CHY 1701 – Engineering

Chemistry

Module – I
Water Technology

Dr. M. Akhila Maheswari

Cabin: SJT 611B
akhila.maheswari@vit.ac.in
akhila.maheswari@gmail.com
1
 Contents
• DO and its determination
• Characteristics of hard water – hardness
• Numerical problems in hardness
determination by EDTA
• Disadvantages of hard water in industries

2
 Water

“Without food, human can survive for number of days, but

water is such an essential that without it one cannot
survive”.
“Water is nature’s most wonderful, abundant and useful
compound yet, is also the most misused one”.

3
Distribution of water

4
Deep Ground Water No pathogens, rich in
dissolved solids
carbonates & sulphates Ca
and Mg or Fe
Shallow Ground Variable bacteriological
water quality, soluble materials
including toxic metals of
As, Zn & Cu
Upland Lakes & Bacteria levels usually low,
Reservoirs rich in organic & inorganic
matters, pH adjustment
required
Rivers, Canals & Low Significant Bacterial levels,
land Reservoirs suspended solids &
dissolved constituents
 Impurities in water

Physical Biological
Temperature, Microorganisms
Dust Bacteria
Clay Chemical
Fungi
Sand Algae
Other suspended Acid rain
Dissolved CO2 Pathogens
particles
Minerals
Dissolved salts
Synthetic organic compounds
Radioactive substances
Oxygen demanding wastes
Plant nutrients
Effect of impurities on water

• Bad taste, colour & odour

• Hardness, corrosiveness, staining
• Decrease in DO level
• Increase in BOD/COD
• Causes various diseases and
infections
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases

Hardness

Alkalinity
Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2
Magnesium Carbonate other suspended matter H2 S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

8
 Total Dissolved Solids
Total Dissolved Solids (TDS) are the total amount of mobile charged
ions, including minerals, salts or metals dissolved in a given volume of
water, expressed in units of mg per unit volume of water (mg/L), also
referred to as parts per million (ppm).

Total dissolved solids (TDS) is a measure of the combined content of all

inorganic and organic substances contained in a liquid in molecular,
ionized or micro-granular (colloidal sol) suspended form.

Generally, the operational definition is that the solids must be small

enough to survive filtration through a filter with two-micrometer
(nominal size, or smaller) pores.

Total dissolved solids are normally discussed only for freshwater systems,
as salinity includes some of the ions constituting the definition of TDS.

The principal application of TDS is in the study of water quality for

streams, rivers and lakes, although TDS is not generally considered a
primary pollutant (e.g. it is not deemed to be associated with health
effects). 9
TDS continued---

Primary sources for TDS in receiving waters are agricultural and

residential runoff, leaching of soil contamination and point source
water pollution discharge from industrial or sewage treatment plants.

The most common chemical constituents are calcium, phosphates,

nitrates, sodium, potassium and chloride.

The chemicals may be cations, anions, molecules or agglomerations

on the order of one thousand or fewer molecules, so long as a soluble
micro-granule is formed.

More exotic and harmful elements of TDS are pesticides arising from
surface runoff.

Water can be classified by the amount of TDS per liter:

•Fresh water < 1000 mg/L TDS
•Brackish water 1000 to 10,000 mg/L TDS
•Saline water 10,000 to 30,000 mg/L TDS
•Brine > 30,000 mg/L TDS
10
 DO (Dissolved Oxygen)

• Number of molecules of O2 dissolved in one litre of water –

Expressed as mg/L (ppm).
• One of the best indicators to understand the health of the water
body and life sustaining ability.
• Most life supporting water systems – 4-6 mg/L of DO
• Factors affecting DO levels
– Water temperature
– Organic waste
– Aquatic plant populations
– Water flow
– Altitude (atm. Pressure)
– Human activities

11
DO levels

12
DO vs Aquatic life

13
14
 DO determination - Winkler’s method
• Iodometric titration
• Redox chemistry is involved
• Sources of error – presence of nitrites and hydrogen
sulphide in the water sample.

15
16
 Calculation - DO

1 mole of O2 = 2 moles of I2 = 4 moles of Na2S2O3

1 mole of Na2S2O3 = ¼ mole of O2 = 8 g of O2
1mL of 1N Na2S2O3 = 8 mg of O2
‘V’ mL of ‘N1’N Na2S2O3 = 8 x V x N1

DO of water sample = 8 x Vol. of Na2S2O3 consumed x Normality of Na2S2O3 x 1000

Volume of water sample taken

DO of the water sample is expressed in mg/L (ppm)

17
 Biological Oxygen Demand
Biological oxygen demand (BOD) is the amount of dissolved oxygen
needed by aerobic biological organisms in a water body to break down
organic material present in a given water sample at certain
temperature over a specific time period.
The BOD value is most commonly expressed in milligrams of oxygen
consumed per litre of sample for the biologically oxidizable impurities
during 5 days of incubation at 20 °C and is often used as a robust
surrogate to determine the degree of biodegradable organic pollution
in water.
BOD is similar in function to COD, in that both measure the amount of
organic compounds in water. However, COD is less specific, since it
measures everything that can be chemically oxidized, rather than just
levels of biologically active organic matter.

18
 Chemical Oxygen Demand (COD)
Chemical oxygen demand (COD) test is commonly used to
indirectly measure the amount of organic compounds in water.

Most applications of COD determine the amount of organic

pollutants found in surface water (e.g. lakes and rivers) or
wastewater, making COD a useful measure of water quality.

The chemical oxygen demand determines the

amount of oxidizable organic pollutants found in
surface water, making COD a useful measure of
water quality.

It is expressed in milligrams per litre (mg/L), which indicates the

mass of oxygen consumed per litre of solution.

The basis for the COD test is that nearly all organic compounds
can be fully oxidized to carbon dioxide with a strong oxidizing
agent under acidic conditions. The amount of oxygen required to
oxidize an organic compound to carbon dioxide, ammonia, and
19
water.
 COD Estimation

The COD is determined by refluxing the sample in the presence of

excess K2Cr2O7, which serves as oxidizing agent. The solution is
acidified with H2SO4, and Ag2SO4 is added as a catalyst to speed the
oxidation of low-molecular-weight fatty acids.

Mercuric sulfate, HgSO4, is added to complex any chloride that is

present, thus preventing the precipitation of the Ag+ catalyst as AgCl.

After refluxing for 30 min, the solution is cooled to room temperature,

and the excess Cr2O72- is determined by a back titration, using ferrous
ammonium sulphate as the titrant and ferroin as the indicator.

Since it is difficult to completely remove all traces of organic matter

from the reagents, a blank titration must be performed.

The difference in the amount of FAS needed to titrate the blank and the
sample is proportional to COD.

20
 Calculation
COD of water (mg/L) = (A-B) x M x 8 x 1000
V

A = FAS used for Blank (mL)

B = FAS used for sample (mL) = unreacted dichromate
M = Molarity of FAS
V = Volume of water sample (mL)

21
 Hard Water
What’s hard water?

Practically speaking, measurement of:

•Calcium (Ca) ions
•Magnesium (Mg) ions

Hardness as calcium carbonate

mg/L (ppm)

Soft 0-17
Moderately hard (Medium) 60-120
Hard 120-180
Very hard 180 & over

22
 Why be concerned about Hard Water?

• Originally, water hardness was defined as the measure of

the capacity of the water to precipitate soap

• Hard water does cause soap scum, clogs pipes and clogs
boilers as lime scale

23
 Disadvantages of Hard water
Domestic Use Industrial Use
✓ Washing ➢ Textile industry
do not lather with soap, silky (wastage of soap, precipitates of Ca
& Mg adhered to the fabric- which
precipitates of Mg and Ca
don’t produce the exact shades)
C17H35COONa + H2O C17H35COOH + NaOH
➢Sugar Industry
Lather
C17H35COOH + C17H35COONa
(water containing sulphates,
✓ Bathing nitrates, alkali carbonates etc.
Cleansing quality of soap is poor causes difficulties in sugar
crystallization)
✓ Cooking
elevated boiling point; more fuel for ➢Concrete making
cooking (hydration of cement as well as
concrete strength)
✓ Drinking
bad effect in digestive ➢Pharmaceutical Industry
system; possibility of forming calcium (May produce undesirable
oxalate crystals in urinary tracks substance)
 Hard water and soap

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

Sodium stearate Hardness
Calcium stearate (Scum)
(sodium soap)

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

Sodium stearate
Hardness Magnesium stearate (Scum)
(sodium soap)

25
 Hardness of Water

• Hardness in Water is characteristic that prevents the

‘lathering of soap’ thus water which does not produce lather
with soap solution readily, but forms a white curd is called
hard water.

• Type of Hardness

– Temporary or Carbonate Hardness

– Permanent Hardness or non-carbonate Hardness.

