Chem Unit 1

Unit-I: Treatment of Water for Municipal and Industrial Uses
Sources of Water
A) Surface Waters
Rain Water - Pure but contaminated with gases

River Water - High dissolved salts moderate organics
Lake Water - Const. composition but high organics
Sea Water - High salinity, pathogens, organics
B) Underground Waters
Spring/Well Water - Crystal clear but high dissolved salts and high purity from organics
Classification of Impurities in water

Physical Impurities - Dissolved Solids/Salts
Impact: 1) Colour, 2) Turbidity, 3) Taste, 4) Odour, 5) Conductivity
Chemical Impurities - Inorganic & Organic Chemicals
Impact: 1) Acidity (pH), 2) Gases (CO2- O2, NH3), 3) Minerals, 4) pH, 5) Salinity, 6) Alkalinity
7) Hardness
Biological Impurities - Pathogens, algae, fungi,viruses...
Impact: Microorganism, Water Bodies
Colour:
 Colour in water is due to metallic salts of Fe, Mn and due to organic substances like humus,
peat, algae, and weed.
 Industrial activities such as textile, paper & pulp, dyeing, tanneries.
 Colour intensities of water sample can be measured using tintometer using Platinum cobalt
standard coloured complex.
Turbidity
 It is due to colloidal, extremely fine suspension such as clay, slit, finely divided matters,
sometimes microorganisms.
 It reflects the optical properties of water in terms of light scattering ability instead of
transmitting in straight lines.
Conductivity
 The ability of water to conduct electricity indicates the amount of dissolved minerals and
gases in water.
 Conductivity measured in micro mhos/cm or MicroSiemns/cm3
Taste
 Presence of dissolved salts and gases imparts bitter, soapy, brackish and palatable taste which
normally co-related with odour but it is not applicable always the case.
 Bitter (Fe, Al, Mn, SO4, Ca(OH)2)
 Soapy (NaHCO3)
 Brackish (High salt content - NaCl)
 Palatable (CO2 and NO3)
Odour
 Domestic and industries activities cause undesirable odour to water.
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 Industrial effluent of organics, sewage discharge, presence of N, S and P contains compounds,

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metal ion pollution like Fe.

 Substances like algae, peat, bacterias

 Grassy odour, peaty odour, offensive odour, tarry and faint odour
pH
 pH a measure of hydrogen ion activity is used to express the intensity of acidic or alkaline
condition of a solution.
 The pH scale runs to 0 from 14 with 0 representing maximum acidity and 14 maximum basicity.
pH = -log [H+]
Acidity of Water
 Acidity is a measure of the effects of combination of compounds and conditions in water.
 It is the power of water to neutralize hydroxyl ions and is expressed in ppm in terms of CaCO 3
equivalence.
 Acidity - - - - Free Mineral Acidity, - - - - CO2 Acidity
MAJOR IMPURITIES OF WATER
Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases
Alkalinity
Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2

Magnesium Carbonate other suspended matter H2S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria
Requirements of Water for Municipal use or Drinking

 It should be crystal clear and odourless.
 It should be pleasant in taste.
 It should be perfectly cool.
 Its turbidity should not exceed 10 ppm.
 It should be free from objectionable gases: Hydrogen sulphide
 It should be free from objectionable chemicals: Pb/As/Cr/Mn etc.
 Its alkalinity should not be high, preferable pH~8
 It should be reasonably soft
 Total dissolved solids should be within range of 500 ppm.
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 It should be free from disease causing microbes.

Wastewater Treatment
Wastewater treatment refers to the process of removing pollutants from water previously employed
for industrial, agricultural, or municipal uses. The techniques used to remove the pollutants present in
wastewater can be broken into biological, chemical, physical and energetic. These different
techniques are applied through the many stages of wastewater treatment.
Purification of water for Domestic Use
Removal of suspended impurities Removal of Micro-Organism
Screening
Boiling
Sedimentation/Coagulation
Bleaching Powder
Filtration
Chlorination
Chloramine
Ozone
Screening: It is the first unit operation used at wastewater treatment plants (WWTPs). It removes objects
such as rags, paper, plastics, and metals to prevent damage and clogging of downstream equipment,
piping, and appurtenances. Some modern waste water treatment plants use both coarse screens and fine
screens.
Sedimentation: It is the process of removing relatively large particles (suspended solids). In this process
water is allowed to stand undisturbed in a big tank (5m deep), when most of the particle settle down at the
bottom, due to force of gravity. The suspended matter settle-down and water is clarified. Retention period
in a tank ranges from 2-6 hrs. The rate of settling depends upon: The size and Shape of particles,
horizontal flow velocity, temperature and viscosity of water.
Summer: Viscosity of water decreases result less sedimentation time.
Winter: Viscosity of water increases result more sedimentation time.
Plain sedimentation generally removes 70-75% of the suspended matter.
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Fig. Screening Fig. Sedimentation

Sedimentation with Coagulation: Fine suspended and colloidal impurities (0.06mm) take more than
10 hours to settle and water cannot be retained for such a long time. Moreover, most of the particles
are of colloidal in nature (negatively charged e.g., clay, silica etc) and do not settle because of mutual
repulsion. Such particles are removed by addition of certain chemicals called coagulants). Coagulant
forms an insoluble gelatinous precipitate with large surface area which adsorb/entangle very fine
suspended impurities forming a bigger mass (floc) which settle in still water by sedimentation. The
most common coagulant: aluminum sulfate (alum, Al2(SO4)3), poly-aluminum chloride, ferric
chloride, and ferric sulfate. Coagulants, such as alum/ferrous sulphate provide Al3+ or Fe3+ ions,
which neutralize the negative charge on the colloidal clay particles. Thus 95% of suspended matter is
removed.
Chemical Reactions:
1. ALUM (K2SO4.Al2(SO4)3.24H2O)
 Most commonly used in water treatment plants
Al2(SO4)3 + Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

 Gelatinous Floc of Aluminum Hydroxide
2. Sodium Aluminate (NaAlO2)

 Used for treating water with no alkalinity
 Best results at 5.5-8 pH
NaAlO2 + 2H2O Al(OH)3 + NaOH

2NaOH + MgSO4 Mg(OH)2 + Na2SO4
3. Cu(II) or Fe(II) Sulphate (FeSO4.7H2O)

