Unit 1 Water and its Treatment

Dr Samriti Thakur
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Introduction
• Earth surface area covered with water 70%

• Water is Universal solvent

• Properties of water- Colourless, odourless, non-toxic,

renewable source, self-ionization, thermal properties

• Important Engineering material

• Water is used various industrial processes and

domestic purposes.
Sources of Water
Water
Sources

Freshwater Ocean

Rain Surface Ground

Springs,
Still Flowing wells
water water

Ponds, lakes, Streams and

and reservoirs rivers
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Impurities in Water
• Carbonates, bicarbonates, chlorides, and sulfates of
Dissolved Na, Mg, Ca, and Fe.
Impurities • Dissolved gases like oxygen and carbon dioxide

• Inorganic impurities like clay, sand

Suspended • Organic impurities like oil globules, animal matter, and
vegetables.
Impurities

Colloidal • Products from organic waste like silica

Impurities

• Bacteria, fungi, and algae

Microorganisms
Types of Water
➢ Soft Water

➢ Hard Water
Why soap doesn’t form foam with
hard water ?

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

Sod. Stearate From hard water Cal. Stearate
(scum)

2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

(scum)
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Hardness of Water
❖ The property of water to prevent lathering of soap is called hardness of water.
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 Types of Hardness
➢ Temporary hardness of water
(carbonate or alkaline hardness)
• due to presence of bicarbonates of Ca & Mg

Ca(HCO3)2 Mg(HCO3)2

➢ Permanent hardness of water

(noncarbonate or nonalkaline hardness)

• due to presence of sulphates, chlorides,

& nitrates of Ca & Mg
MgSO4 MgCl2 CaSO4 CaCl2
 Removal of temporary hardness
Boiling
Ca(HCO3)2 CaCO3 + H2O + CO2

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

Harmful effects of hard water
13

Water hardness limits

Type of Water Dissolved Ca and Mg (mg/l)

Soft 0-50

Moderately soft 50-100

Slightly hard 100-150

Moderately hard 150-200

Hard 200-300

Very Hard > 300

Degree hardness of water and its determination

Total hardness causing salt present in the water

Equivalents weights of CaCO3 Mass of hardness causing salt

Equivalents of CaCO3 =
Equivalent weight of hardness causing salt

50 Mass of hardness causing salt

Equivalents of CaCO3 =
Equivalent weight of hardness causing salt
❖ Units of hardness

• Parts Per million (ppm)

• Milligrams per liter (mg/l)
• Degree Clarke (oCl)
• Degree French (oFr)

❖ Important Relationship
1 ppm = 1 mg/l = 0.1 oFr = 0.07 oCl
? Calculate the temporary hardness in terms of
calcium carbonate equivalents in a water sample
containing calcium bicarbonate (12.2 mg/l) in degree
Clarke. Given that at. Wt. of Ca=40 amu, O=16 amu,
C=12 amu, H=1 amu.

7.53 mg/l
17

? How many grams of MgCl2 dissolved per liter gives

60 ppm of hardness? Given that at. Wt. of Ca=40 amu,
O=16 amu, C=12 amu, H=1 amu.

57 mg/l
? Calculate the temporary hardness, permanent
magnesium hardness, total permanent hardness & total
hardness in terms of calcium carbonate equivalents in a
water sample containing calcium bicarbonate (12.2 mg),
magnesium bicarbonate (8.2 mg), magnesium sulphate
(5.6 mg), magnesium chloride (6.2 mg), calcium sulphate
(10.3 mg) & sodium sulphate (7.5 mg). Given that at.
Wt. of Mg=24 amu, S=32 amu, Cl=35.5 amu, Ca=40
amu, O=16 amu, C=12 amu, H=1 amu.
? A water sample contains 200 mg of
CaSO4 per liter. Calculate the hardness in
terms of CaCO3 equivalent in mg/L, ppm,
degree Clarke and degree French
 Determination of
hardness of EDTA method
 Complexometric Titration
HOOC H2C CH2 COOH
N CH2 CH2 N
HOOC H2C CH2 COOH