26
 Types of Hardness

Temporary Hardness (or) Permanent Hardness (or)

carbonate hardness noncarbonate hardness
-Dissolved bicarbonate salts of Ca - presence of chlorides and
and Mg and other heavy metals such sulphates of Ca, Mg and
as iron other heavy metals)
-Can be removed easily by boiling - Can’t be removed by simple
boiling
Ca(HCO3)2 CaCO3 + H2O + CO2

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

 Temporary Hardness (Alkaline hardness)
– Temporary Hardness is caused by the presence of dissolved
bicarbonate of calcium, magnesium

It is mostly destroyed by more boiling of water, when bicarbonates

are decomposed yielding insoluble carbonates.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Calcium bicarbonate Calcium Carbonate

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

Magnesium Bicarbonate Magnesium hydroxide

Permanent Hardness (Non-alkaline hardness)

Non-Carbonate Hardness is due to the presence of chlorides,
sulfates of calcium, Magnesium

Permanent hardness cannot be removed by boiling

28
HOW TO EXPRESS
HARDNESS OF WATER ?
 CaCO3 equivalent hardness

Mass of hardness X Molecular

producing substance weight of CaCO3
Calcium carbonate equivalent =
Molecular weight of hardness producing
substances
Problem 1
Calculate the calcium carbonate equivalent hardness of a water sample
containing 204mg of CaSO4 per litre

Solution :
204 X 100
Calcium carbonate equivalent hardness = = 150 mg of CaCO3/L
136
= 150 ppm

Note : Mol. Weight of CaCO3 = 100

Mol. Weight of CaSO4 = 136

30
 Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO3 equivalence hardness causing substance present in
106 parts of water

• Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 equivalence hardness causing substance present in
one liter of water

1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm

• Clare's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water

• Degrees French (oFr)

1o Fr = 1 part of CaCO3 eq per 105 parts of water 31
1oFr = 1 part of CaCO3 equivalent hardness per 105 parts
1 ppm = 1 part per 10,00,000 parts of water
1o cl = 1 part per 70,000 parts of water

1 ppm = 0.07 o cl = 0.1o Fr Problem:

If the hardness of water is
1 o cl = 1.42o Fr = 14.2 ppm 210.5 ppm Calculate its
hardness in o cl.
1 o Fr = 0.7 o cl = 10 ppm 1 ppm = 0.07 o cl
210.5 ppm = 0. 07 × 210.5
= 14.735o cl
Calcium carbonate equivalence conversion during hardness
calculation

Hardness Molecular Multiplication factor

producing weight (in terms of CaCO3
substance equivalence)
Ca(HCO3)2 162 100/162 or 50/81
Mg(HCO3)2 146 100/146 or 50/73
CaSO4 136 100/136 or 50/68
CaCl2 111 100/111 or 50/55.5
MgSO4 120 100/120 or 50/60
MgCl2 95 100/95 or 50/47.5
CaCO3 100 100/100 or 50/50
MgCO3 84 100/84 or 50/42
CO2 44 100/44 or 50/22
HCO-3 61 100/61 or 50/61
OH- 17 100/17 or 50/17
CO32- 60 100/60 or 50/30

33
 Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, Ca(HCO3)2 = 20 ppm, MgSO4
=24.0mg/L and KOH = 1 ppm. Calculate the temporary, permanent and total
hardness of the water sample.

Solution
Step 1 conversion in to CaCO3 equivalent

Constituent quantity Conversion Hardness

present factor
Mg(HCO3)2 16.8 mg/L 100/146 16.8 *100/146 = 11.5ppm
MgCl2 19.0 mg/L 100/95 19.0*100/95 = 20ppm
20.0*100/162 = 12.3 ppm
Ca(HCO3)2 20 ppm 100/162
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculation

Temp. Hardness = 23.8 ppm P. Hardness = 40 ppm

Tot. Hardness =63.8 ppm

34
Example 1. How many grams of FeSO4 dissolved per litre gives 210.5
ppm of hardness?
(Fe = 56, S = 32, O = 16, Ca = 40, C = 12).

Solution. FeSO4 = CaCO3

(56 + 32 + 64 = 152g) =100g
100 ppm of hardness = 152 ppm of FeSO4

210.5 ppm of hardness = 152 × 210.5 = 319.9 ppm of FeSO4

100
= 319.9 mg/L or 0.319 g/L of FeSO4
Example 2. Calculate the temporary hardness and permanent hardness of a
sample water containing Mg(HCO3)2 = 7.3 mg/L ; Ca(HCO3)2 = 16.2 mg/L ; MgCl2
= 9.5 mg/L; CaSO4 = 13.6 mg/L (atomic weight of Mg and Ca are 24 and 40
respectively, Cl and S are 35.45 and 32 respectively)

Solution: Conversion into CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 7.3mg/L 100/146 7.3 × 100/146 = 5mg/L

Ca(HCO3)2 = 16.2mg/L 100/162 16.2 × 100/162 = 10mg/L

MgCl2 = 9.5mg/L 100/95 9.5 × 100/95 = 10 mg/L

CaSO4 = 13.6/L 100/136 13.6 × 100/136 = 10mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (5 + 10) mg/L = 15 mg/L or 15 ppm

Permanent hardness, due to MgCl2 and CaSO4

= (10 + 10) mg/L= 20mg/L or 20 ppm

Total hardness = Temporary hardness + Permanent hardness

Example 3. Calculate the temporary hardness and total hardness of a sample
water containing Mg(HCO3)2 = 73 mg/L ; Ca(HCO3)2 = 162 mg/L ; MgCl2 = 95
mg/L; CaSO4 = 136 mg/L (atomic weight of Mg and Ca are 24 and 40
respectively, Cl and S are 35.45 and 32 respectively)

Solution: Calculation of CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 73mg/L 100/146 73 × 100/146 = 50mg/L

Ca(HCO3)2 = 162mg/L 100/162 162 × 100/162 = 100mg/L

MgCl2 = 95mg/L 100/95 95 × 100/95 = 100 mg/L

CaSO4 = 136/L 100/136 136 × 100/136 = 100mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (50 + 100) mg/L = 150 mg/L or 150 ppm

Total hardness, = (50 + 100 + 100+100) mg/L= 350 mg/L or 350 ppm

Permanent hardness = Total hardness - Temporary hardness

 EDTA method: Hardness
• Complexometric titration.
• Pipette solution: water sample
EBT
• Titrant: EDTA (Strong complexing agent)
• Condition for titration: pH-9-10 – Ammonia-ammonium chloride
buffer added.
• Indicator: Eriochome Black – T (EBT)
• End point: wine red to steel blue
Colorless

Ca2+ Color of Ca-EBT

Color of free EBT

EDTA
Colorless 38
Ca-EDTA Complex
EDTA forms permanent complex with Ca2+ and Mg2+ present in the hard water

EDTA: Colorless solution

Eriochrome Black T

EBT is blue in a buffered solution at pH 10, it turns red when Ca2+

ions were added

The characteristic blue end-point is reached when sufficient EDTA is

added and metal ions is chelated by EDTA, leaving the free indicator
molecule
 Experiment
1. Preparation of EDTA solution (0.01 M)
i.e. dissolve 3.72 g of sodium salt of EDTA crystals in 1 litre of
distilled water

2. Preparation of standard Hard Water

a. Dissolve 1.0 g of pure, dry CaCO3 in small quantity of conc.
HCl and evaporate the solution to dryness
b. Dissolve the residue in distilled water (1 litre)
1ml of this solution contains 1 mg of CaCO3 equ. hardness

3. Preparation of buffer solution

Add 67.5 g of NH4Cl to 570 ml of conc. Ammonia soln. and dilute
with distilled water to 1 litre

4. Preparation of indicator
Dissolve 0.5 g of EB-T in 100 ml alcohol
 5. Standardization of EDTA solution

Burette - EDTA solution (0.01 M)

50 ml of 10-15 ml of few drops of

Conical Flask - std. hard + ammonia + EB-T
water buffer indicator

Volume of EDTA consumed = V1 ml

6.Estimation of total Hardness

50 ml of 10-15 ml of few drops of

Conical Flask - sample + ammonia + EB-T
hard water buffer indicator

Volume of EDTA consumed = V2 ml

7.Estimation of permanent Hardness

50 ml of 10-15 ml of few drops of

Conical Flask - boiled + ammonia + EBT indicator
sample buffer
hard water
Volume of EDTA consumed = V3 ml

Boiled water preparation:

250mL of Hard water – boiled it – reduced the volume about 50mL
Bicarbonates are decomposed to insoluble CaCO3 and Mg(OH)2
Filter, wash the precipitate with distilled water – collect the filtrate –
make up to 250mL

50mL of boiled water + EDTA

 Calculation: Estimation of Total Hardness

50ml of standard hard water = V1 mL of EDTA

1mL of EDTA = 50 / V1 mg of CaCO3 eqvt.

50ml of given hard water = V2 mL of EDTA

= V2 X 50 / V1 mg of CaCO3 eqvt.

1mL of Given hard water = V2 X 50 / V1X 50 mg of CaCO3 eqvt.

1000mL of Given hard water = 1000 V2 / V1 mg of CaCO3 eqvt.

Total Hardness of water = 1000 V2 / V1 mg/L

= 1000 V2 / V1 ppm
 Calculation: Estimation of Permanent Hardness
50ml of boiled water = V3 mL of EDTA

= V3 X 50 / V1 mg of CaCO3 eqvt.

1mL of boiled water = V3 X 50 / V1X 50 mg of CaCO3 eqvt.

1000mL of boiled water = 1000 V3 / V1 mg of CaCO3 eqvt.

Permanent Hardness of water = 1000 V3 / V1 mg/L

= 1000 V3 / V1 ppm

Temporary Hardness of water = [Total – Permanent] hardness

= 1000{(V2-V3)/V1} ppm
Disadvantages of hard water in industries

46
 Boiler troubles due to Hard Water

1. Scales and sludges

2. Caustic embrittlement
3. Priming and foaming
4. Boiler corrosion
 Scale & Sludge Formation in Boilers

In boilers
– Concentration of the dissolved salts increases progressively when water
evaporates during continuous steam generation. When their
concentration reaches saturation point, the salts gets precipitated
probably on the inner walls of the boiler.