 Good results in slightly alkaline pH
FeSO4 + Mg(HCO3)2 Fe(OH)2 + MgCO3 + CO2 + 6CO2
Coagulant
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3

Heavy Floc
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Filtration: It is a process of removing colloidal matters and microorganisms etc by passing water
through a bed of fine sand other proper-sized granular materials. Filtration is carried out by using
sand filter.
Mechanism: Involves following steps;
1. Straining: When water passes through the filter the straining occurs at the interface of the filter
medium and water. The particles larger than the pore openings at the interfaces are strained.
2. Flocculation: Water containing flocculated matter comes in contact with filter medium. The
smaller floc particles may come in close inside the pores and grow in size and then trapped in the
pores.
3. Sedimentation: A filter medium acts as a large number of minute sedimentation tanks. The pore
space acts as tiny sedimentation basin. Particles smaller than pore space are settle down on the
surface of the medium while passing through the bed.
Filters: Generally sand filters are used. They may be classified as (a) slow sand filter, (b) Rapid sand filter
and (c) Pressure filter.
Operation of sand filter:

A sand filter consists of a thick top layer of fine sand placed over coarse sand layer and gravels. It provides
with an inlet for water and an under drain channel at the bottom for exit filtered water which uniformly distributed
over the entire fine sand bed. Usually, sand pores get clogged due the retention of impurities during filtration
process. Heavy clogging severely decrease in the rate of filtration. Now the top fine sand layer (2-3cm) is scrapped
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off and replaced with clean sand and the filter is put back into the use again.
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Water disinfection:
Disinfection can be attained by means of physical or chemical disinfectants

CHEMICALS PHYSICAL
 Chlorine (Cl2)  Ultraviolet (UV)
 Hypo chlorite (OCl-)/Bleaching
Poder
 Ozone (O3)
 Chloramine
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Why chlorination is the most common method of disinfection?
Chlorination
As we know,
Cl2 + H2O HCl + HOCl
GERMS + HOCl Germs get killed
Mechanism
1. Old believe:
Due to generation of nascent oxygen, which oxidizes harmful bacteria etc.,
HOCl HCl + [O]
2. Work by Chang-1944, Green and Stumpf-1946:
HOCl H+ + OCl‒
 Inactivation of cell enzymes due to action of hypochlorous acid on microorganism. Because
hypochlorous acid (HOCl) is uncharged, it is better able to penetrate cell walls than other
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chlorine species. HOCl is about 80 times more effective than OCl‒

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Factors affecting efficiency of chlorine:

1. pH value of water: Lower pH value-5 to 6.5 favours
2. Temperature of water: Temperature favours disinfection by chlorine, rate of diffusion through the
cell membrane occurs faster at high temperature.
3. Time of contact: CT=disinfectant concentration x contact time = C mg/L×Tminutes.
It has been experimentally shown that number of micro-organism destroyed by chlorine per unit time
is proportional to the no. of microorganism alive. .
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Chloramine (ClNH2): When chlorine and ammonia are mixed in the ratio 2:1 v/v.
Cl2 + NH3 NH2Cl + HCl
Chloramine is much more lasting than chlorine alone and also it is better bactericidal agent.
NH2Cl + H2O HOCl + NH3
There are three stages of chloramines:

(a) Monochloramine (cause eye burn)
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(b) Dichloramine (causes ‘smell’ and ‘chlorine odour’)

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(c)Trichloramine (reduced oxidation, algae encouraged, time to Super Chlorinate!)

Disinfection by OZONE
The nascent oxygen is very powerful oxidizing agent and kills all the bacteria as well as
oxidizes organic matter present in water.
Advantages of Ozone treatment
 Remove colour, taste, and odour
 Pleasing and tasty water
Disadvantages
 Costlier than chlorination
 Possible where electricity is easily and cheaply available
Treatment with UV Radiation

 UV light is electromagnetic radiation with wavelengths in the range of 100-400 nanometers (nm).
 UV light doesn’t damage or destroy cellular structures like chemical disinfectants do (e.g.,
chlorine, ozone, chlorine dioxide). Rather, UV light prevents microorganisms from reproducing
by damaging their deoxyribonucleic and ribonucleic acids (DNA and RNA). Microorganisms that
cannot reproduce cannot infect and are thereby inactivated.
Advantages
1.UV disinfection does not add chemicals to the water.
2. UV is effective against bacteria and viruses
3. UV disinfection has no residual disinfection.
4. UV often last device in a treatment process of water treatment devices.
5. Regular maintenance and lamp replacement is essential.
Disadvantages
There are three potential health risks associated with using UV devices –
formation of disinfection byproducts, mercury exposure due to UV lamp
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breakage and direct exposure to UV light .

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Hardness of Water
Hardness in Water is characteristic that prevents the ‘lathering of soap’ thus water which does not
produce lather with soap solution readily, but forms a white curd is called hard water.
Type of Hardness
a. Temporary or Carbonate Hardness
b. Permanent or non-carbonate Hardness.
Temporary Hardness
Temporary Hardness is caused
Temporary by the presence of dissolved bicarbonate of calcium,
Hardness
magnesium and–other heavy metals and the carbonate of iron.
Temporary Hardness is caused by the presence of dissolved bicarbonate
of calcium,by
It is mostly destroyed magnesium and other
more boiling of heavy
water,metals
whenand the carbonateare
bicarbonates of iron.
decomposed
It is mostly destroyed by more boiling of water, when bicarbonates are
decomposed
yielding insoluble yielding insoluble carbonates.
carbonates.
Ca(HCO3)2 Heat CaCO3 + H2O + CO2
Calcium bicarbonate Calcium Carbonate
Mg(HCO3)2 Heat Mg(OH)2 + 2CO2

Magnesium Bicarbonate Magnesium hydroxide
Calcium/Magnesium Carbonates thus

– Calcium/Magnesium formedthus
Carbonates being almost
formed beinginsoluble, are deposited
almost insoluble, are as a
deposited as a scale at the bottom of vessel, while carbon dioxide escapes
scale at the bottom
out.
of vessel, while carbon dioxide escapes out.
Permanent Hardness
Non Carbonate Hardness is due to the presence of chlorides, sulfates of calcium,
Magnesium, iron and other heavy metals.
2C17H35COONa + CaCl 2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Hardness Calcium stearate
(sodium soap) (Insoluble)
2C17H35COONa + MgSO4 (C17H35COO)2Mg + 2Na2SO4

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)
Disadvantages of Hard Water
Domestic Use Industrial Use
1. Washing 1. Textile Industry

2. Bathing 2. Sugar Industry
3. Drinking 3. Dyeing Industry
4. Cooking 4. Paper Industry
5. Pharmaceutical Industry
The sticky precipitate adheres
on the fabric/cloth and gives
spots and streaks. Fe salts stain
6. In Steam generation in
the cloths. Boilers
Produces sticky scum on the

bath tub and the body
Bad to the digestive system

and calcium oxalate formation
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is possible in urinary tracts
Requires more fuel and time.

