Standards for drinking water, Water Quality

parameters, Determination of alkalinity of water,

Hardness of water: Units and determination.
Demineralization of water, Softening of water:
Lime-soda Process, Ion exchange process, Zeolite
process. Internal and external conditioning:
Carbonate conditioning, Phosphate conditioning,
Colloidal conditioning, Calgon conditioning,
Desalination of brackish water.
  • Source of Water
 • A) Surface Waters
 – Rain Water
 – River Water
 – Lake Water
 – Sea Water
 • B) Underground Waters
 – Spring Water
 – Well Water

2
Surface water
 River water – dissolved minerals
Cl-, SO42-, HCO3- of
Na+, Mg2+, Ca2+ and Fe2+
suspended impurities- Organic matter,
sand, rock

composition is NOT constant – depends on the contact

with soil.
 Lake water: High in organic and less in minerals.
composition is constant.

3
 Rain water – pure form
dissolved organic and inorganic particles and
dissolved industrial gases CO2, NO2,SO2 etc

 Underground water- free from organic

impurities due to filtering action of the soil

 Sea water – very impure; too saline for industrial use

except cooling

4
Impurities in water
 Suspended impurities
inorganic (clay, sand) organic (oil, plant, and animal
matter)
 Colloidal impurities- finely divided silica and clay
 Dissolved impurities – salts and gases
 Microorganisms – bacteria, fungi and algae

5
MAJOR IMPURITIES OF WATER
 Turbidity, silt, mud, dirt
 Magnesium Carbonate, Calcium Bicarbonate , Sodium
Hydroxide
 Potassium Sulfate, Ammonium Chloride, Iron Nitrate
 Manganese
 Phosphate
 Hydrogen sulfide and Carbon dioxide , Ammonia,
Methane , Oxygen , Chlorine
 Other suspended matter
 Colloidal silica, Silica Oil
 Bacteria, viruses, etc.
 Organic Matter* ,Corrosion products (condensate) 6
Important Properties in water
chemistry

Natural Water may have:

1) Conductivity 2) Turbidity
3) Color 4) pH
5) Alkalinity 6) Solids
7) Hardness

7
 ALKALINITY
 Alkalinity of water refers to the total
amount of those substance present in water
which tend to increase the concentration of
hydroxide ions on account of dissociation
and hydrolysis in water.
 It is a measure of ability of water to
neutralize acids.
Total Alkalinity = Methyl Orange Alkalinity + Phenolphthalein Alkalinity

8
CAUSE OF ALKALINITY:

 Presence of HCO3- , HSiO3- ,SiO3- :

 Hydroxides and carbonates

 Presence of salts of Weak acids:

 Presence of Buffer forming salts:

9
CLASSIFICATION OF ALKALINITY:

 IT IS OF THREE TYPES:

 1) OH- (hydroxyl) ALKALINITY

 2) CO32- (carbonate) ALKALINITY
 3) HCO3- (bicarbonate) ALKALINITY

10
 COMBINATION POSSIBLE
1) OH- (hydroxyl) ALKALINITY
2) CO32- (carbonate) ALKALINITY
3) HCO3- (bicarbonate) ALKALINITY
4) OH- + CO32- ALKALINITY
5) HCO3- + CO32- ALKALINITY

Hydroxide and bicarbonate can’t exist together, why ??

11
DETERMINATION OF ALKALINITY:

 PRINCIPLE: The type and extent of alkalinity of water

sample is determined by TITRIMETRIC METHOD.

 OH- + H+ H2 O
 CO32- + H+ HCO3- P
 HCO3- + H+ H2CO3 M

1. CO2 Alkalinity: pH around 4.2-4.5

2. Bicarbonate: pH around 8.2-8.4
3. Carbonate: pH ~9.6
4. Hydroxide: pH>9.6

12
STRUCTURE OF PHENOLPHTHALEIN
¯ ¯
¯

Chromophore
λmax = 500 nm

13
STRUCTURE OF METHYL ORANGE:

14
 PROCEDURE:
1. KNOWN VOLUME OF WATER SAMPLE + 1-2 DROPS
of Phenolphthalein.
2. APPERANCE OF PINK COLOR
3. TITRATE WITH STD. ACID
4. END POINT PINK TO COLORLESS
Volume = P (mL)
M-Reading:
1. TITRATE the SAME SAMPLE WITH SAME Titrant
2. STD. ACID BY USING Methyl Orange
3. END POINT:YELLOW to RED/PINK
4. THE VOLUME OF ACID CONSUMED IS NOTED(M).
15
 TYPE of ALKALINITY
 P-Alkalinity  M-Alkalinity
P = NaOH + ½(Na2CO3) M = NaOH + (Na2CO3)+ HCO3-

Change in color around Change in color around

pH = 8.2 pH = 4.4
(pink to colorless) (yellow to pink/red)

