WATER AND ITS TREATMENT

Hardness and alkalinity of water: Units and

determination, External and internal method of
Softening of water: Lime-soda Process, Ion exchange
process, Desalination of brackish water
WATER

 Most precious, wonderful and useful gift of nature

 Covers nearly 70% of the earth’s surface
 Water on earth
 Ocean seas (97%)
 Polar ice and glaciers (2%)
 Fresh water (1%) in rivers, lakes, streams, ground
water, etc.
 Source of Water
A) Surface Waters
– Rain Water
– River Water
– Lake Water
– Sea Water
B) Underground Waters
– Spring Water
– Well Water
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 – depend on the contact with soil.

Lake water:
• High in organic and less in minerals.
• composition is constant.
Surface Water
Rain water:
 Pure form
 dissolved organic and inorganic suspended particles
 dissolved industrial gases CO2, NO2,SO2 etc

Underground water:
 free from organic impurities due to filtering action of
the soil
 Rich in dissolved salts

Sea water:
 very impure; contain ~ 3.5% of dissolved salt (of
which ~2.6% NaCl), used mainly for cooling
Common Impurities in water

 Water is a very good solvent and hence dissolves

many substances
 The common impurities in water:
 Dissolved impurities: salts, ions, dyes, gases-
change in taste/color/hardness
 Suspended impurities: like inorganic (clay, sand)
organic (oil, plant, and animal matter)-Make water
turbid
 Colloidal impurities- finely divided silica and clay
 Microorganisms – bacteria, fungi and algae –Foul
smell/cause diseases
 Water quality standards
 Water is used for domestic as well as industrial uses
 Potential application will determine the quality
parameters
 Environmental (ambient) water quality vary significantly
according to the source: lakes, rivers, ocean etc.,
 Water quality parameters broadly fall in three categories
 Physical characteristics (Color, Taste, odor, temperature,
etc.)
 Chemical characteristics (pH, hardness, Total Dissolved
Solids (TDS), dissolved oxygen (DO), Cl-, F-, NO3-, etc.)
 Biological characteristics (E. coli, coliform, etc.)
Hardness of water
It is defined as a characteristic property of water that
prevents the lathering of soap.

Hardness of water may also be defined as the soap-

consuming capacity of water, or the capacity of
precipitation of soap.
It is due to the presence soluble salts of Ca, Mg, Al, Fe,
Mn, etc. in water

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

2NaCl
The Cleansing Action of Soap
HARDNESS of Water
Hard water does not produce lather with soap solutions,
but produces white precipitate (scum). For example,
sodium stearate reacts with calcium:
Soap (C17H35COONa) – Na or K salts of long chain
fatty acids

2C17H35COONa + CaCl2 → (C17H35COO)2Ca + 2NaCl2

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

 Also known as Carbonate or Alkaline hardness

 Due to the presence of carbonate, bicarbonates and

hydroxides of Ca & Mg in solution

 Can be removed by boiling the water or by the

addition of lime.

 Responsible for the deposition of scale in hot water

pipes and kettles.
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’

Determined by titration with HCl using methyl orange
as indicator
Permanent Hardness: Non-
carbonate/non-alkaline hardness
Due to sulphates or chlorides of Ca and Mg ( e.g.
CaCl2, MgCl2, CaSO4, MgSO4, etc.,)

Cannot be destroyed on boiling the water

Also known as non-carbonate or non alkaline hardness

Total hardness = Temporary + permanent hardness

= non alkaline + alkaline hardness
Hard Water
Advantages Disadvantages

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 Excess hardness causes
CaCO3, preventing any the health problem such as
poisonous lead dissolving stone formation in the body
in drinking water
 EXPRESSION OF HARDNESS
 Always calculated in terms of equivalent of CaCO3
 Calculation is easy as Mol wt of CaCO3 = 100

 Insoluble CaCO3 precipitated out from water:

Equivalent of CaCO3 = W X E/C.E.