EDTA: Ethylenediamine tetraacetic acid

➢ Used for determining the conc. of hardness causing agents

➢ Form complexes with metal ions viz. Ca2+, Mg2+

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How to determine hardness of water
What we need ?
?
➢EDTA solution
➢Hard water (Temporary/Permanent)
➢Eriochrome black-T (Indicator)
➢ Ammonia based buffer solution Eriochrome black-T (EBT)
Procedure
➢Take known quantity of hard water
➢ Add 2-3 ml of ammonium buffer solution to maintain pH 9-10
➢Add 2-3 drops of EBT indicator (solution becomes wine red)
➢ Titrate the hard water sample against the standard EDTA solution (till the color

changes to blue)
➢ Note the EDTA volume used by burette reading.
 M2+ EBT complex EDTA
wine red colourless
(Unstable complex)
Titration

M2+ EDTA complex Free EBT

colourless blue
(stable complex)

❖ Use of ammonia-ammonium chloride buffer

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1000ml of 1M EDTA= 100g of CaCO3

1ml of 1M EDTA= 100mg of CaCO3
A 100 ml sample of water require 13.5 ml of 0.02
M EDTA for titration using EBT as indicator.
Another 100 ml of water from the same source
was boiled and precipitate removed by filtration,
the filtrate requires 6 ml of 0.02 M EDTA for
titration. Calculate the total hardness, permanent
hardness & carbonate hardness of water sample.

Total hardness=270 mg/L

Permanent hardness= 120 mg/L
Tem. hardness = 150 mg/L
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1g of CaCO3 was dissolved in dilute HCl and the

solution diluted to 1L. Then 100ml of this solution
required 90ml of EDTA solution. Also, 100ml of
water sample required 36ml of same EDTA
solution. The water sample (100ml) on boiling was
titrated against 18ml of EDTA solution. Calculate
the total and permanent hardness.

Total hardness= 400mg/l

Permanent hardness= 200mg/l
29

Total hardness= 400mg/l

Permanent hardness= 200mg/l
Alkalinity of water
Alkalinity: ability of water to neutralize acids
❖ Alkalinity of water is due to presence of carbonates,
bicarbonates & hydroxides of sodium, potassium,
magnesium & calcium, alone or in combination.

❖It is expressed as mg/L or ppm of CaCO3

❖ Caustic Alkalinity presence of OH- and CO32- ions

❖ Biocarbonate Alkalinity presence of HCO32- ions

Significance:
➢ Lowers the acidity of water
➢ Its amount determines its suitability for irrigation processes or waste
water treatment
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Estimation of Alkalinity:
33

Determination of Alkalinity
❖ Principle: Alkalinity can be estimated by titration against a standard acid,
using phenolphthalein and methyl orange as indicators.
❖ Total Alkalinity = Methyl orange alkalinity + phenolphthalein alkalinity

(1)

(2)

(3)

Estimation of Alkalinity:
➢ titration against standard acid solution, in presence of suitable indicators.
➢ volume of acid used up to the phenolphthalein end point marks half neutralization
of carbonate ions: resulting in completion of reaction 1 and 2, P-alkalinity.
➢ volume of acid used up to methyl orange end point indicates complete
neutralization of OH-, CO32-, HCO32- ions, M-alkalinity.
34

➢ All the three ions (OH- + CO32- + HCO32- ) cannot be present together.
➢ OH- and HCO32- cannot be present together because they form CO32-,
which is itself responsible for alkalinity.
Procedure
➢ Water sample x ml
➢ Add 2-3 drops of phenolphthalein indicator (pink colour)
➢ Titrate it against standard acid solution till colour get
disappearance of pink colour
➢ Volume of titrate (V1) is noted
➢ Add 2-3 drops of Methyl orange indicator to solution
➢ Titrate it against standard acid solution till the pink
colour develops
➢ The titrate value is noted (V2)
37

Calculations
Identification of ions present and calculations
39
❑ 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
present in the water.