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Certains food don’t cook soft

and also gives unpleasant taste
Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO 3 equivalence hardness causing substance present in 10 6 parts
of water
• Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 equivalence hardness causing substance present in one liter
of water
1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 10 6 mg
1mg/L = 1mg of CaCO 3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm
• ClarKe's Degree(oCl)
1o Clarke= 1part of CaCO 3 equivalent hardness in 70000 parts of water
• Degrees French (oFr)

1o Fr = 1 part of CaCO 3 eq per 105 parts of water
Measurements of Hardness:
The hardness of water is expressed in terms of milli-equivalent/liter.
1milli equivalent=50 mgs of CaCO3/lit
The concentrations of hardness as well as non-hardness constituting ions are usually expressed in terms of
equivalent amount of CaCO3.
Hardness is expressed in CaCO3 equivalence. Because,

i) It is the most insoluble and easily precipitatable salt.
ii) Its molecular weight is 100 and equivalent weight is 50. As these are whole numbers, it is very easy to
use them in calculations.
CaCO3 equivalent hardness
Mass of hardness Chemical

producing substance
X equivalent of CaCO3
Calcium carbonate equivalent =
Chemical equivalent of hardness producing
substances
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1. Calculate the calcium carbonate equivalent hardness of a water sample containing 204mg of
CaSO4 per litre.
Solution : 204 X 50
Calcium carbonate equivalent hardness = = 150 mg of CaCO3/L
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Note : Mol. Weight of CaCO 3 = 100 = 150 ppm
Mol. Weight of CaSO4 = 136
2. A water sample from an industry in Bombay had the following data Mg(HCO 3)2 = 16.8mg/L,
MgCl2 = 19 mg/L, CaCO3 = 20 ppm, MgSO4 =24.0mg/L and KOH = 1 ppm. Calculate the
temporary, permanent and total hardness of the water sample.
Constituent quantity Conversion Hardness
present factor
Mg(HCO3)2 16.8 mg/L 50/73 16.8 *50/73 = 11.5ppm
MgCl2 19.0 mg/L 50/47.5 19.0*50/47.5 = 20ppm
CaCO3 20 ppm 50/50 20.0*50/50 = 20 ppm
24.0*50/60 = 20 ppm
MgSO4 24.0 mg/L 50/60
Temp. Hardness = 31.5 ppm P. Hardness = 40 ppm

Tot. Hardness =71.5 ppm
3. Calculate the total hardness from the data given below.
4. Three samples A, B and C were analyzed for their salt contents:

(i) Sample A was found to contain 200mg of magnesium carbonate per liter.
(ii) Sample B was found to contain 800mg calcium nitrate and 2 mg silica per liter.
(iii) Sample C was found to contain 10g of potassium nitrate and 2 g of calcium carbonate per
500ML. Determine the hardness in all three samples in ppm and in grains per gallon.
5. Calculate the total hardness of a sample of water containing following impurities 16.2 mg/L of
Ca(HCO3)2, 11.1 mg/L of CaCl2, 60 mg/L of CaSO4 and Mg(HCO3)2, 11.2 mg/L of MgCl2, 60
mg/L of MgSO4 and 19 mg/L of Mg(NO3)2. Ans: 90,000 mg/L
6. Calculate temporary hardness and total hardness of a sample of water containing Mg(HCO 3)2 =
7.3 mg/l; Ca(HCO3)2 = 16.2 mg/l; MgCl2 = 9.5 mg/l; CaSO4 = 13.6 mg/l. (Atomic weights of Mg
and Ca are 24 and 40 respectively).Temporary hardness= 15mg/l, Permanent hardness= 20mg/l.
7. Calculate the CaCO3 equivalent hardness of a water sample containing 200 mg of CaSO4 per liter.
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Determination of hardness by SOAP and EDTA method:

SOAP METHOD: When soap is added to hard water, it does not give lather, until a sufficient quantity
has been added to precipitate all the hardness-producing metal ions. When all hardness-producing ions
have been precipitated, further addition of soap gives lather.
Procedure
1. Preparation of standard hard water: A standard solution of CaCl2 prepared by dissolving 1 g

of pure CaCO3 in a small quantity of dilute HCl. The solution is then evaporated to dryness to
remove excess acid and CO2. The residue is thereafter dis-solved in one liter of distilled water.
Hardness= 1g/L or 1mg/mL or 1,000 ppm
2. Preparation of Soap Solution: Dissolve 100 g of pure dry castile soap in 800 mL of alcohol
+200 mL of distt. Water.
3. Standardization of soap solution: Fill the burette with soap solution. Take 50mL of hard water
in 250mL glass-stoppered bottle. Start titration and note the point till lather persist after vigorous
shaking
5. Totalfor two minutes. Reading of burette: V1
Hardness:
4. Lather factor
Now, repeat the of distilled
titration water:
by taking 50 Titrate 50mL
mL of water of distilled water and note the volume of burette
sample.
(V mL), of
Reading tillburette:
the lather
V2 mLpersist for two minutes.
5. Total Hardness:
6. Permanent Now, repeat the titration by taking 50 mL of water sample. Reading of burette:
hardness:
VKeep
2 mL Boiling the 250 mL of water sample, till volume is reduced to 50 mL. Filter
6. Permanent
and wash the hardness: Keep boiling
residue. Finally, make upthe
the250 mL of
volume uptowater
250 sample, till volume is reduced to 50
mL by adding
mL. Filter and wash the residue. Finally, make up the volume
distilled water. Then titrate the 50 mL and note the burette reading. upto 250 mL by adding distilled
water.
Reading Then titrateVthe
of burette: 3 mL50 mL and note the burette reading. Reading of burette: V3 mL
Calculations:
Total hardness of water (ppm): 1,000 (V2-V)
(V1-V)
Permanent Hardness (ppm): 1,000 (V3-V)
(V1-V)
Temporary Hardness (ppm): Total – Permanent
EDTA METHOD: Ethylenediaminetetraacetic acid
Ca2+ and Mg2+

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 This is a complexometric method.