If the precipitate is
- Soft, Loose, slimy precipitate - Sludge
- Hard, adhering crust/coating on the inner walls of the boiler- Scale
 Sludge Scale
Hard adhering
coating to the
Loose precipitate
suspended in water
Boiler wall inner walls of the
boiler

water

Heat Heat
 Sludge
Slimy loose
precipitate called
sludge suspended in
water

wate
r
Boiler
wall
Sludge is a soft, loose and slimy precipitate formed within the boiler.
It can be easily scrapped off with a wire brush.
It is formed at comparatively colder portions of the boiler and collects
in areas of the system, where the flow rate is slow or at bends.
It is formed by substances which have greater solubility's in hot water
than in cold water, e.g. MgCO3, MgCl2, CaCl2, MgSO4 etc.,

Remedy: Sludges can be removed using wire brush or mild acid

51
Disadvantages of sludges Prevention
• Poor conductor of heat – wastage of
energy •By using soft water

• If sludge formed along with the scale, •Frequent blowdown operation

sludge get entrapped within scale and
both gets deposited as scale

• Excessive sludge formation disturbs

the working condition of the boiler
 Scale
Hard adherent coating on
inner walls of boiler

water

Boiler
wall

Scales are hard substances which sticks very firmly to the inner
surfaces of the boiler wall.
Scales are difficult to remove even with the help of a hammer
and chisel.
Examples: CaSO4, CaCO3, Mg(OH)2 53
 Formation of Scales
Decomposition of calcium bicarbonate

• Scales are the main source of boiler troubles. Scale composing

chiefly of calcium carbonate is soft and is the main cause of scale
formation in low-pressure boilers.

Scale (low pressure boilers)

• But in high-pressure boilers, CaCO3 is soluble.

CaCO3+ H2O Ca(OH)2 (Soluble) + CO2

54
 Decomposition of calcium sulphate
• The solubility of calcium sulphate in water decreases
with increase of temperature

• The solubility of CaSO4 is 3,200 ppm at 15°C and it

reduces to 55 ppm at 230°C and 27 ppm at 320°C

• CaSO4 gets precipitated as hard scale on the heated

portion of the boiler. This is the main cause of scales
in high-pressure boilers.

Gypsum is composed of calcium sulfate (CaSO4)

and water (H2O), i.e. Calcium Sulphate Dihydrate
(CaSO4.2H2O) 55
 Hydrolysis of magnesium salts
Dissolved magnesium salts undergo hydrolysis
forming magnesium hydroxide precipitate which
forms a soft type of scale
MgCl2 + 2H2O Mg(OH)2 + 2HCl

Presence of Silica
Presence of silica in small quantities deposits as calcium silicate
(CaSiO3) or magnesium silicate (MgSiO3). These deposits stick
very firmly on the inner side of the boiler surface and are very
difficult to remove.
56
 Disadvantage of scale formation

• Low thermal conductivity

Thickness of scale in 0.325 0.625 1.25 2.5 12
(mm)
Wastage of fuel 10% 15% 50% 80% 150%

• Lowering boiler safety

• Decrease in efficiency

• Danger of explosion
57
 Removal of Scales

• By giving thermal Shock if they are brittle (heating the

boiler and then suddenly cooling with cold water)

• If they are adherent and hard dissolving them with help of

chemicals.
– Calcium carbonate scales can dissolved by using 5-10% HCl.
– Calcium Sulphate scales can be dissolved by adding EDTA
(ethylene diamine tetra acetic acid) with which they form
soluble complex.

• Frequent blow-down operation

58
 Caustic embitterment
❖Formed by highly alkaline water in the boiler.

❖Excess sodium carbonate (Lime soda process) used up for removing hardness
can also result in the formation of NaOH in high pressure boilers.

❖NaOH has better mobility and can percolate into fine cracks present in boiler
walls.
Na2CO3 + H2O → 2 NaOH + CO2

❖ NaOH gets concentrated in the fine cracks present in the boiler walls.

❖ A concentration cell corrosion is established between the conc. NaOH and

dilute NaOH solution in contact with boiler walls.

❖ Concentrated NaOH region behaves as anode thus resulting in corrosion of

boiler leading to the formation of sodium ferroate.
59
 Corrosion by Caustic Embrittlement
• Its a kind of boiler corrosion, caused by using highly
alkaline water in the boiler
Na2CO3 + H2O 2NaOH +CO2

Minute cracks – present in boilers

Water evaporates – dissolved caustic soda concentration increases
progressively
This causes embrittlement of
boiler parts particularly
stressed parts (bends,
joints, rivets, etc.)

Sodium Ferrate
ANODE CATHODE

Iron at Conc. Dil. Iron at

stressed NaOH NaOH plane
parts solution solution surfaces
60
 Caustic embrittlement can be avoided
•By using sodium phosphate as softening reagent instead of
sodium carbonate

•By adding tannin or lignin to the boiler water which block

the hair cracks and pits

•By adding sodium sulphate to boiler water, which also blocks

the hair cracks and pits

[Na2SO4] 1:1 2:1 3:1

[NaOH] 10 atm 20 atm >20

atm
Lignin – derived from
wood
 Priming and foaming
Foaming
It is the production of continuous foam or
hard bubblers in boilers. Foaming is due to
the presence of substance like oil in
boiling water.
Foaming
Normal bubble
Priming
It is the process in which some particles
in water are carried along with the
steam. The resulting process is called as
wet steam or carry over. The process of
formation of wet steam in boilers is
called as priming.
Priming
Carry over bubble
Priming can be avoided by Causes of Priming
Fitting mechanical steam
purifier 1. Presence of dissolved salts
avoid rapid change in steaming rate
2. High velocity steam due to
Foaming can be avoided by sudden boiling
Removing oil from boiler water
by adding compounds like sodium 3. Improper boiler design 63
aluminate
 Boiler corrosion

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

chemical or electrochemical attack of dissolved gases or salts
is called boiler corrosion

Three major causes of boiler corrosion are

1. Corrosion due to dissolved O2
2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts

64
 Dissolved oxygen – a nuisance for boiler
material

Dissolved oxygen in water at high temperature attack boiler material.

Fe + H2O + ½ O2 Fe(OH)2

Fe(OH)2 + O2 [Fe2O3.nH2O]
(Ferrous hydroxide) (Rust)

Removal of DO – Chemical method

By adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide

Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4
 Removal of DO – By mechanical deaeration
Water feed

It comprises of a tall stainless

tower with different layers capped
with baffles to facilitate multiple
O2 To vacuum
equilibration.

The entire chamber is Steam jacket

vacuumized and also maintained
at high tempt using perforated
heating plates on the walls.
Perforated plate
Principle: High T and low P
favors lower solubility of
gases in water (Henry’s and
Deaerated water
dalton’s law)
 Dissolved Carbon dioxide
H2CO3 is carbonic acid which has corrosive effect on the boiler material

Removal of CO2
By adding calculated quantity of ammonia

2NH4OH + CO2 (NH4)2CO3 + H2O

Acids from Dissolved Salts

Water containing dissolved magnesium salts liberate acids on hydrolysis
MgCl2 + 2H2O Mg(OH)2 + 2HCl
The liberated acid reacts with iron of the boiler in chain-like reactions
producing HCl again and again. As a result presence of even a small
amount of MgCl2 will cause corrosion of iron to a large extent.

Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl 67
 Prevention of scale formation
• External Treatment
– The treatment includes efficient ‘softening of water’
– Removing hardness-producing constituents of
water

• Internal Treatment

– Phosphate conditioning
– Calgon conditioning

68
 Prevention of scale formation
Internal Treatment

In this process, an ion is prohibited to exhibit its original

character by ‘Complexing’ or converting into other more stable
salt by adding appropriate reagent.
Internal conditioning methods to prevent scale formation

1. Phosphate conditioning – addition of phosphate compound

2. Carbonate conditioning – addition of carbonate compound

3. Calgon conditioning – addition of sodium hexa meta

phosphate

4. Colloidal conditioning – spreading of organic compounds

like tannin, agar gel

5. Sodium Aluminate – removes oil, Mg salts and silica

6. Complexometric method – using EDTA

1. Phosphate conditioning – For High-Pressure boilers

Scale formation can be prevented by adding sodium

phosphate to the boiler water which reacts with the hardness
producing ions and forms easily removable phosphate salts
of respective ions

3CaCl2 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

Calcium Sodium calcium phosphate
chloride phosphate (non adherent and can be
removed by blow down method)
pH
Na3PO4 (Alkaline)
Optimum pH to precipitate Ca
is pH 9.5 – 10.5 Na2HPO4 (Weakly alkaline)
NaH2PO4 (Acidic)
71
 2. Carbonate conditioning

CaSO4 (Boiler water) + Na2CO3 CaCO3 + Na2SO4

Calcium Sodium calcium
sulfate carbonate carbonate
(non adherent
loose and soft
ppt and can be
removed by
blow down
method)

Caution: Excess Na2CO3 can result in caustic embrittlement

72
 3. Calgon conditioning

Na2[Na4(PO3) 6 ] 2Na+ + [Na4(PO3) 6]2-

Calgon – sodium hexa meta phosphate

2CaSO4 (Boiler water) + [Na4(PO3) 6]2- [Ca2(PO3) 6]2- + 2Na2SO4

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

Calgon tablets are used in the cleaning of

washing machine drums

73
Module 1– Numerical Problems

Dr. M. Akhila Maheswari

HOW TO EXPRESS HARDNESS OF
WATER ?
 CaCO3 equivalent hardness

Mass of hardness X Molecular

producing substance weight of CaCO3
Calcium carbonate equivalent =
Molecular weight of hardness producing
substances
Problem 1
Calculate the calcium carbonate equivalent hardness of a water sample containing
204mg of CaSO4 per litre

Solution :
204 X 100
Calcium carbonate equivalent hardness = = 150 mg of CaCO3/L
136
= 150 ppm

Note : Mol. Weight of CaCO3 = 100

Mol. Weight of CaSO4 = 136

3
 Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO3 equivalence hardness causing substance present in 106
parts of water

• Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 equivalence hardness causing substance present in one
liter of water

1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm

• Clare's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water

• Degrees French (oFr)

1o Fr = 1 part of CaCO3 eq per 105 parts of water 4
1oFr = 1 part of CaCO3 equivalent hardness per 105 parts
1 ppm = 1 part per 10,00,000 parts of water
1o cl = 1 part per 70,000 parts of water

1 ppm = 0.07 o cl = 0.1o Fr Problem:

If the hardness of water is 210.5 ppm
1 o cl = 1.42o Fr = 14.2 ppm Calculate its hardness in o cl.
1 ppm = 0.07 o cl
1 o Fr = 0.7 o cl = 10 ppm 210.5 ppm = 0. 07 × 210.5
= 14.735o cl
Calcium carbonate equivalence conversion during hardness
calculation

Hardness Molecular Multiplication factor

producing weight (in terms of CaCO3
substance equivalence)
Ca(HCO3)2 162 100/162 or 50/81
Mg(HCO3)2 146 100/146 or 50/73
CaSO4 136 100/136 or 50/68
CaCl2 111 100/111 or 50/55.5
MgSO4 120 100/120 or 50/60
MgCl2 95 100/95 or 50/47.5
CaCO3 100 100/100 or 50/50
MgCO3 84 100/84 or 50/42
CO2 44 100/44 or 50/22
HCO-3 61 100/61 or 50/61
OH- 17 100/17 or 50/17
CO32- 60 100/60 or 50/30

6
 Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, Ca(HCO3)2 = 20 ppm, MgSO4
=24.0mg/L and KOH = 1 ppm. Calculate the temporary, permanent and total
hardness of the water sample.

