1

UNIT–I Soft Water

Soft water is water which easily produces lather with soap.
WaTer ChemIsTry
Soft water does not contain Ca²⁺ and Mg²⁺ ions.
1. Introduction
Example: Mineral water.
Water treatment is the process of removing impurities from water
Hard Water
and making it suitable for domestic and industrial use.
Hard water does not produce lather easily with soap.
Water is the most common and abundant substance on Earth.
Instead, it forms white precipitate called scum.
• It exists as solid (ice), liquid (water), and gas (vapour).
Example reaction:
• Nearly 70% of the Earth’s surface is covered by water.

In living organisms also, a large portion of body tissues consists of 2𝐶17 𝐻35 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝑎𝐶𝑙2 →(𝐶17 𝐻35 𝐶𝑂𝑂)2 𝐶𝑎+2𝑁𝑎𝐶𝑙
water. The compound formed is insoluble calcium soap (scum).

Chemically, water is a compound of hydrogen and oxygen. CaUses of hardNess

Formula: 𝐻2 𝑂 Hardness occurs when rainwater passes through rocks and soil
Water reacts with: containing calcium and magnesium salts.

• Metals → forms bases These salts dissolve in water and produce hardness.

• Non-metal oxides → forms acids Types of hardNess

hardNess of WaTer There are two types of hardness.

Hardness of water is due to the presence of certain dissolved salts 1. Temporary Hardness
which prevent the formation of soap lather.
Also called carbonate hardness.
Common hardness producing salts are: Calcium bicarbonate –
It is due to the presence of Calcium bicarbonate, Magnesium bicarbonate
Ca(HCO₃)₂, Magnesium bicarbonate – Mg(HCO₃)₂, Calcium chloride –
CaCl₂, Magnesium chloride – MgCl₂, Calcium sulphate – CaSO₄, Example: 𝐶𝑎(𝐻𝐶𝑂3 )2
Magnesium sulphate – MgSO₄ Temporary hardness can be removed by boiling.
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Reaction: 𝐶𝑎(𝐻𝐶𝑂3 )2 → 𝐶𝑎𝐶𝑂3 ↓ +𝐻2 𝑂 + 𝐶𝑂2
esTImaTIoN of hardNess by edTa meThod
2. Permanent Hardness
Hardness of water can be determined by complexometric titration
Also called non-carbonate hardness. using EDTA.
It is due to the presence of Calcium chloride, Magnesium chloride, EDTA = Ethylene Diamine Tetra Acetic Acid
Calcium sulphate, Magnesium sulphate
EDTA is a strong complexing agent that forms stable complexes with
Permanent hardness cannot be removed by boiling. metal ions.
It can be removed by: Lime soda process, Zeolite process Example metal ions: Ca²⁺, Mg²⁺
Example reactions Since EDTA is not very soluble in water, its disodium salt is used.
𝐶𝑎𝐶𝑙2 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 ↓ +2𝑁𝑎𝐶𝑙 Indicator used: Eriochrome Black-T (EBT)
𝐶𝑎𝐶𝑙2 + 𝑁𝑎2 𝑍𝑒 → 𝐶𝑎𝑍𝑒 + 2𝑁𝑎𝐶𝑙
Ammonium buffer solution is used.
UNITs of hardNess
𝑁𝐻4 𝐶𝑙 + 𝑁𝐻4 𝑂𝐻
Hardness is expressed in the following units. pH maintained around 8–10.

1. Parts per million (ppm) Colour change

Number of parts of CaCO₃ equivalent hardness per 10⁶ parts of Initially:

water.
Metal ion + EBT → Wine red colour
2. mg/L
During titration:
Number of mg of CaCO₃ equivalent hardness per 1L of water.
Metal ion + EDTA → Stable complex
1𝑝𝑝𝑚 = 1𝑚𝑔/𝐿
Indicator becomes free and colour changes to: Steel blue
3. Degree French (°Fr)
Endpoint Colour change is Wine red → Steel blue
1°𝐹𝑟 = 10𝑚𝑔/𝐿
4. Degree Clarke (°Cl) This indicates end point of titration.