1. CO2 Alkalinity: pH around 4.2-4.5

2. Bicarbonate: pH around 8.2-8.4
3. Carbonate: pH ~9.6
4. Hydroxide: pH>9.6

16
CALCULATIONS
 FOR Phenolphthalein ALKALINITY:
 N1V1 = N2V2
(AWS) (STD. ACID)
N1 = N2V2/ V1
 PALK = N1 X 50 X 1000 ppm (1 ppm = 1 mg/L)

 FOR METHYL ORANGE ALKALINITY:

 N1V1 = N2V2
(AWS) (STD. ACID)
N1 = N2V2/ V1
 MALK = N1 X 50 X 1000 ppm

17
 Alkalinity relationships as determined by
titrations.
Hydroxide Carbonate Bicarbonate
P=0 0 0 M
P=M P 0 0
P = 1/2M 0 2P 0
P >1/2M 2P - M 2(M - P) 0
P <1/2 M 0 2P M - 2P

P = NaOH + ½(Na2CO3)
M = NaOH + (Na2CO3)+ HCO3-

 RESULT: OH- (hydroxyl) ALKALINITY=--------ppm

 2) CO32- (carbonate) ALKALINITY=-----------ppm
 3) HCO3- (bicarbonate) ALKALINITY=-----------ppm
18
Numerical Problem
1. A 100 mL water sample required 25 mL of 0.05 N
sulphuric acid for phenolphthalein end point and
another 10 mL for methyl orange end point.
Determine the nature and amount of alkalinity
present.

P- Alkalinity: 625 ppm Hydroxide: 375 ppm

M-Alkalinity: 875 ppm Carbonate: 500 ppm

19
 Take Home Message
 P-Alkalinity
P = NaOH + ½(Na2CO3)

 M-Alkalinity
M = NaOH + (Na2CO3)+ HCO3-

20
 Hardness of water
 Hardness prevents the formation of lather.
due to the presence of salts of Ca, Mg, Al, Fe and Mn
dissolved in it.
 Hardness of water may also be defined as the soap-
consuming capacity of water, or the capacity of
precipitation of soap.

Soap – Na or K salts of long chain fatty acids (C17H35COONa)

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

(Scum)
2C17H35COONa + MgSO4 → (C17H35COO)2Mg↓ + Na2SO4
21
 CAUSE OF HARDNESS
 Hard water does not produce lather with soap solutions,
but produces white precipitate (scum). For example,
sodium stearate reacts with calcium:

 2C17H35COONa + Ca2+ → (C17H35COO)2Ca + 2Na+

calcium stearate
(insoluble in water)
2C17H35COONa + MgSO4 → (C17H35COO)2Mg↓ + Na2SO4

22
The Cleansing Action of Soap

23
 Hard Water  Soft Water
Does not produce lather with Produces lather easily with
soap soap

Contains Ca and Mg salts Does not contain dissolved Ca

and Mg salts
Soap is wasted and cleaning Cleaning quality of soap not
quality is depressed depressed.

Boiling point elevated, more Less fuel and time required for
time and fuel for cooking cooking

24
Degree of Hardness of Drinking Water

 Soft 0-60 mg/L

 Medium 60-120 mg/L

 Hard 120-180 mg/L

 Very hard >180 mg/L

25
TYPES OF HARDNESS
a)TEMPORARY HARDNESS /carbonate/Alkaline
This hardness refers to the amount of bicarbonates of Ca & Mg
in solution
It can be removed or precipitated by boiling.
This type of hardness is responsible for the deposition of scale in
hot water pipes and kettles.

b) Permanent/ Non-carbonate hardness/non-alkaline

This hardness is caused by sulfate, chloride or nitrate of Ca & Mg
.
This type of hardness cannot be removed by boiling.

26
 Temporary Hardness
• Caused by dissolved bicarbonates of Ca and Mg
• Temporary hardness can be removed by boiling of
water
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑

Mg(HCO3)2 → Mg(OH)2↓ + 2 CO2↑

Also known as ‘alkaline or carbonate hardness’

27
Permanent Hardness
CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2(SO4)3

Cannot be destroyed on boiling the water

Also known as non-carbonate or non alkaline hardness

Non-alkaline hardness = Total hardness – alkaline hardness

Determined by complexometric titration with EDTA

28
Hard Water
 Advantages  Disadvantages

Tastes better produces scum with soap

Ca in water helps produce Boiler feed water should be

strong teeth and bones free from hardness or even
explosions can occur
Hard water coats lead pipes
with layer of insoluble
CaCO3, preventing any
poisonous lead dissolving in
drinking water 29
UNITS OF HARDNESS:
 There are several different scales used to describe the
hardness of water in different contexts.
 1)ppm of CaCO3
 2)mg/L of CaCO3
 3)Clark’s Degree
 4)Degree French

30
 UNITS
 Parts per million (ppm)
Defined as one milligram of calcium carbonate (CaCO3) per litre of
water.

 Clark degrees (°Clark or °Cl)/English degrees (°e or e)

One degree Clark is defined as milligrams of calcium
per 70,000 parts of water.

