl will not cause any hardness.
For Magnesium sulphate Hardness = Mass of salt X 100 / Mol.wt of salt
= 600 X100 / 120 =500 ppm
3. 50 ml of sample of hard water required 35 ml of 0.01M EDTA in the titration.50 ml of the
same sample of water after boiling required 12 ml of 0.01M EDTA.Calculate total and
temporary hardness of water. (June 2012)
Std. Formula : 1ml of 1 M EDTA = 100 mgs of CaCO3
Therefore, 1ml of 0.01 M EDTA = 1 mg of CaCO3
Total hardness:
50 ml of sample requires = 35 ml of 0.01M EDTA
= 35x 1 mg = 35 mg of CaCO3
Therefore, 1000 ml of sample requires = 35 x 1000 / 50 = 700mgs of CaCO3
i.e., Total hardness = 700 mg / L = 700 ppm
Permanent hardness:
50 ml of boiled sample requires = 12 ml of 0.01M EDTA
= 12 x 1 mg = 12 mg of CaCO3
Therefore, 1000 ml of boiled sample requires = 12 x 1000 / 50 = 240 mgs of CaCO3
i.e., Non- Cardbonate ( Permanent) hardness = 240 mg / L = 240 ppm
Carbonate hardness:
Carbonate hardenss = Total hardness – Non carbonate hardness
= 700 – 240 = 460 ppm 20
4. 100 ml of a water sample required 20 ml of 0.01 M EDTA for the titration with Eriochrome
Black-T indicator.. 100ml of the same water sample after boiling and filtering required 10 ml of
0.01 M EDTA. Calculate the total, carbonate and non carbonate hardness of the sample.
(June 2009)

Std. Formula : 1ml of 1 M EDTA = 100 mgs of CaCO3

Therefore, 1ml of 0.01 M EDTA = 1 mg of CaCO3

Total hardness:
100ml of sample requires = 20 ml of 0.01M EDTA
= 20 x 1 mg = 20mg of CaCO3
Therefore, 1000 ml of sample requires = 20 x 1000 / 100 = 200mgs of CaCO3
i.e., Total hardness = 200 mg / L = 200 ppm

Non carbonate hardness:

100ml of boiled sample requires = 10 ml of 0.01M EDTA
= 10 x 1 mg = 10mg of CaCO3
Therefore, 1000 ml of boiled sample requires = 10 x 1000 / 100 = 100mgs of CaCO3
i.e., Non- Cardbonate ( Permanent) hardness = 100 mg / L = 100 ppm

Carbonate hardenss = Total hardness – Non carbonate hardness

= 200 – 100 = 100 ppm

5. 0.28 g of CaCO3 was dissolved in HCl and the solution was made upto one litre with
distilled water. 100 ml of the above solution required 28 ml of EDTA solution on titration.
100 ml of a hard water sample required 33 ml of same EDTAsolution on titration. Another
100 ml of the same water, after boiling, cooling and filtering required 10 ml of EDTA
solution on titration. Calculate the temporary and permanent hardness of water. (June 10)
Given :
1000 ml of std. hard water contains = 0.28 gm of CaCO3 = 280 mgs of CaCO3
Therefore, 1 ml of std. hard water = 0.28 mg of CaCO3
28 ml of EDTA = 100 ml of the std hard water = 100 x 0.28 mgs of CaCO3
Hence, 1 ml of EDTA = 100 x 0.28 x 1 / 28 = 1 mg of CaCO3
Total hardness:
100ml of sample requires = 33 ml of 0.01M EDTA
= 33 x 1 mg = 33mg of CaCO3
Therefore, 1000 ml of sample requires = 33 x 1000 / 100 = 330mgs of CaCO3
i.e., Total hardness = 330 mg / L = 330 ppm

Non carbonate hardness(Permanent)

100ml of boiled sample requires = 10 ml of 0.01M EDTA
= 10 x 1 mg = 10mg of CaCO3
Therefore, 1000 ml of boiled sample requires = 10 x 1000 / 100 = 100mgs of CaCO3
i.e., Non- Cardbonate ( Permanent) hardness = 100 mg / L = 100 ppm

Temporary hardenss = Total hardness – Non carbonate( permanent) hardness

= 330 – 100 = 230 ppm

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