1°𝐶𝑙 = 0.07𝑚𝑔/𝐿 Total Hardness Determination

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Total hardness is estimated by titrating the water sample against 3. Free from harmful microorganisms
EDTA using EBT indicator.
4. Free from poisonous gases (CO₂, H₂S, NH₃)
Permanent Hardness 5. Hardness less than 500 ppm
Permanent hardness is determined by boiling the water first and 6. Chloride less than 250 ppm
removing temporary hardness.
7. Fluoride less than 1.5 ppm
Then the remaining hardness is measured.
8. Total dissolved solids less than 500 ppm
Temporary Hardness Formula
9. pH value between 6.5 and 8.5
Temporary hardness = Total hardness − Permanent hardness
sTeps INvolved IN The TreaTmeNT of
Procedure for EDTA Titration
porTable WaTer
Step 1
Take 20 ml of water sample in a conical flask. The main purification steps are:
Step 2
Add: 5 ml ammonium buffer, 4–5 drops of EBT indicator
Solution becomes wine red.
Step 3
Titrate with EDTA solution from burette.
Step 4
End point occurs when colour changes to steel blue.
Step 5
Repeat titration to obtain concordant values.

speCIfICaTIoNs of porTable WaTer

Portable water means water suitable for drinking.
1. Screening: Screening removes large floating materials such as:
According to WHO and ICMR, good drinking water should have the
Leaves, Wood pieces, Plastic waste
following properties:
Water passes through metal screens which trap these impurities.
1. Clear, colourless and odourless

2. Pleasant taste
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2. Aeration 5. Filtration
Aeration is the mixing of water with air. Filtration is the process of removing remaining suspended particles
by passing water through filter beds.
Purpose:
Filter beds contain layers of:
1. Remove dissolved gases like CO₂ and H₂S
• Fine sand
2. Remove bad taste and odour
• Coarse sand
3. Convert ferrous salts into insoluble ferric salts
• Gravel
3. Sedimentation
Sand Filter Structure
Sedimentation is the process of removing suspended impurities by
allowing water to stand undisturbed in a tank. From top to bottom:

During this process: 1. Water inlet

2. Fine sand layer
• Heavy suspended particles settle at the bottom due to gravity.
3. Coarse sand layer
• These settled impurities form sediment.
4. Fine gravel
Time required: 2–6 hours, Sedimentation removes about 75% of
5. Coarse gravel
suspended impurities.
6. Water outlet
4. Coagulation Working
Sometimes very fine suspended particles do not settle easily. Water passes slowly through these layers.
These particles are removed by coagulation. In this method, chemicals
During filtration:
called coagulants are added to water.
• Suspended particles get trapped
Common coagulant: Alum (Al₂(SO₄)₃
• Some bacteria are also removed
Reaction: 𝐴𝑙2 (𝑆𝑂4 )3 + 6𝐻2 𝑂 → 2𝐴𝑙(𝑂𝐻)3 ↓ +3𝐻2 𝑆𝑂4
The gelatinous precipitate Al(OH)₃ traps fine impurities and settles Over time, the sand pores get blocked.
down. This process removes: Colloidal particles, Suspended impurities,
Then the top layer of sand is removed and replaced with clean
Some bacteria
sand.
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6. Sterilization / Disinfection Reaction: 𝑂3 → 𝑂2 + [𝑂]
Nascent oxygen kills microorganisms.
Sterilization means destroying harmful microorganisms present in
water. Production of Ozone

Several methods are used. Ozone is produced by passing oxygen through ultraviolet light or
electrical discharge.
Methods of Sterilization
Ozone Sterilizer
1. Boiling
In this system:
2. UV radiation
• Ozone is passed into water in a contact tank.
3. Ozonization
• It mixes with water and disinfects it.
4. Chlorination

1. Boiling
Water is boiled for 10–15 minutes.

This kills most harmful bacteria and microorganisms.

2. UV Radiation
Ultraviolet rays are produced using mercury vapour lamps.

UV rays destroy bacteria by damaging their genetic material.

