Chapter 19 Water and Its Treatment-1

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Unit -1

By - Dr. Ashish Kumar


PROPERTIES OF WATER

GENERAL INFORMATION

Structure Water consists of covalent molecules of formula H2O.

Physical colourless, odourless liquid.


properties boils at 100°C freezes at 0°C
(if pure and at atmospheric pressure)

Chemical Reacts with some metals to produce hydrogen.


properties

Uses Essential for life.


An important solvent.
A coolant for many industrial processes (e.g. power stations)
Raw material in the manufacture of ammonia.
Raw material in the conversion of ethene to ethanol.

Test Turns blue cobalt chloride pink... or


Turns white anhydrous copper(II) sulphate blue.
By - Dr. Ashish Kumar
Some facts about water

By - Dr. Ashish Kumar


PURITY OF WATER

Natural water is never pure. It is such a good solvent that


it contains dissolved substances whatever its origin.

RAIN dissolved gases from the air e.g. CO2, SO2

RIVERS dissolved salts from rocks and soils; also oxygen.

SEA dissolved sodium and magnesium salts (e.g. NaCl) and CO2

water also
Contains man-made chemicals such as detergents, acids,
fertilizers and other pollutants.

By - Dr. Ashish Kumar


Sources of Water
Oceans and seas contain 96.5% water,
and snow and groundwater hold 1.74%
and 1.7%, respectively.
Impurities in Water
 Biological impurities: Microorganisms

 Suspended impurities: Organic matter

 Colloidal impurities: Metal hydroxides, oil globules

 Dissolved impurities: Dissolved gases and salts

By - Dr. Ashish Kumar


Types of Water
 Soft Water

 Hard Water
Hardness of Water
• DEFINITION:
“ The property of water to form an insoluble curd with
soap instead of lather. In other words hardness is the
soap destroying property due to the presence of
Bicarbonates, Sulphates and Chlorides of Calcium
and Magnesium.”

Hardness of water may also be defined as the soap-


consuming capacity of water, or the capacity of
precipitation of soap.
By - Dr. Ashish Kumar
Using hard and soft water
Soft water forms a lather easily with soap.

Hard water needs more


soap to form a lather, adding
additional cost to cleaning
processes.

This is because dissolved


chemicals in the hard water
react with soap to form a
scum.

How could you test water


samples to see if they are
hard or soft?

By - Dr. Ashish Kumar


Hardness of water

Contains ions of calcium and magnesium and form scum with soap thus
preventing formation of lather.

The soap will only form a lather when all the dissolved calcium
hydrogen carbonate in the water has reacted.
Using hard water can cause problems:
 More soap is needed to get a lather.
 It can be difficult to clean the scum from bathtubs and sinks.
 Hard water can be unsuitable for industrial processes
like dying. By - Dr. Ashish Kumar
“Hard water is water which does not readily form a lather with soap”

Method
Place a sample of one of the solutions in a test-tube to a depth of about 2cm.
Using a dropping pipette, place a measured amount of soap solution into the
water and shake vigorously for five seconds. Record the height of the lather.
Repeat with another sample; decide which ions are responsible for hardness.

A sodium sulphate
B magnesium sulphate
C potassium chloride
D calcium chloride
E sodium nitrate
F magnesium nitrate
G calcium nitrate
H sodium chloride
A B C D E F G H

By - Dr. Ashish Kumar


WHICH IONS CAUSE HARDNESS?

“Hard water is water which does not readily form a lather with soap”

Method
Place a sample of one of the solutions in a test-tube to a depth of about 2cm.
Using a dropping pipette, place a measured amount of soap solution into the
water and shake vigorously for five seconds. Record the height of the lather.
Repeat with another sample; decide which ions are responsible for hardness.

A sodium sulphate
B magnesium sulphate
C potassium chloride
D calcium chloride
E sodium nitrate
F magnesium nitrate
G calcium nitrate
H sodium chloride
A B C D E F G H

By - Dr. Ashish Kumar


WHICH IONS CAUSE HARDNESS?

“Hard water is water which does not readily form a lather with soap”

Method
Place a sample of one of the solutions in a test-tube to a depth of about 2cm.
Using a dropping pipette, place a measured amount of soap solution into the
water and shake vigorously for five seconds. Record the height of the lather.
Repeat with another sample; decide which ions are responsible for hardness.

Solution used ions present lather


+ ive - ive
A sodium sulphate Na+ SO42- YES
B magnesium sulphate Mg2+ SO42- NO
C potassium chloride K+ Cl- YES
D calcium chloride Ca2+ Cl- NO
E sodium nitrate Na+ NO3- YES
F magnesium nitrate Mg2+ NO3- NO
G calcium nitrate Ca2+ NO3- NO
H sodium chloride Na+ Cl- YES

Conclusions The ion(s) responsible forKumar


By - Dr. Ashish hardness is / are...
WHICH IONS CAUSE HARDNESS?