 French degrees (°Fr)

One degree French is defined as 1 milligrams of calcium carbonate
per 105 parts of water, equivalent to 10 ppm.

 1 ppm= 1 mg/L = 0.07 °Clark (°Cl) = 0.1 °Fr

31
 DETERMINATION OF HARDNESS:
EDTA METHOD
FOR TOTAL HARDNESS:
N1V1 = N2V2
(HWS) (STD. EDTA)
N1 = N2V2/ V1
TOT. HARDNESS = N1 X 50 X 1000 ppm of CaCO3

AFTER BOILING:
N1V1 = N2V2
(HWS) (STD.EDTA)
N1 = N2V2/ V1
PERMANENT HARDNESS = N1 X 50 X 1000 ppm of
CaCO3

TEMPORARY HARDNESS = Total hardness ‒ Permanent hardness 32

STRUCTURE OF EDTA:

33
It is also represented as H2Y2- it is a strong chelating
ligand, forms complex with bivalent cations like Ca &
Mg ions. The complex formed are stable in alkaline
medium i.e. pH=8-10.
Metal-EDTA complex:
 Edta being a chelating
ligand react with
multivalent metal ions to
form stable complex.
 In hard water, bivalent
cations like Ca & Mg ions
are present which form
complex with EDTA.
 That`s why this method
is used to determine
M = Ca2+, Mg2+ hardness in water.
35
STRUCTURE OF EBT:

36
Numerical Problem
1. A 100 mL water sample required 13.5 mL of 0.02M
EDTA for titration with EBT. The 100 mL of boiled
water required 6.0 mL of 0.02 M EDTA for titration.
Determine the Total, permanent, and temporary
hardness in the sample. Express in °Cl and °Fr.

Total Hardness: 270 ppm of CaCO3 (27 °Fr and 0.07 X 270 °Cl)
Permanent Hardness: 120 ppm of CaCO3(12 °Fr and 0.07 X 120°Cl)
Temporary Hardness: 150 ppm of CaCO3(15 °Fr and 0.07 X 150°Cl)

37
Seating Plan for Quiz (F-block)
CSE-1 F-201
CSE-2 F-202
CSE-3 F-203
CSE-4 F-204
CSE-5 F-205
CSE-6 F-206
CSE-7 F-207
CSE-8 F-208

Report at 5:45 PM

38
Draw backs (or) Disadvantages of Hard Water
Domestic Use Industrial Use

1. Washing 1. Textile Industry

2. Bathing 2. Sugar Industry
3. Drinking 3. Dye Industry
4. Cooking 4. Paper Industry
5. Pharmaceutical Industry
The sticky precipitate adheres on the
fabric/cloth and gives spots and
streaks.

Produces sticky scum on the

bath tub and the body

Bad to the digestive system and

calcium oxalate formation is
possible in urinary tracts

Requires more fuel and time.

Certain food don’t cook soft and
also gives unpleasant taste
39
 Boiler troubles due to Hard Water

1. Scale and Sludge 1. Sludge

Slimy loose precipitate
called sludge suspended in
2. Caustic embitterment water

3. Priming and Foaming

4. Boiler corrosion water

Boiler wall

Sludge is a soft, loose and slimy precipitate formed within the boiler. It can be
easily scrapped off with a wire brush.
It is formed at comparatively colder portions of the boiler and collects in areas of
the system, where the flow rate is slow or at bends.
It is formed by substances which have greater solubility in hot water than in cold
water, e.g. MgCO3, MgCl2, CaCl2, MgSO4 etc.,

Remedy: Sludges can be removed using wire brush or mild acid 40

 SLUDGE FORMATION IN BOILERS:

 In boilers, because of continuous evaporation of water,

the concentration of salts increase progressively and
after the saturation point is reached, precipitate form
on the inner walls of boiler.
 SLUDGE: Sludge is a soft, loose, and silky precipitate
formed within the boiler. It is formed at comparatively
colder portions of the boiler and collects in the area
where flow rate is slow.
These are formed by substances which have greater
solubilities in hot water than in cold-water.
e.g.. MgCO3, MgCl2, CaCl2, MgSO4.
41
 1. Scale
Hard adherent coating on
inner walls of boiler

water

Boiler
wall

Scales are hard substances which sticks very firmly to the inner surfaces
of the boiler wall.
Scales are difficult to remove even with the help of a hammer and chisel.
Examples: CaSO4, CaCO3, Mg(OH)2, MgCl2, SiO2
42
 Reasons for formation of scale