W = Mass of hardness producing substance

E = Equivalent mass of CaCO3 (50)
C.E. = Equivalent weight of hardness producing
substance
 A water sample contain 248 mg
CaSO4/l. Calculate the hardness in
terms of CaCO3 equivalent.
CaSO4 ≡ CaCO3
Mol wt 136 100
Eq. wt 68 50
68 mg CaSO4 ≡ 50 mg CaCO3
248 mg CaSO4 ≡ (50/68) 248 CaCO3
= 182.35 CaCO3 equivalent
How many grams of FeSO4 (mol wt = 152)
dissolved per litre gives 300 ppm of
hardness
Equivalent of CaCO3 = W X E/C.E.
W = Mass of hardness producing substance (x)
E = Equivalent mass of CaCO3 (50)
C.E. = Equivalent weight of hardness producing
substance = 152/2 = 76
300 = X 50/76
X = 300 x 76/50 = 456 ppm = 456 mg/l
= 0.456 g/l
UNITS OF HARDNESS: several
different scales used to describe the
hardness of water
1) ppm : Number of parts by weight of CaCO3
equivalent hardness present in million (106)
parts by weight of water
2) mg/l : Usually defined as one milligram of
calcium carbonate (CaCO3) per litre of water.
1 mg/l = 1 mg of CaCO3 in 1 l water
1 l water = 1 Kg water = 1000 x 1000 mg = 106 mg
Thus, 1 mg CaCO3 in 1 Kg (1 l) of water = 1 ppm
3) Clark’s Degree : Clark degrees (οCl)/
English degrees (°e or e)
One degree Clark is defined as one grain
(64.8 mg) of CaCO3 per Imperial gallon (4.55
litres) of water, (equivalent to 14.254 ppm)
64.8 mg CaCO3 present in 4.55 Kg water
= 4.55 x106 mg water
1 mg CaCO3 will be in = (4.55/64.8) x106 mg water
= 70, 000 mg water
Thus 1 οC = parts of CaCO3 equivalent hardness
per 70,000 parts of water
1 ppm = 1 mg/l = 0.07 οCl
4) Degree French: (°F or f)
One degree French is defined as 10
milligrams of calcium carbonate per litre
of water.
10 mg CaCO3 present in = 106 mg water
= 10 ppm
1 °F = 10 ppm

1ppm= 1 mg/l = 0.07 °Clark =0.1 °F

A sample of water on analysis was found to Ca(HCO3)2 = 4
mg/l, Mg(HCO3)2 = 6 mg/l, MgSO4 = 10 mg/l, CaSO4 = 8 mg/l.
Calculate the temporary, permanent and total hardness of
water in ppm, οFr and οCl.
Mol wt of Ca(HCO3)2 = 162, Mg(HCO3)2 = 146, MgSO4 = 120,
CaSO4 = 136

Constituent Amount Eq. of CaCO3

(mg/l) (ppm = mg/l)
Ca(HCO3)2 4 4 x 50/81 = 3.469
Mg(HCO3)2 6 6 x 50/73 = 4.11
CaSO4 8 8 x 50/68 = 5.88
MgSO4 10 10 x 50/60 = 8.33
 Temporary hardness due to = 7.579 ppm
 Permanent hardness due to = 14.21 ppm
 Total hardness = 21.789 ppm

 ppm = mg/l
 1 ppm = 0.07 οCl,
 21.789 = 21.789 x 0.07 = 1.525 οCl
 1 ppm = 0.1 οFr
 21.789 = 21.789 x 0.1 = 2.179 ο Fr
Determination of hardness
 Complexometric titration
 Hard water contain Ca, Mg ions
 EDTA is used as standard solution
 EBT (Eriochrome Black T) as indocator
 Titration was performed at pH ~9 ?
Na+ H+

H+ Na+

[Na2H2Y; mol wt 372]

EDTA [H4Y] is used in the form of [Na2H2Y; mol wt
372] as it is more soluble than pure EDTA.
It is a strong chelating ligand, forms complex
(1:1) with bivalent cations like Ca2+ & Mg2+
The complexes formed are stable in alkaline
medium i.e. pH=8-10.
  EDTA being a chelating
Metal- EDTA complex: ligand (hexadentate)
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
hardness in water.
DETERMINATION OF HARDNESS:
 EDTA METHOD
CALCULATIONS
FOR TOTAL HARDNESS:
N 1V 1 = N2V2
(HWS) (STD. EDTA)
N1 = N2V2/ V1
TOT. HARDNESS = N1 X 50 g/l
= N1 X 50 x 1000 ppm