“Hard water is water which does not readily form a lather with soap”

Method
Place a sample of one of the solutions in a test-tube to a depth of about 2cm.
Using a dropping pipette, place a measured amount of soap solution into the
water and shake vigorously for five seconds. Record the height of the lather.
Repeat with another sample; decide which ions are responsible for hardness.

Solution used ions present lather


+ ive - ive
A sodium sulphate Na+ SO42- YES
B magnesium sulphate Mg2+ SO42- NO
C potassium chloride K+ Cl- YES
D calcium chloride Ca2+ Cl- NO
E sodium nitrate Na+ NO3- YES
F magnesium nitrate Mg2+ NO3- NO
G calcium nitrate Ca2+ NO3- NO
H sodium chloride Na+ Cl- YES

Conclusions The ion(s) responsible forKumar


By - Dr. Ashish hardness is / are... Ca2+ and Mg2+
Water Hardness Rating
mg/L as CaCO3 Degree of Hardness

0-60 Soft water

61-120 Moderately hard water

121-180 Hard water

>180 Very hard water

By - Dr. Ashish Kumar


How hardness arises: Sources of hardness

Causes Arises from the solvation of compounds out of rocks / soils.


The compounds are SOLUBLE magnesium or calcium salts.

RAIN DISSOLVES
THE SOLUBLE
SALTS IN ROCKS

ROCKS CONTAINING LIMESTONE


SOLUBLE CALCIUM OR (CALCIUM CARBONATE)
MAGNESIUM COMPOUNDS

WATER CONTAINING
BySOLUBLE CALCIUM
- Dr. Ashish Kumar OR MAGNESIUM IONS
HARD WATER – HOW DOES IT ARISE?

Causes Arises from the solvation of compounds out of rocks / soils.


The compounds are SOLUBLE magnesium or calcium salts.

LIMESTONE IS
INSOLUBLE IN WATER
BUT DOES DISSOLVE IN
RAIN WHICH IS ACIDIC
DUE TO DISSOLVED CO2

ROCKS CONTAINING
LIMESTONE
SOLUBLE CALCIUM OR
(CALCIUM CARBONATE)
MAGNESIUM COMPOUNDS

WATER CONTAINING
BySOLUBLE CALCIUM
- Dr. Ashish Kumar OR MAGNESIUM IONS
HARD WATER – HOW DOES IT ARISE?

Causes Arises from the solvation of compounds out of rocks / soils.


The compounds are SOLUBLE magnesium or calcium salts.

RAIN DISSOLVES LIMESTONE IS


THE SOLUBLE INSOLUBLE IN WATER
SALTS IN ROCKS BUT DOES DISSOLVE IN
RAIN WHICH IS ACIDIC
DUE TO DISSOLVED CO2

ROCKS CONTAINING
LIMESTONE
SOLUBLE CALCIUM OR
(CALCIUM CARBONATE)
MAGNESIUM COMPOUNDS

WATER CONTAINING
BySOLUBLE CALCIUM
- Dr. Ashish Kumar OR MAGNESIUM IONS
Types of Hardness

Temporary hardness: due to presence of bicarbonates and


carbonate of calcium and magnesium; can be Removed by
boiling.

Permanent hardness: due to presence of chlorides and


sulphates of calcium and Magnesium; cannot be removed by
boiling; removed by softening agents.

Ex. MgCl2 ,MgSO4 , CaCl2 , CaSO4


By - Dr. Ashish Kumar
Temporary hardness
• Rainwater becomes slightly acidic as carbon dioxide from the air
dissolves in it, forming carbonic acid.
• Limestone contains calcium carbonate. As the slightly acidic rainwater
trickles through rocks, the calcium carbonate reacts to form soluble
calcium hydrogen carbonate

carbonic calcium calcium hydrogen carbon


+  + + water
acid carbonate carbonate dioxide
H2CO3 (aq) + CaCO3 (s)  Ca(HCO3)2 (aq) + CO2 (g) + H2O (l)

By - Dr. Ashish Kumar


Permanent Hardness
• Permanent hard water is mainly caused by
sulphates and chlorides of Calcium and
magnesium
• These salts are slightly soluble and dissolve
when rain water runs over the rocks like
granite
• Permanent hard water is not softened by
boiling

By - Dr. Ashish Kumar


Degree of hardness:
It is defined as the number of parts by weight of calcium carbonate
hardness per particular number of parts of water , depending upon
the units employed.

Expressed in terms of CaCO3 equivalent (in mg/l or ppm)


1kg=106mg
1mg/l= 1mg of CaCO3 per 106 mg of water
= 1part of CaCO3 per 106 mg of water= 1ppm.

Why expressed in CaCO3 equivalent ?


•Mol. Wt = 100
• MostClarke
Degree insoluble salt= that
( 0 Cl) can be ppted
It’s number out fromofwater.
of equivalent CaCO present in
3
70,000 parts of water

Degree French (0Fr) = It’s number of equivalent of CaCO3 present in 105


parts of water
By - Dr. Ashish Kumar

1 ppm = 1 mg/l = 0.10Fr = 0.070Cl


Degree of hardness:

Hardness in term of calcium carbonate equivalent

= strength of hardness prod. substance (mg/L) x Mol. Wt. Of CaCO3


Mol. Wt. Of Substance

In ppm or mg/l

By - Dr. Ashish Kumar


What is the temporary , permanent and total
hardness of a 1L of water sample containing 12.2
mg of Ca(HCO3)2 and 5.6 mg of MgSO4 ?