1. Presence of Ca(HCO3)2 in low pressure boilers

Ca(HCO3)2 CaCO3 + H2O + CO2 Low pressure boilers but in high

pressure boilers it is soluble by forming
Calcium bicarbonate Calcium Carbonate (scale) Ca(OH)2

2. Presence of CaSO4 in high pressure boilers

ToC Solubility of CaSO4

4. Presence of SiO2
Cold water soluble
Super heated water Insoluble (scale)
It forms insoluble hard adherent CaSiO3
and MgSiO3 as scales

3. Presence of MgCl2 in high temperature boilers

MgCl2 + 2 H2O Mg (OH)2 + 2HCl

Magnesium chloride scale

Mg(OH)2 can also be generated by thermally decomposing Mg(HCO3)2

43
 Disadvantages of scale formation

1. Fuel wastage – scales have low thermal conductivity

2. Degradation of boiler material and increases of risk of accident
3. Reduces the efficiency of the boiler and- deposit on the valves and
condensers
4. The boiler may explode – if crack occurs in scale

Remedies: Removal of scale

1. By thermal shock- heating and cooling suddenly with cold water

2. Using chemicals – 5-10% HCl and by adding EDTA

44
PREVENTION:
 a. External treatment: Efficient softening of water is to be
carried out.

 b.Internal treatment: Suitable chemicals are added to the

boiler water either to precipitate or to convert scale into
compounds.
 A) to precipitate the scale forming impurities in the form
of sludge, which can be removed
 B) to convert them into compounds, which will stay in
dissolved form in water and thus do not cause any harm.
45
Diagrams of scale and sludge:

46
 Prevention of scale formation

Scale formation can be prevented by two methods

1. Internal conditioning or Internal Treatment
2. External conditioning or External treatment- will be discussed later

1. Internal conditioning methods - of boiler water to prevent scale formation

1. Phosphate conditioning – addition of phosphate compound

2. Carbonate conditioning – addition of carbonate compound
3. Calgon conditioning – addition of sodium hexa meta phosphate
4. Colloidal conditioning – spreading of organic compounds like tannin, agar gel, glue
5. Sodium Aluminate – removes oil and silica
6. Complexometric method – using EDTA (refer expt. 1 chemistry lab manual)

1. Phosphate conditioning

Scale formation can be prevented by adding sodium phosphate to the boiler water which reacts with the
hardness producing ions and forms easily removable phosphate salts of respective ions

3CaCl2 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

Calcium Sodium calcium phosphate
chloride phosphate (non adherent and can be
removed by blow down
method)
47
 Selection of Phosphate compound

Calcium can not be precipitated below a pH = 9.5, hence the selection of phosphate has to be
based on the pH of the boiler feed water.

NaH2PO4 (acidic in nature) ,

Na2HPO4 (weakly alkaline in nature),
Na3PO4 (Alkaline in nature)

2. Carbonate conditioning

CaSO4 (Boiler water) + Na2CO3 CaCO3 + Na2SO4

Calcium Sodium calcium carbonate
sulfate carbonate
(non adherent loose
sludge and can be
removed by blow down
method)

Caution: Excess Na2CO3 can result in caustic embrittlement

48
3. Calgon conditioning

Na2[Na4(PO3)6] 2Na+ + [Na4P6O18]2-

Calgon – sodium hexa

meta phosphate

2CaSO4 (Boiler water) + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

Calcium
Soluble complex ion of
sulfate
calcium - can be removed
easily

Calgon tablets are used in the cleaning of washing machine drums

49
 Caustic Embitterment
 Excess sodium carbonate used up for removing hardness can also result in the
formation of NaOH in high pressure boilers.

NaOH has better mobility and can percolate into fine cracks present in boiler
walls.
Na2CO3 + H2O → 2 NaOH + CO2

 NaOH gets concentrated in the fine cracks present in the boiler walls.

 A concentration cell corrosion is established between the conc. NaOH and dilute
NaOH solution in contact with boiler walls.

 Concentrated NaOH region behaves as anode thus resulting in corrosion of

boiler leading to the formation of sodium ferroate.

Remedies: (i) Use phosphate salts instead of sodium carbonate

(ii) use Na2SO4
(iii) agar-agar gel, tannin, or glue to fill the fine cracks.