TEMPORARY HARDNESS
=TOTAL- Permanent hardness
A 100 ml sample of water required 13.5 ml of 0.02 M EDTA solution
for titration using Eriochrome black –T as indicator. Another 100 ml
of water from the same source was boiled and precipitate was
removed by filtration. The filtrate required 6 ml of 0.02 M EDTA for
titration. Calculate total, permanent and temporary hardness of
water sample

1 mol EDTA ≡ 1 mol CaCO3

M1V1 = M2V2
13.5 x 0.02 = 100 x M2; M2 = 0.0027,
Total Hardness in g/l = M2 x Mol wt of CaCO3
= 0.0027 x 100 = 0.27 g/l = 270 mg/l (ppm)
Permanent hardness
6 x 0.2 = 100 x M3
M3 = 0.0012
Permanent hardness = 0.0012 x 100 g/l
= 0.12 g/l = 120 mg/l (ppm)
 ALKALINITY OF WATER
 The total amount of those substance,
present in water, which tend to increase the
concentration of hydroxide ions on account
of dissociation and hydrolysis.
 It is a measure of ability of water to
neutralize acids.

Total Alkalinity = Methyl Orange Alkalinity +

Phenolphthalein Alkalinity
CAUSE OF ALKALINITY:
Presence of HCO3-, HSiO3-, SiO3- , OH-
Presence of salts of weak acids
Presence of buffer forming salts

CLASSIFICATION OF ALKALINITY : It is
of three types:
1) OH- (hydroxyl) ALKALINITY
2) CO32- (carbonate) ALKALINITY
3) HCO3- (bicarbonate) ALKALINITY
 Determination of Alkalinity
PRINCIPLE: The type and extent of alkalinity of
water sample is determined by TITRIMETRIC
METHOD using acid as standard solution.

OH- + H+  H2O
CO32- + H+  HCO3-
HCO3- + H+  H2CO3
Indicator Used: Phenolphthalein (pink above
pH ~8, and colorless below pH ~8), methyl
orange (yellow above pH ~4 and orange
below pH~4)
Structure of phenolphthalein and Methyl orange

phenolphthalein

METHYL ORANGE
 PROCEDURE:
 Known volume of water sample + 1-2 drops of
phenolphthalein.
 Pink color appeared
 Titration with std. Acid solution
 Initially hydroxide neutralizes followed by
conversion of carbonate into bicarbonate
OH- + H+  H 2O
CO32- + H+  HCO3-
Color changes pink to colorless (pH ~8 )
phenolphthalein end point
 Titration continued with same sample
with same std. acid by using methyl
orange Indicator.
HCO3- + H+  H2O + CO2

 End point, yellow to orange at pH ~4

 The total volume of acid consumed is
noted. (methyl orange end point)
 CALCULATIONS:
For phenolphthalein alkalinity (P):
N1V1 = N2V2
(AWS) (Std. Acid)
N1 = N2V2/ V1
PALK = N1 X 50 X 1000 ppm

For methyl orange alkalinity (M):

N1V1 = N2V2
(AWS) (Std. Acid)
N1 = N2V2/ V1
MALK = N1 X 50 X 1000 ppm
 Interpretation of alkalinity values
Alkalinity OH- CO32- HCO3-

P=0 0 0 M

P=½M 0 2P 0

P<½M 0 2P M-2P

P>½M 2P-M 2(M-P) 0

P=M P 0 0

P = phenolphthalein end point, M = methyl orange end point

A 100 ml water sample required 25 ml of 0.05N sulphuric acid for
phenolphthalein end point and another 10 ml for methyl orange end
point. Determine the nature and amount of alkalinity
 N 1V 1 = N 2V 2
 100 x N1 = 25 x 0.05
 N1 = 0.00125
 Phen alkalinity as CaCO3 eq. = 0.00125 x 50 = 0.625 g/l
= 0.625 x 1000 = 625 mg/l (ppm)
Methyl orange alkalinity: Total Vol of acid used
= 25 + 10 = 35 ml
N2 = 35 x 0.05/100 = 0.0175
MO alkalinity as CaCO3 eq.=0.0175 x 50 =0.875 g/l
=875 mg/l (ppm)
Since P-alk > M-alk/2, alkalinity is due to OH- and carbonate
Hard Water Soft Water