Due to carbonates=500 PPM

Due to hydroxides= 375 PPM
 Significance of Alkalinity
➢Alkalinity is important for fish and aquatic life because it protects or
buffers against rapid pH changes.
➢Large amount of alkalinity imparts bitter taste in water.
➢The resultant precipitate can corrode pipes and other accessories of
water distribution systems.
➢Alkalinity as carbonate and bicarbonate of saline water is very
important in tertiary recovery processes for recovering petroleum.
➢The alkalinity value is necessary in the calculation of carbonate
scaling tendencies of saline waters.
➢The alkalinity acts as a pH buffer in coagulation and lime-soda
softening of water.
➢In wastewater treatment, alkalinity is an important parameter in
determining the amenability of wastes to the treatment process and
control of processes such as anaerobic digestion.
 Clark’s method (Lime process)

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

Hard water Lime

Mg(HCO3)2 + Ca(OH)2 CaCO3 + MgCO3 + 2H2O

Hard water Lime

*Solubility of CaCO3 in water = 0.013 g/L (25 °C)

Removal of Permanent hardness

✓ Use of Softening agents

✓ Ion exchange method

 Soda process
CaSO4 + Na2CO3 CaCO3 + Na2SO4

MgCl2 + Na2CO3 MgCO3 + 2NaCl

 Boiler
Feed Water
Water Absorb heat Expand as steam (carry heat)

Eg : power generation, space heating, sterilization

Impurities: hardness, dissolved gases, some dissolve salts metal etc,.

Requirements depends upon: quantity of feed water, design

of boiler, other operating parameters.
Low pressure fire-
tube boiler

Sectioned fire-tube
boiler from a DRB
Class 50 locomotive.
Characteristics of boiler feed water:

➢Impurities should not be exceeding tolerance limit

➢Feed water should be pretreated if it is not meeting the standards/

requirements

➢Dissolved oxygen below 0.02 mg/L

➢Total hardness below 0.5 ppm

➢Fe below 0.03 mg/L, Cu below 0.01 mg/L & Silica 5 mg/L

➢P-alkalinity below 0.5 ppm & M-alkalinity below 1 ppm.

Boiler Trouble/ Problem

➢ Precipitation of impurities as scale (Ca(HCO-3) 2, CaSO4, Mg(HCO-3) 2

, MgCl2) or sludge (MgCl2 , Mg CO3 , MgSO4, CaCl2)

Scales: Ca(HCO-3)2 CaCO3 + CO2 + H2O

Mg(HCO-3) 2 Mg(OH)2 + 2 CO2
Effects of Scales

➢Danger of explosion
➢Lowering the boiler efficiency
➢Waste of fuel
➢Expenses

Effects of Sludges:

➢ Colder part may get plugged

➢Wastage of fuel
➢Effect on efficiency
➢Expenses
Priming & Foaming
Wet steam/ carryover

➢Priming: large drops of water into outlet steam.

occur due to: impurities in BFW

improper constructed boiler

avoided by: lowering impurities, proper construction, maintain

proper level of water and slow discharge of steam

➢ Foaming: persistent bubble on boiler water surface

Occur due to: alkalis, oils, fats, organic matter & suspended solids

Avoided by: antifoaming agents, removal of oils & greases, removal

of clay & suspended particles, removal of silica with ferrous sulphate
etc.
Caustic Embrittlement

➢ Boiler material become brittle due to exposure to caustic

solution
H2O + Na2CO3 CO2 + NaOH

Alkaline water steeps inside the cracks, NaOH react to boiler

surface and cause embrittlement
2Fe + 2NaOH + O2 NaFeO2 + H2
➢ May cause explosion

Prevention
➢ Using Sod. Phosphate
➢ Adding lignin & tanning
➢ Addition of Sod. Sulphate to avoid cracks
➢Maintaing pH between 8 & 9
Boiler Corrosion

Decay process due to dissolve gases

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

4Fe(OH)2 + O2 2[Fe2O3.2H2O]
Softening Methods:
External Treatment:
Pre-treatment of water
❖ Lime soda process
❖ Ion exchange process