50
 IV. Boiler corrosion

Degradation or destruction of boiler materials (Fe) due to the chemical or

electrochemical attack of dissolved gases or salts is called boiler corrosion

Boiler corrosion is of three types

1. Corrosion due to dissolved O2

2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts

1. Corrosion due to dissolved oxygen (DO)

2 Fe + 2 H2O + O2 2 Fe(OH)2

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous Rust
hydroxide

51
 IV. Boiler corrosion

Degradation or destruction of boiler materials (Fe) due to the chemical or

electrochemical attack of dissolved gases or salts is called boiler corrosion

Boiler corrosion is of three types

1. Corrosion due to dissolved O2

2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts

1. Corrosion due to dissolved oxygen (DO)

2 Fe + 2 H2O + O2 2 Fe(OH)2

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous Rust
hydroxide

52
2. Corrosion due to dissolved CO2

Presence of bicarbonate salts of either magnesium or calcium also causes the release of CO2 inside the
boiler apart from the dissolved CO2

Mg(HCO3)2 MgCO3 + H2O + CO2

CO2 + H2O H2CO3 (causes slow corrosion)

Removal
1. It can be removed by the addition of ammonia
2 NH4OH + CO2 (NH4)2CO3 + H2O

3. Corrosion due to dissolved salts

MgCl2 + 2 H2O Mg(OH)2 + 2HCl

Fe + 2 HCl FeCl2 + H2

FeCl2 + 2 H2O Fe(OH)2 + 2HCl

53
Softening of hard water –
External treatment

54
II External treatment of water – External Conditioning of water
Softening of hard water can be done by the following methods
1. Lime soda process
2. Zeolite methods
3. Ion exchange resin method
4. Mixed bed deionizer method

1. Lime soda process

It is a process in which Lime (Ca(OH)2) and soda (Na2CO3) are added to the hard water to convert
the soluble calcium and magnesium salts to insoluble compounds by a chemical reaction. The
CaCO3 and Mg(OH)2 so precipitated are filtered off and removed easily.

It is further divided in to two types

1. Cold lime soda process
2. Hot lime soda process

55
 1. Cold lime soda process

Step 1
In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are mixed
with water at room temperature and added to the hard water. The following reactions
takes place depending on the nature of hardness

Chemical reactions

If it is permanent hardness and due to calcium salt

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)
slimy suspended precipitate

If it is due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime)
slimy suspended precipitate

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)

slimy suspended precipitate

56
 Chemical reactions contd..

If it is Temporary hardness and due to calcium salt

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
If it is due to Magnesium salt
Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 +
slimy suspended precipitate

Step 2 Even HCl and CO2 are neutralized with Ca(OH)2

The precipitates CaCO3 and Mg(OH)2 are very fine and forms sludge like precipitates
in the boiler water and are difficult to remove because it does not settle easily making it
difficult to filter and the removal process. Finally reduces the efficiency of the boiler.

Therefore, it is essential to add small amount of coagulant (such as Alum, Aluminium

sulfate, sodium aluminate etc) which hydrolyses to flocculent precipitate of Al(OH)3
which entraps the fine precipitates.

NOTE: Particles finer than 0.1 µm (10-7m) in water remain continuously in motion due to electrostatic charge (often
negative) which causes them to repel each other. Once their electrostatic charge is neutralized by the use of coagulant
chemical, the finer particles start to collide and agglomerate (combine together) under the influence of Van der Waals's
forces. These larger and heavier particles are called flocs.
57
When coagulants are added flocculation takes place followed by the
formation of flocculants.

NaAlO2 + 2H2O NaOH + Al(OH)3

Coagulant Flocculent- Gelatinous
precipitate which entraps
the fine precipitates of
CaCO3 and Mg(OH)2

Al2(SO4)3 + 3 Ca(HCO3)2 2Al(OH)3 + CaSO4 + CO2

Aluminium Hard water
sulfate sample Flocculent- Gelatinous
precipitate which entraps
the fine precipitates of
CaCO3 and Mg(OH)2

The Al(OH)3 formed by the addition of coagulants initiates the process of

flocculation and entraps the fine precipitates and becomes heavy. The heavier
flocs then settles at the bottom and filtered off easily.

58
 Continuous cold lime soda softener

Chemicals
Hard water
(soda+lime+
feed
coagulant)
feed
Softened
water
Wood fiber
filter

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2

59
2. Hot lime soda Process

In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are
mixed with hot water at a temperature range of 80 to 150oC and added to the
hard water. The following reactions takes place depending on the nature of
hardness

Chemical reactions

If it is permanent hardness and due to calcium salt

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)
slimy suspended precipitate

If it is due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime)
slimy suspended precipitate

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)

slimy suspended precipitate

60
Chemical reactions contd..

If it is Temporary hardness and due to calcium salt

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
slimy suspended precipitate

If it is due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O
slimy suspended precipitates

61
 Advantages of Hot Lime Soda Process

1. The reaction between hardness producing substance and lime soda

proceeds at a faster rate, decreases the viscosity of water.
2. The precipitates and sludge formed are settled at the bottom easily and
hence No coagulants are required
3. The dissolved gases such as CO2 escapes and the water becomes free from
dissolved gases
4. It produces soft water with the residual hardness of 15-30 ppm in contrast to
the cold lime soda process which produces soft water with 50-60 ppm of
residual hardness

Hot lime soda Plant consists of three parts

1. Reaction tank: water, chemicals and steam are mixed

2. Conical sedimentation tank : sludge settles down
3. Sand filter : complete removal of sludge from the soft water is ensured

62
 Continuous Hot Lime soda Process
Hard water feed

Super heated steam

Chemicals feed (lime and
soda)

Reaction tank
Soft water

Conical sedimentation
tank

Precipitated sludge
(CaCO3, Mg(OH)2 Sludge
outlet

Filtered soft
water

63
Advantages of Lime soda process

1. It is very economical compared to other methods

2. Iron and manganese salts are also removed by this process
3. It increases the pH of the softened water hence corrosion is minimized
4. Not only the hardness but the alkalinity, silica, and TDS is also reduced.
5. The levels of CO2 are also reduced by hot soda-line process.