Hint: Mol. Wt of Ca(HCO3)2 = 162

Hint: Mol. Wt of MgSO4 = 120


Hint: Mol. Wt of CaCO3 = 100

By - Dr. Ashish Kumar


Temporary hardness = 12.2 × 100 (Molar Mass of CaCO3)/ 162

(Molar Mass of Ca(HCO3)2

= 7.53 mg/l of CaCO3

Permanent hardness = 5.6 × 100/ 120 = 4.67 mg/l of CaCO3.

Total hardness = 7.53+4.67 = 12.2 mg/l of CaCO3.

By - Dr. Ashish Kumar


Calculate the hardness in terms of CaCO3 equivalent
in mg/l, ppm, 0 Cl and 0 Fr of a water sample containing
200mg of CaSO4 per Litre ?
Hint: Mol. Wt of CaSO4 = 136

By - Dr. Ashish Kumar


• Hardness in term of calcium carbonate equivalent

= strength of hardness prod. substance (mg/L) x Mol. Wt. Of CaCO3

Mol. Wt. Of Substance

= 200 × 100/ 136 = 147.05 mg/l .

As 1 mg/l=1ppm, therefore hardness = 147.05 ppm

As 1 mg/l = 0.10Fr, therefore hardness = 14.705 0Fr

As 1 mg/l = 0.070Cl, therefore hardness = 10.290Cl


By - Dr. Ashish Kumar
How many grams of MgCl2 dissolved in water will give
hardness of 76 ppm ?

Hint: Mol. Wt of MgCl2 = 95

By - Dr. Ashish Kumar


• Hardness in term of calcium carbonate equivalent

= strength of hardness prod. substance (mg/L) x Mol. Wt. Of CaCO3


Mol. Wt. Of Substance

76 = strength of MgCl2 × 100/ 95

strength of MgCl2 = 76 × 95/100mg/l


= 72.2 ppm or mg/l

By - Dr. Ashish Kumar


Determination of Hardness of Water

Soap Solution Method

Hard water does not produce lather until all the ions
causing hardness have precipitated.

Complexometric Titration Method:

EDTA reacts with calcium and magnesium ions


which cause hardness and forms complex
compounds.

By - Dr. Ashish Kumar


Complexometric Titration Method using EDTA:

1.When indicator is added to hard water it combines with free metal ions present in
water.
HIn-2 + M+2 → MIn- + H+ {M = Mg or Ca}
(Blue) (Wine red)
2.When EDTA solution is added to the titration flask it combines with the free metal ions
giving metal EDTA complex, which is stable and colorless.

H2Y2- + M+2 → MY-2 + 2H+

3.When all the free metal ions are exhausted, next drop of EDTA removes the metal ion
engaged with indicator and the original blue color is restored.
H2Y2- + MIn- → MY-2 + HIn2- + H+
( Blue)
By - Dr. Ashish Kumar
Determination of hardness by EDTA method

• Ca2+ and Mg2+ ions along with other metal ions such as
Fe2+ and Pb2+ undergoes complexation with EDTA
(ethylenediaminetetraacetic acid).
• H2EDTA2- binds to a Ca2+ ion by forming four special
covalent bonds called coordinate covalent bonds.

+ + 2 H+
Ca2+

H2EDTA2- Ca2+ ion


chelated by
EDTA
By - Dr. Ashish Kumar
EDTA Complex of Lead

By - Dr. Ashish Kumar


Determination of Total Hardness
Principle
Principle::
Ca
Ca and Mg2+ion
2+and Mg2+
2+
ionin
inwater
watertitrated
titratedwith
withEDTA
EDTAstandard
standardsolution
solutionatat
pH
pH1010with
withEBT
EBTindicator.
indicator. The
Theend
endpoint
pointshown
shownbybythe
thecolor
color
change
changefrom
fromgrape
grapered
redto
toclear
clearblue.
blue.
Eq.
Eq.Point:
Point:mol
molCa
Ca2+++Mg
2+
Mg2+==mol
2+
molEDTA
EDTA

Reactions :
Ca2+ + HIn2-  CaIn- + H+
Mg2+ + HIn2-  MgIn- + H+
Ca2+ + H2Y2-  CaY2- + 2H+
Mg2+ + H2Y2-  MgY2- + 2H+
MgIn-(grape red) + H2Y2-  MgY2- + HIn2- (blue) + H+
By - Dr. Ashish Kumar
Determination of Permanent Hardness