 Commercially available as disodium salt as Na2H2Y
 To determine the end point an indicator is employed: EBT (Eriochrome Black T)
EBT Indicator
Procedure
1. Preparation of standard hard water: A standard solution of CaCl2 prepared by dissolving 1 g of pure
CaCO3 in a small quantity of dilute HCl. The solution is then evaporated to dryness to remove excess acid
and CO2. The residue is thereafter dis-solved in one liter of distilled water. Hardness= 1g/L or 1mg/mL or
1,000 ppm
2. Preparation of EDTA solution: Dissolve 4 g of EDTA + 0.1 g MgCl2 in 1 L of distilled water.
3. Preparation of Indicator: Dissolve 0.5 g of EBT in 100 mL of alcohol.
4. Preparation of buffer solution: Add 67.5 g of NH4Cl to 570 mL of conc. NH3 sol and then dilute
with distilled water to 1L.
(a) Standardization of EDTA solution: Fill the burette with EDTA solution. Pipette out 50 mL of
standard hard water in a conical flask + 10 ml buffer solution + 4 drops EBT. Continue the titration, wine-
red color changes to clear-blue. Volume of burette=V1
(b) Titration of water sample: Repeat the above step and note down burette reading (V2).
(c) Titration of boiled water sample: Keep Boiling the 250 mL of water sample, till volume is reduced
to 50 mL(when all bicarbonate decomposed to CaCO3+ Mg(OH)2). Filter and wash the residue. Finally,
make up the volume upto 250 mL by adding distilled water. Then titrate the 50 mL and note the burette
reading. Reading of burette: V3 mL
Calculations:
Total hardness of water (ppm): 1,000 V2/V1
Permanent Hardness (ppm): 1,000 V3/V1
Temporary Hardness (ppm): Total – Permanent
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Mechanism:
1. To the hard water sample the blue coloured indicator EBT is added along with the NH 4Cl,
NH4OH buffer solution. EBT forms an unstable, winered complex with Ca2+ & Mg2+
Mechanism:
2. The wine red coloured [Ca-EBT/Mg-EBT] complex is titrated with EDTA replaces EBT from
[Ca-EBT/Mg-EBT]
1. When hard water complex
comes inand form
contact withstable
EDTA,colourless
at pH 9-10,[Ca-EDTA] [Mg-EDTA]
the Ca2+ & Mg 2+ forms complex
releasing thecolourless
stable, blue coloured indicator
complex EBT into H2O.
with EDTA.
Ca2+
+ + EBT pH 9-10  Ca-EBT + EDTA  Ca-EDTA + EBT
Mg2+ Mg-EBT Mg-EDTA
hard water unstable stable, colorless

wine red colour)
Requirements of water for

2+
industrial use (boiler water):
1. Free fromCahardness causing salts
+ pH 9-10
2. Free from oil and greases
2+
3. Mg (Complex)
Free form dissolved salts and impurities
4. Free from dissolved gases and suspended salts
(from hard water)
Boiler feed water: The setup used to produce steam in industries is known as ‘Boiler’. Water is fed to the
boiler and heated to produce steam. The water fed into the boiler is known as “Boiler feed water”. Boiler
troubles: Sludge, scale, priming and foaming, caustic embrittlement, boiler corrosion 70are collectively
known as boiler troubles.
Sludge and Scale

When hard water is boiled in the boiler to generate the steam, the dissolved salts starts
separating in order to their solubilities after the saturation point. The list soluble salts separate out first
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and the precipitate forms as a layer inside the boilers. When the precipitation of dissolved salts takes
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place inside the boiler in the form of soft, slimy and non-adharent layer It is called sludge and if the
precipitation takes place in the form of hard-adharing coating inside the boilers walls, it is called scales.
Sludge
Sludge:
 It is formed inside the boiler walls.
 Salts have greater solubilities in hot water than in cold water.
 Formed at colder portion of the boiler.
 Collect in the area where flow rate is slow.
Composition:
MgCO3, MgCl2, MgSO4, CaCl2 etc.
Disadvantages
 Poor conductor of heat so they waste lot amount of heat.
 Decrease the efficiency of the boiler.
 Excess formation may results chocking of the water pipes in the industry.
Prevention
 By using soft water.
 Minimized by frequent cleaning operation.
 Removed by scraping off with hard brush.
Scale
This is hard and adherent, coating formed on inner wall of boilers, during
steam generation
Low pressure boilers Ca(HCO3)2, MgCl2
High pressure boilers CaSO4, Silica
Disadvantages
(i) It is poor conductor of heat so reduce the rate of heat transfer.
(ii) Due to scale formation on heating surfaces, overheating occurs,
so metal becomes soft and weak, and this make boiler unsafe.
(iii) Boiler tubes may clog due to scale formation.
(iv) Scale formation leads to uneven expansion of boiler metal, thick scale cracks and when water
comes suddenly in contact with overheated iron plate. This result in the formation of large
amount of heat suddenly, which in turn develops a sudden high pressure that may lead to
explosion of boiler
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Scale Formation
Prevention of scales
Internal treatment External treatment

(Sequestration) lime soda process
Conditioning Method zeolite
Ion exchange process

This treatment method will be discussed in details under heading: Boiler water treatment
Sequestration:
The process where suitable chemicals are added to the boiler
containing hard water with which scales are either precipitated or
converted in to soluble complexes. The chemical used is called
Sequestrating agent
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Internal Treatments or Internal Conditioning

In this method appropriate chemicals are added to water in the boiler when
the hardness producing ions are converted in to either more soluble salts or
insoluble precipitates. The following are the important internal treatment
methods done inside the boiler.
1. Colloidal Conditioning (Low Pressure Boiler)

Certain organic substances like tannin, kerosene, agar-agar etc. is added to the
boiler water they get absorbed over scale forming substances, thereby yielding
non-sticky and loose deposits which can easily be removed, thus preventing scale
deposition.
2. Phosphate conditioning (high Pressure Boiler)

In high pressure boilers, scale formation is prevented by adding sodium phosphate
to boiler feed water. This reacts with Ca2+ and Mg2+ ions in water forming non
adherent and easily removable soft sludge of Ca and Mg phosphate. The commonly
used phosphate are NaH2PO4, Na2HPO4 andNa3PO4.
2Na3PO4 + 3CaCl2 → Ca3(PO4)2 + 6NaCl
The choice of phosphate depends up on alkalinity of boiler feed water.