Disadvantages of Lime soda process

1. Disposal of large amount of sludge (insoluble precipitates) poses a

problem
2. Can’t completely remove the hardness. Treated water has 15 ppm of
hardness.
3. Feedwater quality may change and hence quantities of soda and lime
needs to be adjusted.

64
Calculation of lime and soda required for the softening of hard water by the lime
soda process

Hardness producing Chemical reaction with lime and soda Need

substance

Permanent Hardness
Ca Salts CaCl2 + Na2CO3 CaCO3 + 2NaCl S

Mg salts MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L+S

CaSO4 + Na2CO3 CaCO3 +Na2SO4

Temp. Hardness
Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O L
Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O 2L

Acids
HCl 2H+ + Ca(OH)2 Ca2+ + 2H2O L+S
H2SO4 Ca2+ + Na2CO3 CaCO3 + 2Na+

HCO3- HCO3- + Ca(OH)2 CaCO3 + H2O + CO32- L-S

Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+

FeSO4 Ca2+ + Na2CO3 CaCO3 + 2Na+ L+S

NaAlO2 NaAlO2 + H2O Al(OH)3 + NaOH

L/2
65
Rules
1. If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca2+ + 2HCO3-) and (Mg2+ + 2HCO3-)
respectively then the calculation result will be the same based on the ability of the ions to take up
bicarbonate ions
2. If treated water found to contain excess of OH- and CO32- ions these are formed from excess
equivalent each of Ca(OH)2 and Na2CO3 and hence these excess amounts should be added to the
calculation (in temp. hardness and perm. hardness)
3. When the impurities are given as CaCO3 and MgCO3 present in water it should be considered as
due to bicarbonates of calcium and magnesium respectively
4. Substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc do not contribute to hardness and therefore,
they do not consume any soda or lime and hence if these present need not be taken in to
consideration during calculation.
5. Soda (Na2CO3) neutralizes only permanent hardness

Molecular weight of lime = 74

Molecular weight of soda = 106
Molecular weight of CaCO3 = 100

Therefore, 100 parts by mass of CaCO3 are equivalent to

(i) 74 parts by mass of Ca(OH)2
(ii) 106 parts by mass of Na2CO3
66
Therefore, Lime requirement for softenening

= 74 T.H of Ca2++ 2 x T.H of Mg2+ + P.H of (Mg2+ + Fe2+ + Al3+) + CO2 + H+ +

100 HCO3- - NaAlO2/2
X Vol .of water (L)

T.H = temporary hardness

P.H = Permanent Hardness

llIly, Soda requirement for softenening

= 106 P.H of (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ - HCO3- X Vol .of water (L)
100

Problem 1
Calculate the amount of lime required for softening 5,000 litres of hard water containing
72 ppm of MgSO4 (mol wt = 120) Ans = 222g

67
Solution
Step 1 List out the given data
Given data : Hardness 72 ppm due to MgSO4; water qty = 5000 litres; mol. wt. MgSO4 = 120

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
MgSO4 72 100/120 72 X (100/120) = 60

68
Problem 2
Calculate the temporary and permanent hardness of water containing: Mg(HCO3)2 = 144 ppm, CaCO3 = 25
ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 = 25ppm and Na2SO4 = 15ppm

Solution

Step 1 List out the given data

Given data : Mg(HCO3 )2 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 =
25ppm and Na2SO4 = 15ppm

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
Mg(HCO3)2 144 100/84 144 x(100/84) = 171.4
CaCO3 025 100/100 25 x (100/100) = 25.0
MgCl2 095 100/95 95 x (100/95) = 100.0
CaCl2 111 100/111 111 x (100/111) = 100.0
Fe2O3 025 (does not cause hardness)
Na2SO4 015 (does not cause hardness)

69
Step 3 calculation of lime requirement

Lime required = 74/100 ( {2 x MgHCO3} + CaCO3 + MgCl2 in terms of CaCO3 eq) x vol. of water

= 74/100 (2 x 171.4 + 25.0 +100.0) mg/L x 50,000 L

= 74/100 (467.8) mg x 50,000
= 17, 309,000 mg
Answer = 17. 31 kg

Step 4 calculation of soda requirement

soda required = 106/100 ( MgCl2 + CaCl2 in terms of CaCO3 eq) x vol. of water

= 106/100 (100 +100.0) mg/L x 50,000 L

= 106/100 (200) mg x 50,000
= 10, 6,00,000 mg
Answer = 10. 6 kg

70
 II. Zeolite (Permutit) method of Softening of water

Zeolite is a Hydrated Sodium Alumino Silicate (HSAS),

capable of exchanging reversibly its sodium ions for
hardness producing ions in water.