Principle
Principle::
The
Thetemporary
temporaryhardness
hardnessin inwater
waterremoved
removedby byboiling
boilingfor
for15
15minutes,
minutes,
Ca
Ca2+and
2+
andMg
Mg2+ion
2+
ionin
inthe
thesupernatant
supernatanttitrated
titratedwith
with EDTA
EDTA standard
standard
solution
solutionatatpH
pH10 10with
with EBT
EBTindicator.
indicator. The
Theend
endpoint
pointshown
shown with
withthe
the
color
colorchange
changefrom
from grape
grapered
redtotoclear blue...
clearblue.
Eq.
Eq.point
point::mol
molCa Ca2+++Mg
2+
Mg2+==mol
2+
molEDTA
EDTA

Reaction :
Ca(HCO3)2 (heated)  CaCO3(s) + H2O +CO2
Mg(HCO3)2 (heated)  Mg(OH)2(s) + CO2
Ca2+ + HIn2-  CaIn- + H+ // Mg2+ + HIn2-  MgIn- + H+
Ca2+ + H2Y2-  CaY2- + 2H+
Mg2+ + H2Y2-  MgY2- + 2H+
MgIn-(grape red) + H2Y2-  MgY2- + HIn2- (blue) + H+
By - Dr. Ashish Kumar
Determination of Temporary Hardness

Indirect
Indirect determination
determination ::
Temporary
Temporary Hardness
Hardness == Total
Total –– Permanent
Permanent

By - Dr. Ashish Kumar


100 ml of water sample required 13.5 ml of 0.02 M EDTA.
Another 100 ml of water from same source was boiled and ppt
removed . The filtrate require 6 ml of 0.02 M EDTA. What is the
total hardness, permanent and carbonate hardness?

By - Dr. Ashish Kumar


N1V1 = N2V2,

so molarity of water sample = 0.0027 (M).

1 M means 100 gm of CaCO3 in 1L

 1M means 100,000 mg of CaCO3 in 1L,

 total hardness=0.0027 (M) means 270 mg/L (ppm) of CaCO3

equivalent.

 Similarly permanent hardness= 120 mg/L or ppm

 temporary hardness=total
Molarity hardness
× 105 = Hardness - permanent
in mg/L of CaCO3 hardness=
equivalent. 150 ppm
By - Dr. Ashish Kumar
1gram of CaCO3 was dissolved in dil. HCL and the solution is
diluted to 1litre. 100 ml of this water required 90 ml of EDTA
solution. Another 100 ml of water sample required 36 ml of
EDTA solution. 100 ml of water from same source was boiled
and ppt removed . The filtrate require 18 ml of EDTA. Calculate
total hardness and permanent hardness?

By - Dr. Ashish Kumar


Standard solution contains 1g/l of CaCO3.
Therefore 100ml of solution = 100mg of CaCO3
90ml of EDTA= 100mg of CaCO3
1 ml of EDTA= 100/90 mg of CaCO3

a. 100ml of water require 36 ml of EDTA= 36 X 100/90 mg of CaCO3


= 40 mg of CaCO3
So, 1000 ml of water contains 400 mg of CaCO3
Total hardness = 400mg/l

b. 100 ml of sample after boiling require 18ml of EDTA


= 18 X 100/90 mg of CaCO3
= 20 mg of CaCO3
So, 1000 ml of water contains 200 mg of CaCO3
Temporary hardness = 200mg/l
permanent hardness=total hardness - temporary hardness= 200 ppm
Alkalinity of water
It is a measure of ability of water to neutralize acids.
Types of Alkalinity
 carbon dioxide (pH = 4.2-4.5 or lower )

 carbon dioxide and bicarbonate-(pH range of 4.2-4.5 at the low


and 8.2-8.4 at the high end. At pH 8.2-8.4, there is no carbon
dioxide and all alkalinity is in the form of bicarbonates)

 bicarbonate and carbonate-(pH range of 8.2-8.4 at the low and 9.6


at the high end. At pH 9.6, there is no carbon dioxide or
bicarbonate and all alkalinity is in the form of carbonates)

 Hydroxyl Alkalinity-(As the pH increases above 9.6, hydroxyl


alkalinity starts.

Alkalinity is estimated by titration of water with a standard acid


By - Dr. Ashish Kumar
solution using phenolphthalein and methyl orange as indicators.
Method of Analysis
1. Phenolphthalein Alkalinity-P
A. Phenolphthalein indicator
B. Pink at pH 8.3 to colorless at pH 8.2
endpoint of titration
C. Measures Carbonates and Hydroxide ions

2. Methyl orange Alkalinity=M


A. Methyl Orange indicator
B. Yellow at pH 4.5 to orange at pH 4.4
endpoint of titration
C. Measures Bicarbonates

By - Dr. Ashish Kumar


By - Dr. Ashish Kumar
By - Dr. Ashish Kumar
Alkalinity Relationships

By - Dr. Ashish Kumar


Case 1: Alkalinity due to HCO32- ions only

V2
V2 = M
V1 or P =0
M = 10 V2 ppm

So when P=0 , both OH- and CO32 – are absent and alkalinity
is due to HCO32-

By - Dr. Ashish Kumar


Case2. Alkalinity due to OH- ions only
:

Both phenolphthalein and methyl orange indicators are


suitable for end point. Irrespective of the indicator, same
volume say V1 of standard acid(N/50) was needed for
neutralization of OH – ions.

