Course Name:

Water Treatment Applied Chemistry

Course Code: CHL-101

Instructor: Dr. Sangesh P. Zodape

Department of Chemistry, Visvesvaraya National Institute of Technology (VNIT), Nagpur

 About The Course
Course name: CHEMISTRY
Department: Chemistry
Course code: CHL-101
Total Credits: 4
Total marks: 100

Main Topics to be discussed: Mark distribution for the course

1. Water Treatment
2. Corrosion and it’s control
3. Adsorption
4. Spectroscopy
5. Chemical Kinetics
6. Refractories
7. Polymers
8. Coordination Chemistry
9. Organic Reaction Mechanisms
 About The Course
Course name: CHEMISTRY
Department: Chemistry
Course code: CHL-101
Total Credits: 4
Total marks: 100
 Sources of water

1. Rain Water
2. Surface Water
3. Underground water

River Lake Sea

 Impurities in water: Broad classification
A. Dissolved impurities
• Carbonates/bicarbonates/nitrates/sulfates and • animal and
Organic
chlorides of Ca, Mg, Na,K, Fe, Mn, Al, etc. vegetable
• Dissolved gases like O2, CO2, SO2, NH3, N2 and oxides matter, wood
of nitrogen pieces, leaves,
oil globules,
B. Colloidal impurities etc
• Impurities whose particle size is from 1 to 100 nm
e.g. finely divided silica, clay, aluminium hydroxide,
ferric hydroxide, organic waste products, coloring
matter, etc. Suspended
impurities
C. Suspended impurities
• Impurities with particle size> 100 nm
• Can be removed by filtration or settling.
• Give turbidity and color to water Inorganic Microorganisms

• They may be organic, inorganic or microorganism.

• clay, silica, sand, etc • algae, protozoa,

bacteria and fungi
Type Constituents Effect
1. Suspended impurities Bacteria Diseases
Alagae, protozoa Color, odor, turbidity, diseases
Silts Turbidity
2. Dissolved impurities Salts
• Ca and Mg-bicarbonates Alkalinity, hardness
-carbonates/sulfates/chlorides Hardness
• Na-bicarbonate/carbonate Alkalinity
-sulfate Foaming
-fluoride Dental Problems
-chloride Affect Taste
Metals and compounds
• Oxides of Fe Taste, color, corrosion, hardness
• Mn Black and brown color
• Pb Poisoning
• As Poisoning
• Ba Effect on heart and nerves
• Nitrates Poisoning, color, blue baby syndrome
• Gases-oxygen Corrodes metals
• H2S Odor, acidity, corrosiveness
• CO2 acidity, corrosion
 Water Quality standards
Drinking water specification according to BIS 1500-2012

Technical Terms:
• BIS-Bureau of Indian standard(BIS)
• Permissible limits Acceptable limit Permissible limit
• ppm
• NTU Turbidity
• Hazen color

BIS (IS 10500:2012) has specifications in

Uniform Drinking Water Quality
Monitoring Protocol.
If the water is bacteriology
contaminated (E-coli and viruses etc.),
or if chemical contamination exceeds
maximum permissible limits, the BIS
considers that water unfit for drinking.

⇒ CHECK WHO standard

 Impurities in water: Broad classification
A. Dissolved impurities
• Carbonates/bicarbonates/nitrates/sulfates and • animal and
Organic
chlorides of Ca, Mg, Na,K, Fe, Mn, Al, etc. vegetable
• Dissolved gases like O2, CO2, SO2, NH3, N2 and oxides matter, wood
of nitrogen pieces, leaves,
oil globules,
B. Colloidal impurities etc
• Impurities whose particle size is from 1 to 100 nm
e.g. finely divided silica, clay, aluminium hydroxide,
ferric hydroxide, organic waste products, coloring
matter, etc. Suspended
impurities
C. Suspended impurities
• Impurities with particle size> 100 nm
• Can be removed by filtration or settling.
• Give turbidity and color to water Inorganic Microorganisms

• They may be organic, inorganic or microorganism.

• clay, silica, sand, etc • algae, protozoa,

bacteria and fungi
Type Constituents Effect
1. Suspended impurities Bacteria Diseases
Alagae, protozoa Color, odor, turbidity, diseases
Silts Turbidity
2. Dissolved impurities Salts
• Ca and Mg-bicarbonates Alkalinity, hardness
-carbonates/sulfates/chlorides Hardness
• Na-bicarbonate/carbonate Alkalinity
-sulfate Foaming
-fluoride Dental Problems
-chloride Affect Taste
Metals and compounds
• Oxides of Fe Taste, color, corrosion, hardness
• Mn Black and brown color
• Pb Poisoning
• As Poisoning
• Ba Effect on heart and nerves
• Nitrates Poisoning, color, blue baby syndrome
• Gases-oxygen Corrodes metals
• H2S Odor, acidity, corrosiveness
• CO2 acidity, corrosion
 Water Quality standards
Drinking water specification according to BIS 1500-2012

Technical Terms:
• BIS-Bureau of Indian standard(BIS)
• Permissible limits Acceptable limit Permissible limit
• ppm
• NTU Turbidity
• Hazen color

BIS (IS 10500:2012) has specifications in

Uniform Drinking Water Quality
Monitoring Protocol.
If the water is bacteriology
contaminated (E-coli and viruses etc.),
or if chemical contamination exceeds
maximum permissible limits, the BIS
considers that water unfit for drinking.

⇒ CHECK WHO standard

Fluoride contamination of water

Sources:
• Fluoride in groundwater from fluoride-bearing rocks such as fluorspar, cryolite, fluorapatite and hydroxylapatite

• Content in water depends on solubility of fluoride minerals, velocity of flowing water, temperature, pH,
concentration of calcium and bicarbonate ions in water, etc.

• Acceptable limit: 1 mg/L and maximum permissive limit: 1.5 mg/ L as per BIS norms
• 0.7 to 1.2 mg/ L

Health Effects:
Brownish
Fluorosis discoloration
• Dental and skeletal fluorosis
of teeth
• Due to its strong electronegativity, fluoride is attracted by
positively charged calcium in teeth and bones.
Arsenic contamination of water
• Contamination of ground water by arsenic (crucial water quality problem in West Bengal belt)
• Leaching from the arsenic containing source rocks and sediments (natural), coal mining, pesticides, industrial etc.
• Acceptable limit : 0.01 mg/L as per BIS norms and 0.05 mg/L as maximum permissible limit
• WHO revised in1993 c& recommended limit in drinking water 0.01 mg/L

As(V) exists in four forms in aqueous solution based on pH: H3AsO4, H2AsO4– HAsO 2– , and AsO 3–.
4 4
As(III) exists in five forms: H4AsO3+ , H3AsO3, H2AsO3– HAsO 2– and AsO 3-
3 3
arsenite
The ionic forms of As(V) dominate at pH >3
(NaAsO2) • Toxic

Chronic health effects INORGANI

C ARSENIC
➢ Dermal lesions, carcinogenic, peripheral neuropathy,
endocrine disruption arsenate
(Na2HAsO 4) • Toxic
Nitrate contamination of water

• NO − is mainly leached to groundwater from agricultural fields.

3
• Also released from manure storage facilities, Human sewage

HEALTH EFFECTS
Nitrate (>2 mg/L) in drinking water adverse health effects.
Acceptable limit : 45 mg/L as per BIS norms, No relaxation
(10 mg/L)

Methemoglobinemia or “blue baby” disorder

➢ Ingestion of nitrate by infants can cause low oxygen levels in the blood,
a potentially fatal condition

Methemoglobinemia in livestock and other animals

Courtesy image: https://images.app.goo.gl/UZZG65Yrs9Ss9Rbq5
➢ High nitrate and nitrite levels
Eutrophication
➢ Excessive phosphorus and nitrates in water can be produced large quantities of algae and
aquatic plants. When these algae die, bacteria decompose them, and use up
oxygen. Dissolved oxygen concentrations can drop too low for fish to breathe, killing
them
 Common Concentration units used for Aqueous Solutions
1. Normality: Defined as the number of gram equivalents of solute dissolved per liter of Solvent

2. Molarity: Defined as the number of mols of solute dissolved per liter of Solvent

3. Parts per million (ppm): Defined as the number of grams of solute dissolved in one million (106) grams of Solvent

4. Parts per million in equivalents of CaCO3 (ppm): Defined as the number of grams of solute as CaCO3 equivalents dissolved
in one million (106) grams of Solvent
Interconversion between the Concentration units

1. n x Molarity = Normality

2. ppm = Normality x Equivalent weight (gm) x 1000

= Molarity x Molecular weight (gm) x 1000

3. ppm CaCO3 equivalent = Normality x Equivalent weight of CaCO3 (50 gm) x 1000
= Molarity x Molecular weight of CaCO3 (100 gm) x 1000

𝑝 𝑝 𝑚 𝗑 𝐸𝒆𝒆𝑢𝒆𝒆𝑣𝑎𝑙𝑒𝑛𝑡 𝒘𝒘𝑒𝒆𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂 𝟑 𝑔 𝑚 )

4. 𝑝𝑝𝑚 𝐶𝑎𝐶𝑂𝟑𝟑 𝑒𝒆𝒆𝑢𝒆𝒆𝑣𝑎𝑙𝑒𝑛𝑡 = (
𝐸𝒆𝒆𝑢𝒆𝒆𝑣𝑎𝑙𝑒𝑛𝑡 𝒘𝒘𝑒𝒆𝒆𝑔ℎ𝑡𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑔𝑚)
 Alkalinity
Chemical • Measure of the buffering capacity of water, or the capacity
characteristic of to neutralize acids
• Does not refer to pH, but instead refers to the ability of
water: Alkalinity water to resist change in pH

- 2- -
Causes: Presence of Bicarbonate (HCO3 ), carbonate (CO3 ), and hydroxide (OH ).

Alkalinity not only helps regulate the pH of a water body, but also the metal content.
Bicarbonate and carbonate ions in water can remove toxic metals (such as lead, arsenic,
and cadmium) by precipitating the metals out of solution.

Alk = [HCO3−] + 2[CO32-] + [OH-] – [H+]

 TYPES OF ALKALINITY IN
WATER
2-
Alkalinity in water is caused due to the presence of OH-, CO3 and
HCO3-, or their combinations thereof.

• Principle for determination of alkalinity

(double indicator method)
P: Phenolphthalein end point
M: methyl orange end point
Importance of Phenolphthalein and Methyl orange indicators
towards determining the type and extent of Alkalinity
Importance of Phenolphthalein and Methyl orange indicators
towards determining the type and extent of Alkalinity
➢ Phenolphthalein adopts at least four different states in aqueous solution as a result of pH changes.

❖ Between strongly acidic and slightly basic conditions [pH 0 – 8.2], the lactone form (HIn) is colorless.
❖ The doubly deprotonated (In2-) phenolate form (the anion form of phenol), formed above pH 8.2,
gives the familiar pink color.
➢ Methyl orange is a pH indicator frequently used in titration because of its clear and distinct color variance at different
pH values.

Methyl orange shows red color in acidic medium and yellow color in basic medium.
Because it changes color at the pKa of a mid strength acid, it is usually used in titration for acids.

➢ In the estimation of alkalinity, phenolphthalein indicates the neutralization of OH- ion and the conversion of
carbonate to bicarbonate reactions only. It is this selectivity of phenolphthalein that is utilized for the estimation
of type and extent of alkalinity.
Assignment 1:

By providing appropriate structures explain the change in color of the indicators

methyl orange and phenolphthalein from acidic to alkaline pH conditions.