For eg. Ca2+ cannot be precipitated below pH 9.5. Hence Na3PO 4 is selected to
remove Ca2+ ions.
NaH2PO4, Na2HPO4 and Na3PO4
Acidic Weakly Alkaline Alkaline

The choice of phosphate depends up on alkalinity of boiler feed water
Low
Alkalinity of boiler water: Medium
Very high
3. Carbonate Conditioning
In low pressure boilers, scale formation can be prevented by adding Na 2CO3 to boiler feed
water. Ca2+ salts are precipitated as loose sludge of CaCO 3 which can be removed by blow down
operation.
CaCl2 + Na2CO3 → CaCO3 + 2NaCl
4. Calgon Conditioning
Addition of sodium hexameta phosphate called calgon prevents scale formation by converting
Ca2+ and Mg2+ ions in to soluble complexes.
Na2[Na4(PO3)6] → Na+ + [Na4(PO3)6]2-

2Ca2+ + [Na4(PO3)6]2- → 4Na+ + [Ca2(PO3)6]2-
5. Aluminium conditioning
Boiler water is treated with sodium meta aluminate when NaOH and Al(OH)3 are formed. NaOH
precipitates Mg salt as Mg(OH)2.Both Al(OH)3 and Mg(OH)2 ppts formed entraps all the scale
forming materials. These loose ppt formed can be removed by blow down operation.
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NaAlO2 + 2H2O → NaOH + Al(OH)3

2NaOH + MgCl2 → Mg(OH)2 + 2NaCl
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6. Electrical conditioning:
Sealed glass-bulb containing Hg connected to power supply, are set to rotate in the boiler.
When water boils , it starts emitting electrical discharge. This results scale forming particles to
stick together.
7. Radioactive Conditioning:
Radioactive salt tablets are kept inside boiler water, the emission of radiation prevents
formation of scale.
8. Complexometric Methods:
It Involves addition of 1.5% alkaline solution of EDTA, it binds with scale forming cations.
Removal of scales
 By scraping: scraper/wood/wire brush
 By giving thermal shocks (Heating followed by sudden cooling)
 By dissolving them by chemicals: Means calcium carbonate in hydrochloric acid
solution.
 Frequent blow down operation
Blow Down Operation:

Extent of hardness becomes alarmingly high, partial removal of hard water through
top at the bottom of the boiler.
Make up water
Addition of fresh softened water after blow down operation.
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Priming and Foaming

Priming (Carry over): When steam produced rapidly in boilers some droplets of water are carried
along with the steam. This process of wet steam formation is called priming.
Causes of Priming:
Presence of suspended impurities and dissolved salts
Sudden boiling
High steam velocity, High water levels
Sudden increase in steam production rate
Priming can be avoided by:
Fitting mechanical steam purifiers
Controlling rapid change in steam velocities
Maintaining low water level
Efficient softening of boiler water.
Normal Bubble Carry Over

Foaming
It is the production of froath/bubbles which do not break easily on the surface of boiler water. It
may occur when the pH of the solution is between 7 and 9.
Causes
Presence of dissolved impurities and suspended oil content which will reduce the surface tension
of water resulting in bubble formation.
Presence of finely divided sludge particles
Prevention
By removing oil or sludge by addition of coagulants .e.g FeSO4, NaAlO2 etc.
By addition of antifoaming chemicals e.g. Caster oil
Disadvantages of Priming and Foaming
Water hammer which disrupts operation of the equipment.
Uneven heating of water
Actual height of water column in the boiler cannot be judged properly, thereby maintenance
of boiler pressure becomes difficult.
Dissolved solids in boiler water are carried by the wet steam to super heater and turbine
blades where they get deposited as water evaporates.
This deposit reduces the efficiency of the machine.
Erosion of turbine blades
Boilers Defects: Cause and Prevention

Caustic Embrittlement (Caustic Cracking):"Caustic embrittlement" was first used to describe the
cracking of riveted mild steel boiler plates due to local deposition of concentrated hydroxide at
temperatures of 200 to 250 oC (400 to 480 oF). It was later known as "stress corrosion cracking" which is
in turn replaced by "caustic cracking".
21
It is a form of stress corrosion takes place in boilers operating at high temperature and
pressure. Caustic embrittlement focus at stressed part of boilers such as cracks, rivets,
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bents, joints etc.

Caustic embrittlement results from the conjoint action of three components:

(1) a susceptible material (carbon steel)
(2) a specific chemical species (concentrated hydroxide) and
(3) tensile stress (around the riveted holes)
Mechanism:
 The boiler fed water usually contains some residual sodium carbonate (used for
softening process). At high temperature and pressure it undergoes hydrolysis to
form sodium hydroxide.
Na2CO3 + H2O 2 NaOH + CO2
 The alkali water sweeps through the minute cracks, crevices between the rivets
and joints by capillary action. Inside the cracks water gets evaporated leaving
behind NaOH. The concentrations of the NaOH gradually increase on these sites
due to poor circulation of water. When concentrations of the NaOH reaches a
value of 10% it attacks the metal at the stressed region dissolving it in the form
of sodium ferroate (Na2FeO2 ). Sodium ferroate undergoes hydrolysis-depositing
magnetite as follows
3Na2FeO2 + 4H2O 6NaOH + Fe3O4 + H2
6Na2FeO2 + 6H2O + O2 12NaOH + 2Fe3O4
So, NaOH is regenerated in the process and its concentration is keep on increasing
maintaining a required environment. Thus corrosion process develops cracks and
making the metal brittle by the deposition of the product.
The corrosion cell can be represented as
Fe (under stress) conc. NaOH dil. NaOH Fe (stress free)

Anode Cathode
Caustic embrittlement can be prevented through:

• Control of stress level (residual or load) and hardness.
• Avoid alkalis.
• Use of materials known not to crack in the specified environment.
• Control temperature and or potential
• By using sodium phosphate as softening agent instead of sodium
carbonate.
• Blocking the cracks by adding tannins or lignin to boiler water.
• By using sodium sulphate to block hair-cracks thereby preventing
infiltrations of caustic soda.
22
Na2SO4/NaOH = 1:1, 2:1, 3:1 at pressure 10, 20 and above 20 atm