Solution
Step 1 conversion in to CaCO3 equivalent

Constituent quantity Conversion Hardness

present factor
Mg(HCO3)2 16.8 mg/L 100/146 16.8 *100/146 = 11.5ppm
MgCl2 19.0 mg/L 100/95 19.0*100/95 = 20ppm
20.0*100/162 = 12.3 ppm
Ca(HCO3)2 20 ppm 100/162
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculation

Temp. Hardness = 23.8 ppm P. Hardness = 40 ppm

Tot. Hardness =63.8 ppm

7
Example 1. How many grams of FeSO4 dissolved per litre gives 210.5 ppm of
hardness?
(Fe = 56, S = 32, O = 16, Ca = 40, C = 12).

Solution. FeSO4 = CaCO3

(56 + 32 + 64 = 152g) =100g
100 ppm of hardness = 152 ppm of FeSO4

210.5 ppm of hardness = 152 × 210.5 = 319.9 ppm of FeSO4

100
= 319.9 mg/L or 0.319 g/L of FeSO4
Example 2. Calculate the temporary hardness and permanent hardness of a sample water
containing Mg(HCO3)2 = 7.3 mg/L ; Ca(HCO3)2 = 16.2 mg/L ; MgCl2 = 9.5 mg/L; CaSO4 =
13.6 mg/L (atomic weight of Mg and Ca are 24 and 40 respectively, Cl and S are 35.45
and 32 respectively)

Solution: Conversion into CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 7.3mg/L 100/146 7.3 × 100/146 = 5mg/L

Ca(HCO3)2 = 16.2mg/L 100/162 16.2 × 100/162 = 10mg/L

MgCl2 = 9.5mg/L 100/95 9.5 × 100/95 = 10 mg/L

CaSO4 = 13.6/L 100/136 13.6 × 100/136 = 10mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (5 + 10) mg/L = 15 mg/L or 15 ppm

Permanent hardness, due to MgCl2 and CaSO4

= (10 + 10) mg/L= 20mg/L or 20 ppm

Total hardness = Temporary hardness + Permanent hardness

Example 3. Calculate the temporary hardness and total hardness of a sample water containing
Mg(HCO3)2 = 73 mg/L ; Ca(HCO3)2 = 162 mg/L ; MgCl2 = 95 mg/L; CaSO4 = 136 mg/L (atomic weight of
Mg and Ca are 24 and 40 respectively, Cl and S are 35.45 and 32 respectively)

Solution: Calculation of CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 73mg/L 100/146 73 × 100/146 = 50mg/L

Ca(HCO3)2 = 162mg/L 100/162 162 × 100/162 = 100mg/L

MgCl2 = 95mg/L 100/95 95 × 100/95 = 100 mg/L

CaSO4 = 136/L 100/136 136 × 100/136 = 100mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (50 + 100) mg/L = 150 mg/L or 150 ppm

Total hardness, = (50 + 100 + 100+100) mg/L= 350 mg/L or 350 ppm

Permanent hardness = Total hardness - Temporary hardness

 Sample problems for EDTA method
1. 0.5 g of CaCO3 was dissolved in HCl and the solution made up to 500 ml with
distilled water. 50 ml of the solution required 48 ml of EDTA solution for
titration. 50 ml of hard water sample req. 15 ml EDTA and after boiling and
filtering req. 10 ml of EDTA solution calculate the hardness.

1 ml of standard hard water contain 1 mg of CaCO3

50 ml of standard hard water contain 50 mg of CaCO3

50 ml of standard hard water consumes 48 ml of EDTA (V1)

48 ml of EDTA = 50 mg of CaCO3 equivalent hardness

1 ml of EDTA = 50 mg of CaCO3 equivalent hardness
= 50 mg of CaCO3 equivalent hardness
48

11
Calculation of total hardness:
50 ml of water sample consumes 15 ml of EDTA (V2)

Total Hardness = (15/48) x 1000 x 1 mg of CaCO3

= 312.5 ppm

Permanent hardness: (non – carbonate hardness)

50ml of water sample = 10 ml of EDTA (V3)

Permanent Hardness = (10/48) x 1000 x 1 mg of CaCO3

= 208.4 ppm

Temporary Hardness (1L) = Total hardness – Permanent hardness

= 312.5 – 208.4 = 104.1 ppm

12
2. In an EDTA titration, 50 ml of standard hard (1mg CaCO3 in 1ml) water sample consumed
25 ml of EDTA, 50 ml of hard water sample consumed 35 ml of EDTA and the 50ml
sample hard water (after boiling, cooling and filtering) required 10ml EDTA . Calculate
the permanent and temporary hardness of the given water sample.

1 mL std. hardwater = 1mg CaCO3

50 mL std. hardwater = 25 mL EDTA (V1)

Therefore, 1 mL EDTA = (50/25) x 1mg CaCO3

50 ml of hard water = 35 ml of EDTA (V2)

1000 mL of hardwater contains = ( 35/25) x 1000 x 1mg CaCO3
Total hardness = 1400 ppm

After boiling, EDTA consumed = 10 mL

50 mL of sample hardwater = 10 mL of EDTA (V3)
1000 mL of hardwater after boiling contains = (10/25) x 1000 x 1mg CaCO3
Permanent hardness = 400 ppm

Therefore, temp. hardness = 1400 - 400 = 1000 ppm

13
3. Calculate Total, Temporary and Permanent hardness of the given hard water sample with
following analysis report:-
[i] 50 mL of standard hard water sample consume 42 mL of EDTA solution.
[ii] 50 mL of hard water sample consume 19.9 mL of EDTA solution before boiling.
[iii] 50 mL of hard water sample consume 8.9 mL of EDTA solution after boiling.
Standard hard water is prepared by dissolving 1.5 gram of CaCO3 per Litre.

Solution:
1mL of SHW contains 1.5mg of CaCO3
[i] total hardness: 710.7 ppm
[ii] permanent hardness: 317.8 ppm
[iii] Temporary hardness: 392.9

14
 CHY 1701
Engineering Chemistry

Module 2-Water Treatment

(Part A)

Dr. M. Akhila Maheswari

1. Phosphate conditioning – For High-Pressure boilers

Scale formation can be prevented by adding sodium

phosphate to the boiler water which reacts with the hardness
producing ions and forms easily removable phosphate salts
of respective ions

3CaCl2 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

Calcium Sodium calcium phosphate
chloride phosphate (non adherent and can be
removed by blow down method)
pH
Na3PO4 (Alkaline)
Optimum pH to precipitate
Ca is pH 9.5 – 10.5 Na2HPO4 (Weakly alkaline)
NaH2PO4 (Acidic)
2
 2. Carbonate conditioning

CaSO4 (Boiler water) + Na2CO3 CaCO3 + Na2SO4

Calcium Sodium calcium carbonate
sulfate carbonate
(non adherent loose and
soft ppt and can be
removed by blow down
method)

Caution: Excess Na2CO3 can result in caustic embrittlement

3
 3. Calgon conditioning

Na2[Na4(PO3) 6 ] 2Na+ + [Na4(PO3) 6]2-

Calgon – sodium hexa meta phosphate

2CaSO4 (Boiler water) + [Na4(PO3) 6]2- [Ca2(PO3) 6]2- + 2Na2SO4

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

Calgon tablets are used in the

cleaning of washing machine drums

4
Softening of hard water –
External treatment

5
 External treatment of water – External
Conditioning of water

Softening methods
The process of removing the hardness producing substance
from the water is called softening of water.

Softening of hard water can be done by the following methods

1. Lime soda process
2. Zeolite methods
3. Ion exchange resin method
4. Mixed bed deionizer method

6
 1. Lime-Soda process
Soluble calcium and magnesium salts in water are chemically converted
into insoluble compounds by adding calculated amount of lime
[Ca(OH)2] and Soda [Na2CO3].
Calcium carbonate [CaCO3] and Magnesium hydroxide [Mg(OH)2] so
precipitated, are filtered off.

It is further divided in to two types

i. Cold lime soda process
ii. Hot lime soda process

7
 Cold lime soda process

Step 1
1. A calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are mixed
with water at room temperature and added to the hard water.
2. The following reactions takes place depending on the nature of
hardness

Chemical reactions
If it is permanent hardness and due to calcium salt
CaCl2 + Na2CO3 CaCO3 + 2NaCl (soda) …S
slimy suspended precipitate

CaSO4 + Na2CO3 CaCO3 + Na2SO4 (soda) …S

slimy suspended precipitate

If it is permanent hardness and due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime) ….L
slimy suspended precipitate
Chemical reactions contd..