Due date: 00.00.0000 (Tuesday) via Google Classroom

Procedure for the Estimation of Alkalinity in Water: Type and Extent

Step 1: Take acid in burette and take alkaline water in conical flash
Pink color due to (via pipette)
OH ions

Step 2: Add phenolphthalein indicator to water. Observe color.

❖ If the color of the solution is pink, proceed to step 3,
❖ If color of solution remains colorless, proceed to step 4
directly.

Step 3: Titrate pink colored solution with acid to obtain colorless

solution. Note burette reading. This is your P value.

Step 4: Add methyl orange indicator to same water solution. Observe

color.
❖ If solution color is yellow, continue titration till red color is
obtained. Note burette-reading. This is your value of M.
❖ If solution color is red, no more titration is required. Note
burette-reading. This is your value of M.
 Scenarios possible in Alkaline Water

Scenario 1: Only OH- is present

Reaction(s): OH- + H+ H2O P

Scenario 2: Only CO32- is present

Reaction(s): CO32- + H+ HCO3- P
M
HCO3- + H+ H2O + CO2

Scenario 3: Only HCO3- is present

Reaction(s): HCO - + H+ H2O + CO2 M
3
 Scenarios possible in Alkaline Water

Scenario 4: Both OH- and CO32- are present

Reaction(s): OH- + H+ H2O

HCO3- P
CO32- + H+ M
HCO3- + H+ H2O + CO2

Scenario 5: Both CO32- and HCO3- are present

CO32- + H+ HCO3- P
M
HCO3- + H+ H2O + CO2
Estimation of Alkalinity in Water: Type and Extent

Scenario 1: Only OH- is present, P = M

Chemical reaction(s) involved: OH- + H+ H2O P or M

Observations: When only OH- is present

❖ P = +ve value,
❖ No more titration required after phenolphthalein end-point obtained,
❖ Therefore, P = M,
❖ Volume of acid required for [OH-] = P or M
Estimation of Alkalinity in Water: Type and Extent

Scenario 2: Only CO32- is present, P = M/2

Chemical reaction(s) involved : CO 32- + H+ HCO3- P

M
HCO3- + H+ H2O + CO2
2-
Observations: When only CO3 is present

❖ P = +ve value, M = +ve value

❖ Amount of acid required to reach M will be exactly twice the amount to reach P,
❖ Therefore, 2P = M or P = M/ 2
❖ Volume of acid required for [CO3 2-] = 2P or M
Estimation of Alkalinity in Water: Type and Extent

Scenario 3: Only HCO3- is present, P = 0

Chemical reaction(s) involved : HCO3 - + H+ H2O + CO2 M

Observations: When only HCO3 -is present

❖ P = 0, M = +ve value,
❖ Volume of acid required for [HCO3 ]- = M
Estimation of Alkalinity in Water: Type and Extent
Scenario 4: Both OH- and CO32- are present, P > M/2

Chemical reaction(s) involved : OH-+ H+ H2O

HCO3- P
CO32-
+ H+ M
HCO3- + H+ H2O + CO2
Observations: When both OH- and CO3 2- are present

❖ P = [OH-] + ½[CO3 2-],

equation (1)
2-
M = [OH-] + [CO3 ], equation (2)
❖ Equations (2) – (1), 1/2[CO3 2-] = M – P,

❖ Volume of acid required for [CO3 2-] = 2(M – P)

❖ Volume of acid required for [OH-] = M – [CO3 2-] = M – 2(M – P) = 2P – M

Estimation of Alkalinity in Water: Type and Extent

Scenario 5: Both CO32- and HCO3- are present, P < M/2

Chemical reaction(s) involved : CO32- + H+ HCO3- P

M
HCO3- + H+ H2O + CO2
Observations: When both CO 32- and HCO 3- are present

❖ P = ½[CO3 2-],
equation (1)
2- -
M = [CO3 ] + [HCO3 ], equation (2)
❖ According to equation (1), 1/2[CO3 2-] = P

❖ Volume of acid required for [CO3 2-] = 2P

❖ Volume of acid required for [HCO3 ]- = M – [CO3 2-] = M – 2P
 Determination of alkalinity of water

• By titrating with standard acid N/40 HCl

• Color of water sample changes to pink on addition of phenolphthalein indicator if pH> 8.3
• P end point: Pink to colorless, note the volume of titrant V1 (mL)
• Color of water sample changes to yellow on addition of methyl orange indicator
• M end point: Color changes to orange/red, note the volume of titrant V2( mL)
Representative Problem: Determination of type and extent of
alkalinity in water
A 10 mLaqueous solution when titrated with 0.05 (N) HCl gave phenolphthalein end-point of 7.8 mLand methyl
orange end-point of 10.2 mL.

Estimate the type and extent of alkalinity of the solution.

Step 1: Determine the relationship between P and M. Based upon this relation determine the type of alkalinity

Step 2: Once the type of alkalinity has been established, estimate the amount of acid required for each
ion using table, V1 and/or V2 mL, respectively.
 Representative Problem: Determination of type and extent of
alkalinity in water
A 10 mLaqueous solution when titrated with 0.05 (N) HCl gave phenolphthalein end-point of 7.8 mLand methyl
orange end-point of 10.2 mL.

Estimate the type and extent of alkalinity of the solution.

➢ Given P = 7.8 mLand M = 10.2 mL

Solution: ➢ Relation between P and M, P > M/2
➢ Therefore, type of alkalinity present: OH- and CO3 2-

➢ Volume of acid required for OH- = 2P – M = 2(7.8) – 10.2 = 5.4 mL

➢ Volume of acid required for CO3 2- = 2(M - P) = 2(10.2 – 7.8) = 4.8 mL

Strength of [OH-]=0.027x17 g/L

Alk. due to [OH-] in term of CaCO3 equivalent=0.027x17x(50/17)x 1000 mg/L
Alk. due to [OH-] in term of CaCO3 equivalent=1350 mg/L
Strength of [CO32-]=0.024x30 g/L
Alk. due to [CO32-] in term of CaCO3 equivalent=0.024x30x(50/30)x 1000 mg/L
Alk. due to [CO32-] in term of CaCO3 equivalent=1200 mg/L
1. 100 ml of a raw water sample on titration with N/50 H2SO4 required 12.4 ml of the acid to
phenolphthalein end point and 15.2 ml of the acid to methyl orange end point. Determine the type and
extent of alkalinity present in the water sample.
2. A water sample is not alkaline to phenolphthalein. However, 100 ml of the sample. On titration with
N/50 HCl required 16.9 ml to obtain the end point, using methyl orange as indicator. Determine the
type and extent of alkalinity present in the water sample.
3. A water sample is alkaline to both phenolphthalein as well as methyl orange. 100 ml of a raw water sample
on titration with N/50 HCl required 5.8 ml of the acid to phenolphthalein end point. When a few drop of
methyl orange are added to the same solution and the titration further continued, the yellow colour of the
solution just turned red after addition of another 10.5 ml of the acid solution. Elucidate on the type the type and
extent of alkalinity present in the water sample.
Chemical characteristic of water: Hardness

Hardness:
The characteristic of water that prevents lathering of soap/ the soap-consuming capacity of water.
Due to the presence of soluble salts of calcium and magnesium in water
General Range of hardness

Hard water forms curd like ppt with soap:

Disadvantages of Hardness
1.Wastage of soap
2.Wastage of fuel
3.Formation of scales on metallic boilers.

Harmful Effects of Hard Water

Types of Hardness of Water:
•Temporary Hardness ( due to magnesium
and calcium carbonates/bicarbontes in
water)
•Permanent Hardness ( due to soluble
chlorides, sulphides and nitrates of
Ca/Mg)
Some of the most common signs of hard water include:
•Clothes look dull and feel rough.
•Stains on white porcelain and scale build-up on faucets
•Low water pressure from showers due to clogged pipes.
•Chalky, white residue/spots appear on dishes.
•Boiler Troubles/corrosion in industry
Carbonate and Non-carbonate hardness

Carbonate hardness:
• Amount of carbonates and bicarbonates in solution that can be removed or precipitated by boiling.
• Responsible for the deposition of scale in hot water pipes and kettles.
• When total hardness is numerically greater than that of total alkalinity expressed as CaCO3, the amount
of hardness equivalent to total alkalinity is called ‘carbonate hardness’.

Non-carbonate hardness(NCH):
• The amount of hardness in excess of total alkalinity expressed as CaCO3 is noncarbonate hardness.
• Caused by the association of the hardness causing cation with sulphate, chloride or nitrate
• Also referred to as “permanent hardness” because it can not be removed by boiling.

NCH (mg/L) = Total hardness-Carbonate hardness

 Degree of Hardness
Hardness is expressed as mg/L CaCO3 because
(i) Calculations become easy as its molecular weight is exactly 100 (and equivalent weight is exactly 50).
(ii) It is the most insoluble salt that can be precipitated in water treatment

ppm Equivalent of CaCO3

Units of Hardness:
Removal of Hardness of water

Removal of Temporary hardness

• Boiling: Soluble bicarbonates are converted into insoluble carbonates which are removed by filtration.
Reactions: Ca(HCO3)2 → ΔCaCO3↓ + H2O + CO2
⇒ Mg(HCO3)2 → ΔMgCO3↓ + H2O + CO2
Removal of Permanent hardness

• Permutit Method: By using sodium aluminum ortho silicate(permutit /zeolite)

Reaction: Na2 Al2 Si2 O8.xH2O + Ca++→ 2Na+ + Ca Al2 Si2 O8.xH2O

• Calgon’s Process: By using sodium-hexa-meta-phosphate (NaPO3)6 known as Calgon.

• The hardness in water is removed by the adsorption of Ca++ and Mg++ ions.

• Ion Exchange Resin Method: by using resins.

• Ca++/Mg++ ions are exchanged with Cl–,
• SO4-2 ions are exchanged with anion exchange resin (RNH 2OH).
• Demineralized water is formed in this process.

⇒ 2RCOOH + Ca++ → (RCOO)2Ca + 2H+

⇒ RNH2OH + Cl– → RNH2Cl + OH–
⇒ H+ + OH– → H2O
Estimation of hardness in water
1. Soap Solution method
2. Estimation of hardness by EDTA Method (Greater accuracy/More rapid)
• This is a complexometric titration as ethylene diamine tetra-acetic acid (EDTA) forms a stable complex with Ca2+
and Mg2+ ions in the pH range 8–10.

Structure of dianion of EDTA, H2Y2– Structure of an M2+-EDTA chelate MY2-

The reaction for Hardness estimation:

M2+ + Na2H2edta M(edta) + 2 Na+ 2 H+, M = Ca, Mg
Estimation of Hardness in given water sample: Complexometric Titration
Estimation of Hardness in water involves two separate sets of experiment: Total Hardness and Calcium-only Hardness
Estimation of Total Hardness in water: Procedure
Step 1: EDTA solution of known concentration is taken in burette and water sample of known volume is taken in
conical flask via pipette

Step 2: To the water sample the following solutions are added –

(i) Basic buffer: Ammonium chloride in Ammonia (NH4Cl/NH3) – maintain pH in the range 8 – 10.
(ii) Indicator: Eriochrome Black T (EBT). Color change: Wine-Red to Blue.