UV sterilization is commonly used in:

• Swimming pools
• Drinking water plants

3. Ozonization
Ozone (O₃) is a powerful disinfectant.

Ozone decomposes easily to produce nascent oxygen, which destroys

bacteria.
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4. Chlorination 2. Adding chloramine
Chlorination is the process of adding chlorine to water for Chloramine is formed when chlorine reacts with ammonia.
disinfection. Reaction: 𝐶𝑙2 + 𝑁𝐻3 → 𝑁𝐻2 𝐶𝑙 + 𝐻𝐶𝑙
Methods of chlorination: Chloramine slowly decomposes and releases chlorine.
1. Adding chlorine gas
Advantages:
2. Adding chloramine
3. Adding bleaching powder • Long lasting disinfectant
1. Adding chlorine gas
• Less taste and no odour problem
Chlorine gas is bubbled into water.
3. Adding bleaching powder
Reaction: 𝐶𝑙2 + 𝐻2 𝑂 → 𝐻𝐶𝑙 + 𝐻𝑂𝐶𝑙
HOCl = Hypochlorous acid Bleaching powder = CaOCl₂

Hypochlorous acid further dissociates: When bleaching powder is added to water, it produces hypochlorous
acid.
𝐻𝑂𝐶𝑙 → 𝐻 + + 𝑂𝐶𝑙 −
Hypochlorous acid is a very strong disinfectant. Reaction: 𝐶𝑎𝑂𝐶𝑙2 + 𝐻2 𝑂 → 𝐶𝑎(𝑂𝐻)2 + 𝐶𝑙2
Then: 𝐶𝑙2 + 𝐻2 𝑂 → 𝐻𝐶𝑙 + 𝐻𝑂𝐶𝑙
Chlorinator: A chlorinator is used to mix chlorine gas with water. HOCl kills bacteria.

Break Point Chlorination

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Break point chlorination is the stage at which chlorine demand of 22 × 10
= 220𝑚𝑔/𝐿
water is satisfied and free chlorine starts appearing. 1000
Hardness = 220 ppm
During chlorination:

1. Chlorine reacts with impurities

Problem 2
2. Chlorine reacts with ammonia 100 ml of water sample requires 22 ml EDTA.
3. Chloramines are destroyed Strength of standard hard water = 1 g CaCO₃ per litre.
4. Free chlorine appears Step 1: Strength of EDTA
At this point, effective disinfection occurs.
Using formula:
Impurities removed during chlorination
𝑀1 𝑉1 = 𝑀2 𝑉2
Bacteria, Organic impurities, Reducing substances (Fe²⁺, H₂S), Free 100 × 0.01 = 22 × 𝑀2
ammonia 𝑀2 = 0.04545𝑀

problems based oN edTa meThod

Strength of EDTA = 0.04545 M
Problem 1
Step 2: Total hardness calculation
100 ml of water sample requires 20 ml of EDTA solution for titration.
𝑀3 𝑉3 = 𝑀4 𝑉4
1 ml EDTA = 1.1 mg CaCO₃. Calculate hardness. 𝑉4 𝑀4
𝑀3 =
𝑉3
Solution 18 × 0.04545
𝑀3 =
Given: 100
𝑀3 = 0.008181𝑀
1 ml EDTA = 1.1 mg CaCO₃

20 ml EDTA = ? Total hardness:

20 × 1.1 0.008181 × 100 × 1000
= 22𝑚𝑔 𝐶𝑎𝐶𝑂3
1
100 ml water contains = 22 mg CaCO₃
= 818.1 ppm
1000 ml water contains: ?
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NUmerICal problems oN hardNess of WaTer Problem 4
Problem 3 500 ml of water sample is boiled for 1 hour, cooled and filtered.

100 ml of water sample requires 25 ml of 0.01 M EDTA for titration using The filtrate is diluted to 500 ml again.
Eriochrome Black-T indicator. 50 ml of this solution requires 10 ml of EDTA using EBT indicator.
Calculate the total hardness of water. Calculate permanent hardness.
Solution Solution
Given Given
Volume of EDTA (V₁) = 25 ml Volume of EDTA = 10 ml
Strength of EDTA = 0.01 M Normality of EDTA = 0.02 N
Volume of water sample = 100 ml Volume of sample = 50 ml
Formula: Formula
𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 × 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴 × 100 × 1000 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 × 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴 × 50 × 1000
= =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒
Calculation Calculation
25 × 0.01 × 100 × 1000 10 × 0.02 × 50 × 1000
= =
100 50
= 250 𝑝𝑝𝑚 = 200 𝑝𝑝𝑚

Total hardness = 250 ppm Permanent hardness = 200 ppm

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Problem 5 Defluoridation is the process of removing excess fluoride from water.