Does not produce Produces lather

lather with soap easily with soap

Contains Ca and Mg Does not contain

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

Boiling point Less fuel and time

elevated, more time required for cooking
and fuel for cooking
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

 Disadvantages of Hard Water

Domestic Use (potable water) Industrial Use

1. Washing: The sticky precipitate 1. Textile Industry

adheres on the fabric/cloth and 2. Sugar Industry
gives spots and streaks. Fe salts 3. Dyeing Industry
stain the cloths. 4. Paper Industry
2. Bathing: Produces sticky scum 5. Pharmaceutical Industry
on the bath tub and the body 6. In Steam generation in
Boilers
3. Drinking: Bad to the digestive
system and calcium oxalate
formation is possible in urinary
tracts
4. Cooking: Requires more fuel and
time. Certain food don’t cook soft
and also gives unpleasant taste
Boiler Feed Water
Boiler Feed Water
 On heating, water absorbs large amount of
heat and expand to form steam
 The steam is capable of carrying out large
quantities of heat
 Thus, water is an ideal raw material for
heating and power generation
 A boiler is a closed vessel in which water
under pressure is transformed into steam by
application of heat
 The water used in boilers is called boiler feed
water
Characteristics of boiler feed water
 Dissolved and suspended matter and dissolved
gases cause boiler problem
 The amount of impurities permitted in boiler feed
water are based on the pressure at which boiler
works
 For pressure upto 100 bar, the boiler feed water
should have the following charactersitics
 Dissolved oxygen < 0.02 mg/l
 Total hardness < 0.5 ppm
 Total iron below < 0.03 ppm, Cu < 0.01 ppm and Si
< 5 ppm
 Caustic alkalinity (P-alkalinity) < 0.5 ppm and soda
(M-alkalinity) < 1 ppm
 Boiler troubles due to Hard Water
1. Scale and Sludge
2. Caustic embitterment
3. Priming and Foaming
4. Boiler corrosion
 SLUDGE FORMATION IN BOILERS:
 Due to 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 slimy

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.
 Formed by substances which have greater solubility
in hot water than in cold-water.
E.g.. MgCO3, MgCl2, CaCl2, MgSO4.
1. Sludge
Slimy loose
precipitate called
sludge suspended
in water

water

Boiler wall

Remedy: Sludge can be removed using

wire brush or mild acid
 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
 Reasons for scale formation
1. Presence of Ca(HCO3)2 in low pressure boilers

Ca(HCO3)2  CaCO3 + H2O + CO2

Calcium Carbonate (scale)

In high pressure boilers it is soluble by forming Ca(OH)2

CaCO3 + H2O  Ca(OH)2 + CO2

2. Presence of SiO2

It forms insoluble hard adherent CaSiO3 and MgSiO3 as scales

 Reasons for formation of scale
3. Presence of CaSO4 in high pressure boilers (solubility
decreases with increasing the temperature)

T (oC) Solubility of CaSO4

-------------------------------------------------------------------------------------------------
15 3200 ppm
230 15 ppm
320 27 ppm
Cold water soluble
Super heated water Insoluble (scale)

4. Presence of MgCl2 in high temperature boilers

MgCl2 + 2 H2O  Mg(OH)2 + 2HCl
Magnesium chloride soft scale
Mg(OH)2 can also be generated by thermal decomposition
of Mg(HCO3)2
 Disadvantages of scale formation
 Fuel wastage – scales have poor thermal conductivity
 Lowering boiler safety- Due to poor conductivity of
scale, the boiler over heating is required which will
make the boiler material softer and weaker. Thus boiler
becomes unsafe at high pressure
 Decrease in efficiency: Scale deposition partially
chokes the valves and condensers
 Danger of explosion: Due to cracking of scales, a gap
between boiler wall and scale is formed. When water
comes in contact with overheated boiler walls, it
generate the excessive steam which may cause the
boiler explosion
Removal of Scale
 Loosely adhering scale can be removed either
by scraping or wire brush or by blow down
operation
 Brittle scales by thermal shock (i.e. heating
the boiler followed by sudden cooling)
 Hard and adherent scales (CaCO3) can be
dissolved in 5-10% HCl.
CaSO4 can be removed by adding EDTA
as Ca-EDTA complex is highly water soluble
Prevention of scale formation
Lime soda
process
External
Zeolite process
Prevention of scale treatment
Ion exchange
process
formation