Estimation of Calcium-only Hardness in water: Procedure

Step 1: EDTA solution of known concentration is taken in burette and water sample of known volume is taken in
conical flask via pipette

Step 2: To the water sample the following solutions are added –

(i) NaOH solution: Increase the pH >12. Precipitate Magnesium ions as Magnesium hydroxide
(ii) Indicator: Murexide. Color change: Purple to Blue.
Calculations
Representative Problem: Estimation of Hardness in water

A 10 mL aqueous solution containing 1500 ppm of CaCl2 and 2000 ppm of Mg(NO3)2 is titrated with 0.02 (M) EDTA.
Calculate the amount of EDTA required to estimate the total hardness in the solution.

Given the reaction for Hardness estimation:

M2+ + Na2H2edta M(edta) + 2 Na+ 2 H+
1 mol 1 mol 1 mol

Step 1: Convert all concentrations of metal ions for hardness (Ca2+ and Mg2+) into molar concentration

Step 2: Add the individual molar concentrations of these ions to obtain the total molar concentration for hardness.
Use: M1V1 = M2V2 where, M1 = Molar concentration of Hard ions
V1 = Volume of Hard water
M2 = Molar concentration of EDTA
V2 = Volume of EDTA
Representative Problem: Estimation of Hardness in water

A 10 mL aqueous solution containing 1500 ppm of CaCl2 and 2000 ppm of Mg(NO3)2 is titrated with 0.02 (M) EDTA.
Calculate the amount of EDTA required to estimate the total hardness in the solution.

➢ Given CaCl2 concentration = 1500 ppm = 1500 =0.0135 (𝑀)

111x1000
Solution: 2020 2000
Mg(NO3)2 concentration = 2000 ppm = = 0.0135 (𝑀)
148x1000
➢ Total Hardness = 0.027 (M)
➢ Therefore, Volume of EDTA required for titration = 𝑀𝑵𝑵𝗑 𝑉𝑵𝑵 = 𝟎𝟎.𝟎𝟎𝑽𝑽𝟎𝟎𝗑 𝑵𝑵𝟎𝟎= 13.5 mL
𝑀𝑽𝑽 𝟎𝟎.𝟎𝟎𝑽𝑽
 Softening of Hard water

1.Lime – Soda Process

2.Zeolite or Permutit Process

3.Demineralization/ion-exchange Process
External Treatment of Water: Lime – Soda process
Principle involved is to chemically convert all the soluble hardness-causing impurities into
insoluble precipitates that are removed by settling and filtration. Requisite amount of Lime
(Ca(OH)2 ) and sodium carbonate (Na2CO3 ) soda is added

Cold Hot
Performed of 25°C Performed around 90
to 100°C
Residual hardness at Residual hardness at
25°C is 50-60 ppm. 96°C is 15-30 ppm.

Coagulants are Coagulants not

required required
10% extra chemicals extra chemicals not
required required
External Treatment of Water: Lime – Soda process
➢ Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓+ 2H2O
1 equiv. 1 equiv.
• For one equivalent of Calcium temporary hardness, one equivalent of lime is required

➢ Mg(HCO3)2 + 2 Ca(OH)2 → Mg(OH)2↓ +2CaCO3↓ + 2H2O

1 equiv. 2 equiv.
• For one equivalent of Magnesium temporary hardness, two equivalents of lime are required

➢ CaCl2 + Na2CO3 → CaCO3↓ + 2 NaCl

1 equiv. 1 equiv.
• For one equivalent of Calcium permanent hardness, one equivalents of soda is required

➢ MgCl2 + Ca(OH)2 → Mg(OH)2↓ + CaCl2

CaCl2 + Na2CO3 → CaCO3↓ + 2 NaCl
Net reaction: MgCl2 + Ca(OH)2 + Na2CO3 → Mg(OH)2↓ + CaCO3↓ + 2 NaCl
1 equiv. 1 equiv. 1 equiv.
• For one equivalent of Magnesium permanent hardness, one equivalents of lime and one equivalent of soda
are required
External Treatment of Water: Lime – Soda process
➢ 2HCO3- + Ca(OH)2 → CaCO3 ↓ + CO32- + H2O
1 equiv. 1 equiv. 1 equiv.
• One equivalent of bicarbonate ions present reacts with one equivalent of lime and produces one
equivalent of carbonate ions, thereby producing equivalent amount of soda.
• For one equivalent of bicarbonate ions present, one equivalent of lime is added and one equivalent soda
is subtracted.

➢ 2HCl + Ca(OH)2 → CaCl2 ↓+ 2H2O

CaCl2 + Na2CO3 → CaCO3 ↓+ 2NaCl + H2O
Net reaction: 2HCl + Ca(OH)2 + Na2CO3 → CaCO3↓ + 2 NaCl
1 equiv. 1 equiv. 1 equiv.
• For one equivalent mineral acid present, one equivalent of lime and one equivalent of soda are required

➢ CO2 + Ca(OH)2 → CaCO3 ↓

1 equiv. 1 equiv.

• For one equivalent of dissolved gases, one equivalent of lime is required

External Treatment of Water: Lime – Soda process
Presence of coagulants
➢ NaAlO2 + 2H2O → NaOH + Al(OH)3
1 equiv. 1 equiv.
• NaOH formed acts as a replacement for lime without producing calcium ion impurity.
• For one equivalent of sodium aluminate present, both one equivalent of lime and one equivalent soda is
subtracted.

➢ Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3 ↓ + 3CaSO4

FeSO4 + Ca(OH)2 → Fe(OH)2 ↓+ CaSO4
1 equiv. 1 equiv.
• For one equivalent of coagulant iron sulphate and aluminium sulphate, one equivalent of lime is required
External Treatment of Water: Lime – Soda process
Some rules/exceptions

• If CaCO3 and MgCO3 are shown to be present, they are to be considered as temporary hardness

• If Ca2+ and Mg2+ ions are shown to be present, they are to be considered as permanent hardness
External Treatment of Water: Lime – Soda process
Type of impurity Lime Soda
Calcium temporary +1 -
Magnesium temporary +2 -
Calcium permanent - +1
Magnesium permanent +1 +1
Bicarbonate, HCO3- +1 -1
Gases +1 -
Mineral Acids +1 +1
Coagulant: NaAlO2 -1 -1
Coagulant: FeSO4 +1 +1
Coagulant: Al2(SO4)3 +1 +1
Impurity Conversion Lime Soda Reactions
factor
Calcium Temporary Hardness Simplest form or way of solving Lime Soda Numerical
Ca(HCO3)2 100/162 L – Ca (HCO 3 )2 + Ca (OH)2 → 2CaCO3  +2H 2 O Note: Substances which do not contribute towards hardness are KCl , NaCl , SiO 2 ,
CaCO3 100/100 L – It may be assumed that temporary Ca hardness has already Na 2SO4 , Fe 2 O3 , K 2SO4 and ignore while calculating hardness.
been converted into CaCO3 equivalent and hence lime is
required
All carbonates and bicarbonates of calcium and magnesium are taken as
Magnesium Temporary Hardness temporary hardness.
Mg(HCO3)2 100/146 2L – Mg (HCO 3 )2 + 2Ca (OH)2 → 2CaCO 3  + Mg (OH)2  +2H 2 O All chlorides, sulphates and nitrates of calcium and magnesium are taken as
MgCO3 100/84 2L – It may be assumed that temporary Mg hardness has already
permanent hardness.
been converted into MgCO3 equivalent and hence lime is
required
Magnesium Permanent Hardness
Mg2+ 100/24 L S Mg 2+ + Ca(OH) 2 → Mg(OH) 2  +Ca 2+
Ca 2+ + Na 2 CO3 → CaCO3  +2Na +
MgCl2 100/95 L S MgCl 2 + Ca(OH) 2 → Mg(OH) 2  +CaCl 2
CaCl 2 + Na 2 CO 3 → CaCO3  +2NaCl
MgSO4 100/120 L S MgSO 4 + Ca(OH) 2 → Mg(OH) 2  +CaSO 4
CaSO 4 + Na 2 CO3 → CaCO3  + Na 2SO 4
Mg(NO3)2 100/148 L S Mg(NO 3 ) 2 + Ca(OH) 2 → Mg(OH) 2  +Ca(NO3 ) 2
Ca(NO3 ) 2 + Na 2 CO 3 → CaCO3  +2NaNO3
Calcium Permanent Hardness
Ca2+ 100/40 – S Ca 2+ + Na 2 CO 3 → CaCO3  +2Na +

CaCl2 100/111 – S CaCl 2 + Na 2 CO 3 → CaCO 3  +2NaCl

CaSO4 100/136 – S CaSO 4 + Na 2 CO 3 → CaCO 3  + Na 2 SO 4

Ca(NO3)2 100/164 – S Ca(NO 3 ) 2 + Na 2 CO 3 → CaCO 3  +2NaNO3

Free mineral acids

HCl 100/(36.5x2 L S 2HCl + Ca(OH) 2 → 2H 2 O + CaCl 2
) CaCl 2 + Na 2 CO 3 → CaCO3  +2NaCl
Free mineral acids
HCl 100/(36.5x2 L S 2HCl + Ca(OH) 2 → 2H 2 O + CaCl 2
) CaCl 2 + Na 2 CO 3 → CaCO3  +2NaCl
H2SO4 100/98 L S H 2SO 4 + Ca(OH) 2 → 2H 2 O + CaSO 4
CaSO 4 + Na 2 CO 3 → CaCO3  + Na 2SO 4
H+ 100/2 L S 2H + + Ca(OH) 2 → 2H 2 O + Ca 2+
Ca 2+ + Na 2 CO3 → CaCO3  +2Na +
Dissolved gases
H2S 100/34 L – H 2S + Ca(OH) 2 → CaS  +2H 2 O
CO2 100/44 L – CO 2 + Ca(OH) 2 → CaCO 3  + H 2 O

Coagulants
FeSO4.7H2 100/278 L S FeSO 4  7H 2 O + Ca(OH) 2 → CaSO 4 + Fe(OH) 2 + 7H 2 O
O 1
2Fe(OH) 2 + H 2 O + O 2 → 2Fe(OH) 3 
2
CaSO 4 + Na 2 CO 3 → CaCO3  + Na 2 SO 4

Al2(SO4)3 100/(342/3) L S Al 2 (SO 4 ) 3 + 3Ca(OH) 2 → 2Al(OH) 3  +3CaSO 4

CaSO 4 + Na 2 CO3 → CaCO3  + Na 2SO 4
NaAlO2 100/(82x2) –L –S 2NaAlO 2 + 4H 2 O → 2NaOH + 2Al(OH) 3 

Miscellaneous
HCO 3− 100/(61x2) L –S 2HCO 3− + Ca(OH) 2 → CaCO 3  +CO 32− + 2H 2 O

NaHCO3 100/(84x2) L –S 2NaHCO 3 + Ca(OH) 2 → CaCO3  + Na 2 CO 3 + 2H 2 O

CO 32 − 100/60 – S This is found in treated water and must come by addition of

soda
OH– 100/34 L S This is supplied by lime and therefore shown as requirement
for lime. Due to the excess of lime the Ca2+ ions will require
soda
Note
Let V be the volume of water which to be softened and x be the percentage purity of
commercial lime and soda available in the market, then