Thus P=M= 10V1ppm (for 100 ml sample water and


N/50 acid)

By - Dr. Ashish Kumar


Case 3: Alkalinity due to CO32- ions only
: V1 or P

V2
V1 + V2 = M

Now chemically both reaction are 1:1 neutralization


reactions. Thus same volume of acid must be needed in
both cases..
V1 = V2
P= 10 V1 ppm and M= 10(V1 + V2 )ppm or 20 V1

Thus P= 1/2M

By - Dr. Ashish Kumar


Case 4: Alkalinity due to CO32- and HCO32- ions only
CO32- + H+ HCO32- P (V1 ml) ©

Total volume of acid up to methyl orange end point M= V1 +


V2
The extra acid added leads to neutralization of both the
HCO32-
Ions originally(0) present and by half neutralization of CO32-
©

(0)HCO32- + ©HCO32- 2H2 O + 2CO2 V2

P tells alkalinity due to half of CO32- ions


Thus alkalinity due to CO32- ions = 2P
Thus alkalinity due to HCO32- ions = M-2P
By - Dr. Ashish Kumar
Case 5: Alkalinity due to OH – and CO32- ions only

Let volume of acid up to phenolphthalein end point = V1


Total volume of acid up to methyl orange end point = V1 + V2

Thus half of CO32- ions equals to M-P


So alkalinity due to complete CO32- ions = 2(M-P)
But water sample also contains OH- ions with CO32- ions
.Total alkalinity =M
Thus alkalinity due to OH- ions= M-2(M-P)= 2P-M
2P-M>0 0r P > ½ M or V1 > V2
By - Dr. Ashish Kumar
100 ml water sample required 25 ml of 0.05N acid for
phenolphthalein end point and another 10 ml for methyl
orange end point. Determine alkalinity.

By - Dr. Ashish Kumar


From N1V1 = N2V2,
Normality of Phenolphthalein alkalinity= (.05 X 25) / 100
Phenolphthalein alkalinity in terms of CaCO3 equivalent
P = (.05 X 25) / 100 X 50g/l = .625g/l = 625mg/l = 625 ppm

Normality of Methyl orange alkalinity = (.05 X 35) / 100


alkalinity in terms of CaCO3 equivalent
M = (.05 X 35) / 100 X 50g/l = .875g/l = 875mg/l = 875ppm
As P > M/2 , Alkalinity is due to both OH- and carbonate ions

alkalinity due to Carbonate ions = 2(M-P) = 500ppm


alkalinity due to hydroxyl ions = 2P-M= 375ppm

By - Dr. Ashish Kumar


Disadvantages of Hard Water
• Are in the form of economic loss of a community and a
country at large such as:
1. More consumption of soap & detergents
2. More consumption of fuel due to scaling formation in
the boilers in industries
3. Discoloration of foods
4. Short life of clothes due to deposition of salts in fabrics
5. Disturbance of dyeing process
6. High prices of products
7. Decreased life of cisterns and Pipes

By - Dr. Ashish Kumar


Lime scale
When hard water is heated, the dissolved calcium hydrogen
carbonate decomposes to form solid calcium carbonate.
These deposits of calcium carbonate are called lime scale.

calcium hydrogen  calcium


+ water + carbon dioxide
carbonate carbonate

Ca(HCO3)2 (as)  CaCO3 (s) + H2O (l) + CO2 (g)

Lime scale can block pipes and coat the


heating elements in kettles, washing
machines and heaters.

Lime scale is a poor heat conductor, and


reduces the efficiency of appliances.
By - Dr. Ashish Kumar
Removing lime scale
Weak acids, such as ethanoic acid
(acetic acid), can be used as
descalers.
The acid reacts with the lime scale to
form soluble compounds, which are
then washed away.

ethanoic calcium calcium carbon


+  + + water
acid carbonate ethanoate dioxide

2CH3COOH (aq) + CaCO3 (s)  (CH3COO)2Ca (aq) + CO2 (g) + H2O (l)

By - Dr. Ashish Kumar


By - Dr. Ashish Kumar
By - Dr. Ashish Kumar
Specification of Boiler Feed water

S.No Parameter Specifications


.
1 Hardness < 0.2 ppm
2 pH 7.5-10
3 Caustic Alkalinity 0.15- 0.45 ppm
4 Soda Alkalinity 0.15- 1.00 ppm

5. Soda Ash 0.3-0.55 ppm


6. Dissolved Oxygen 0.02 ppm

By - Dr. Ashish Kumar


Hard water causes
• Scale formation: When pption of the dissolved salts takes
place in the form hard deposits which sticks to inner
wall/surface of the boilers and hard to remove, then they
are called scale.

• The impurities responsible for Scales are: Ca(HCO3)2 , CaSO4, Mg(HCO3)2, MgCl2
and Silica.
Harmful Effects of Scale formation:
1. Danger of Explosion.
2. Lowering of boiler Efficiency
3. Wastage of fuel
4. Increase in cleaning expenses.