If it is Temporary hardness and due to calcium salt

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O (lime) …..L
slimy suspended precipitate

If it is due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O (2 *lime)….. 2L
slimy suspended precipitates
 Cold lime soda process

Step 2

The precipitates CaCO3 and Mg(OH)2 are very fine and forms sludge like
precipitates in the boiler water and are difficult to remove because it
does not settle easily making it difficult to filter and the removal
process. Finally reduces the efficiency of the boiler.

Therefore, it is essential to add small amount of coagulant (such as

Alum, Aluminium sulfate, sodium aluminate etc) which hydrolyses to
flocculent precipitate of Al(OH)3 which entraps the fine precipitates.

NOTE: Particles finer than 0.1 µm (10-7m) in water remain continuously in motion due to
electrostatic charge (often negative) which causes them to repel each other. Once their
electrostatic charge is neutralized by the use of coagulant chemical, the finer particles start to
10
collide and agglomerate (combine together) under the influence of Van der Waals's forces. These
larger and heavier particles are called flocs.
Reactions with coagulants

When coagulants are added flocculation takes place followed

by the formation of flocculants.
NaAlO2 + 2H2O NaOH + Al(OH)3
Coagulant
Flocculent- Gelatinous precipitate
which entraps the fine precipitates
of CaCO3 and Mg(OH)2

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

Aluminium Hard water
sulfate sample

The Al(OH)3 formed by the addition of coagulants initiates the

process of flocculation and entraps the fine precipitates and
becomes heavy. The heavier flocs then settles at the bottom and
filtered off easily.
Cold lime-soda process
• Occurring at room temperature

• precipitate formed are finely divided

hence do not settle down easily

• It is essential to add small amount of

coagulant (alum, sodium aluminate)

• Coagulant hydrolyse to form

gelatinous ppt. and entraps the fine
ppt.

• NaAlO2 + H2O→ NaOH + Al(OH)3

• It provides water with a residual

hardness of 50 to 60 ppm

Al2(SO4)3+3Ca(HCO3)2 →2Al(OH)3+3CaSO4+6CO2
12
 Continuous cold lime soda softener

Chemicals Hard water feed

(soda+lime+
coagulant) feed Softened
water
Wood fiber
porous filter

Stirrer
paddles

Sedimented sludge
CaCO3, Mg(OH)2
13
 2. Hot lime soda Process

Similar to Cold lime soda process.

Temperature is maintained at 80-110oC.
No need of coagulants.

Advantages of Hot Lime Soda Process

1. The reaction between hardness producing substance and lime soda

proceeds at a faster rate – Softening rate faster.
2. The precipitates and sludges formed are settled at the bottom easily -
No coagulants are required.
3. The dissolved gases such as CO2 escapes and the water becomes free
from dissolved gases.
4. It produces soft water with the residual hardness of 15-30ppm in
contrast to the cold lime soda process which produces soft water with
50-60ppm of residual hardness.
5. Filtration process is simple.

14
 Continuous Hot Lime 1. Reaction tank: water, chemicals and
steam are mixed
soda Process
2. Conical sedimentation tank : sludge
Hard water feed settles down
3. Sand filter : complete removal of
sludge from the soft water is ensured
Super heated steam
Chemicals feed (lime
and soda)

Reaction tank
Soft water

Conical sedimentation
tank

Precipitated sludge
(CaCO3, Mg(OH)2 Sludge
outlet

Filtered soft
water

15
16
Advantages of Lime soda process
1. It is very economical compared to other methods.
2. Iron and manganese salts are also removed by this process.
3. It increases the pH of the softened water hence corrosion is
minimized also pathogenic bacteria.

Disadvantages of Lime soda process

1. Disposal of large amount of sludge (insoluble precipitates)

poses a problem.
2. This can remove hardness to the extent of 15ppm which is
not good for boilers.

18
Rules
1. If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca2+ + 2HCO3-) and (Mg2+ +
2HCO3-) respectively then the calculation result will be the same based on the
ability of the ions to take up bicarbonate ions
2. If treated water found to contain excess of OH- and CO32- ions these are formed
from excess equivalent each of Ca(OH)2 and Na2CO3 and hence these excess
amounts should be added to the calculation (in temp. hardness and perm.
hardness)
3. When the impurities are given as CaCO3 and MgCO3 present in water it should
be considered as due to bicarbonates of calcium and magnesium respectively
4. Substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc do not contribute to
hardness and therefore, they do not consume any soda or lime and hence if
these present need not be taken in to consideration during calculation.
5. Soda (Na2CO3) neutralizes only permanent hardness

Molecular weight of lime = 74

Molecular weight of soda = 106
Molecular weight of CaCO3 = 100

Therefore, 100 parts by mass of CaCO3 are equivalent to

(i) 74 parts by mass of Ca(OH)2
(ii) 106 parts by mass of Na2CO3 19
Calculation of lime and soda required for the softening of hard water by the
lime soda process

Hardness producing Chemical reaction with lime and soda Need

substance

Permanent Hardness
Ca Salts CaCl2 + Na2CO3 CaCO3 + 2NaCl S

Mg salts MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L+S

CaSO4 + Na2CO3 CaCO3 +Na2SO4

Temp. Hardness
Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O L
Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O 2L

Acids
HCl 2H+ + Ca(OH)2 Ca2+ + 2H2O L+S
H2SO4 Ca2+ + Na2CO3 CaCO3 + 2Na+

HCO3- HCO3- + Ca(OH)2 CaCO3 + H2O + CO32- L-S

Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+

FeSO4 Ca2+ + Na2CO3 CaCO3 + 2Na+ L+S

NaAlO2 NaAlO2 + H2O Al(OH)3 + NaOH

L/2
20
Calculation of Lime and Soda requirements to soften water

All in terms of CaCO3 eq

X Volume of water

21
Lime Soda Process - Reactions of Lime and Soda

L+S

L-S

2L
22
 L

L+S

L+S

23
O

L+S

-L

24
 Lime-soda treatment is very slow – super saturated solution – results “after deposition”
- form sludge
- corrosion
Removed: - thorough mixing
- accelerators – bring down the particles of precipitates (activated charcoal)
- Coagulants

Ca(HCO3)2 and Mg(HCO3)2 - calculation results will be the same

Ca2+ + 2HCO3-

If the treated water contains OH- and CO32- due to excess of Ca(OH)2 and Na2CO3
- account to the calculations

NaCl, KCl, Na2SO4, SiO2, Fe2O3 – do not impart any hardness

- do not consume any lime or soda
- do not account for calculating lime or soda requirement
Dissolved Salt/ion Molar Mass MF for eq. CaCO3
Ca(HCO3)2 162 100/162
Mg(HCO3)2 146 100/146
CaSO4 136 100/136
MgSO4 120 100/120
MgCl2 95 100/95
MgCO3 84 100/84
CO2 44 100/44
Ca(NO3)2 164 100/164
Mg(NO3)2 148 100/148
HCO3- 61 100/(61x2) 100/122
OH- 17 100/(17x2) 100/34
CO32- 60 100/60
NaAlO2 82 100/(82x2) 100/164
Al2(SO4)3 342 100/(342/3) 100/114
FeSO4.7H2O 278 100/278
H+ 1 100/(1x2) 100/2
HCl 36.5 100/(36.5x2) 100/73
Zeolite process
Zeolite – Sodium Aluminosilicate

Na+

28
 Zeolite (Permutit) method of Softening of water

Zeolite is a Hydrated Sodium Alumino

Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.

The general chemical structure of zeolite is

given below Na2O.Al2O3.xSiO2.yH2O (x = 2-10
and y = 2-6)

Micro pores of Zeolite Porous Structure of zeolite

❖ Porosity or cavity size of synthetic zeolite structures can be

controlled by varying the Si/Al ratio
❖ Ion-exchange process of zeolite structure is associated with sodium ions
29
Zeolite – Sodium Aluminosilicate

Na+

30
Why synthetic zeolite is better than natural zeolite for the
softening of water? Ans: Natural zeolites are non-porous
Natural Zeolite

Natrolite

32
 Hard water
in

Hard water
spray

Zeolite bed

Gravel

Injector

Softened
NaCl To water
storage sink

33
10% NaCl - brine
35
36
 Limitations and disadvantages of Zeolite process

1. If the water is turbid ---- the turbidity causing particles clogs the pores
of the Zeolite and making it inactive.
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can
not be regenerated that easily as both metal ions bind strongly and
irreversibly to the zeolite structure.
3. Any acid present in water (acidic water) should be neutralized with soda
before letting the water to the plant, since acid will hydrolyze SiO2
forming silicic acid.
4. Soft water contains more sodium salts than in lime soda process.
5. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like
HCO3- and CO32- in the softened water (then it may form NaHCO3 and
Na2CO3 which releases CO2 when the water is boiled and causes
corrosion).
6. It also causes caustic embitterment when sodium carbonate hydrolyses
37
to give NaOH.
38
Cation Resin after
exchange Resin treatment

Ion exchange resin

39
• Ion-exchange resins are insoluble, cross-linked, long chain
organic polymers with a micro-porous structure and the
functional groups attached to the groups are responsible for
the ion-exchanging properties.