Temporary Ca hardness + 2  Temp. Mg hardness 

 2+ 
74  + Permenent Mg hardness + dissolved CO 2 + Fe  100
Total requirement of Lime =  3+ −  
100  + Al + HCl + H 2SO 4 + HCO3 − NaAlO 2  x 1
 + OH from treated water(All expressed in CaCO Equivalent) 
−
 3 
OR
74 100 V
Total requirement of Lime =   Lime   kg
100 x 106

 Permanent Ca hardness + Permenent Mg hardness 

106 
 2+ 3+ −

 100 V
Total requirement of Soda = + Fe + Al + H 2SO 4 + HCl − HCO3 − NaAlO 2  
100   x 1

 + ( OH −
+ CO 3
2−
) from treated water(All expressed in CaCO 3 Equivalent) 

OR
106 100 V
Total requirement of Soda =   Soda   kg
100 x 106
 Temporary Ca hardness + 2  Temp.Mg hardness 
 2+ 
74 + Permenent Mg hardness + dissolved CO 2 + Fe  100 V
Total requirement of Lime =  3+ −  
1. Calculate the amount of lime and soda for the treatment of 1 million litres of 100 + Al + HCl + H 2SO 4 + HCO3 − NaAlO 2  x 10
+OH − from treated water(All expressed in CaCO Equivalent) 
water containing:  3 
Mg ( HCO3 )2 = 14.6 mg L, Ca ( HCO3 )2 = 8.1mg L,
OR
MgCl 2 = 38 mg L,
74 100 V
CaCl2 = 33.3mg L, HCO3− = 91.5 mg L. Total requirement of Lime =   Lime   kg
100 x 106
74 106
Total requirement of Lime = 5 + 2  10 + 40 + 15 + 75 6 kg

The coagulant Al2 (SO4 )3 was added at the rate of 17.1mg L of water.
100 10
74
= 155 kg = 114.7 kg
Solution 100
Impurity CaCO3 equivalent Lime Soda Permanent Ca hardness + Permenent Mg hardness 

106  2+ 3+ −
 100 V
Mg ( HCO3 )2 = 14.6 mg L 100 Total requirement of Soda = + Fe + Al + H 2SO4 + HCl − HCO3 − NaAlO2  
 14.6 = 10 mg L 100   x 10
+ ( OH + CO3 ) from treated water(All expressed in CaCO3Equivalent) 
− 2−
146 20
OR
Ca ( HCO3 )2 = 8.1mg L 100 5
 8.1 = 5 mg L 106 100 V
162 Total requirement of Soda =   Soda   kg
100 x 106
MgCl2 = 38mg L 100 40 40
 38 = 40 mg L
95
CaCl2 = 33.3mg L 100 30
 33.3 = 30 mg L
111 106 106
Total requirement of Soda = 30 + 40 + 15 − 75  6 kg
HCO3− = 91.5 mg L 100 75 -75 100 10
 91.5 = 75 mg L
122 106
= 10 kg = 10.6 kg
100
Al2 (SO4 )3 = 17.1mg L 100 15 15
17.1 = 15 mg L
114
Total 155 10 Thus, Lime required = 114.7 kg and Soda required = 10.6 kg.
1. A water sample gave the following constituents on analysis:
Mg ( HCO3 )2 = 73mg L, Ca ( HCO3 )2 = 81mg L, MgCl 2 = 95mg L,
CaSO4 = 68mg L, MgSO4 = 12 mg L, NaCl = 4.5mg L.

Calculate the cost of the chemicals required for softening 20,000 L of water, if
the purity of lime is 95 % and that of soda is 90 %. The costs per 100 kg each
of lime and soda are Rs. 75 and Rs. 2,480 respectively.
Solution
Impurity CaCO3 equivalent Lime Soda

Mg ( HCO3 )2 = 73mg L 100

 73 = 50 mg L 100
146
Ca ( HCO3 )2 = 81mg L 100 50
 81 = 50 mg L
162
MgCl2 = 95mg L 100 100 100
 95 = 100 mg L
95
CaSO4 = 68mg L 100 50
 68 = 50 mg L
136
MgSO4 = 12 mg L 100 10 10
 12 = 10 mg L
120
NaCl = 4.5mg L Ignored

Total 260 160

 Temporary Ca hardness + 2  Temp.Mg hardness  Permanent Ca hardness + Permenent Mg hardness 
 2+  106 
  100
74 + Permenent Mg hardness + dissolved CO 2 + Fe
2+ 3+ −
 Total
100 requirement
V of Soda = + Fe + Al + H 2SO4 + HCl − HCO3 − NaAlO2 
Total requirement of Lime =    6 kg 100   x
3+ −
100 + Al + HCl + H 2SO 4 + HCO3 − NaAlO 2  x 10  + ( OH −
+ CO 3
2−
) from treated water(All expressed in CaCO 3 Equivalent) 
+OH − from treated water(All expressed in CaCO Equivalent)  OR
 3 
OR 106 100 V
Total requirement of Soda =   Soda   kg
74 100 V 100 x 106
Total requirement of Lime =   Lime   kg
100 x 106 106 100 20, 000
Total requirement of Soda = 100 + 50 + 10   6 kg
100 90 10
Total requirement of Lime =
74
 50 + 2  50 + (100 + 10 ) 
100 20, 000
 kg 106 100 20, 000
100 95 106 = 160   6 kg = 3.76 kg
74 100 20, 000 100 90 10
= 260   6 kg = 4.05 kg
100 95 10
The cost of lime is Rs. 75 per 100 kg,
75
 Total cost of lime = Rs.4.05  = Rs.3.03
100

The cost of soda is Rs. 2480 per 100 kg,

2480
 Total cost of Soda = Rs.3.76  = Rs.93.25
100

Total cost of Lime-soda treatment = Rs. (3.03 + 93.25) = Rs. 96.3

Thus, Lime required = 4.05 kg and Soda required = 3.76 kg.

Total Cost of Lime-Soda treatment is Rs.96.3.

 Representative Problem: Estimation of Lime and Soda

A water sample upon analysis gave the following results.

Ca(HCO3)2 = 64.8 ppm, Mg(HCO3)2 = 43.8 ppm, CaCl2 = 22.2 ppm, MgSO4 = 180 ppm,MgCl2 = 71.25 ppm,, NaCl = 4.5 ppm, turbidity=120 ppm 60000 L
of this water softened using NaAlO2 @20ppm, the purity of lime is 99% and that of soda is 90%. On the basis of above data calculate 1) Ca hardness ,Mg hardness
and total alkanity2) Quantities of lime and soda required 3) Dry weight of total sediments formed during the softening process (Novenber2012) (2+3+3)

Impurity present Concentration (ppm) Concentration (ppm Lime Soda

CaCO3 equiv)
Ca(HCO3)2 64.8 64.8x(100/162)=40
Mg(HCO3)2 43.8 43.8x(100/146)=30
CaCl2 22.2
22.2x(100/111)=20
MgSO4 180
180x(100/120)=150

MgCl2 71.25
71.25x(100/95)=75

NaCl 4.5 -----

Turbidity 120 -------
NaAlO2 20
2-
20x(100/(82x2))=12.195
OH-/CO3 ------- Total
Representative Problem: Estimation of Lime and Soda
A water sample upon analysis gave the following results.
Mg(HCO3)2 = 73 ppm, Ca(HCO3)2 = 81 ppm, MgCl2 = 95 ppm, CaSO4 = 68 ppm, MgSO4 = 12 ppm, NaCl = 4.5 ppm
Calculate the amount of lime required to treat 20,000 Lof water if the purity of lime is 95% and that of soda is 90%.

Impurity present Concentration (ppm) Concentration (ppm Lime Soda

CaCO3 equiv)
Mg(HCO3)2 73
Ca(HCO3)2 81
MgCl2 95
CaSO4 68
MgSO4 12
NaCl 4.5
If treated water analysis shows presence of OH¯ and CO 32¯ and quantity of L&S
that was used during softening of water has to be determined, then,.
For OH¯: The given equivalents of OH¯ should have been supplied by Ca(OH)2.
Ca(OH)2 Ca2+ + 2 OH-
But, the corresponding quantity of Ca2+ so incorporated needs to be removed by
adding equivalent quantity of soda.
Thus equivalent quantity is added in both, lime and soda used.
Or (Presence of OH¯ is due to excess quantity of lime used during softening process. Excess lime carried with it calcium which required
soda for its removal. Thus equivalent quantity is added in both lime and soda used.)

For CO32¯
The Carbonate CO32¯ present in the treated water must have been supplied by
its equivalent quantity of Na2CO3.
Na2CO3 2 Na+ + CO32-
Thus equivalent quantity is added to only soda used calculation.
2
(The CO3 ¯ appearing in treated water indicates excess soda used. Thus equivalent quantity is added to soda used calculation only.)

**Alkalinity present in water is first bound to Ca2+, then to Mg2+, and only then to Na+.
 Representative Problem: Estimation of Lime and Soda
A water sample upon analysis gave the following results.
CaCl2 = 11.1 ppm, CaSO4 = 68 ppm, Ca(HCO3)2 = 324 ppm, MgCl2 = 9.5 ppm, NaCl = 140 ppm, MgSO4 = 48 ppm, Mg(HCO3) = 146 ppm. After
treatment the water was observed to contain 8.5 ppm of OH- and 30 ppm of CO32-. Calculate the amount of lime (90% pure) and soda (94% pure)
used to soften 10,000 Lof water, using NaAlO2 as coagulant @16.4 ppm. (B) Volume of 0.01 (M) EDTA required to titrate 10 mL of water.

Impurity present Concentration (ppm) Concentration (ppm CaCO3 equiv) Lime Soda
𝟎𝟎𝟎𝟎
CaCl2 11.1 𝗑 𝑵𝑵𝑵𝑵. 𝑵𝑵 = 𝑵𝑵𝟎𝟎 - +10
𝟎𝟎𝟎𝟎. 𝟎𝟎
𝟎𝟎𝟎𝟎
CaSO4 68 𝗑 𝟏𝟏𝟖𝟖 = 𝟎𝟎𝟎𝟎 - +50
𝟏𝟏𝟖𝟖
𝟎𝟎𝟎𝟎
Ca(HCO3)2 324 𝗑 𝟑𝟑𝑽𝑽𝟒𝟒 = 𝑽𝑽𝟎𝟎𝟎𝟎 +200 -
𝟖𝟖𝑵𝑵
𝟎𝟎𝟎𝟎
MgCl2 9.5 𝗑 𝟗𝟗. 𝟎𝟎 = 𝑵𝑵𝟎𝟎 +10 +10
𝟒𝟒𝟎𝟎. 𝟎𝟎
𝟎𝟎𝟎𝟎
MgSO4 48 𝗑 𝟒𝟒𝟖𝟖 = 𝟒𝟒𝟎𝟎 +40 +40
𝟏𝟏𝟎𝟎
𝟎𝟎𝟎𝟎
Mg(HCO3)2 146 𝗑 𝑵𝑵𝟒𝟒𝟏𝟏 = 𝑵𝑵𝟎𝟎𝟎𝟎 +200 -
𝟎𝟎𝟑𝟑
𝟎𝟎𝟎𝟎
NaAlO2 16.4 𝗑 𝑵𝑵𝟏𝟏. 𝟒𝟒 = 𝑵𝑵𝟎𝟎 -10 -10
𝟖𝟖𝑽𝑽
𝟎𝟎𝟎𝟎
OH- 8.5 𝗑 𝟖𝟖. 𝟎𝟎 = 𝑽𝑽𝟎𝟎 +25 +25
𝑵𝑵𝟎𝟎
CO32- 𝟎𝟎𝟎𝟎
30 𝗑 𝟑𝟑𝟎𝟎 = 𝟎𝟎𝟎𝟎 - +50
𝟑𝟑𝟎𝟎
Σ lime = 465 Σ Soda = 175
 Representative Problem: Estimation of Lime and Soda
A water sample upon analysis gave the following results.
CaCl2 = 11.1 ppm, CaSO4 = 68 ppm, Ca(HCO3)2 = 324 ppm, MgCl2 = 9.5 ppm, NaCl = 140 ppm, MgSO4 = 48 ppm, Mg(HCO3) = 146 ppm. After
treatment the water was observed to contain 8.5 ppm of OH- and 30 ppm of CO32-. Calculate the amount of lime (90% pure) and soda (94% pure)
used to soften 10,000 Lof water, using NaAlO2 as coagulant @16.4 ppm. (B) Volume of 0.01 (M) EDTA required to titrate 10 mL of water.