By - Dr. Ashish Kumar


Hard water causes
• Sludge formation : When pption of the dissolved salts takes
place in the form of loose, non adherent, slimy ppt it is
called sludge. Generally occurs in colder and less turbulent
sections of boiler
• The impurities responsible for Sludge are: CaCl2 , MgSO4, MgCO3, MgCl2
iron and Silica.
Harmful Effects of Sludge formation:
1. Colder part of boiler and distribution lines may plugged by sludge.
2. Lowering of boiler Efficiency
3. Wastage of fuel
4. Increase in cleaning expenses.

By - Dr. Ashish Kumar


Hard water causes
• Caustic embrittlement: The material of the boiler becomes brittle
due to accumulation of caustic substance(like NaOH) at high temp. and
pressure, it is known as caustic embrittlement. Sodium carbonate is
often used for softening of boiler feed water in lime-soda process. There
is conc. of residual amount of Na2CO3 as water evaporates on boiling. It
then undergo hydrolysis to form NaOH making water alkaline which
seeps inside the cracks on boiler walls
• Na2CO3 +H2O 2NaOH +CO2
• The conc. NaOH reacts with iron of boiler to cause caustic
embrittlement. Iron forms sodium ferrate at high temp.
• 2NaOH +2Fe+O2 2NaFeO2 +H2
• Prevented by using sodium phosphate for softening, adding lignins or
By - Dr. Ashish Kumar
tannins to seal cracks and maintaining pH between 8 to 9.
Hard water causes
• Boiler corrosion: Boiler corrosion is the decay of boiler material
due to attack of certain chemicals on its surface, resulting into the
formation of compounds such as oxides , sulphides etc. The material
of the boiler thus gets dissolved and rusted ,thereby reducing the life
of boiler .it is due to:
a. Presence of dissolved oxygen
4Fe + 2H2O +O2 4Fe(OH)2
4Fe(OH)2 +O2 2[Fe2O3. 2H2O ] ------Rust
b. Presence of carbon dioxide: It dissolve in water to foam carbonic acid
which is acidic and corrosive in nature.
H2O +CO2 H2CO3 H+ +HCO3 -
By - Dr. Ashish Kumar
Hard water causes
• Priming : The phenomenon of formation of wet steam i.e. steam
associated with liquid water droplets with dissolved impurities is
called priming.
• Priming lowers the efficiency of the steam and leads to deposition of
salt crystals on the heaters and the turbines.

• Prevented by proper construction of boiler, maintaining proper level of water


and slow discharge of steam

By - Dr. Ashish Kumar


Hard water causes

• Foaming : is the formation of small persistent bubbles at the surface


of water in the boiler which may completely or partially fill the steam
space of the boiler.
• It is due to alkalis , oils, fats, certain types of organic matter and
suspended solids in boiler feed water. The suspended solids collect in
the surface film surrounding a steam bubble and make it tougher,
resist breaking and build up foam.

• It can be prevented by:


• Use of antifoaming agent, removal of oils and grease using sodium aluminates,
removal of clay and suspended matter etc
By - Dr. Ashish Kumar
Curing hardness or softening of water

• Due to disadvantages of hard water, many


times it become necessary to eliminate the
hardness of water and the method of
removing hardness from water is called
softening. softening of water

External Internal

By - Dr. Ashish Kumar


External Treatment for Softening Water

 Lime soda process

By - Dr. Ashish Kumar


Removal of Carbonate Hardness

CaCO3 is precipitated out of the water (sludge) and it’s filtered off.

Lime

Removal of Mg- Noncarbonate Hardness: MgCl2 and MgSO4

Lime is used to remove temporary hardness + Mg-


permanent hardness, Soda Ash is used mainly to remove
permanent hardness.
Soda Ash: Removal of Ca permanent Hardness: CaCl2 and CaSO4

By - Dr. Ashish Kumar


Lime-Soda Softening method

Batch Softening ( Lime and soda Continuous Softening ( Lime and soda
Both are mixed together with hard water are added to hard water into different
tank. After completing of reaction, the compartment.)
sludge is filtered off)

Advantage: It not only reduce hardness but also reduce the TDS, alkalinity.

Disadvantage: It cannot remove the water hardness completely.

By - Dr. Ashish Kumar


Before solving numerical problems –take a look

By - Dr. Ashish Kumar


Only for Reference:

By - Dr. Ashish Kumar


Calculate the lime and soda required for softening 50,000 l of water containing
the following salts: Ca(HCO3)2 = 8.1 mg/l, Mg(HCO3)2 = 7.5 mg/l and CaSO4 = 13.6

mg/l, MgSO4 = 12 mg/l, MgCl2 = 2 mg/l

Hint Mol. Wt.


Ca(HCO3)2 = 162
Mg(HCO3)2 = 146
CaSO4=136
MgSO4 = 120
MgCl2 = 95

By - Dr. Ashish Kumar


Calculate the lime and soda required for softening 50,000 l of water containing
the following salts: Ca(HCO3)2 = 8.1 mg/l, Mg(HCO3)2 = 7.5 mg/l and CaSO4 = 13.6

mg/l, MgSO4 = 12 mg/l, MgCl2 = 2 mg/l

Ca(HCO3)2 = 8.1 mg/l = 8.1 × 100/ 162 = 5 mg/ l CaCO3.