Carbonate
conditioning
Phosphate
Chemical conditioning
method Calgon
conditioning
NaAlO2
Internal conditioning
treatment
Colloidal
conditioning
Physical Electrical
method conditioning
Radioactive
conditioning
Prevention of scale formation:
External treatment:
 Carried out before water enter into the boiler

Internal treatment:
 conditioning of water in the boiler itself by adding
suitable chemicals
 Also known as sequestration or Conditioning
 Involves the treatment of boiler water inside the
boiler by adding suitable chemicals which either
 precipitate the scale forming substance or
 convert them into compounds, which will remain water
soluble.
 Prevention of scale formation
Internal conditioning of boiler water

 Phosphate conditioning – addition of phosphate compound

 Carbonate conditioning – addition of carbonate compound
 Calgon conditioning – addition of sodium
hexametaphosphate
 Colloidal conditioning – spreading of organic compounds like
tannin, agar gel
 Sodium Aluminate – removes oil and silica
 Complexometric method – using EDTA (refer expt. 1
chemistry lab manual)
 Prevention of scale formation
1. Phosphate conditioning

Sodium phosphate is added 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)
 Selection of Phosphate compound

The choice of phosphate salt depends upon the

alkalinity of the feed water
Calcium can be precipitated at a pH of 9.5 or more,
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

 3. Calgon conditioning

Na2[Na4(PO3)6]  2Na+ + [Na4P6O18]2-

Calgon – sodiumhexametaphosphate

2CaSO4 + [Na4P6O18]2-  [Ca2P6O18]2- + 2Na2SO4

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

Calgon tablets are used in the cleaning of washing

machine drums
Problems due to impurities in boiler
feed water
Priming
Foaming
Priming

Carry over bubble

Priming
When water is heated rapidly water droplets are carried along with
the steam to form wet steam and the process of formation of wet
steam in boilers is called as priming.
Lowers the energy efficiency of steam and deposition of salt
crystals on heaters and turbines
Causes of Priming:
Presence of dissolved salts, high velocity steam due to
sudden boiling and Improper boiler design

Prevention of Priming:
 Proper construction of boiler
 Low water flow
 Slow discharge of stem
 Foaming

Normal bubble
Foaming
Foaming
 Formation of small but persistent foam which do not break easily
 Fill completely or partially the steam space
 Foaming is due to the presence of oil, alkalis, organic matter and
suspended particles in boiler feed water
 Can be prevented by anti foaming agents, removing oil and silica
by NaAlO2, and suspended particles by coagulating agents
Caustic embrittelement
Excess sodium carbonate used for removing hardness
can also result in the formation of NaOH in high pressure
boilers.

Na2CO3 + H2O → 2 NaOH + CO2

NaOH has better mobility and can penetrate into fine

cracks present in boiler walls.

A tube damaged by caustic embrittlement.

 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.

 The iron in the anodic area undergoes corrosion and to

make the boiler walls brittle.

Fe + 2NaOH  Na2FeO2 + H2
Na2FeO2 + 4H2O  6 NaOH + Fe3O4 + H2
6Na2FeO2 + 4H2O + O2  12 NaOH + 2Fe3O4

Thus conc. of NaOH keep on increasing

Preventions
 Addition of tannin or lignin block the minute cracks
and prevent the accumulation of NaOH