𝟎𝟎𝟒𝟒 𝑵
𝑵𝟎𝟎
Amount of lime used = 𝗑 𝟒𝟏𝟏𝟎𝟎𝗑 𝑵
𝑵𝟎𝟎𝟎𝗑 = 3.82 kg
𝑵
𝑵𝟎𝟎 𝟗𝟗𝟎𝟎

𝑵𝑵𝟎𝟎𝟏𝟏
Amount of soda used = 𝗑 𝑵𝑵𝟎𝟎𝟎𝟎𝗑 𝑵𝑵𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝗑 𝑵𝑵𝟎𝟎𝟎𝟎= 1.973 kg
𝑵𝑵𝟎𝟎𝟎𝟎 𝟗𝟗𝟒𝟒
 Representative Problem: Estimation of Hardness in water
A water sample upon analysis gave the following results.
CaCl2 = 11.1 ppm, CaSO4 = 68 ppm, Ca(HCO3)2 = 324 ppm, MgCl2 = 9.5 ppm, NaCl = 140 ppm, MgSO4 = 48 ppm, Mg(HCO3) = 146 ppm. After
treatment the water was observed to contain 8.5 ppm of OH- and 30 ppm of CO32-. Calculate the amount of lime (90% pure) and soda (94% pure)
used to soften 10,000 Lof water, using NaAlO2 as coagulant @16.4 ppm. (B) Volume of 0.01 (M) EDTA required to titrate 10 mL of water.

Impurity present Concentration (ppm) Concentration (ppm CaCO3 equiv) Lime Soda
𝟎𝟎𝟎𝟎
CaCl2 11.1 𝗑 𝑵𝑵𝑵𝑵. 𝑵𝑵 = 𝑵𝑵𝟎𝟎 - +10
𝟎𝟎𝟎𝟎. 𝟎𝟎
𝟎𝟎𝟎𝟎
CaSO4 68 𝗑 𝟏𝟏𝟖𝟖 = 𝟎𝟎𝟎𝟎 - +50
𝟏𝟏𝟖𝟖
𝟎𝟎𝟎𝟎
Ca(HCO3)2 324 𝗑 𝟑𝟑𝑽𝑽𝟒𝟒 = 𝑽𝑽𝟎𝟎𝟎𝟎 +200 -
𝟖𝟖𝑵𝑵
𝟎𝟎𝟎𝟎
MgCl2 9.5 𝗑 𝟗𝟗. 𝟎𝟎 = 𝑵𝑵𝟎𝟎 +10 +10
𝟒𝟒𝟎𝟎. 𝟎𝟎
𝟎𝟎𝟎𝟎
MgSO4 48 𝗑 𝟒𝟒𝟖𝟖 = 𝟒𝟒𝟎𝟎 +40 +40
𝟏𝟏𝟎𝟎
𝟎𝟎𝟎𝟎
Mg(HCO3)2 146 𝗑 𝑵𝑵𝟒𝟒𝟏𝟏 = 𝑵𝑵𝟎𝟎𝟎𝟎 +200 -
𝟎𝟎𝟑𝟑
𝟎𝟎𝟎𝟎
NaAlO2 16.4 𝗑 𝑵𝑵𝟏𝟏. 𝟒𝟒 = 𝑵𝑵𝟎𝟎 -10 -10
𝟖𝟖𝑽𝑽
𝟎𝟎𝟎𝟎
OH- 8.5 𝗑 𝟖𝟖. 𝟎𝟎 = 𝑽𝑽𝟎𝟎 +25 +25
𝑵𝑵𝟎𝟎
CO32- 𝟎𝟎𝟎𝟎
30 𝗑 𝟑𝟑𝟎𝟎 = 𝟎𝟎𝟎𝟎 - +50
𝟑𝟑𝟎𝟎
Σ lime = 465 Σ Soda = 175
 Representative Problem: Estimation of Hardness in water
A water sample upon analysis gave the following results.
CaCl2 = 11.1 ppm, CaSO4 = 68 ppm, Ca(HCO3)2 = 324 ppm, MgCl2 = 9.5 ppm, NaCl = 140 ppm, MgSO4 = 48 ppm, Mg(HCO3) = 146 ppm. After
treatment the water was observed to contain 8.5 ppm of OH- and 30 ppm of CO32-. Calculate the amount of lime (90% pure) and soda (94% pure)
used to soften 10,000 Lof water, using NaAlO2 as coagulant @16.4 ppm. (B) Volume of 0.01 (M) EDTA required to titrate 10 mL of water.

Total Hardness = 10 + 50 +200 + 10 + 40 +100 = 410 ppm CaCO3 equiv.

Merits and Demerits of Lime soda process

Merits of lime-soda process

1. Very economical.
2.During softening, the treated water has pH >7; hence it is alkaline and therefore has less
corrosion tendencies.
3. Alkaline nature of softened water prevents the growth of bacteria.
4. Fe, Mn and dissolved minerals are also reduced in this process.

Demerits of the process

1. Requires careful and skilled supervision.
2. Sludge disposal is a problem.
3. It can remove hardness only up to 15 ppm which is still not appropriate for boilers.
4.The softened water contains appreciable amount of soluble salts such as sodium sulphate and cannot be
used in high pressure boilers.
5. It cannot be used in households as it is not possible to calculate the amount of lime and soda required.
 Zeolite or Permutit Process/ Method for Water Treatment
• Zeolites are also known as permutit and in Greek it means ‘boiling stone’.
• They occur naturally as hydrated alumino silicate minerals like Na2O.Al2O3. x SiO2. y H2O where x = 2–
10 and y is 2–6. They can exchange reversibly sodium ions for hardness producing ions in water.

Zeolites
Natural Zeolites: Nonporous,
amorphous and durable, for
example, Natrolite
(Na2O.Al2O3.4SiO2.2H2O)

Synthetic Zeolites: Porous with

gel-like structure. They are
prepared by heating sodium
carbonate (Na2CO3), alumina
(Al2O3) and silica (SiO2).
Reactions: Na2Ze + Ca(HCO3)2 → CaZe + 2 NaHCO3
Na2Ze + Mg(HCO3)2 → MgZe + 2 NaHCO3
Na2Ze + CaCl2(Or CaSO4)2 → CaZe + 2 NaCl or Na2SO4
Na2Ze + MgCl2 (or MgSO4)2 → MgZe + 2 NaCl or Na2SO4
i) Outgoing water contains sodium salts.
ii) The exhausted zeolite bed is regenerated by treating the bed with a
concentrated (10%) brine (NaCl) solution which is cheaper.
CaZe + 2 NaCl → Na2Ze + CaCl2
MgZe + 2 NaCl → MgCl2 + Na2Ze
iii) The washings are led to drain and the regenerated zeolite bed is used
again.
Regeneration of Zeolite

• When the zeolite bed is exhausted the supply of hard water is stopped and it is regenerated by treating with a
concentrated brine (10% NaCl) solution.

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

MgCl2)
(exhausted zeolite) (Brine) Reclaimed (Washings)
Zeolite
• The washings (containing CaCl2, MgCl2, etc.) are led to drain and the regenerated zeolite bed is used again for
softening.
• NaNO3, KCl, KNO3, etc. can also be used for regeneration instead of NaCl, but NaCl is mostly used because of its
low cost and the products of regeneration process (CaCl2 or MgCl2) are highly soluble and can be easily rinsed out
of the zeolite bed.
• By knowing the amount of NaCl used for regeneration of the exhausted zeolite bed, the hardness of the water
sample can be calculated.
Advantages
(i) It removes hardness almost completely (hardness about 100%)
(ii) The equipment used here is compact.
(iii) It automatically adjusts itself to water of varied hardness.
(iv) It operates under pressure.

Limitation
(i) Water containing excess of acidity or alkalinity may attack the zeolite.
(ii) Acid radicals are not removed by this process because it produces NaHCO3
which breakdown in boiler and form NaOH. The presence of NaOH leads to a
caustic embrittlement in the boiler.
NaHCO3 ⎯⎯
→ NaOH + CO 2

(iii) The byproduct CO 2 in above reaction renders water acidic corrosive.

(iv) Fe 2 + and Mn 2 + when passed through the zeolite bed are converted into their
respective zeolites which cannot be regenerated.
Fe2+ + Na 2 Ze ⎯⎯
→ FeZe + 2Na + ( Irreversible )
Mn 2+ + Na 2 Ze ⎯⎯
→ MnZe + 2Na + ( Irreversible )
Numerical based on the Zeolite Softner:

Volume of water ( V ) xHardness of water ( y ) in ppm Volume of NaCl ( X ) xConcentraion of NaCl in g/L ( c )
= x1000
Equivalent weight of CaCO3 Equivalent weight of NaCl

( V ) x ( y ) = ( X ) x ( c ) x1000
50 58.5
An exhausted Zeolite softener was regenerated completely by passing 400 L of brine solution containing
3.5% NaCl. How many litre of hard water sample having hardness 560 ppm can be softened using this
softener?

Given Data:
Volume of Hard Water (V) =?
Hardness of Water Sample in ppm (y) = 560
Volume of NaCl (X) = 400 L
Concentration of NaCl in (c) = 3.5% =3.5 g/100 ml =35 g/L

( V ) x ( y ) = ( X ) x ( c ) x1000
50 58.5
Volume of Hard water ( V ) =
( X ) x ( c ) x50 x1000
(y)x58.5
400x35 x50
Volume of Hard water ( V ) = x1000
560x58.5

Volume of Hard water (V) = 21367.52 L

Limitations and Advantages of Zeolite Process
Limitations of Zeolite Process
1. Turbidity/suspended matter is to be removed (by coagulation, filtration, etc.) before the water is admitted to the zeolite bed.
Otherwise turbidity will clog the pores of zeolite bed making it inactive.
2. Ions like Mn2+and Fe2+must be removed first because these ions react with zeolite bed which cannot be easily regenerated.
3. Minerals acids, if present in water, destroy the zeolite bed and hence they must be neutralized with soda in advance, before
feeding water into the zeolite bed.
4. This method does not remove anions. The bicarbonates present in hard water get converted into NaHCO3 which goes into
soft water effluent. If this water is used in boiler, NaHCO3 dissociates as
2 NaHCO3 Na2CO3 + H2O + CO2
NaOH leads to caustic embrittlement and CO2 makes the water acidic and corrosive.
5. The treated water contains more sodium salts than in lime-soda process.
6. Moreover high cost of the plant and material also acts as limiting factor.