The general chemical structure of zeolite is given

below Na2O.Al2O3.xSiO2.yH2O (x = 2-10 and y = 2-6)

Why synthetic zeolite is better than natural zeolite for the

softening of water? Ans: Natural zeolites are non-porous

Micro pores of Zeolite Porous Structure of zeolite

 Porosity or cavity size of synthetic zeolite structures can be

controlled by varying the Si/Al ratio
 Ion-exchange process of zeolite structure is associated with sodium ions
71
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

72
 Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through the zeolite bed at a
specified rate. The hardness causing ions such as Ca2+, Mg2+ are retained by the zeolite bed as CaZe
and MgZe respectively; while the outgoing water contains sodium salts. The following reactions takes
place during softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3 Scale formation

Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

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

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained

73
Limitations of Zeolite process

1. If the water is turbid ---- then the turbidity causing particles clogs the pores of the Zeolite and making
it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can not be regenerated that
easily as both metal ions bind strongly and irreversibly to the zeolite structure.
3. Any acid present in water (acidic water) should be neutralized with soda before admitting the water
to the plant, since acid will hydrolyze SiO2 forming silicic acid

Advantages of Zeolite process

1. Soft water of 10-15 ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation in the treated water
4. It does not require more time and more skill

Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3- and CO32- in
the softened water (then it may form NaHCO3 and Na2CO3 which releases CO2 when the water
is boiled and causes corrosion)
3. It also causes caustic embitterment when sodium carbonate hydrolyses to give NaOH
74
 III. Ion-Exchange resin (or) deionization (or) demineralization process

Ion exchange resin

Ion exchange resins are insoluble, cross linked, long

chain organic polymers with a microporous structure,
and the functional groups attached to the chain is
responsible for the “ion-exchange” properties.

Cation Resin after

exchange Resin treatment
75
In general the resins containing acidic functional groups (-COOH, -SO3H etc) are capable of exchanging
their H+ ions with other cations, which comes in their contact; whereas those containing basic functional
groups ( -NH2, =NH as hydrochlorides) are capable of exchanging their anions with other ions, which
comes in their contact.

Based on the above fact the resins are classified into two types
1. Cation exchange resin (RH+) –
Strongly acidic (SO3-H+) and weakly acidic (COO-H+) cation exchange resins
2. Anion Exchange resin (ROH-) –

Strongly basic (R4N+OH-) and weakly basic (RNH2+OH-) anion exchange resins

Continued… next slide

76
Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

R = CH3

77
 Ion exchange purifier or softener

Hard
water

Cation exchange Resin Anion exchange Resin

Gravel
bed

Injector
Injector

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

Soft water 78
 Process or Ion-exchange mechanism
involved in water softening

Reactions occurring at Cation exchange resin

2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+

Reactions occurring at Anion exchange resin

2 ROH- + SO42- (hard water) R2SO42- + 2 OH-

2 ROH- + Cl- (hard water) R2Cl- + 2 OH-

At the end of the process

H+ + OH- H2O

79
 Regeneration of ion exchange resins

Regeneration of Cation exchange resin

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

Regeneration of Anion exchange resin

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

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

Disadvantages
1. The setup is costly and it uses costly chemicals
2. The water should not be turbid and the turbidity level should not be more
than 10ppm
80
 IV. Softening of water by Mixed Bed deioniser

Description and process of mixed bed deionizer

1. It is a single cylindrical chamber containing a mixture of anion and cation exchange resins bed
2. When the hard water is passed through this bed slowly the cations and anioins of the hard water
comes in to contact with the two kind of resins many number of times
3. Hence, it is equivalent to passing the hard water many number of times through a series of cation
and anion exchange resins.
4. The soft water from this method contains less than 1ppm of dissolved salts and hence more
suitable for boilers

Hard water

c a c a Anion exchange
resin
c Mixed bed Mixed resin
a deionizer a bed
a
c a cc Cation exchange
resin

Demineralised
water

81
Regeneration of mixed bed deionizer

1. When the bed (resins) are exhausted or cease to soften the water, the mixed bed is back washed by
forcing the water from the bottom in the upward direction
2. Then the light weight anion exchanger move to the top and forms a upper layer above the heavier cation
exchanger
3. Then the anion exchanger is regenerated by passing caustic soda solution (NaOH) from the top and then
rinsed with pure water
4. The lower cation exchanger bed is then washed with dil.H2SO4 solution and then rinsed.
5. The two beds are then mixed again by forcing compressed air to mix both and the resins are now ready
for use
Low
NaOH
density
resin

c a c a c a c a c aa c a
aa a a a a cRegenerated
c Mixed bed c Exhausted Back washed a
a deionizer a a Mixed bed a
Mixed bed

a a ccccc c
deionizer
a
c a cc c a cc c a c c

Back Compressed
wash High air
water density 82
resin
Desalination of seawater
 Desalination, refers to any process that removes
some amount of salt and other minerals from
water.

