MODULE- I

WATER TECHNOLOGY

Dr. RupamSingh
CY1701 ENGG. CHEM.
1
“Without food, human can survive for number of
days, but water is such an essential that without it
one cannot survive”.
“Although water is nature’s most wonderful,
abundant and useful compound yet is also the
most misused one”.

2
Distribution of water

3
 Sources of Water
A) Surface Waters
Rain Water - Pure but contaminated with gases
River Water - High dissolved salts moderate organics
Lake Water - Const. composition but high organics
Sea Water - High salinity, pathogens, organics

B) Underground Waters
Spring/Well Water - Crystal clear but high dissolved
salts and high purity from organics

4
 Classification of Impurities in water
 Physical Impurities - Dissolved Solids/Salts
 Chemical Impurities - Inorganic & Organic Chemicals
 Biological Impurities - Pathogens, algae, fungi,viruses...

1) Acidity (pH)
2) Gases (CO2-
1) Colour
O2, NH3) 1) Microorganism
2) Turbidity
3) Minerals 2) Water Bodies
3) Taste
4) pH
4) Odour
5) Salinity
5) Conductivity
6) Alkalinity
5
7) Hardness
Colour
• Colour in water is due to metallic salts of Fe, Mn and due to organic
substances like humus, peat, algae, weed …
• Industrial activities such as textile, paper & pulp, dyeing, tanneries
• Colour intensities of water sample can be measured using
tintometer using Platinum cobalt standard colour complex

Turbidity
• It is due to colloidal, extremely fine suspension such as clay, slit,
finely divided matters, sometimes microorganisms…
• It reflects the optical properties of water in terms of light scattering
ability instead of transmitting in straight lines.

6
Taste
• Presence of dissolved salts and gases imparts bitter, soapy, brackish
and palatable taste which normally co-related with odour but it is
not applicable always the case
• Bitter (Fe, Al, Mn, SO4, Ca(OH)2)
• Soapy (NaHCO3)
• Brackish (High salt content - NaCl)
• Palatable (CO2 and NO3)

Odour
• Domestic and industries activities cause undesirable odour to water
• Industrial effluent of organics, sewage discharge, presence of N, S
and P contains compounds, metal ion pollution like Fe
• Substances like algae, peat, bacterias
• Grassy odour, peaty odour, offensive odour, tarry and faint odour
7
 pH

• pH a measure of hydrogen ion activity is used to

express the intensity of acidic or alkaline condition of a
solution.

• The pH scale runs to 0 from 14 with 0 representing

maximum acidity and 14 maximum basicity

pH = -log [H+]

8
Total dissolved solids (TDS):
TDS is a measure of the combined content of all
inorganic and organic substances contained in a
liquid in molecular, ionized or micro-granular
suspended form.
The two principal methods of measuring total
dissolved solids are gravimetry and
conductometry. Gravimetric methods are the most
accurate and involve evaporating the liquid solvent
and measuring the mass of residues left. 9
Dissolved Oxygen (DO): The stream system both
produces and consumes oxygen. It gains oxygen from the
atmosphere and from plants as a result of photosynthesis
Oxygen is measured in its dissolved form as dissolved
oxygen (DO).

Dissolved oxygen is an important factor in

corrosion. Oxygen is poorly soluble in water. The solubility
of oxygen decreases with increase in conc. of the salt
under a pressure of one atmosphere, the solubility is less in
saline water. The estimation of dissolved oxygen in water is
useful in studying corrosion effect of boiler feed water and
in studying water pollution. Dissolved oxygen is usually
determined by Winkler’s method.

10
Chemical Oxygen Demand: 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 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. 11
Biological Oxygen Demand (BOD):
BOD is the amount of dissolved oxygen
needed by aerobic biological organisms in a
body of water to break down organic
material present in a given water sample at
certain temperature over a specific time
period.

12
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases
Alkalinity

Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2

Magnesium Carbonate other suspended matter H2 S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

13
 Hard Water
What’s hard water?

Practically speaking, measurement of:

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

Hardness as calcium carbonate

mg/L (ppm)

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

14
 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

15
 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.

16
Temporary Hardness

– Temporary Hardness is caused by the presence of dissolved bicarbonate

of calcium, magnesium and other heavy metals and the carbonate of iron.
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

– Calcium/Magnesium Carbonates thus formed being almost insoluble, are

deposited as a scale at the bottom of vessel, while carbon dioxide escapes
out.

17
 Permanent Hardness

Non Carbonate Hardness is due to the presence of chlorides,

sulfates of calcium, Magnesium, iron and other heavy metals

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

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

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

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

18
 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
1 ppm = 1 mg/lit = 0.1 oFr = 0.07 oCl 19
 CaCO3 equivalent hardness

Mass of hardness Molecular weight

producing substance
X 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

20
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

21
 Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, CaCO3 = 20 ppm, MgSO4 =24.0mg/L
and KOH = 1 ppm. Calculate the temporary, permanent and total hardness of
the water sample.