Advantages of Zeolite Process

▪ Hardness is removed almost completely, and the residual hardness is about 10 ppm.
▪ The equipment is compact and occupies less space.
▪ It is a clean and rapid process. Sludge is not formed as the impurities are not precipitated.
▪ It requires less skill for maintenance as well as operation.
 Comparison of Permutit Process with Lime-Soda Process
Zeolite/Permutit Process
1. Residual hardness of water obtained is 10-15 ppm
2. Cost of plant and zeolite are higher i.e capital cost is high
3. Operation expenses are low as cheap NaCl is required for
regeneration
4. Occupies less space as it is compact
5. It cannot be used for treating acidic water, because the
zeolite undergoes disintegration
6. The treated water contains large amount of sodium salts
than in original raw water. The NaHCO3 in treated water
causes caustic embrittlement
7. Raw water to be softened, must be free from suspended
matter, otherwise the pores of zeolite block and the bed
loses its ion exchange capacity
8. It can be operated under pressure and can be designed for
fully automatic operation
9. It is clean process as no sludge is formed
10. Control test comprises in checking the hardness of treated
water. The process adjusts itself to water of different
hardness
Lime-Soda Process
1. Water of generally 15-50 ppm residual hardness is
obtained
2. Capital cost is lower
3. Operation expenses high as costly chemicals (lime,
soda and coagulants) are consumed
4. Plant occupies more space as it depends on the
amount of water to be softened
5. There is no such limitation
6. Treated water contains lesser %of sodium salts. It is
completely free from NaHCO3 as it is removed in the
form of insoluble CaCO3 and Mg(OH)2
7. The process is free from such limitation
8. This process cannot be operated under pressure.
9. Large amount of sludge is formed
10. In order to meet the changing hardness of incoming
water frequent control and adjustment of reagents is
needed
Ion Exchange Process (Ion Exchange Resin) – Deionization or Demineralization of Water
• Ion exchange process is defined as the reversible exchange of ions in the structure of an ion exchanger to ions in
solution that is brought in contact with it.
• The resins used for the purpose are called ion exchange resins. They are porous, insoluble, cross linked, long chain
organic polymers capable of exchanging ions.
• Materials capable of exchanging a cation in their structure to the cation in
solution.
• For softening of water, the resins used should be capable of exchanging H+ ions in
their structure to other cations in solution.
Cation
• Commonly used resins are styrene divinyl benzene copolymers, which on
exchange sulphonation or carboxylation become capable of exchanging hydrogen ions with
resin the cations in water.
• They are represented as R–H+ (R represents insoluble polymer matrix and H is
the exchangeable ion).
• Amberlite IR-120 and Dowex-50 are examples of commercially available cation
exchange resins.
• Materials capable of exchanging an anion in their structure (for water softening
the exchangeable anion should be OH– ion) to anion in solution.
• Anion exchangers employed for water softening are styrene divinyl benzene or Cation exchange resin Anion exchange resin
amine formaldehyde copolymers, which contain basic functional group such as
Anion amino or quaternary ammonium or quaternary phosphonium or tertiary
exchange sulphonium groups as an integral part of the resin matrix.
resin • After treatment with dilute NaOH solution become capable of exchanging OH–
ions with the anions in water. They are represented as R+OH– (where R+ is the
insoluble polymer matrix and OH– is the exchangeable ion).
• Amberlite 400 and Dowex-3 are examples of commercially available anion
exchange resins.
 Process of Ion exchange
➢ The hard water is first passed through a column containing cation exchange resin. All cations are removed and equivalent
amount of H+ ions are released from this column to water. The water coming out of this chamber has low pH.
❖ The exchange reactions are

2RH + Ca2+ R2Ca + 2H+

2RH + Mg2+ R2Mg + 2H+
➢After this the water is passed into second column containing anion exchange resin.
All the anions are removed and an equivalent amount of OH- ions are released.

ROH + Cl- RCl + OH- R ( OH )2 + 2Cl− → RCl 2 + 2OH −

2ROH + SO4 2- R2SO4 + 2OH- R ( OH )2 + SO 4 2− → RSO 4 + 2OH −
Ion exchange process
2ROH + CO3 2- R2CO3 + 2OH–
➢ The H+ ions released from cation exchange column and OH- ions released from anion exchange column combine to
produce water molecule.
H+ + OH- H 2O

➢The water coming out of the exchanger is free from all cations (except H+) and anions (other than OH-).
This ion free water is known as deionised water or demineralised water and has a neutral pH.
Advantages of demineralization
1. Highly acidic or alkaline water can be softened by this process.
2. It produces water of very low hardness (2-5 ppm).
3. The water produced by this method can be used in high pressure boiler.
Regeneration
When capacities of cation and anion exchangers to exchange H+ and OH − ions
respectively are lost, they are said to be exhausted.
The exhausted cation exchange resin is regenerated by passing a solution of dil. HCl:
RCa + 2HCl ⎯⎯
→ RH2 + CaCl2

The exhausted anion exchange resin is regenerated by passing a solution of dil. NaOH:
→ R ( OH )2 + 2NaCl
RCl2 + 2NaOH ⎯⎯

→ R ( OH )2 + Na 2SO 4
RSO4 + 2NaOH ⎯⎯

Advantages of demineralization
1. Highly acidic or alkaline water can be softened by this process.
2. It produces water of very low hardness (2-5 ppm).
3. The water produced by this method can be used in high pressure boiler.
 Ion exchange Numerical
𝑎 ×𝑉
𝑚𝑒𝒆𝒆𝑢𝒆𝒆𝑣/𝑔, 𝒘𝒘ℎ𝑒𝑟𝑒 𝑎 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝒆𝒆𝑜𝑛 𝑜𝑓 𝑏𝑎𝑠𝑒 𝑢𝑠𝑒𝑑 𝑓𝑜𝑟 𝑡𝒆𝒆𝑡𝑟𝑎𝑡𝒆𝒆𝑜𝑛 (𝑁),
Ion exchange capacity of resin = 𝒘𝒘
𝑉 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑎𝑠𝑒 𝑚𝐿 ,
𝒘𝒘= 𝑾𝑾𝑒𝒆𝑔ℎ𝑡 𝑜𝑓 𝑟 𝑒 𝑠 𝒆 𝒆 𝑛 (𝑔 )
Ex. During determination of cation exchange capacity of 0.5 g cation exchange resin after eluting the column with 0.5 N excess
sodium sulphate solution released some quantity of sulfuric acid that required 22 mL of 0.1 N NaOH using phenolphthalein
indicator. If 1000 liters of water sample containing hardness of 585 ppm CaCO3 is to be made free from cations, how much cation
exchanger resin (theoretical weight) would be required?

Ion exchange capacity= 𝟎𝟎.𝑵𝑵× 𝑽𝑽𝑽𝑽

𝟎𝟎.𝟎𝟎
= 4.4 meq/g
Concentration of water = 585 ppm CaCO3 = 11.7 mN (mequiv/L)
𝑚𝑒𝒆𝒆𝑢𝒆𝒆𝑣
𝑵
𝑵
𝑵𝑵
.𝟎𝟎 ×𝑵
𝑵
𝟎(𝐿)
𝐿
Weight of resin required to deionize 1000 Lof water = = 2659 g
𝟒.𝟒
𝑔
(𝑚 𝑒 𝒆 𝒆 𝑢𝒆 𝒆 𝑣 )
Regeneration of Ion exchange resin
When the resin is The exhausted cation exchange resin is
exhausted, it loses all its regenerated by passing a solution of HCl The column is then
H+ and OH– ions and or H2SO4. rinsed with distilled
then its capacity to • R2Ca + H2SO4/ 2HCl 2RH + CaSO4/ CaCl2
water to remove the salts
exchange ions is lost. • R2Mg + H2SO4/ 2HCl 2RH + MgSO4/ MgCl2 formed.

The anion exchange resin is NaCl, Na2SO4 are

HCl is used for regenerated by passing a dilute
regeneration as CaCl2 solution of NaOH and then removed by
and MgCl2 are more washing with distilled water washing with
soluble. • R2SO4 + 2NaOH 2ROH + Na2SO4 distilled water.
• RCl + NaOH ROH + NaCl
Advantages and Disadvantages of Ion exchange Process

Advantages
• The process can be used to soften highly acidic or alkaline water.
• Unlike zeolite process the soft water does not contain sodium ions.
• It removes all cations and anions other than H+ and OH– ions.
• All ionizable impurities are removed.
• It produces water of very low residual hardness (about 2 ppm).

Disadvantages
• The process is expensive; both the equipment and resin are costly.
• Turbid water decreases the efficiency of the process.
 Domestic Water Treatment
Municipal water treatment OR Water treatment for domestic purpose

Water when collected from natural sources contains several types of

impurities:

1. Rocks and boulders

2. Hay and straw

3. Colloidal impurities: Particulate matter

4. Dissolved impurities: Biological, organic and inorganic

Domestic Water Treatment

1. • Used to remove suspended impurities by passing water through screens

Screening having large number of holes when the floating materials are retained

• Water is allowed to stand undisturbed in big tanks where heavy suspended

2.
particles settle down due to gravity. The retention period in a sedimentation tank
Sedimentation
ranges from 2–6 hours.

3. • Process of removing fine suspended and colloidal impurities by

Coagulation addition of requisite amount of chemicals (coagulants) to water

• Separation of colloidal and suspended impurities by passing through

4. porous bed made of fine sand and other proper sized granular
Filtration
materials.
5.
• process of removing pathogenic bacteria, viruses and
6. Sterilization/
Disinfection protozoa from water
Public
distribution
 3. Coagulation of Water
Coagulants, when added to water, form insoluble gelatinous, flocculent
precipitates, which trap finely suspended/colloidal impurities forming bigger
flocs, which settle down.
Common coagulants:

• Alum, ferrous sulphate (FeSO4.7H2O),sodium aluminate, etc. Image courtesy : https://images.app.goo.gl/UJAJx68kRAJkAkpz8

• They provide positive ions Fe3+ or Al3+ which neutralise the negative charge on the colloidal particles (impurities)

• The partially clarified water is filtered through sand filters

A general reaction of coagulation is given as

Al2(SO 4)3 + 3Ca(HCO 3)2 2Al(OH)3 + 3CaSO 4 + 6 CO 2

Coagulant Calcium flocculent
bicarbonate precipitate
present in water
Coagulation of sedimented water
1.Alum

Ca(HCO3 ) 2 + H 2SO 4 ⎯⎯
→ CaSO 4 + 2H 2 O + 2CO 2

Thus the net reaction as

Al2 (SO 4 )3 + 3Ca(HCO3 ) 2 ⎯⎯

→ 2Al(OH)3 + 3CaSO 4 + 6CO2

• Alum reacts in the presence of alkalinity in water.