 Using phosphate salts instead of sodium carbonate

 Using Na2SO4 to block the hair cracks

 Avoiding excess use of Na2CO3 and adjusting the pH

between 8-9
Boiler corrosion

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

chemical or electrochemical attack of dissolved gases or
salts
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
 Boiler corrosion
1. Corrosion due to dissolved oxygen (DO)
Water contain ~ 8 ppm of dissolved oxygen
At high temp O2 reacts with iron to form ferric
oxide (rust)
2 Fe + 2 H2O + O2  2 Fe(OH)2
4 Fe(OH)2 + O2  2 [Fe2O3.2H2O]
Ferrous hydroxide Rust
Removal: dissolved oxygen can be removed by:
i. Addition of chemicals (hydrazine)
N2H4 + O2  N2 + 2H2O
ii. Mechanical deaeration
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

(again reacts as in step 2)

Prevention:
By adding calculated quantity of alkali to neutralizes
acid thus formed
External treatment:
Softening of hard water
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
 Lime soda process

Lime soda
process

Cold lime Hot lime

soda process soda process

Intermittent Continuous Intermittent Continuous

1. Lime-soda process

 Lime (Ca(OH)2) and soda (Na2CO3) are added

to the hard water
 The soluble calcium and magnesium salts
converted to insoluble compounds, CaCO3
and Mg(OH)2
 The insoluble precipitates are filtered off and
removed easily.
It is further divided in to two types
1. Cold lime soda process
2. Hot lime soda process
1. Cold lime soda process
Step 1
A calculated quantity of Ca(OH)2 (lime) and
Na2CO3 (soda) are mixed in cold water and
added to the hard water.
The reaction of lime and soda with hardness
causing salts will result into insoluble precipitates,
which are removed by settling and filtration
 Chemical reactions contd..
Permanent Hardness:
due to calcium salt

Ca2+ + Na2CO3  CaCO3 + 2Na+

slimy suspended precipitate
due to Magnesium salt
Mg2+ + Ca(OH)2  Mg(OH)2 + Ca2+
slimy suspended precipitate
 Chemical reactions contd..
Temporary Hardness:
due to Calcium salt
Ca(HCO3)2 + Ca(OH)2  2CaCO3 + 2H2O
slimy suspended precipitate

due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2  2CaCO3 +Mg(OH)2+ 2H2O
slimy suspended precipitates
 Step 2
The precipitates CaCO3 and Mg(OH)2 are very fine
particles and forms sludge like precipitates does not
settle easily
Small amount of coagulant (such as Alum,
Aluminium sulfate, sodium aluminate etc) are
added.

NOTE: Particles finer than 0.1 µm (10-7m) in water remain

continuously in motion due to electrostatic charge (often negative).
Coagulants are added to settle the precipitate:

NaAlO2 + 2H2O  NaOH + Al(OH)3

Coagulant Flocculent

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

Aluminium Hard water
sulfate sample

The Al(OH)3 (Flocculent) formed initiates the

process of flocculation. It entraps the fine
precipitates (CaCO3 and Mg(OH)2), which
becomes heavy and settled down at the bottom
and filtered off easily.
 Continuous cold lime soda softener

Soda + lime + Hard water feed

coagulant feed

Softened water
Wood
fiber filter

Stirrer
paddles

Sedimented sludge
(CaCO3, Mg(OH)2
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
 Hot lime soda Process..
Same chemical reaction as in case of cold lime soda process

Permanent Hardness:
due to calcium salt

Ca2+ + Na2CO3  CaCO3 + 2Na+

precipitate
due to Magnesium salt
Mg2+ + Ca(OH)2  Mg(OH)2 + Ca2+
precipitate
 Chemical reactions contd..
Temporary Hardness:
due to Calcium salt
Ca(HCO3)2 + Ca(OH)2  2CaCO3 + 2H2O
precipitate
due to Magnesium salt
Mg(HCO3)2 + 2Ca(OH)2  2CaCO3 +Mg(OH)2+ 2H2O
precipitates
Advantages of Hot Lime Soda Process
1. The reaction proceeds at a faster rate
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 while cold lime soda process 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
 Continuous Hot Lime soda Process

Hard water feed

Chemicals feed (lime

Super heated steam
and soda)

Reaction tank Soft water

Conical
sedimentation tank
Coarse sand
Precipitated sludge layer
(CaCO3, Mg(OH)2 Sludge
outlet Gravel layer