Technologies for desalination process

 Reverse Osmosis (Pressure membrane process)
 Electrodialysis membrane process

83
 Pressure Membrane Processes

 Microfiltration (MF), which can remove particles ranging in size

from 10-100 μm. It is operated in the pressure range of 10 psig.

 Ultrafiltration (UF), which can remove particles ranging in size

from 0.01 to 10 μm. It is operated in the pressure range of 15 psig.

 Nanofiltration (NF), which can remove particles size from 0.001

μm to 0.01 μm. It is operated in the pressure range of 75-250 psig.

 Reverse osmosis (RO), which can remove particles in the size

range of 0.1-1.0 nm. It operates in the pressure range of 200-1200
psig.
84
 Principle - Reverse osmosis
 When two solutions of unequal concentration are separated by a semi-
permeable membrane, flow of solvent takes place from dilute to
concentration side, due to increase in osmostic pressure, which is termed
as osmosis.
 However, when a hydrostatic pressure in excess of osmotic pressure is
applied on the concentrated side, the solvent flow is reversed from
concentrated side to dilute side, across the membrane. This principle is
termed as reverse osmosis.

 The semi-permeable membrane (in reverse osmosis) is selective in not

permitting the passage of dissolved solute particles such as molecules,
ions, etc.) It permits only the flow of water molecules (solvent) from the
concentrated to dilute side.

 Cellulose acetate, polyamide, etc., are used as membrane

 Reverse osmosis process requires only mechanical force to generate the

required hydrostatic pressure. 85
Reverse Osmosis

86
 Principle -Electrodialysis
 Electrodialysis is an electrochemical process whereby electrically charged
particles, ions, are transported from a raw solution (retentate, diluate) into a
more concentrated solution (permeate, concentrate) through ion-selective
membranes by applying an electric field.

87
 Theory of Electrodialysis
 Electrodialysis chamber comprises of sheet like barriers made out
of high-capacity, highly cross-linked ion exchange resins that allow
passage of ions but not of water.
 There are two types : (a) Cation exchange and (b) Anion exchange
membranes
 Cation exchange membranes consists of an insoluble matrix and
mobile cation reside in the pore space that allows the pass through
of only cations.
 Anion exchange membranes consists of an insoluble matrix and
mobile anion reside in the pore space that allows the pass through
of only anions.
 Cation- and Anion- exchange membranes are installed alternatively
in the tank.
 By impressing electricity on the electrodes, the positive anode
attracts negative ions in solution, while the negative cathode
attracts positive ions in the solution.
88
Alkalinity relationships as determined by
titrations.

Hydroxide Carbonate Bicarbonate

P=O O O M
P=M P O O
P = 1/2M O 2P O
P >1/2M 2P - M 2(M - P) O
P <1/2 M O 2P M - 2P

89
 EXPRESSION OF HARDNESS
 THE EQUIVALENT OF CaCO3 FOR A HARDNESS
CAUSING SALT IS GIVEN BY:

 EQUIVALENT OF CaCO3 = W X 50
E
Where
W=MASS OF HARDNESS PRODUCING SUBSTANCE
E= EQUIVALENT MASS OF HARDNESS PRODUCING
SUBSTANCE

90
Numerical Problem
1. Calculate the temporary, total and permanent hardness
containing the following:
Ca(HCO3)2 : 12.2 mg/L = 7.53 mg/L CaCO3
Mg(HCO3)2 : 8.2 mg/L = 5.61 mg/L CaCO3
MgSO4: 5.6 mg/L = 4.67 mg/L CaCO3
MgCl2: 6.2 mg/L = 6.52 mg/L CaCO3
CaSO4: 10.3 mg/L = 7.57 mg/L CaCO3

91
Numerical Problem
1. A Zeolite bed was exhausted after completely removing the
total hardness of 10000 L of hard water. The zeolite was
regenerated using 8 L NaCl containing 150g/L of NaCl.
Calculate the hardness of water.

Total NaCl: 150 X 8 = 1200 g

Eq. of CaCO3: 1200 X(100/58.5)X(1/2) = 1025.64 g CaCO3
Total hardness per L= 1025.64/10000 = 0.1025 g/L
= 102.5 mg/L = 102.5 ppm
of CaCO3

92