2. Sodium Aluminates(NaAlO2)

NaAlO 2 + Ca (HCO3 ) 2 + H 2O → Al(OH)3 + CaCO3 + NaHCO3

NaAlO2 + 2H2O Al(OH)3 + NaOH

(This gives result in pH range 5.5-8.0. Al(OH)3 floc causes sedimentation whereas NaOH reacts with magnesium salts
in water)
MgSO4 + 2NaOH Mg(OH)2 + Na2SO4
 3. Ferrous Sulphate (FeSO4.7H2O)
FeSO 4 .7H 2 O + Ca(HCO3 ) 2 → Fe(OH) 2 + CaSO 4 + 2CO 2 + 7H 2 O

1
2Fe(OH) 2  + O 2 + H 2 O → 2Fe(OH)3
2
• FeSO4 also reacts in slightly alkaline medium

FeSO 4 .7H 2 O + Mg(HCO3 ) 2 → Fe(OH) 2 + MgSO 4 + 2CO 2 + 7H 2 O

4Fe(OH) 2  +O 2 + 2H 2 O → 4Fe(OH) 3
Heavy floc which causes
quick sedimentation
4. Filtration
a. Gravity Sand Filter
b. Pressure Filter

Gravity Sand Filter

Pressure Filter
Sterilization of water
The process of destroying or killing these disease–causing bacteria and
micro-organisms etc. known as disinfection or sterilization of water. This as follows:

A) Boiling
B) Chlorination
1. By using chlorine (Cl2)
2. By using bleaching power (CaOCl2)
3. By using Chloramines (ClNH2)
C) Ozonisation (O3)
D) Aeration
E) Ultra-Violet Rays
 5. Sterilization (Disinfection) methods
A) Boiling

• Simplest and easiest method

• useful for small quantities of water. For proper disinfection, water should be boiled vigorously for 20–25 minutes.

B) Chlorination
1) By adding bleaching powder
• Bleaching powder (CaOCl2) is a very good disinfectant.
• The chemical action produces hypochlorous acid which is a powerful germicide

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl
HOCl HCl + [O]

Drawbacks
• Introduces calcium in water thereby increasing its hardness.
• Bleaching powder deteriorates during storage.
• Excess CaOCl2 gives bad taste and odor to treated water.
5. Sterilization (Disinfection) methods: Chlorination
Direct chlorination
• Chlorine (either gaseous or in concentrated solution form) is used
• Produces hypochlorous acid, which is a powerful germicide.
Cl2 + H2O HCl + HOCl
HOCl HCl + [O] ̶ Germs are
killed.
*Free chlorine: Part of residual chlorine that does not bond to any reactants in water.
Treated water should not have more than (0.1-0.2 ppm) free chlorine
* Combined chlorine: Bonded with chemicals like nitrates

Advantages of chlorine as disinfectant

Chlorinator
(i) It is stable and does not deteriorate on keeping.
(ii) It can be used at high and low temperature.
(iii) It introduces no salt impurities in treated water.

Disadvantages of chlorination
(i) It is effective disinfectant at lower pH.
(ii) Excess chlorine produced unpleasant taste and odour in the water.
(iii) Excess chlorine cause irritation to the mucous membranes.
(iv) The formation of trimethanes which is carcinogenic.
5. Sterilization (Disinfection) methods
Chlorination Methods:

Advantages Disadvantages

(1) Economical, requires little space for (1) Excess chlorine produces unpleasant
storage. taste and odor.

(2) Stable, does not deteriorate on (2) Excess produces irritation on

storage. mucous membrane.

(3) Does not introduce calcium. (3) Not effective at higher pH

By adding chloramines (ClNH ) 2

• Chloramine is formed by reacting chlorine and ammonia in the ratio 2:1 Cl2 + NH3 ClNH2 +HCl
Chloramine
• It is more lasting than chlorine alone, hence it is a better disinfectant ClNH2 + H2O HOCl + NH3
Disinfectant
• Excess does not produce irritating odor.

It is produced by mixing of Cl2 & NH3 in the ratio of 2: 1

Cl2 + NH3 NH2Cl + HCl
This is quite stable compound. It slowly decomposes with evaluation of Cl2.
It is particularly useful when the water is stored after treatment.
NH2Cl + H2O HOCl + NH3Cl
HOCl HCL + [ O ]
Germs + [O] kill the germs

Advantages
1. It imparts good taste to water
2. It removes irritating small due to excess Cl2
3. Excess chlorine can be removed by treatment with ammonia. Ammonia reacts with
chlorine and forms tasteless compound chloramines ( NH 2Cl )
5. Sterilization (Disinfection) methods
Ozonation (Advanced oxidation Process, AOP)
• Ozone is produced by passing silent electric discharge through cold and dry
silent electric discharge
oxygen3O2 2O3
Oxygen Ozone
• Ozone is highly unstable and breaks down liberating nascent oxygen, a powerful oxidizing agent which can
kill all the bacteria as well as oxidize the organic matter
O3 O2 + [O] Nascent oxygen
• Process: Ozone is passed through water in a sterilizing tank.
Disinfected water is removed from the top.
Contact period is about 10–15 minutes and dose is ~(2–3) ppm.
Image courtesy: https://images.app.goo.gl/XUYZU2Yo2RSSbPrb9
Advantages
• Ozone sterilizes, bleaches, decolorizes, deodorizes water and rapidly reacts with bacteria, viruses and protozoa over a wide
pH range and is efficient for organics degradation and inorganics removal
• No chemicals are added, hence, excess of ozone in water is not harmful as it decomposes to give oxygen.
• Stronger germicidal properties than chlorination
• Ozone improves the taste of water. Highly potable water is thus sterilized with ozone.
Disadvantages
• Relatively high equipment costs.
• Requires large amounts of energy.
• Qualified professionals required for design and system maintenance.
• Ozone being corrosive agent, corrodes stainless steel, cast iron, copper, rubber and ebonite.
• Potential fire hazard and toxicity associated with ozone generation
 D) Aeration
E) Ultra-Violet Rays

After that water passed to public distribution

Break point Chlorination
Chlorination to such an extent that not only the pathogenic bacteria but also the organic
matter, reducing impurities, coloring matters and odors from water are oxidized, leaving
free chlorine in water which has further disinfecting action.

Relationship between amount of

chlorine added to water and free
residual chlorine or Breakpoint curve.
Break point Chlorination
Stage I: No residual chlorine in water as the added chlorine is used in
oxidizing the reducing compounds in water (part ab of the graph).

Stage II: Formation of chloro-organic compounds and chloramines

takes place. Chloramines act as chlorine reserve and contribute to an
increase in residual chlorine to a maximum level (bc in the curve).

Stage III: Amount of residual chlorine decreases as the oxidation of

chloramines and chloro-organic compounds takes place and reaches a
minimum (point d in the graph). This point is termed as the break
point. At this point water is completely free of all kinds of impurities
and is of potable water quality. Addition of chlorine until this point is
termed as break point chlorination

Stage IV: Added chlorine is equal to the available chlorine and the
graph shows an increase in the level of residual chlorine (part de in
the graph.)
Break point Chlorination

Advantages of break point chlorination:

(1)It removes all compounds that impart color, bad
odor and unpleasant taste to water.
(2)It destroys all organic matter, dissolved ammonia
and microorganisms in water and prevents
algal/weeds growth in water.
(3) It destroys all the disease producing bacteria.
(4)Minimizes hardness arising from the use of
bleaching powder.
 Boiler Troubles

Boiler Feed water: The water that is used in industries to generate steam.

Specification of Boiler Feed water

• Free from dissolved gases, acids, alkalies and organic matter. Image courtesy:

• Its hardness should be below 0.2 ppm

https://images.app.goo.gl/awjsXqbPL1wUQ9Fg9

• Its caustic alkalinity (due to OH–) should lie in between 0.15 and 0.45 ppm
• Its soda alkalinity (due to Na2CO3) should be 0.45–1 ppm

Excess of impurities, if present, in boiler feed water generally cause the following problems

(i) Scale and sludge formation

(ii) Boiler corrosion
(iii) Caustic embrittlement
(iv) Priming and foaming
A. Scale & Sludge formation: Scales
Scale and sludge formation

Water evaporates continuously inside the boiler and the

concentration of dissolved salts increases gradually. When the
Sludge and Scales in boilers
solution is saturated with respect to the salt concentration, the
salts start precipitating out on the inner walls of the boiler.

If the precipitate formed is soft, slimy and loose, it is called

sludge and if the precipitate formed is hard and adhering on
the inner walls of the boiler it is termed as scale.

Boiler scales

Image courtesy: https://images.app.goo.gl/Qjvv9aPkgbsfZro69

A. Scale & Sludge formation: Sludge
SLUDGE : It is soft, slimy and loose precipitate formed on the inner walls of the boiler.

Formation
(a) Formed by substances whichhave greater solubility in hot water than in cold water
e.g. MgSO4, MgCl2, MgCO3, CaCl2 etc.
(b)Formed at colder parts of the boiler and get collected at places where the flow rate is slow or at bends,
plug opening, glass gauge connection, thereby causing even choking of the pipes.
(c) They are poor conductors of heat.
(d) They can be removed easily by scraping off with wire brush.

Prevention
(i) By using softened water.
(ii)By frequent ‘blow-down operation’, that is, drawing off a portion of the concentrated water from the
boiler and replacing it with fresh water.
A. Scale & Sludge formation: Sludge
SLUDGE : It is soft, slimy and loose precipitate formed on the inner walls of the boiler.

Disadvantages of sludge formation

(i) Waste of heat generated and thus decreasing the efficiency of the boiler.

(ii) Excessive sludge formation disturbs working of the boiler.

Scale formation: Causes and Effects
Scales are hard deposits on the inner walls of the boilers which are hard to remove.
Causes:
(i) Decomposition of Calcium bicarbonate
Ca(HCO3)2 CaCO3 + H2O + CO 2

CaCO3 scale is soft and it is the main cause of scale formation in low-pressure boilers.
However, in higher pressure boilers CaCO3 is soluble due to the formation of Ca(OH)2.

CaCO3 + H2O Ca(OH)2 + CO 2

(ii) Deposition of Calcium sulfate

Calcium sulfate has a negative solubility co-efficient with respect to temperature. The solubility of CaSO4 decreases as
temperature increases. CaSO4 is soluble in cold water and is completely insoluble in superheated water. Therefore, CaSO4 gets
precipitated as hard scale on the hot portion of the boiler.
Scale formation: Causes and Effects
Causes:

(iii) Hydrolysis of Magnesium salts

At high temperature, dissolved magnesium salts undergo hydrolysis forming a soft scale of magnesium hydroxide

MgCl2 + 2 H 2 O Mg(OH)2 + 3 HCl

(iv) Formation of Calcium and Magnesium silicates

Very small quantities of silica (SiO2) present in hard water react with calcium and magnesium forming their respective silicates

MO + SiO2 MSiO3 (M = Ca, Mg)

Scale formation: Causes and Effects
Disadvantages of scale formation

1.Wastage of fuel: Scales have poor thermal conductivity, therefore the rate of heat transfer from
boiler to the water inside is greatly reduced. Hence extra heat is to be supplied to the boiler and this
increases the fuel consumption.

2. Lowering boiler safety: Due to scale formation, the boiler is to be over heated to provide steady
supply of heat. Distortion of boiler tubes takes place, and the boiler becomes unsafe to bear the
pressure of the steam (in high-pressure boilers).

3. Decrease in efficiency: Deposition of scale in the valves and condensers of the boiler, chokes them
partially.

4. Danger of explosion: Due to uneven expansion the thick scales crack, which can lead to boiler
explosion
Removal of scale

• Loosely adhering scale can be removed either by scraper or wire brush or by blow-
down operation

• Brittle scales can be removed by thermal shocks (i.e heating the boiler and then
suddenly cooling with cold water)

• Hard and adherent scales can be removed by dissolving in chemicals,

e.g, CaCO3 scale can be dissolved by using 5–10% HCl.
CaSO4 scale can be removed by adding EDTA since the Ca-EDTA complex is
highly soluble in water.