Filtered soft
water
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. Pathogenic bacteria also removed
 Disadvantages of Lime soda process

1. Disposal of large amount of sludge (insoluble

precipitates) poses a problem
2. This can remove hardness to the extent of 15
ppm which is not good for boilers
Calculations: Lime and soda required for the
softening of hard water during lime soda process
Chemical reaction with lime and soda Need

Permanent
Hardness
Ca Salts CaCl2 + Na2CO3 CaCO3 + 2NaCl S
CaSO4 + Na2CO3  CaCO3 + Na2SO4 S
Mg salts MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L
MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 L
Temporary
Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3+ 2H2O L

Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2  2CaCO3 + 2L

Mg(OH)2 + 2H2O
 Calculation of lime and soda required for the
softening of hard water by the lime soda process

CaCl2 + Na2CO3 CaCO3 + 2NaCl

CaCl2/CaSO4 ≡ Na2CO3 ≡ CaCO3

111 / 136 106 100

• Removal of one equivalent of permanent calcium hardness

(CaCl2 + CaSO4) requires one equivalent of soda Na2CO3

• Thus soda required =

106/100 x (amount of CaCl2 + CaSO4 in terms of CaCO3)
Calculation of lime and soda required for the
softening of hard water by the lime soda process

MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

MgCl2/MgSO4 ≡ Ca(OH)2 ≡ CaCO3

95.2 / 120.4 74 100

• Removal of one equivalent of permanent Mg hardness

(MgCl2 + MgSO4) requires one equivalent of lime equivalent

• Thus lime required =

74/100 x (amount of MgCl2 + MgSO4 in terms of CaCO3)
 Calculate the amount of lime required for softening 5,000 liters of
hard water containing 72 ppm of MgSO4 (mol wt = 120)
MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

1. Convert the MgSO4 hardness in CaCO3 equivalent:

MgSO4 ≡ CaCO3
120 100
CaCO3 equivalent hardness = (100/120) x 72 = 60 ppm (mg/l)

2. Since Ca(OH)2 has been used for the removal of hardness, so Ca(OH)2
amount equivalent to CaCO3 must be calculated:

CaCO3 ≡ Ca(OH)2
⸪ 100 g of CaCO3 is equivalent to = 74 g of Ca(OH)2
⸫ 60 mg of CaCO3 is equivalent to = (74/100) x 60 mg of Ca(OH)2 (lime)

60 mg lime would be required for one liter of water

For 5000 liter, Ca(OH)2 requirement = (74/100) x 60 x 5000 = 222, 000 mg
= 222 g
13-91
 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 Quantity (ppm) Multiplication CaCO3

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

Step 3 calculation of lime requirement

Lime required = 74/100 (hardness due to MgSO4 in terms of CaCO3)
= 74/100 (60 mg/L)
for 5000 L = 74/100 (60 mg/L) x 5000 L = 222,000 mg
= 222 g
 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? Porous Structure of zeolite

Ans: Natural zeolites are non-porous

Micro pores of
Zeolite
 Zeolites are synthetic as well as natural

Synthetic zeolites are used for the water purification

due to their porous structure

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
 Process of softening by Zeolite method

 The hardness causing ions such as Ca2+, Mg2+ are retained

by the zeolite bed as CaZe and MgZe respectively
 The outgoing water contains sodium salts. The following
reactions takes place during softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2  CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2  MgZe + 2NaHCO3

 To remove permanent hardness
Na2Ze + CaCl2  CaZe + 2NaCl
Na2Ze + MgSO4  MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl  Na2Ze + CaCl2 or MgSO4

10% brine Regenerated Washings
Used solution Zeolite drained
Zeolite
 Zeolite
softener
Hard water in

Hard water
spray

Zeolite bed
Gravel
Injector

Softened
NaCl To sink water
storage
 Limitations of Zeolite process
1. If the water is turbid, 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, the strong and irreversible binding will make the
zeolite regeneration extremely difficult.
3. Any acid impurity in water will hydrolyze SiO2 into silicic
acid , hence, acidic water should be neutralized with soda
before zeolite treatment.
Advantages of Zeolite process