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Degradation or destruction of boiler materials (Fe) due to the chemical
or electrochemical attack of
Unit-I: Treatment of dissolved
Water for gases or salts
Municipal is called boiler
and Industrial Uses
corrosion
Boiler corrosion
Boiler Corrosion: is of three
Degradation types
or destruction of boiler materials (Fe) due to the chemical or
1. Corrosion due to dissolved O
electrochemical attack of dissolved gases or salts
2 is called boiler corrosion.
2. Corrosion due to dissolved CO 2
3. Corrosion
Boiler corrosion duetypes
is of three to acids formed by dissolved salts
1. Corrosion due to dissolved O2
2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts
1. Corrosion
1. Corrosion due to due to dissolved
dissolved oxygen
oxygen (DO)(DO)
2 Fe + 2 H2O + O2 2 Fe(OH)2
4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous
Rust
hydroxide
Removal of Dissolved Oxygen (DO)
Removal of Dissolved Oxygen (DO)
1. By the addition of chemicals

The dissolved oxygen present in the boiler feed water can be removed by the addition
of sodium sulphite or hydrazine and the reactions can be written as below
2 Na2SO3 + O2 2 Na2SO4
Sodium DO Sodium
sulphite sulphate Water feed
Na2S + 2O2 Na2SO4
N2H4 + O2 N2 + 2H2O
O2 To vacuum
Hydrazine Nitrogen
Steam jacket
2. By mechanical deaeration
It comprises of a tall stainless tower with different layers
capped with baffles to facilitate multiple equilibration.
Perforated
The entire chamber is vacuumized and also maintained at plate
high tempt using perforated heating plates on the walls.
Principle: High tempt and low pressure favors lower solubility

of gases in water (Henry’s law) Deaerated
water
De-aeration can be achieved by spraying water over a large surface countercurrent to

steam.
Advantages
 O2 and some dissolved CO2 distills off.
 De-aerated water gets heated in this process and is more suitable for boiler feed water.
 If cold de-aerated water is needed, the dissolved gas can be distilled off by lowering the
23
pressure (by steam ejector). This method is called vacuum de-aeration.

 It is easy to remove the first 90-95% O2 by distillation, but it is difficult to remove the
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remaining the O2 specially at low temperature.

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 CO 2
Mg(HCO3)2 MgCO3 + H2O + CO2
CO2 + H2O H 2CO3 (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
Removal of Hardness (Water Softening) 96

The process of removing hardness-producing salts from water:
Boiler Water Treatment
SOFTENING METHODS(Softening Process): The process of removing hardness-producing salts
from water: SOFTENING METHODS
1. Lime-Soda Process
2. 1. Zeolite
Lime-Soda Process
or Permutit Process
3. 2. Ion exchange
Zeolite or De-ionization
or Permutit Process or De-mineralization process
3. Ion exchange or De-ionization or De-mineralization process
Lime-Soda Process
Lime-Soda Process: Chemicals normally used are lime (calcium hydroxide, Ca(OH) 2 and soda ash
Chemicals normally used are lime (calcium hydroxide, Ca(OH)2 and soda ash
(sodium
(sodium carbonate,NaNa
carbonate, 2CO
2CO3).
3).Lime
Lime isisused
usedto to
remove chemicals
remove chemicalsthatthat
cause carbonate hardness. Soda ash
cause
carbonate hardness. Soda ash is used to remove chemicals
is used to remove chemicals that cause non-carbonate hardness. that cause non-
carbonate hardness.
Lime: Ca(OH)2 Carbonate Hardness

Soda: Na2CO3 Non-carbonate Hardness
Types:
Types:
1. 1.Cold
Cold lime-soda
lime-soda process:
process: Mixing
Mixing donedone at room
at room temperature.
temperature
2. 2.HotHot
lime-soda process: Mixing done at 80 oC too 150 oC o
lime-soda process: Mixing done at 80 C to 150 C.
Limitation of lime-soda process
Chemical reaction during lime-soda process is very slow.
Precipitates, CaCO3 or Mg(OH)2 are fine and tends to produce a super-saturated solution.
This leads to after deposition results blockage of pipes and corrode them.
How to overcome these Problems?
Thorough-mixing of chemical with water.
Condition should be optimized to accelerate the reaction (hot lime-soda process).
24
Accelerator which helps in bringing down the precipitate should be added.

Coagulants/Flocculants which helps in formation of coarse particles are added.
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Suitable sedimentation chamber is provided before final filtration.

1. Cold lime soda process
Cold lime soda process

Step 1
Step 1: In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are mixed with
In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are
water at room temperature and added to the hard water. The following
mixed with water at room temperature and added to the hard water. The following
reactions take place depending
reactions on theplace
takes nature of hardness
depending on the nature of hardness
ChemicalChemical
reactions 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)
Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)

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 + 2H2O
slimy suspended precipitates
Step 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, Aluminum 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.
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
25
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.
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Continuous cold lime soda softener: In this method the lime & soda are mixed with hard water at room
temperature with constant stirring. Generally the precipitates formed by this process are finely divided
and in order to settle the precipitates, coagulants like alum, ferrous sulphate etc., are added. The hard
water to be softened is mixed with calculated quantity of chemicals (Lime + Soda + Coagulant) from the
top into the inner chamber on vigorous stirring. The chemical reactions takes place and the hardness
producing salts get converted into insoluble precipitates. The sludge is removed from the bottom of the
outer chamber while the softened water passes through a wood fiber filter to ensure the complete removal
of any residual sludge particles. The clear softened water is withdrawn from the top of the outer chamber.
The softened water from this process contains a residual hardness of 50-60ppm.
Hard water
Chemicals feed
(soda+lime
+coagulant)
feed
Softened
water
Wood fiber
filter
Stirrer
paddles
Sedimented sludge (CaCO 3,

Mg(OH)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.
Advantages of Hot Lime Soda Process
1. The reaction between hardness producing substance and lime soda proceeds at a faster rate
2. The precipitates and sludges 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 15-30ppm in contrast to the cold lime soda
process which produces soft water with 50-60ppm of residual hardness
Hot lime soda Plant consists of three parts
1. Reaction tank: water, chemicals and steam are mixed