40
 ¯H+
SO3¯H+
SO3
RH+

¯H+ SO3¯H+
SO3

Styrene-divinyl benzene copolymers, which on sulphonation or

carboxylation, become capable to exchange their hydrogen ions with
the cations in the water

41
 ROH-

Styrene-divinyl benzene or amine-formaldehyde copolymers, which

contain amino or quaternary ammonium or quaternary phophonium or
tertiary sulphonium groups as an integral part of the resin matrix.
These after treatment with dil. NaOH solution capable to exchange their
OH¯ ions with the anions in the water
42
Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

R = CH3

43
H2O

44
 Ion exchange purifier or softener
Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Acid
solution for Wastages to
regeneratio sink Alkaline solution for
n of resin Wastages to
regeneration of resin
sink
pump

Soft water 45
Hard water in

Soft Water Out

46
 Regeneration of cation exchange column

Regeneration of anion exchange column

Advantage

• The process can be used to soften highly acidic or alkaline water

• it produces water of very low hardness (2 ppm)

Disadvantage

• The equipment is costly and more expensive chemical are needed

• If the water contains turbidity then the output of the process is

reduced
47
 Softening of water by Mixed Bed deioniser
1. It is a single cylindrical chamber containing a mixture of anion and cation
exchange resins bed
2. When the hard water is passed through this bed slowly the cations and anions
of the hard water comes in to contact with the two kind of resins many number
of times
3. Hence, it is equivalent to passing the hard water many number of times
through a series of cation and anion exchange resins.
4. The soft water from this method contains less than 1ppm of dissolved salts
and hence more suitable for boilers

Hard
water

c a c a Anion
c Mixed bed exchange
Mixed
a deionizer a resin
resin bed
a
c a cc Cation
exchange
resin

Demineralise
d water
48
 Regeneration of mixed bed deionizer
1. When the bed (resins) are exhausted or cease to soften the water, the mixed bed is
back washed by forcing the water from the bottom in the upward direction
2. Then the light weight anion exchanger move to the top and forms a upper layer
above the heavier cation exchanger
3. Then the anion exchanger is regenerated by passing caustic soda solution (NaOH)
from the top and then rinsed with pure water
4. The lower cation exchanger bed is then washed with dil.H2SO4 solution and then
rinsed.
5. The two beds are then mixed again by forcing compressed air to mix both and the
resins are now ready for use Low
NaOH
density
resin

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

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

Back Compressed
wash High air
water density
49
resin
The outgoing water from the mixed-bed contains even less than 1 ppm
of dissolved salts

50
 CHY 1701
Engineering Chemistry
Module 2 – Part B

Dr. M. Akhila Maheswari

“Millions of people will die each year from dirty water and water-related
diseases.”
Chairman of the World Commission on
Water for the 21st Century

“Water, this most precious commodity, is in

peril in virtually all parts of the globe.”
Marq De Villiers

2
 Drinking water or Municipal water
Should satisfy the following requirements

4
 Treatment of Municipal Drinking Water
• Screening – to remove floating matters
• Aeration – to remove BOD and improve taste of
water
• Sedimentation & Coagulation – this is done after
chemical treatment (using lime-soda)
• Filtration – Gravity (or) Pressure sand filters
• Sterilization and disinfection – Chlorination, UV
treatment and Ozonolysis
• Storage and distribution

5
6
Coagulant (Alum or Ferrous sulphate)
When added to water, forms an insoluble gelatinous,
flocculant precipitate, which descent through water, adsorbs and
entangles very fine suspended impurities forming bigger flocs, which
settle down easily

7
8
 MgSO4 + 2CO2

FeSO4 + Mg(HCO3)2 → Fe(OH)2 + MgSO4 + 2CO2

9
10
 Removal of micro-organisms

1. Contains the small percentage of pathogenic bacteria –

disease producing
2. Drinking water must be freed from pathogenic bacteria and
micro-organisms
3. The process of destroying /killing the disease producing
bacteria, micro-organism in drinking water is called
disinfection
4. The chemicals or substances – added to water for killing the
bacteria – disinfectants
Disinfection of water – methods:
1. By boiling
2. By adding bleaching powder
3. By chlorination
4. By using chloramine
5. By ozone
• By boiling water for 10-15 min. (only at home not in municipal
process)

-kill only existing germs in water at the time of boiling

-does not provide any protection against future possible

contamination

- very costly

- impossible to employ this in the large scale systems

13
By adding bleaching powder (Municipal
treatment)
About 1kg of bleaching powder per 1000 kiloliters of water is
mixed
Produces hypochlorous acid (powerful germicide)

CaOCl2 + H2O → Ca(OH)2 + Cl2

Cl2 + H2O → HCl + HOCl
Germs + HOCl → Germs are killed

Disadvantages
Introduces Calcium in water, thereby making it more hard

Disintegrates during storage – analyze the chlorine content

Excess of it gives a bad taste and smell to treated water

Chlorination (Municipal treatment)
– Chlorine (either gas or in concentrated solution form)
produces hypochlorous acid, which is a powerful
germicide

Cl2 + H2O HCl + HOCl

Germs + HOCl Germs are killed

Mechanism of Action:
Disinfecting action of Chlorine – nascent oxygen liberated –
oxidizes harmful bacteria
Chemical reaction of HOCl with enzymes – inactivation of enzyme
Enzyme – essential for metabolic processes of the micro-organism

15
Factors affecting efficiency of chlorine
1. Number of micro-organism destroyed by chlorine per unit
time is proportional to the number of micro-organism alive.
2. The rate of reaction with enzymes increases with
temperature.
3. pH values between 5.0 - 6.5, less contact time is enough.

HOCl ↔H+ + OCl-

HOCl is more destructive than OCl-

Advantages
(i) Effective and economical (ii) used low as well as high temp
(iii) most ideal
Disadvantages
(i) should not exceed 0.1 – 0.2 ppm (ii) less effective in higher
pH values (iii) excess chlorine produces unpleasant taste and
odour.
 Break point chlorination or free-residual
chlorination
Involves addition of sufficient amount of chlorine to
oxidize
organic matters,
reducing substances,
free ammonia
Need?
free chlorine to kill bacteria

The addition of chlorine at the dip or break, wherein

the free chlorine is available to kill bacteria is called
break-point chlorination

The point at which free residual chlorine begins to

appear 18
Advantages of Break Point:
-Oxidizes completely organic compounds – remove the color – organic matters
-100% destroys disease producing bacteria
-Removes both odor and taste from the water
De-chlorination:
Over chlorination after the break point
Produces unpleasant taste and smell
Removed through addition of sulphur dioxide or sodium
sulphite
SO2+Cl2 + 2H2O → H2SO4 + 2HCl
Na2SO3 + Cl2 + H2O → Na2SO4 + 2HCL
 Chloramine (ClNH2)

Cl2 + NH3 ClNH2 + HCl

(Chloroamine)

ClNH2 + H2O HOCl + NH3

(Disinfectant)

The best chlorinating way: why?

• Stable than chlorine alone
• Better disinfectant – excess does not produce irritating
taste or smell
• Imparts a good taste to treated water

21
 Disinfection by ozone

3O2 2O3

O3 O2 + [O.]
Nascent oxygen

It is produced by passing silent electric discharge through cold

and dry oxygen
It is highly unstable and breaks down, liberates nascent
oxygent
This method is quite expensive – can not employed for
disinfection of domestic water supply
 UV treatment
• Disinfection of Drinking Water with Ultraviolet Light

23
 UV - Sterilizer
UV radiation
• Low pressure and medium pressure UV lamps are available
• reacts primarily with nucleic acids: pyrimidine dimers and
other alterations
Primary uses:
Primary physical disinfectant

24
Advantages of UV Disinfection:
• Highly effective on broad range of pathogens
• Forms no harmful disinfection by-products
• Inactivation independent of pH and temperature
• No unpleasant taste or odor
• No transportation, storage or handling of chemicals
• Easily installed within existing water treatment facilities
• Low capital and operating costs – only small scale systems
• Simple to operate
• Minimal hazard risk for operators

Limitations

• Limited experience and data with large flows.

• Water with high concentrations of iron, calcium, turbidity, and phenols
25
Membrane Technology for Water Treatment

26
 Membrane Filtration
– Physical separation process
What is filtration?
Filtration is a process of removing particulate matter from
water by forcing the water through a porous media. This
porous media can be natural, in the case of sand, gravel and
clay, or it can be a membrane wall made of various materials.

- Membrane materials
• Organic polymers
• Inorganic materials such as ceramic, glass or metal

Membranes made of organic polymers are dominating the market

27
Polymeric membranes:
Synthetic organic polymeric membranes can divided into two
classes
i.e., hydrophobic and hydrophilic.
Hydrophilic polymers such as
cellulose and its derivatives
Hydrophobic membranes such as
polytetrafluoroethylene (PTFE),
polyvinylidene fluoride (PVDF),
polyethylene (PE), or polypropylene (PP)
Polyacrylonitrile (PAN)
Polysulfone
28
Types of membranes - Membrane Configurations
The principal types of membranes are:
1. Tubular Modules

2. Hollow Fiber

3. Spiral Wound Modules

Spiral-Wound Membranes 29
 Pressure Membrane Processes

• Microfiltration (MF), which can remove particles ranging in size

from 10-100 μm. It is operated in the pressure range of 10 psig.

• Ultrafiltration (UF), which can remove particles ranging in size

from 0.01 to 10 μm. It is operated in the pressure range of 15 psig.

• Nanofiltration (NF), which can remove particles size from 0.001

μm to 0.01 μm. It is operated in the pressure range of 75-250 psig.