100 ml of water sample requires 20 ml EDTA before boiling and 10 ml Excess fluoride causes fluorosis.
EDTA after boiling. Calculate: Total hardness, Permanent hardness, A simple and economical method is the Nalgonda technique.
Temporary hardness
Chemicals Used: Alum (Al₂(SO₄)₃), Lime, Small amount of bleaching
Total Hardness powder
20 × 0.01 × 100 × 1000
𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 200 mg/L Fluoride concentration around 30 mg/L can be reduced by this method.
100

Total hardness = 200 mg/L

Permanent Hardness
10 × 0.01 × 100 × 1000
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 100 mg/L
100
Steps in Nalgonda Technique
Permanent hardness = 100 mg/L
1. Addition of chemicals
Temporary Hardness 2. Mixing
3. Flocculation
Temporary hardness = Total hardness − Permanent hardness 4. Sedimentation
5. Filtration
= 200 − 100
6. Disinfection
= 100 𝑚𝑔/𝐿 Step 1: Addition of Chemicals

Raw water is mixed with: Alum, Lime, Bleaching powder

Temporary hardness = 100 mg/L
Step 2: Mixing

Water is mixed thoroughly using a mechanical stirrer.

Step 3: Flocculation

Slow mixing causes formation of flocs (gel-like particles).

deflUorIdaTIoN – NalgoNda TeChNIqUe These flocs trap fluoride and impurities.
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Step 4: Sedimentation When water is continuously converted into steam inside boilers:

Flocs settle down at the bottom. • The concentration of dissolved salts increases.

This removes suspended particles and fluoride. • When salts reach saturation point, they precipitate.

Step 5: Filtration These precipitates deposit on boiler walls.

Water is passed through filters to remove remaining particles. Sludge

Step 6: Disinfection If the precipitate is soft and loose, it is called sludge.
Finally, water is disinfected using chlorination. Examples: MgCl₂, MgCO₃, MgSO₄, CaCl₂

Sludge has higher solubility in hot water.

boIler TroUbles
Scale
If hard water is used in boilers, several problems occur.
If the precipitate is hard and firmly attached to boiler walls, it is
Major boiler troubles are:
called scale.
1. Scale and sludge formation
Examples: Ca(HCO₃)₂, CaSO₄, Mg(OH)₂
2. Caustic embrittlement
Scale forms a hard coating on boiler walls.

Effects of Scale Formation

• Poor heat transfer
• Fuel wastage
• Reduced boiler efficiency
• Overheating of metal
• Boiler explosion risk

2. Caustic Embrittlement
1. Scale and Sludge Formation
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Caustic embrittlement means intercrystalline cracking of boiler 2. Phosphate Conditioning
metal.
Scale formation in boilers can be prevented by adding sodium
This occurs due to concentration of Na₂CO₃ in boiler water. phosphate.
Reaction Sodium phosphate reacts with calcium and magnesium salts to form
𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐶𝑂2 soft sludge, which can be removed easily.
NaOH formed attacks boiler metal. Reaction
Further reaction 3𝐶𝑎𝑆𝑂4 + 2𝑁𝑎3 𝑃𝑂4 → 𝐶𝑎3 (𝑃𝑂4 )2 ↓ +3𝑁𝑎2 𝑆𝑂4
𝐹𝑒 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝐹𝑒𝑂2 + 𝐻2
This weakens boiler metal and causes cracks. The calcium phosphate formed is soft sludge and can be removed by
Effects: Cracks in boiler metal, Damage to stressed parts, Boiler failure blow-down operation.

Types of Sodium Phosphates Used

INTerNal TreaTmeNT of boIler feed WaTer
1. Trisodium phosphate (Na₃PO₄)
Internal treatment means adding chemicals directly into the boiler
to prevent scale formation. o Used for acidic water

These chemicals are called boiler compounds. 2. Disodium hydrogen phosphate (Na₂HPO₄)

Used for slightly alkaline water

1. Calgon Conditioning o

3. Sodium dihydrogen phosphate (NaH₂PO₄)

Calgon = Sodium hexametaphosphate
o Used for alkaline water
Formula: 𝑁𝑎2 [𝑁𝑎4 (𝑃𝑂3 )6 ]
Calgon reacts with calcium ions to form soluble complex compounds. 3. Colloidal Conditioning
Reaction In this method, colloidal substances are added to boiler water.
2𝐶𝑎𝑆𝑂4 + 𝑁𝑎2 [𝑁𝑎4 (𝑃𝑂3 )6 ] → Soluble complex formation Examples: Kerosene, Agar-agar, Gelatin
This prevents formation of scale. These substances coat scale-forming particles and convert them into
Advantage loose, non-adherent sludge. The sludge can then be removed by blow-
down operation. This method is used in low pressure boilers.
Calgon conditioning is better than phosphate conditioning.
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Types of Ion Exchange Resins
sofTeNINg of WaTer
1. Cation exchange resin
Water used for industrial purposes must be free from hardness-
producing salts and impurities. 2. Anion exchange resin