Mg(HCO3)2 = 7.5 mg/l = 7.5 × 100/146 = 5.13 mg/l of CaCO3
Similarly CaSO4= 10 mg/l, MgSO4 = 10 mg/l, MgCl2 = 2.1 mg/l of CaCO3
equivalent.

So lime required = 74 (MW of Lime)/ 100 (MW of CaCO3)[5+2×5.13 +10 + 2.1] = 20.25
mg/l.

By - Dr. Ashish Kumar


So soda required = 106(MW of soda)/ 100 [ 10 +10 +2.1] = 23.43 mg/l

Now calculate it for 50,000 L.

By - Dr. Ashish Kumar


Ion exchange process- Demineralization
Harmful cations and anions are removed by harmless ions from ion exchange resin.
Resins are high molecular weight cross linked polymer having acidic (-SO3H-COOH)
or basic (substituted anion group) functional group attached with the polymer chain.

Cationic Exchangers:
- Strongly acidic – functional groups derived from strong
acids e.g., R-SO3H (sulfonic).
Weakly acidic – functional groups derived from weak
acids, e.g., R-COOH (carboxylic).

Anionic Exchangers:
 Strongly basic – functional groups derived from
quaternary ammonia compounds, -R3N-OH.
Weakly basic - functional groups derived from primary
and secondary amines, R-NH3OH orBy R-R’-NH OH
- Dr. Ashish Kumar
2
Water is first passed through the cation exchange resin where Ca+2, Mg+2 is
exchanged with H+ from the resin, then the water is passed through the anion
exchange resin where Cl-, SO4-2 is exchanged with OH-

Water containing CaCl2 nRCOOH+ Water containing 2HCl

nRCOOH+ + CaCl2 n[(RCOO)2Ca ]+ 2HCl

n[R-N+(CH3)3OH- ]+ 2HCl n[(R-N+(CH3)3Cl- ]+ 2H2O

Water free of CaCl2 n[R-N+(CH3)3OH- ]


By - Dr. Ashish Kumar
Cation exchange Resin can be regenerated by passing dil H2SO4 and HCL

through it and anion exchange resin can be regenerated by passing NH4OH


and NaOH through it.
(RCOO)2M + 2H+ RCOOH + M2+

[(R-N+(CH3)3Cl- ]+ HO- n[R-N+(CH3)3OH- ]+ Cl-

By - Dr. Ashish Kumar


PERMANENT HARDNESS - REMOVAL

ION-EXCHANGE RESIN

• Ion-exchange resins are special compounds containing Na+ or H+ ions


• Hard water contains soluble calcium and/or magnesium ions

H+ H+ H+ H+

RESIN

H+ H+ H+ H+

By - Dr. Ashish Kumar


PERMANENT HARDNESS - REMOVAL

ION-EXCHANGE RESIN

• Ion-exchange resins are special compounds containing H+ ions

H+
+
H
H+
RESIN H+
H+
+
H
H+ H+

• Ca2+and Mg2+ ions in the hard water swap with those on the resin
• The water comes out with H+ ions in it
• Ca2+and Mg2+ ions remain attached to the resin
• H+ ions do not cause hardness.

Ca2+(aq) + 2H+ ——> Ca2+ + 2H+(aq)


in hard water on resin on resin in softened water

By - Dr. Ashish Kumar


PERMANENT HARDNESS - REMOVAL

ION-EXCHANGE RESIN

• Ion-exchange resins are special compounds containing H+ ions

• Eventually, all the H+ ions get used up so the resin must be replaced or
flushed through with Acid solution to replace the calcium.

By - Dr. Ashish Kumar


Internal Treatment for Softening Water: (Carried out inside boiler)
They function in two ways:
1. They ppt scale forming impurities and the sludge formed can be
removed by blow down operation.
2. They covert scale forming impurities to form more soluble complexes,
which stay in dissolved form without causing any harm

 Complexation: EDTA disodium salt form soluble ppts at pH 10

 Calgon (Sodium Hexametaphosphate) Treatment- form soluble ppts at


pH 10

 Phosphate Treatment: Sodium orthophosphate is used to ppt out


residual Ca and Mg ions as loose Ca and Mg phosphates which can
be easily removed
 2Na3PO4 + 3CaSO4 ——> Ca3(PO4) 2 + 3Na2SO4
By - Dr. Ashish Kumar
Membrane based Process(Desalination)
Reverse Osmosis Process

Water flows from


High conc. of water
To low conc. of water

By - Dr. Ashish Kumar


It results in conc. Of all solutes In
one compartment and all pure
Separation of contaminant
Water in another compartment
is based on charge and
Membrane water treatment
pore size of membrane systems were originally designed
for desalination project
By - Dr. Ashish Kumar 1 Atm = 14.6959488 Psi.
Advantages

• Reverse osmosis is capable of rejecting bacteria, salts, sugars,


proteins, particles, dyes, and other constituents that have a
molecular weight of greater than 150-250

• The maintenance cost is due to replacement of semi-


membrane only which can be done within few minutes for
continuous supply of water.