1. Soft water with < 10-15 ppm hardness 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 (may
form NaHCO3 and Na2CO3 which on boiling releases CO2
and causes corrosion)
3. It also causes caustic embitterment when sodium carbonate
hydrolyses to give NaOH
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.
Resins are classified into two types:
1. Cation exchange resin (RH+) – Acidic functional group
Strongly acidic (SO3-H+) and weakly acidic (COO-H+)
cation exchange resins
2. Anion Exchange resin (ROH-) – Basic functional group
Strongly basic (R4N+OH-) and weakly basic (RNH2+OH-)
anion exchange resins
Ion Exchange Principle:
Cation exchange Resin

Anion exchange Resin Resin after treatment

NR3+OH- NR3+HCO3-

NR3+OH- NR3+HCO3-
HCO3- OH-
NR3+OH- NR3+HCO3-

NR3+OH- NR3+HCO3-
Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

R = CH3
 Ion exchange purifier or softener

Hard
water

Cation exchange Resin Anion exchange Resin

Gravel bed

Injector
Injector

Acid solution for Alkaline solution for

regeneration of Wastages to Wastages to regeneration of resin
resin sink
sink
pump
Soft water
 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
 Regeneration of ion exchange resins

Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4)  2 RH+ + Ca2+

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH)  2 ROH- + SO42-

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
IV. Softening of water by Mixed Bed deioniser

1. It is a single cylindrical chamber containing a mixture of

anion and cation exchange resins bed
2. 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
 Mixed Bed deioniser

Hard
water
Anion
c a c ca exchange
cMixed bed resin Mixed
a a resin bed
deionizer a Cation
c a c exchange
resin
Deminera
lised
water
Regeneration of mixed bed deionizer
1. When the bed (resins) are exhausted, the mixed bed is back
washed by forcing the water from the bottom in the upward
direction
2. Due to this, the light weight anion exchanger move to the
top and forms a upper layer above the heavier cation
exchanger
3. Now, 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
 Regeneration of mixed bed deionizer

Low
NaOH
density
resin

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

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

Back washed High density Compressed

water resin air
 Desalination of brackish water

Desalination : Process of removing common salt from water.

Brackish Water (not as salty as seawater but more salty than fresh
water e.g. Estuaries) : containing dissolved salts with a peculiar
salty (or brackish) taste and unfit for drinking. e.g. Sea water
contain 3.5 % salts.

Commonly used methods for desalination:

1. Electrodialysis
2. Reverse Osmosis
1. Electrodialysis

Method of separation of ions from salt water by

passing electric current.

Consist of three compartments containing:

1. Sea Water
2. Pair of electrodes
3. Semi permeable membrane
• As current applied cations (Na+) moves towards
cathode and anions (Cl-) moves towards anode
• As result NaCl concentration decreases in the middle
compartment.
• Pure water is removed from the central compartment.
• Conc. NaCl solutions (from anodic and cathodic
compartments) are replaced by fresh NaCl solution
• For more effective separation ion selective membranes
are used
 Principle - Reverse osmosis
 Osmosis: Two solutions of unequal concentration are
separated by a semi-permeable membrane, flow of solvent
takes place from dilute to concentration solution and
pressure developed due to this is known as osmotic pressure

 Reverse osmosis: If a hydrostatic pressure in excess of

osmotic pressure is applied on the concentrated solution, the
solvent flow is reversed from concentrated side to dilute
solution, across the membrane.
 The development of osmotic pressure
Reverse osmosis:
Applied pressure > osmotic
osmotic pressure
pressure

pure solution
solvent

semipermeable
membrane

13-117 Figure 13.17

 Principle - Reverse osmosis
• In reverse osmosis the semi-permeable membrane
is selective to solvent (water). It permits only the flow
of water molecules (solvent) from the concentrated
to dilute solution

• Cellulose acetate, polyamide, etc., are used as

membrane

• Reverse osmosis process requires only mechanical

force to generate the required hydrostatic pressure

• Hydrostatic pressure generated is in the order of 15-

40 Kg m-2
Reverse Osmosis

119
 THANK YOU

Copyright 2013-2014
THAPAR UNIVERSITY, PATIALA 120 Thursday, November 24, 2016
Best of luck for your exam and
in all your future endeavors…..