Boiler blowdown is the periodical removal of water from boiler to control boiler water
parameters within prescribed limits to minimize scale, corrosion, carryover, and other
specific problems including suspended solids present in the system.
 B. Boiler Corrosion: Acid Formation by Dissolved Salts
Decay or disintegration of boiler material by chemical or electrochemical attack of the contents of water.
Boiler corrosion generally occurs due to
1. Acid formation by dissolved salts
2. Dissolved carbon dioxide
3. Dissolved oxygen
1. Acid formation by dissolved salts
MgCl2 present in the boiler feed water undergoes hydrolysis producing hydrochloric acid
MgCl2 + 2H2O Mg (OH)2↓ + 2HCl

The acid thus liberated reacts with the boiler material (iron) to form ferrous hydroxide which is then converted to rust
1) Fe + 2HCl FeCl2 + H 2
2) FeCl2 + 2H2O Fe(OH)2 + 2HCl
The HCl formed in step (2) again attacks boiler material. A chain reaction is set up which causes extensive
corrosion.

The Fe(OH)2 formed

4Fe(OH) 2 further
+ O 2 reacts with
2[Feoxygen
2O 3.2Hforming
2O] rust
(Rust)

Prevention Boiler corrosion by acid formation can be prevented by adding calculated quantity of alkali which
neutralizes the acid thus formed.
B. Boiler Corrosion: Dissolved Carbon dioxide

The main source of CO2 in boilers is by the decomposition of bicarbonates of calcium and magnesium.
Mg(HCO3)2 Mg(OH)2 + 2 CO2

Ca(HCO3)2 CaCO3 + H2O + CO2

Carbon dioxide reacts with water forming carbonic acid

H2O + CO2 H2CO3
(Carbonic acid)
Carbonic acid has a slow corrosive effect on the boiler material.

Removal
CO2 can be removed either by adding ammonium hydroxide or by mechanical de aeration.

2NH4OH + CO2 (NH4)2CO3 + H2O

B. Boiler Corrosion: Dissolved Oxygen

Water normally contains 8 ppm of dissolved oxygen (DO) at room temperature. At high temperature, the
dissolved oxygen reacts with iron of the boiler to form ferric oxide (rust):

2Fe + 2H2O + O2 2Fe(OH)2↓

4Fe(OH)2 + O2 2(Fe2O3.2H2O)↓
Ferrous Rust
Hydroxide

Removal of DO
(i) By adding chemicals: (ii) Mechanical deaeration

DO can be removed by adding a reducing agent like hydrazine, sodium • Spraying water over preheated perforated
sulphite or sodium sulphide. plates stacked in tower. Removal of
dissolved O2 is ensured by applying high
N 2H4 + O2 N 2 + 2H2O temperature and vacuum.
2Na2SO3 + O2 2Na2SO4
Na2S + 2O2 Na2SO4 ( may decompose at high temperature forming corrosive sulphurous acid )
Note: Excess of hydrazine should not be used as it decomposes to give NH3.
Mechanism of Scale and Sludge Formation: Carry Over

Carry Over

➢ The phenomenon of carrying of water by steam along with the impurities is called carry over.
➢ As the steam rises from the surface of the boiling water in the boiler, it may be associated with
small droplets of water. Such steam containing liquid water is called wet steam.
➢ These droplets of water naturally carry with them some suspended and dissolved impurities
present in the boiler water.

➢ The two main methods of carry over are ‘Priming’ and ‘Foaming’.
D. Priming and Foaming

PRIMING: When water is heated rapidly inside the boiler or if there is a sudden increase in steam demand then
water droplets are carried along the steam. This steam is termed as ‘wet steam’ and the formation of wet steam is
called ‘priming’.
Causes
• Very high velocity of steam formation, when steam is formed at a great speed in the boiler, some droplets of
water are carried along with steam.
• Presence of considerable quantities of dissolved solids.
• Sudden ebullition/boiling.
• Faulty boiler design.

Minimisation of Priming
• Controlling rapid change in steam velocities.
• Proper boiler design (by putting anti-priming plates or dash plates).
• Maintaining low water level.
• Use of water without suspended impurities.
• By blowing off scales and sludges from time to time.
D. Priming and Foaming

FOAMING: Formation of small but persistent foam or bubbles which do not break easily.

Causes
Presence of surface active materials, surfactants, oil or alkaloids in boiler feed water, which reduces the
surface tension of water.

Minimization of foaming
• By adding anti-foaming agents like castor oil or silicic acid.
• By adding compounds like sodium aluminates or aluminium sulphate, which removes oil from the boiler.
These are hydrolysed to form Al(OH)3, which entraps oil drops
Treatment of Boiler Feed water

Lime Soda Process

Treatment of Boiler Feed External Treatment

(Carried out before the entry of Zeolite Process
water into the boiler)

Ion Exchange Process

water

Carbonate conditioning

Internal Treatment
(Conditioning of water in the Phosphate conditioning
boiler itself by adding chemicals)

Calgon Conditioning
External Treatment of Boiler Feed Water
External Treatment Process
Important methods employed for this process are
1. Lime-Soda Method
2. Zeolite process and
3. Ion Exchange process

Principle of Lime soda process:

• To convert all the soluble hardness causing impurities into insoluble precipitates which can be removed by
sedimentation and filtration.
• Addition of calculated quantities of lime Ca(OH)2 and soda Na2CO3.
• The hardness causing impurities react with these chemicals forming precipitates of CaCO3 and Mg(OH)2.
• These precipitates are then filtered off to obtain soft water.
• The precipitates formed are very fine and do not settle easily causing difficulty in filtration. Therefore small
amount of coagulants like alum (K2SO4.Al2(SO4)3.24H2O), ferrous sulphate(FeSO4) or sodium aluminate
(NaAlO2) are added.
Process of Lime-soda
Cold intermittent lime soda process
It is also called batch process. It consists of a tank which
has an inlet for raw water and chemicals, outlet for
softened water and sludge and a mechanical stirrer.
Calculated quantities of lime, soda and coagulant are
added through the chemical feed inlet and raw
water is added through another inlet simultaneously, and
these are mixed thoroughly with the help of stirrer. For
accelerating the process some sludge, (from previous
operation) is added which acts as nucleus for fresh
precipitation. The sludge (precipitate) formed is allowed
to settle down and is then removed through the sludge
outlet. The softened water is removed through a floating
pipe and sent to the filtering unit.
Cold continuous lime soda process
Hard water is first analysed and then calculated
quantity of chemicals and rawwater are added
simultaneously in the inner chamber. Vigorous
stirring ensures continuous mixing of raw material
and water. Softening of water occurs. The sludge
thus formed settles down. Soft water rises up,
passes through the wood fibre filter where traces
of sludge are removed. Filtered soft water is then
collected from the outlet near the top.
Hot continuous lime-soda process
All the raw materials are put in through the
three inlets in the reaction chamber. Here
thorough mixing of raw materials takes
place in the presence of superheated
steam. Sludges settle down at the conical
mouth of vertical outer chamber and ‘sand
filter’ is provided for filtration to ensure
complete removal of sludge from softened
water giving finally filtered softened water.
Internal Treatment

• It is also called sequestration or conditioning.

• It involves the treatment inside the boiler by adding the suitable chemicals which either
(a) precipitate the scale forming impurities in the form of sludges, which can be
removed by blow-down operation or
(b)convert them into compounds, which will stay in dissolved form in water and
thus do not cause any harm.
Internal Treatment: Conditioning

1. Carbonate conditioning
• In low pressure boilers the scale formation can be avoided by adding sodium carbonate to
boiler
CaSO water
4 + Na2 CO 3 CaCO 3 + Na2 SO4
hard scale loose sludge

2. Phosphate conditioning
• Used equally in low- and high-pressure boilers.
• MgCl2 which hydrolyses to Mg(OH)2 scale can be removed by adding appropriate sodium phosphate
NaH 2PO 4, Na2HPO 4, or Na3PO 4 (choice depends on alkalinity of water)
• Phosphate reacts with calcium/magnesium salts forming loose sludge of calcium or magnesium
phosphate which can be removed by blow-down operation

3MgCl2 + 2Na3PO4 Mg3 (PO4)2+ 6NaCl

Acidic water: trisodium phosphate

Alkaline water: sodium dihydrogen phosphate
Neutral water: disodium hydrogen phosphate
Internal Treatment: Conditioning
3. Calgon conditioning
• Addition of sodium hexametaphosphate (calgon) to boiler water.
• Calgon converts the scale forming impurities into highly soluble complexes.

Na2[Na4(PO 3)6] 2Na+ + [Na4(PO 3)6]2-

2CaSO 4 + [Na4(PO 3)6]2- [Ca2(PO 3)6]2- + 2Na2SO4
Soluble complex ion

2Na+ + [Ca2(PO 3)6]2- Na2[Ca2(PO 3)6]

Soluble complex

4. Sodium metaaluminate (NaAlO2) conditioning

• Sodium metaaluminate gets hydrolysed forming NaOH and a gelatinous precipitate of aluminium hydroxide:
NaAlO2 + 2H2O NaOH + Al(OH)3
Gelatinous precipitate
• The sodium hydroxide so formed precipitates Mg2+ as Mg(OH)2
MgCl2 + 2NaOH Mg(OH)2 + 2NaCl
• The flocculent precipitate of Mg(OH)2 plus Al(OH)3, entraps finely suspended and colloidal impurities (like oil,
silica etc.) which can be removed by blow-down process.
C. Caustic Embrittlement
White caustic deposits
• Boiler material becomes brittle due to the accumulation of excess alkali in the boiler.
• A form of stress corrosion taking place in boilers operating at high temperature and pressure.
• Caused by high alkalinity of water in the boiler, particularly at those places which are under stress
such as rivets, joints and bends with the result that the metal plates become brittle.

When water is softened by lime – soda process, the excess sodium carbonate undergoes Caustic embrittlement
decomposition in high pressure boilers leading to the formation of NaOH.

Na2CO 3 + H 2O 2NaOH + CO 2

This NaOH makes the water alkaline. The alkaline water penetrates into the minute cracks and crevices between the rivets and
joints by capillary action. Inside the cracks, the water evaporates and the concentration of NaOH increases on these sites due to
poor circulation of water. NaOH attacks the iron in boiler material converting it to sodium ferroate (Na2FeO 2). A small quantity
of sodium ferrite (NaFeO2) is also formed.

Fe + 2NaOH Na2FeO 2 + H 2
Formation of concentration cell (Caustic embrittlement)
3Na2FeO 2 + 4H2O 6NaOH + Fe3O 4 + H 2

6Na2FeO 2 + 6 H 2O + O 2 12NaOH + 2Fe3O 4 o Iron at the anodic area undergoes corrosion and
Fe3O 4 + 4NaOH 2NaFeO 2 + Na2FeO 2 + 2H2O boiler becomes brittle
Prevention of Caustic Embrittlement

• By adding tannin or lignin to the boiler water to block the minute cracks and prevent the infiltration of NaOH.
•Adding Na2SO4 to the boiler water to block the hair cracks. Na2SO4/NaOH should be used in different ratio for
boilers operating at different pressures.

• By using sodium phosphate instead of sodium carbonate for softening water.

• By adjusting the pH of boiler water between 8–9.
• Use of excess soda should be avoided in the lime-soda process