26
2. Conical sedimentation tank : sludge settles down

3. Sand filter : complete removal of sludge from the soft water is ensured
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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
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
also pathogenic bacteria
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 15ppm which is not good for
boilers
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 CaCl 2 + 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 + 2H 2O L
Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H 2O 2L
Acids
HCl 2H+ + Ca(OH)2 Ca2+ + 2H 2O L+S
H2SO4 Ca2+ + Na2CO3 CaCO3 + 2Na+
HCO3- 2HCO3- + Ca(OH)2 CaCO3 + H2O + CO32- L-S
Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+

FeSO4
Ca2+ + Na2CO3 CaCO3 + 2Na+ L+S
27
NaAlO2 NaAlO2 + H2O Al(OH)3 + NaOH

-L/2
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Rules
1. If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca 2+ + 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 Na 2CO3 and hence these excess amounts should be added to
the calculation (in temp. hardness and perm. hardness)
3. When the impurities are given as CaCO 3 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 (Na 2CO3) 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
Therefore, Lime requirement for softening
= 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
Soda requirement for softening
= 106 P.H of (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ - HCO3- X Vol .of water (L)
100
1. Calculate the amount of lime required for softening 5,000 litres of hard water containing 72 ppm of
MgSO4 (mol wt = 120)
Step 1 List out the given data
Given data : Hardness 72 ppm due to MgSO 4; water qty = 5000 litres; mol. wt. MgSO4 = 120
Step 2 calculate the CaCO 3 equivalent
Hardness producing Quantity (ppm) Multiplication factor CaCO3 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) x vol. of water

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= 74/100 (60 mg/L) x 5000 L

= 222,000 mg
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= 222 g
2. Calculate the amount of lime and soda required for softening 50,000 litres of hard water
containing: Mg(HCO3)2 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3
Solution
= 25ppm and Na2SO4 = 15ppm.
Step 1 List out the given data
Given data : MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe 2O3 =
25ppm and Na 2SO4 = 15ppm
Step 2 calculate the CaCO 3 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)
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
1. Calculate the amount of lime and soda required to soften 25,000 litres of water having following analysis.
Ca(HCO3)2 4.86 ppm; Mg(HCO3)2 = 7.3 ppm; CaSO4 = 6.8 ppm; MgCl2 = 5.7 ppm; MgSO4 = 9.0 ppm;
SiO2 = 3.5 ppm; NaCl= 5.85 ppm.
2. Calculate the quantity of lime and soda required for softening 50,000 litres of water containing the
following salts per litre Ca(HCO3)2 = 8.1 mg; Mg(HCO3)2 = 7.5 mg; CaSO4 = 13.6 mg; MgSO4 = 12.0 mg
MgCl2= 2.0 mg; and NaCI = 4.7mg.
3. Calculate the amount of lime (84% pure) and soda (92% pure) required for treatment of 20,000 litres of
water, whose analysis is as follows: Ca(HCO3)2 40.5 ppm; Mg(HCO3)2 = 36.5 ppm; MgSO4 = 30.0 ppm;
CaSO4 = 34.0 ppm; CaCl2 = 27.75 ppm; and NaCl = 10.00 ppm. Also calculate the temporary & permanent
hardness of water sample. (L = 1.762 Kg; S = 1.728 Kg).
4. Calculate the amounts of lime and soda needed for softening 100,000 litres of water containing HCI =7.3
29
mg/L; Al = 34.2 mg/L; MgC1 2 9.5 mg/L: NaCI 29.25 mg/L (Al = 27, Mg = 24; Na = 23; H = 1; CI = 35.5;
S = 32; 0 = 16.).
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5. Explain with equations and calculate the- quantity of quick lime and soda ash required to soften 10,000
litres of water containing:
(i) 219 ppm of magnesium bicarbonate and 234 ppm of sodium chloride:
(ii) 36 pm of Mg and 18.3 of HCO3-
(iii)1.5 ppm of the free acids, 144 ppm of sulphate ions and 71 ppm of chloride ions.
6. A water sample using FeSO4 as a coagulant at the rate of 278 ppm, gave following data on analysis for raw
water: Ca2+ = 240 ppm; Mg2+ = 96 ppm; CO2 = 44 ppm HCO3- = 732 ppm, Calculate the lime and soda
required to soften 250,000 litres of water. (L = 222 l S= 132. kg).
7. Calculate the quantities of lime and soda required for softening 300,000 litres of water, using 20 ppm of
sodium aluminate as a coagulant. Impurities in water are as follows Ca 2+ = 160 ppm; Mg2+ = 96 ppm;
HCO3- = 403 ppm, dissolved CO2 34 ppm.
8. Calculate the quantities of lime Ca(OH)2 and soda (anhyd. Na required for cold softening of 125,000 L of
water with the following analysis, using 10 ppm of sodium aluminate as coagulant: Analysis of raw water:
Ca2+ 95 ppm; Mg2+ = 36ppm, CO2 = 66ppm; HCO3- = 264 ppm; H = 2ppm Analysis of treated water: CO2 =
45 ppm; OH- = 34 ppm.
9. Calculate the amount of lime and soda required to soften 10,000 litres of water containing the following
ions per litre: Mg2+ 4.8 mg Ca2+ = 16.0 mg; HCO3- = 73.2 mg.
10. Calculate the cost of lime and soda required for softening 1 million litres of water containing: (MgHCO 3)2
= 73 mg/L; MgSO4 = 120 mg/L; CaSO4 = 68 mg/L; CaCl2 = 111 mg/L. The cost of lime of 80% purity is
Rs. 200 per metric ton and that of soda of 90% purity is Rs. 12,000 per metric ton.
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)
Types
1. Natural: Non-porous
Natrolite Na2O.Al2O3.4SiO2.2H2O
2. Synthetic: Porous, gel structure

ZSM-5
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
30
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Zeolite softener
Hard water in
Hard water spray
Zeolite bed
Gravel
Injector
Softened water
NaCl storage To
sink
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 Ca 2+, 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 + Na 2SO4
Regeneration of Zeolite Bed
CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)
Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
Limitations of Zeolite process

If the water is turbid, then the turbidity causing particles clogs the pores of the Zeolite and
making it inactive.
The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which cannot be regenerated that
31
easily as both metal ions bind strongly and irreversibly to the zeolite structure.
Any acid present in water (acidic water) should be neutralized with soda before admitting the
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water to the plant, since acid will hydrolyze SiO2 forming silicic acid.
Advantages of Zeolite process:

Soft water of 10-15 ppm can be produced by this method.
The equipment occupies less space.
No impurities are precipitated, hence no danger of sludge formation in the treated water.
It does not require more time and more skill.
Disadvantages of Zeolite process

Soft water contains more sodium salts than in lime soda process.
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).
It also causes caustic embitterment when sodium carbonate hydrolyses to give NaOH.
Zeolite process Lime soda process
This process produces water of very low hardness. This process produces water of hardness of 15-60 ppm depending on
whether it is a hot or cold process.
He cost of the plant and zeolite is higher. Hence, capital cost is The capital cost is lower.
higher.
The exhausted zeolite bed can be regenerated with brine which is The chemicals required are consumed in this process thus operating
very cheap. Hence, operating cost is less. cost is higher.
The plant is compact and occupies less space. The plant occupies more space.
Cannot be used for hot water, acidic water and water having The process is free from such limitations.
turbidity and suspended impurities.
This process can operate under pressure and can be designed for This process cannot be operated under pressure.
fully automatic operations.
This process does not involve cumbersome operations like settling, This process involves all the problems associated with settling,
coagulation and filtration. coagulation and filtration.
The water contains larger amounts of sodium salts and greater Treated water contains lesser percentage of dissolved solids and
percentage of dissolved salts. lesser quantities of sodium salts.
This process adjusts itself to water of different hardness. Reagent doses must be adjusted for waters of different hardness.
Salts causing temporary hardness are converted into NaHCO3 which Temporary hardness is completely removed.
will be present in the softened water. The insoluble CaCO 3 and
Mg(OH)2 in water creates problems when used as feed water in
boilers.
32
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Ion-Exchange resin (or) deionization (or) demineralization process:

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.
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
Cation Resin after

exchange Resin treatment
Structure of Cation and Anoin exchange resins
Cation exchange resin Anion exchange resin

They are styrene divinyl benzene polymers which on They have a basic polymeric structure of styrene divinyl
sulphonation or carboxylation become capable to exchange benzene or amine formaldehyde copolymer with basic
hydrogen Tons with cautions in water. functional group, example amino or quaternary ammonium (–
N+R3 ) or quaternary phosphonium or tertiary sulphonium
group. Example-DOWEX 3, AMBERLIT 400
33
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Ion exchange purifier or softener
Hard
water
Gravel
Cation exchange Resin Anion exchange Resin bed
Injector
Injector
Acid solution for

Wastages to
regeneration of sink Alkaline solution for
resin regeneration of resin
Wastages to
sink
Process or Ion-exchange
pump
mechanism
involved in water softeningSoft water
Process or Ion-exchange mechanism involved in water softening
Reactions occurring at Cation exchange resin
2 RH+ + Ca2+ (hard water) R 2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R 2Mg2+ + 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

Regeneration
H+ + OH- of ionH2exchange
O resins
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
The process can be used to soften highly acidic or alkaline waters.
Advantages
It produces water of very low hardness of 1-2ppm. So the treated waters by this method can be used in high
1. Thepressure
process can be used to soften highly acidic or alkaline waters
boilers.
2. It produces water of very low hardness of 1-2ppm. So the treated
Disadvantages
34
waters by this
The setup method
is costly and itcan
usesbe used
costly in high pressure boilers
chemicals.
The water should not be turbid and the turbidity level should not be more than 10ppm.
Page
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

Chem Unit 1

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Chem Unit 1

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Unit-I: Treatment of Water for Municipal and Industrial Uses

Rain Water - Pure but contaminated with gases

Classification of Impurities in water

 Industrial effluent of organics, sewage discharge, presence of N, S and P contains compounds,

metal ion pollution like Fe.

 Substances like algae, peat, bacterias

Ionic and dissolved

Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2

Requirements of Water for Municipal use or Drinking

 It should be free from disease causing microbes.

Purification of water for Domestic Use

Removal of suspended impurities Removal of Micro-Organism

Fig. Screening Fig. Sedimentation

 Most commonly used in water treatment plants

Al2(SO4)3 + Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

2. Sodium Aluminate (NaAlO2)

NaAlO2 + 2H2O Al(OH)3 + NaOH

3. Cu(II) or Fe(II) Sulphate (FeSO4.7H2O)

4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3

Operation of sand filter:

Disinfection can be attained by means of physical or chemical disinfectants

Why chlorination is the most common method of disinfection?

GERMS + HOCl Germs get killed

HOCl HCl + [O]

2. Work by Chang-1944, Green and Stumpf-1946:

chlorine species. HOCl is about 80 times more effective than OCl‒

Factors affecting efficiency of chlorine:

There are three stages of chloramines:

(b) Dichloramine (causes ‘smell’ and ‘chlorine odour’)

(c)Trichloramine (reduced oxidation, algae encouraged, time to Super Chlorinate!)

Treatment with UV Radiation

breakage and direct exposure to UV light .

Mg(HCO3)2 Heat Mg(OH)2 + 2CO2

Calcium/Magnesium Carbonates thus

2C17H35COONa + MgSO4 (C17H35COO)2Mg + 2Na2SO4

Disadvantages of Hard Water

Domestic Use Industrial Use

1. Washing 1. Textile Industry

Produces sticky scum on the

Bad to the digestive system

is possible in urinary tracts

Requires more fuel and time.

Certains food don’t cook soft

• Milligrams per liter (mg/litre)

• Degrees French (oFr)

Hardness is expressed in CaCO3 equivalence. Because,

Mass of hardness Chemical

Temp. Hardness = 31.5 ppm P. Hardness = 40 ppm

3. Calculate the total hardness from the data given below.

4. Three samples A, B and C were analyzed for their salt contents:

Determination of hardness by SOAP and EDTA method:

1. Preparation of standard hard water: A standard solution of CaCl2 prepared by dissolving 1 g

EDTA METHOD: Ethylenediaminetetraacetic acid

Ca2+ and Mg2+

 This is a complexometric method.

hard water unstable stable, colorless

Requirements of water for

Sludge and Scale

(ii) Due to scale formation on heating surfaces, overheating occurs,

(iii) Boiler tubes may clog due to scale formation.

Internal treatment External treatment

Conditioning Method zeolite

Ion exchange process