• Reverse osmosis (RO), which can remove particles in the size

range of 0.1-1.0 nm. It operates in the pressure range of 200-1200
psig.
30
 Brackish Water
The water containing dissolved salts with a peculiar salty taste –
Salt Water

Desalination of Brackish Water

The process of removing common salt from water

• Electrodialysis
• Reverse osmosis (Pressure membrane
process)
 Reverse osmosis
• Reverse osmosis filters have a pore size around 0.0001 micron
• After water passes through a reverse osmosis filter, it is
essentially pure water
• In addition to removing all organic molecules and viruses,
reverse osmosis also removes most minerals that are present
in the water
• Reverse osmosis removes monovalent ions, which means that
it desalinates the water

32
 Principle - Reverse osmosis
❖ When two solutions of unequal concentration are separated by a semi-
permeable membrane, flow of solvent takes place from dilute to concentration
side, due to increase in osmostic pressure, which is termed as osmosis.
❖ However, when a hydrostatic pressure in excess of osmotic pressure is applied
on the concentrated side, the solvent flow is reversed from concentrated side to
dilute side, across the membrane. This principle is termed as reverse osmosis.
❖ The semi-permeable membrane (in reverse osmosis) is selective in not
permitting the passage of dissolved solute particles such as molecules, ions, etc.)
It permits only the flow of water molecules (solvent) from the concentrated to
dilute side.
❖ Cellulose acetate, polyamide, etc., are used as membrane
❖ Reverse osmosis process requires only mechanical force to generate the
required hydrostatic pressure.
❖ Hydrostatic pressure generated is in the order of 15-40 Kg m-2

33
34
 Principle of osmosis and reverse osmosis

• When two solutions of unequal concentrations are separated by

a semipermeable membrane, solvent will flow from lower
concentration to higher concentration
• This phenomenon can be reversed (solvent flow reversed) by
applying hydrostatic pressure on the concentrated side
36
Osmosis Reverse Osmosis

Hydrostatic pressure in excess

of osmotic pressure is applied,
the solvent flow reverses ➢Cellulose acetate
➢Polysulfone
➢Polysulfone amide
➢Polyamide
➢Poly-acrylonitrile
Reverse Osmosis

38
Advantages: Reverse
Osmosis

1. Removes ionic, non-ionic, colloidal and high

molecular weight organic matter

2. Removes colloidal silica

3. Low Maintenance cost -Life time (~2 years)

4. Easy membrane replacement

5. Low operating cost, high reliability

Membrane Applications in Water Treatment

• Desalting seawater
• Treating brackish groundwater
• Water softening – hardness removal
• Waste water recovery
• Removing color, odor, and other organic
contaminants

41
 Principle -Electrodialysis
➢ Electrodialysis is an electrochemical process whereby electrically charged
particles, ions, are transported from a raw solution (retentate, diluate) into a
more concentrated solution (permeate, concentrate) through ion-selective
membranes by applying an electric field.

42
 Theory of Electrodialysis
• Electrodialysis chamber comprises of sheet like barriers made out of high-
capacity, highly cross-linked ion exchange membranes that allow passage of
ions but not of water.
• There are two types : (a) Cation exchange and (b) Anion exchange
membranes
• Cation exchange membranes consists of an insoluble matrix and mobile
cation reside in the pore space that allows the pass through of only cations.
• Anion exchange membranes consists of an insoluble matrix and mobile anion
reside in the pore space that allows the pass through of only anions.
• Cation- and Anion- exchange membranes are installed alternatively in the
tank.
• By impressing electricity on the electrodes, the positive anode attracts
negative ions in solution, while the negative cathode attracts positive ions in
the solution.

43
 Module 2

Water softening methods: - Lime-soda, Zeolite and ion

exchange processes and their applications.

Specifications of water for domestic use (ICMR and WHO);

Unit processes involved in water treatment for municipal

supply - Sedimentation with coagulant- Sand Filtration -
chlorination;

Domestic water purification – Candle filtration- activated

carbon filtration; Disinfection methods- Ultrafiltration, UV
treatment, Ozonolysis, Reverse Osmosis; Electro dialysis
 Water Softening methods
• The process of removing the hardness producing substance from the water is
called softening of water
• In Industry three main methods are employed for softening of water
– Lime soda process
– Zeolite (permutit) process
– Ion-exchange and Mixed bed ion-exchange process

Lime-Soda process
Soluble calcium and magnesium salts in water are chemically converted into
insoluble compounds by adding calculated amount of lime [Ca(OH)2] and
Soda [Na2CO3]. Calcium carbonate [CaCO3] and Magnesium hydroxide
[Mg(OH)2] so precipitated, are filtered off.
1. Lime soda
a) Batch process
b) continuous process
- Cold lime-soda
- Hot lime-soda 2
Lime Soda Process - Reactions of Lime and Soda

3
4
5
• Occurring at room temperature

• precipitate formed are finely divided

hence do not settle down easily

• It is essential to add small amount of

coagulant (alum, sodium aluminate)

• Coagulant hydrolyse to form

gelatinous ppt. and entraps the fine
ppt.

• NaAlO2 + H2O NaOH + Al(OH)3

• It provides water with a residual

hardness of 50 to 60 ppm

6
 Hot lime-soda process
Hot lime-soda process consists of three parts:
a) Reaction tank to mix all ingredients
b) Conical sedimentation vessel where the sludge settles down
c) Sand filter where sludge is completely removed

• Occurring at 80 to 150 °C close to the boiling point of the solution

• Reaction proceed faster

• The precipitate and sludge formed settle down rapidly so no coagulant

needed

• Viscosity of the softened water is lower, so filtration of water becomes

much easier

• Produce water contain the residual hardness of 15 to 30 ppm

7
8
9
10
 Advantages & disadvantages of lime-soda process:

Advantages of Lime – soda process:

o Economical
o Process improves the corrosion resistance of water
o Mineral content of water is reduced
o pH of water raises thus reducing content of pathogenic bacteria
o No skilled labour is required

Disadvantages of Lime – soda process:

o Huge amount of sludge is formed and its disposal is difficult
o Due to residual hardness, water is not suitable for high pressure
boilers

11
 Zeolite or Permutit Process
o Zeolite is hydrated sodium aluminium silicate having a general formula,
Na2OAl2O3.xSiO2.yH2O.
o It exchanges Na+ ions for Ca2+ and Mg2+ ions.
o Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith.
o Other gluconites, green sand (iron potassium phyllosilicate with
characteristic green colour, a mineral containing Glauconite)etc. are used
for water softening.
o Artificial zeolite used for water softening is Permutit.
o These are porous, glassy particles having higher softening capacity
compared to green sand.
o They are prepared by heating china clay (hydrated aluminium silicate),
feldspar (KAlSi3O8-NaAlSi3O8 – CaAl2Si2O8) are a group of rock-forming
tectosilicate minerals which make up as much as 60% of the earth’s crust)
and soda ash (Na2CO3)
12
 Natural Zeolite

Natrolite

Artificial Zeolite

China clay Al2Si2O5(OH)4

Feldspars (KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8)

 Zeolite process
o Method of softening:

Na2Ze + Ca(HCO3)2 2 NaHCO3 + CaZe

Na2Ze + Mg(HCO3)2 2 NaHCO3 + MgZe
Na2Ze + CaSO4 Na2SO4 + CaZe
Na2Ze + CaCl2 2 NaCl + CaZe

o Regeneration of Zeolite:

CaZe (or) MgZe + 2 NaCl Na2Ze + CaCl2 or MgCl2

Brine solution

14
Zeolite process equipment diagram
 Zeolite Process

Advantages:
o Residual hardness of water is about 10 ppm only
o Equipment is small and easy to handle
o Time required for softening of water is small
o No sludge formation and the process is clean
o Zeolite can be regenerated easily using brine solution
o Any type of hardness can be removed without any modifications to
the process
Disadvantages:
o Coloured water or water containing suspended impurities cannot be
used without filtration
o Water containing acidic pH cannot be used for softening since acid will
destroy zeolite.

16
 Ion-Exchange Process

 Ion-exchange resins are insoluble, cross-linked, long chain

organic polymers with a microporous structure and the
functional groups attached to the groups are responsible for the
ion-exchanging properties.
o Cation exchange resins will exchange cations with H+.
o Anion exchange resins will exchange anions with OH-.
o Functional groups present are responsible for ion-exchange
properties.
o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for
cations &
o Basic functional groups (-NH2, =NH etc.) exchange OH- for anions.

17
 Ion-Exchange Process
A. Cation-exchange Resins(RH+):
- Styrene divinyl benzene copolymers
- which on sulphonation or carboxylation, become capable to
exchange their hydrogen ions with the cations in the water

¯H SO3¯H
SO3 +
+

SO3 ¯H SO3¯H
+
+

18
 Ion Exchange Process

Styrene-divinyl benzene or amine-formaldehyde copolymers, which contain

amino or quaternary ammonium or quaternary phophonium or tertiary
sulphonium groups as an integral part of the resin matrix. These after
treatment with dil. NaOH solution capable to exchange their OH¯ ions with
the anions in the water
19
 Ion Exchange Process

The Process of Ion-exchange is:

2 RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2 H+ (Cation exchange)

R’OH- + Cl- R’+ Cl- + OH- (anion exchange)

2 R’OH- + SO42- R’2 SO42- + 2 OH- (anion exchange)

2 R’OH- + CO32- R’2 CO32- + 2 OH- (anion exchange)

Finally,
H+ + OH- H2O
Regeneration of exhausted resins:
Saturated resins are regenerated by treating with strong mineral acid or alkali respectively
R2Ca2+/R2Mg2+ + 2H+ 2 RH+ + Ca2+/Mg2+ (Strong acid)
(washings)
R’2 SO42- + 2 OH- 2 R’OH- + SO42- (Strong base)
(washings) 20
 Ion-exchange process

Note: Hard water should be first passed through the cation exchanger and then
Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed
21
22
The outgoing water from the mixed-bed contains even less than 1 ppm of
dissolved salts

23
Mix bed to be regenerated

NaOH wash
R
C
C C
C
RC R R
R C R
H2SO
R
C
R
C

C
R
C

R
C C

R
C
R
C

C C C

R
C
C C C R C C
RCC C C R
R
C

C R R R R
RCC
R
C

R
C
RR C R C RCC

R
C

R
C
R C R C

R
C

R
C
RR

R
C
R R R RR
R
Compressed Air
Back wash water

Forcing with
R
C

C C
C Compressed air
RC R
for mixing
R
C

R
R
R
C
R
C

C
C
R
C

R
C
R C C
C C R
R R
R
C

C C RCC

R
C
C R C

R
C
R
C
RCC
R
C

C R R RR
R
R
C

R RR
After wash it is regenerated
Regenerated Mix bed read for use
 The mixed bed deionizer consist of cation and anion exchange resins
mixed together in a single pressure vessel.
When water is passed through mixed bed it comes in contact, a number
of times, with the two kinds of exchanges alternatively. As a result the net
effect of mixed bed exchanger is equivalent to passing water through a
series of several cation and anion exchangers.
The quality of water obtained from mixed bed is appreciably higher than
the water produced from two bed plants.
Mixed bed exchange produce water with hardness less than 1 ppm

Regeneration:

The mixed bed is back washed by forcing water in the upward direction.
This separate the cation and anion exchanges from the mixed bed. Being
lighter the cation resin occupes upper part and the denser on at the bottom.
Now they layers will be washed with NaOH and H2SO4 respectively to
regenerate anion and cation exchange resins. After regeneration again
they are mixed by forcing compressed air.