The process of removing hardness is called softening or conditioning 1. Cation Exchange Resin
of water.
Cation exchange resins contain acidic functional groups.
IoN exChaNge (demINeralIzaTIoN) proCess Examples: Sulphonated polystyrene, Sulphonated coal.

This method removes almost all dissolved ions from water. Functional group: 𝑅 − 𝑆𝑂3 𝐻

Both cations and anions are removed.

These resins exchange H⁺ ions with metal ions.
The result is demineralized water.
Reactions

𝑅𝐻 + 𝐶𝑎𝐶𝑙2 → 𝑅𝐶𝑎 + 2𝐻𝐶𝑙

𝑅𝐻 + 𝑀𝑔𝑆𝑂4 → 𝑅𝑀𝑔 + 𝐻2 𝑆𝑂4
𝑅𝐻 + 𝑁𝑎𝐶𝑙 → 𝑅𝑁𝑎 + 𝐻𝐶𝑙
Thus, all metal ions are removed.

2. Anion Exchange Resin

Anion exchange resins contain basic functional groups.

Examples: Quaternary ammonium salts, Cross-linked phenol

formaldehyde resins

Functional group: 𝑅 − 𝑁𝐻2

These resins exchange OH⁻ ions with anions.

Reactions
Principle 𝑅 ′ 𝑂𝐻 + 𝐻𝐶𝑙 → 𝑅 ′ 𝐶𝑙 + 𝐻2 𝑂
𝑅 ′ 𝑂𝐻 + 𝐻2 𝑆𝑂4 → 𝑅 ′ 𝑆𝑂4 + 2𝐻2 𝑂
Ion exchange resins contain functional groups which can exchange
Result
their ions with ions present in water.
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Water coming out of anion exchanger becomes completely free from Classification of Water Based on Salt Content
ions.
1. Fresh water
This water is called:
o Less than 1000 ppm dissolved salts
Demineralized water or Deionized water or Distilled water
2. Brackish water
Regeneration of Ion Exchange Resins o More than 1000 ppm dissolved salts
After some time, resins become exhausted. 3. Sea water
They must be regenerated. o More than 35,000 ppm dissolved salts
Regeneration of Cation Resin Sea water and brackish water can be converted into drinking water by
Cation exchanger is regenerated using dilute hydrochloric acid (HCl). desalination.

𝑅𝐶𝑎 + 2𝐻𝐶𝑙 → 𝑅𝐻 + 𝐶𝑎𝐶𝑙2 Methods of Desalination

𝑅𝑁𝑎 + 𝐻𝐶𝑙 → 𝑅𝐻 + 𝑁𝑎𝐶𝑙 1. Reverse osmosis

2. Electrodialysis
Regeneration of Anion Resin

Anion exchanger is regenerated using dilute NaOH solution.

𝑅 ′ 𝐶𝑙 + 2𝑁𝑎𝑂𝐻 → 𝑅 ′ 𝑂𝐻 + 2𝑁𝑎𝐶𝑙

desalINaTIoN of WaTer osmosIs

When two solutions of different concentration are separated by a semi-
Desalination is the process of removing dissolved salts from water.
permeable membrane, solvent moves from low concentration to high
Water containing high salt content is called brackish water.
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concentration. This process is called osmosis. The pressure required to The membrane allows water molecules to pass but blocks salt ions.
stop osmosis is called osmotic pressure.
Thus, pure water is obtained.

reverse osmosIs (ro) Membrane Materials

Common membranes used are:

If pressure greater than osmotic pressure is applied on the concentrated
solution side, the solvent flow reverses. Water moves from high • Cellulose acetate
concentration to low concentration. This process is called reverse • Cellulose butyrate
osmosis.
Advantages of Reverse Osmosis

• Produces very pure water

• Removes dissolved salts
• Removes bacteria and impurities

Principle

In RO process:

Salt water is forced through a semi-permeable membrane.