• Low capital and low cost for converting seawater to drinking


water.

By - Dr. Ashish Kumar


Type of membranes based processes (RO
based)
• Microfiltration: Microfiltration employs the
larger pore size of membrane and can remove
sand, clay, algae, bacteria and other
microorganism, inorganic compounds and small
organic molecules
• Nanofiltration: Nanofiltration employs smaller
pore size and provide complete protection
against viruses, organic and inorganic matter and
also reduces hardness and alkalinity of water

By - Dr. Ashish Kumar


Mechanism
• Semipermeable membranes based on thin films
of cellulose acetate, polymethyl methacrylate and
polyamide polymers are used
• The water molecule that enter the membrane by
hydrogen bonding and then can be pushed under
pressure
• Most organic substances with mol. Wt. over 100
are sieved out ie oil, pyrogen, bacteria and viruses

By - Dr. Ashish Kumar


Electrodialysis
• Electrodialysis combines
membrane technology with
application of electric current to
separate contaminants based on
charge and size exclusion filtering
process
• Ion selective membrane used in
electrodialysis are electrically
conductive and do not allow the
charge particles to go across
membrane
By - Dr. Ashish Kumar
By - Dr. Ashish Kumar
Disinfection of water?

By - Dr. Ashish Kumar


Treatment

• 3 different disinfection process


– Chlorination
– UV light radiation
– Ozonation

By - Dr. Ashish Kumar


UV light radiation
• Damage the genetic
structure of bacteria,
viruses and other
pathogens.
• Advantages: no chemicals
are used
• water taste more natural
• Disadvantages: high
maintenance of the UV-
lamp

By - Dr. Ashish Kumar


Ozonation
• Oxidized most pathogenic microorganisms
• Advantages: safer than chlorination
fewer disinfection by-product
• Disadvantage: high cost

By - Dr. Ashish Kumar


Chlorination
• Most common
• Advantages: low cost
& effective
• Disadvantages:
chlorine residue could
be harmful to
environment
• By Bleaching Powder:
CaOCl2

CaOCl2 + H2O  Ca(OH)2+ Cl2


By - Dr. Ashish Kumar
Chlorination
Water chlorination is the process of adding the element chlorine to
water as a method of water purification to make it fit for human
consumption as drinking water. Water that has been treated with
chlorine is effective in preventing the spread of waterborne disease.
chlorine is a highly efficient disinfectant, and is added to public
water supplies to kill disease-causing pathogens, such as bacteria,
viruses and protozoans

The chlorination process involves adding chlorine to water, but the chlorinating product
does not necessarily have to be pure chlorine. Chlorination can also be carried out
using chlorine-containing substances.

The three most common types of chlorine used in water treatment are: chlorine gas,
sodium hypochlorite, and calcium hypochlorite.

By - Dr. Ashish Kumar


The passage of chlorine gas through water allowing sufficient time for uniform distribution
Till as light excess of 0.1 -0.2 ppm of free chlorine is obtained after complete disinfection is
known as breakpoint chlorination.
This breakpoint chlorination of water corresponds to the point when all the ammonia present
in water is converted to nitrogen trichloride or free nitrogen.

HOCl + NH3 H2O + NH2 Cl


HOCl + NH2 Cl H2O + NH Cl2
HOCl + NH Cl2 H2O + NCl3
The chloramines act as bactericidal agents.

Cl2 + H2O HOCl + H+ + Cl-

OCl- = Cl- + O This O is also disinfectant.


By - Dr. Ashish Kumar
HOCl, which is electrically neutral and hypochlorite ions (OCl -, electrically
negative) will form free chlorine when bound together. This results in
disinfection. Both substances have very distinctive behavior. HOCl acid is
more reactive and is a stronger disinfectant than hypochlorite. HOCl acid is
split into hydrochloric acid (HCl) and oxygen (O). The oxygen atom is a
powerful disinfectant.

The disinfecting properties is determined by the pH of water. HOCl is more


effective in acidic pH between 5.5 to 7 whereas OCl - is more effective in
basic pH around 8 . Both are equally effective around 7.5 pH.

By - Dr. Ashish Kumar


Specification of drinking water
S.No Parameter ISI (BIS) standards mg/L WHO standards mg/L
.
1 Color, odor and taste Colorless, odorless and tasteless Colorless, odorless and
tasteless
2 pH 6.9 6.9
3 Total dissolved solids - 1500ppm
4 Dissolved oxygen 3.0 -
5 Chloride 600 250
6 Sulphate 1000 400
7 Nitrate - 45
8 Cyanide 0.01 0.2
9 Fluoride 3.0 1.5
10 Chromium 0.05 0.05
11 Lead 0.1 0.05
12 Arsenic 0.2 0.05
13 Mercury 0.001 0.006

By - Dr. Ashish Kumar


Indian Standards Institute(Bureau of Indian Standards

By - Dr. Ashish Kumar

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