Generally soften water (eg RO, etc) will be further purified by this method
25
Advantages & Disadvantages of ion-exchange process
o Advantages:
- Can be used for highly acid and highly alkaline water
- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour

26
Specifications of different materials in drinking water (ICMR and WHO)
S.No. Parameter/Material WHO Standards/ppm ICMR/BIS
Standards/ppm
1 Colour Clear Clear
2 Odour Pleasant Pleasant
3 Turbidity 2.5 2.5
4 pH 6.0 – 8.5 6.0 – 8.5
5 TDS 300 500
6 Total Hardness as CaCO3 200 300

7 Calcium 75 75
8 Chlorides 200 200
9 Sulphates 200 200
10 Fluoride 0.5 1.0
11 Mercury 0.006 0.001
12 Cadmium 0.003 0.01
13 Arsenic 0.01 0.02
14 Chromium as hexavalent 0.01 0.1

15 Lead 0.01 0.01

16 E.Coli No colony Should be present No colony Should be
in 100 mL water present in 100 mL
water
 Water treatment for municipal supply
Removes dirt and other
particles suspended in
water. Alum and other
chemicals are added for
coagulation through floc
Lakes/Reservoirs/
Rivers Storage tanks Coagulation

Multilayer filtration using Heavy particles (floc) settle to

sand, gravel and charcoal the bottom and clear water goes
for filtration
Flocculation &
Filtration Sedimentation Clarification

Calculated amount of
chlorine is added
Storage in
Disinfection closed Supply
containers through
pipelines
Domestic water purification system
Candles
 Activated Carbon Filtration
• Activated carbon filters are generally used in the process of
removing organic compounds and/or extracting free chlorine from
water.
• Coconut shells and coal (anthracite or bituminous) are both
organic sources of activated carbon.

(SiO2)
Working Mechanism in the fabrication of Activated Carbon
• Carbon forms when an organic source is burned in an environment without
oxygen. This process leaves only about 30% of the organic mass intact, driving
off heavy organic molecules.

• Prior to being used for water treatment, the organic mass must then be
"activated by either Steam Activation (800°C-1000°C) or Chemical Activation (a
powerful dehydrating agent like phosphoric acid (P2O5) or zinc chloride
(ZnCl2)."

• The process of activation opens up the carbon’s massive number of pores and
further drives off unwanted molecules. The open pores are what allow the
carbon to capture contaminants, through adsorption.

• The rate of adsorption for a surface area of a just one pound (0.45
kg) of Activated Carbon is equal to 60-150 acres!
 Candle Filtration
The Candle Filters are, like all pressure filters, operating on a batch cycle and may
be seen in process lines handling titanium dioxide, flue gas, brine clarification, red
mud, china clay, fine chemicals and many other applications that require efficient
low moisture cake filtration or high degree of polishing.

The Candle Filter consists of three

major components:
• The vessel
• The filtering elements
• The cake discharge mechanism

• Candle Filters are very well suited for

handling flammable, toxic and
corrosive materials.
 Candle Filtration

• Advantages
• Excellent cake discharge.
• Adapts readily to slurry thickening.
• Minimum floor space.
• Mechanically simple since there are no complex sealing
glands or bearings.
• Disadvantages
• High headroom is required for dismantling the filtering
elements.
• The emptying of the vessel in between cake filtration, washing
and drying requires close monitoring of the pressure inside
the vessel to ensure that the cake holds on to the candles.
 Disinfection Methods
Disinfection methods used for disinfecting water for
drinking purpose are

- Ultrafiltration
- UV treatment
- Ozonolysis
- Reverse Osmosis
 Water purification by Filtration process

The green arrow indicates that the particle is small enough to pass through
the filter, whereas the deflected orange arrow indicates that the filter blocks
the particle from passing through the filter.
 Different filtration processes
A. Ultrafiltration:
o An ultrafiltration filter has a pore size around 0.01 micron.
o A microfiltration filter has a pore size around 0.1 micron, so when water undergoes microfiltration,
many microorganisms are removed, but viruses remain in the water. Ultrafiltration would remove
these larger particles, and may remove some viruses.
o Neither microfiltration nor ultrafiltration can remove dissolved substances unless they are first
adsorbed (with activated carbon) or coagulated (with alum or iron salts).

B. Nanofiltration
o A nanofiltration filter has a pore size around 0.001 micron.
o Nanofiltration removes most organic molecules, nearly all viruses, most of the natural organic
matter and a range of salts.
o Nanofiltration removes divalent ions, which make water hard, so nanofiltration is often used to
soften hard water.

C. Reverse osmosis
o Reverse osmosis filters have a pore size around 0.0001 micron.
o After water passes through a reverse osmosis filter, it is essentially pure water. In addition to
removing all organic molecules and viruses, reverse osmosis also removes most minerals that are
present in the water.
o Reverse osmosis removes monovalent ions, which means that it desalinates the water.
Reverse Osmosis
oWhen two solutions of unequal concentrations are
separated by a Semipermeable membrane, solvent will
flow from lower conc. to higher conc. due to osmotic
pressure

oThis phenomenon can be reversed by making the

solvent to flow in the opposite direction by applying
hydrostatic pressure on the concentrated side (Reverse
Osmosis)

oIn reverse osmosis, pressure of 15-40 kg/cm2 is

applied on the contaminated water compartment.

oThe water gets forced through the semipermeable

membrane leaving behind the dissolved solids.

oThus water is separated from the contaminants rather

than removing contaminants from water.

oBoth ionic and non-ionic impurities as well as colloidal

impurities are left behind.

oThis process is also called as “Super-filtration” or

“Hyper-filtration”
 Advantages of Reverse Osmosis

o Advantage is in removing ionic, non-ionic, colloidal and high molecular

wt. organic matter.

o It removes colloidal silica (which is not removed during

demineralisation)

o Cost is only the replacement cost of membranes (life is 2 years)

o Membrane replacement is fast and hence uninterrupted water supply

can be ensured

o Because of the above reasons this process is being adopted for

converting sea water into potable water and for high pressure boilers.

o It can be used as desalination process for removing salt from sea

water.

40
 Desalination of brackish water

o Water containing dissolved salts with a peculiar salty (brackish) taste is brackish water
o The process of removing common salt from water is desalination

o Electrodialysis consists of a large container with two membrane separators, one

permeable to positive ions and the other permeable to negative ions.

o In the outer compartments anode and cathode are arranged to pass DC Voltage.

o When DC voltage/current is passed through the cell, Na+ will move towards cathode
and Cl- will move towards anode through the membrane.

o Hence, the concentration of salt decreases in the middle compartment and increases
in the side compartments.

o Water from the middle compartment is collected and this water is desalinated water.

41
 Electrodialysis diagram

For efficient separation, ion-selective membranes are used which selectively allow
cations or anions to pass through them.
42
Electrodialysis cell

o Electrodialysis cell consists of

Large number of pairs of
rigid Plastic membranes.

o Saline water at a pressure of

5-6 kg/cm2 is passed
through the membrane pairs.

o DC current is applied
perpendicular to the direction
of water flow.

Advantages are:

1. Unit is compact and

installation is economical

2. Best suited if electricity is

available.
43
Module 2 (Numerical)
Dr. M. Akhila Maheswari
 Numerical on lime-soda process
1. Calculate the amount of lime (74% pure) and soda (95% pure) for the treatment of 70,000 L of water, whose analysis
report is as follows: Ca(HCO3)2 = 40.5 ppm, Mg(HCO3)2 = 39 ppm, MgSO4 = 30 ppm, CaSO4 = 34 ppm, CaCl2 =
27.75ppm, KNO3 = 3 ppm, NaCl = 10 ppm. Also, calculate the temporary and permanent hardness of the water sample
in terms of CaCO3 equiv.

2. Calculate the amount of lime (88.3% pure) and soda (99.2% pure) required to soften 24,000L of water per day in a
year containing the following: Ca(HCO3)2 = 1.85 ppm, Mg(HCO3)2 = 0.42 ppm, MgSO4 = 0,9 ppm, CaSO4 = 0.34
ppm, MgCl2 = 0.76 ppm, NaCl = 2.36 ppm and SiO2 = 2.34 ppm.

3. Calculate the amount of lime and soda (assuming that they are 100% pure) for the treatment of 1,00,000 L of water,
whose analysis report is as follows: Ca(HCO3)2 = 15.3 ppm, Mg(HCO3)2 = 19 ppm, CaSO4 = 24.6 ppm, CaCl2 = 27.75
ppm, MgSO4 = 35 ppm, MgCl2 = 25 ppm, Fe2+ = 30 ppm, Al2(SO4)3 = 16 ppm, NaAlO2 = 16 ppm, Fe2O3 = 3.3 ppm,
KNO3 = 3 ppm, NaCl = 10 ppm. Also, calculate the temporary and permanent hardness of the water sample in terms of
CaCO3 equiv.