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*100/100 = 20 ppm
CaCO3 20 ppm 100/100
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculation

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

Tot. Hardness =71.5 ppm

22
 Draw backs (or) Disadvantages of Hard Water

Domestic Use Industrial Use

1. Washing 1. Textile Industry

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

Produces sticky scum on the

bath tub and the body

Bad to the digestive system

and calcium oxalate formation
is possible in urinary tracts

Requires more fuel and time.

Certains food don’t cook soft
and also gives unpleasant taste
23
 Boiler troubles due to Hard Water

1. Scale and Sludge 1. Sludge

Slimy loose precipitate
called sludge suspended
2. Caustic embitterment in water

3. Priming and Foaming

4. Boiler corrosion water

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.,

24
Remedy: Sludges can be removed using wire brush or mild acid
 1. 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 25
26
 Reasons for formation of scale

1. Presence of Ca(HCO3)2 in low pressure boilers

Ca(HCO3)2 CaCO3 + H2O + CO2 Low pressure boilers but in high

pressure boilers it is soluble by
Calcium bicarbonate Calcium Carbonate (scale) forming Ca(OH)2

2. Presence of CaSO4 in high pressure boilers

ToC Solubility of CaSO4

4. Presence of SiO2
15 3200 ppm
230 55 ppm
It forms insoluble hard adherent
320 27 ppm CaSiO3 and MgSiO3 as scales
Cold water soluble
Super heated water Insoluble (scale)

3. Presence of MgCl2 in high temperature boilers

MgCl2 + 2 H2O Mg (OH)2 + 2HCl

Magnesium chloride scale

Mg(OH)2 can also be generated by thermally decomposing Mg(HCO3)2

27
 Disadvantages of scale formation

1. Fuel wastage – scales have low thermal conductivity

2. Degradation of boiler material and increases of risk of accident
3. Reduces the efficiency of the boiler and- deposit on the valves
and condensers
4. The boiler may explode – if crack occurs in scale

Remedies: Removal of scale

1. Using scrapper, wire brush often

2. By thermal shock- heating and cooling suddenly with cold water
3. Using chemicals – 5-10% HCl and by adding EDTA

28
II. Caustic embitterment

 Excess sodium carbonate 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.

Remedies: (i) Use phosphate salts instead of sodium carbonate

(ii) use Na2SO4 or agar-agar gel compounds to fill the fine cracks.

29
III. 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.

Priming
Foaming It is the process in which some particles
Normal bubble 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.

Causes of Priming,
1. Presence of dissolved salts
Priming 2. High velocity steam due to sudden boiling
Carry over bubble
3. Improper boiler design

30
 IV. 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

Boiler corrosion is of three types

1. Corrosion due to dissolved O2

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

1. Corrosion due to dissolved oxygen (DO)

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

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous Rust
hydroxide

31
 Removal of Dissolved Oxygen (DO)

1. By the addition of chemicals

The dissolved oxygen present in the boiler feed water can be removed by the addition
of sodium sulphite or hydrazine and the reactions can be written as below

2 Na2SO3 + O2 2 Na2SO4
Sodium DO Sodium
sulphite sulphate Water feed

Na2S + 2O2 Na2SO4

N2H4 + O2 N2 + 2H2O
O2 To vacuum
Hydrazine Nitrogen

Steam jacket
2. By mechanical deaeration

It comprises of a tall stainless tower with different layers

capped with baffles to facilitate multiple equilibration. Perforated
plate

The entire chamber is vacuumized and also maintained at

high tempt using perforated heating plates on the walls.

Principle: High tempt and low pressure favors lower Deaerated 32

water
solubility of gases in water (Henry’s law)
2. Corrosion due to dissolved CO2

Presence of bicarbonate salts of either magnesium or calcium also causes the release of
CO2 inside the boiler apart from the dissolved CO2

Mg(HCO3)2 MgCO3 + H2O + CO2

CO2 + H2O H2CO3 (causes slow

corrosion)
Removal
1. It can be removed by the addition of ammonia
2 NH4OH + CO2 (NH4)2CO3 + H2O

3. Corrosion due to dissolved salts

MgCl2 + 2 H2O Mg(OH)2 + 2HCl

Fe + 2 HCl FeCl2 + H2

FeCl2 + 2 H2O Fe(OH)2 + 2HCl

33
 Softening of Water

Softening of water can be done by two methods

1. Internal conditioning or Internal Treatment
2. External conditioning or External treatment

1. Internal conditioning methods - of boiler water 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. Complexometric method – using EDTA

1. Phosphate conditioning

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

3CaSO4 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 3 Na2SO4

Calcium Sodium calcium phosphate
chloride phosphate (non adherent and can
be removed by blow 34
down method)
 Selection of Phosphate compound

Calcium can not be precipitated below a pH = 9.5, hence the selection of

phosphate has to be based on the pH of the boiler feed water.

NaH2PO4 (acidic in nature) ,

Na2HPO4 (weakly alkaline in nature),
Na3PO4 (Alkaline in nature)

35
2. Calgon conditioning

Na2[Na4(PO3)6 2Na+ + [Na4P6O18]2-

Calgon – sodium hexa

meta phosphate

2CaSO4 (Boiler water) + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

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

Calgon tablets are used in the cleaning of washing machine drums

36