Internal Treatment:
Inside BFW (Boiler feed water)
❖ Treatment via chemicals (colloidal, calgon,
carbonate & phosphate condition)
Lime: to remove temporary hardness
Removal of Carbonate Hardness

CaCO3 is precipitated out of the water (sludge) and

it’s filtered off.
Removal of Non-carbonate Hardness

MgCl2 + Ca(OH)2 → Mg(OH)2 +

CaCl2
Lime is used to remove temporary hardness + Mg-permanent
hardness, Soda Ash is used mainly to remove permanent
hardness.
Soda ash: to remove Ca permanent hardness

Na2CO3 + CaCl2 CaCO3 + 2NaCl

Na2CO3 + CaSO4 CaCO3 + Na2SO4

 Lime-Soda Softening method

Batch Softening ( Lime and soda Continuous Softening ( Lime

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

Advantage: It not only reduce hardness but also reduce the

TDS, alkalinity.
Disadvantage: It cannot remove the water hardness
completely.
 [temp. hardness of Ca +
(2x temp hardness of mg) +
Permanent hardness of Mg] x
Molar mass of Ca(OH)2
Lime requirement =
Molar mass of CaCO3

[Permanent hardness]x Molar mass of Na2CO3

Soda requirement =
Molar mass of CaCO3
Q. Calculate the lime and soda required for softening 50,000 l of
water containing the following salts:
Ca(HCO3)2 = 8.1 mg/l,
Mg(HCO3)2 = 7.5 mg/l
CaSO4 = 13.6 mg/l,
MgSO4 = 12 mg/l,
MgCl2 = 2 mg/l

1.01 Kg
1.17 kg
 Ion exchange process
➢Also known as
demineralization of water

➢Ion exchange resins are high

molecular weight cross-linked,
porous polymers

➢ Ion exchange property is

due to acidic (R-SO3H, R-
COOH) or basic (R-N-OH, R-
NH3OH or R-R’-NH2OH)
functional groups.
➢Acidic gr. exchange H+ or Na+
➢Basic gr. Exchange OH-
Regeneration
Advantage:
➢ easy to operate and control
➢ works well for variety of hardness of water
➢ takes less space, better quality and more economical

Disadvantage:
➢ corrosion may occur when cation exchange takes
place with H exchanger
➢ Na exchanger when used TDS, alkalinity & silica are
not reduced
➢ Ion exchange material should not be allowed to get
contaminated
Internal Treatment for Softening Water: (Carried out inside boiler)

➢ Complexation

➢ Calgon (Sodium Hexametaphosphate) Treatment

Sod. Hexametaphosphate
➢ Carbonate Treatment
Reverse Osmosis Process

Water flows from

High conc. of water
To low conc. of water
It results in conc. Of all solutes
In one compartment and all pure
Water in another compartment
Electro Dialysis (ED) is a membrane process, during
which ions are transported through semi permeable membrane, under the
influence of an electric potential. The membranes are cations (+) or anions
(-) selective, which basically means that either positive ions or negative
ions will flow through.
Water Disinfection Process
Properties:
➢Should kill microorganism
➢Inexpensive
➢Non toxic to human
➢Should provide protection against any contamination

Bleaching Powder:

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl

HOCl HCl + [O]

Hypochlorous acid
Draw backs:

• Excess can Imparts bad odour and taste to

water
• Not stable deteriorates on long storage
• Increase hardness of water by introducing
Calcium in water.
Chlorination

Most common
Employed directly (gas or conc. solution)
Advantages:
low cost & effective
stable, small space required, doesn’t decompose on storage.
work at range of temperature
doesn’t introduce any impurity
Disadvantages:
chlorine residue could be harmful to environment
bad taste and odour
imparts irritation in mucus membrane
not effective at higher pH
Chloramine (ClNH2)
2NH3 + Cl2 → 2ClNH2 + H2
ClNH2 + H2O → HOCl + NH3
HOCl → HCl + [O]

➢ more stable
➢ don’t produce any irritating odor