MODULE - I

WATER TECHNOLOGY
Dr. K. Rajendra Kumar
[email protected]
Associate Professor
Chemistry Division
School of Advanced Sciences
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

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 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

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

Conductivity
• The ability of water to conduct electricity, indicates the amount
of dissolved minerals and gases in water.
• Conductivity measured in micro mhos/cm or MicroSiemens/cm3 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 industrial 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
(means potential of hydrogen)
• 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
pH values of some liquids encountered in day-to-day life

The optimum pH for

the body fluids is
7.0

www.chemwiki.ucdavis.edu
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Alkalinity Anionic Nonionic and undissolved Gases
Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2
Magnesium Carbonate other suspended matter H2S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium ChlorideColloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

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

11

http://water.usgs.gov/owq/hardness-alkalinity.html
 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
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 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.

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Temporary Hardness

– Temporary Hardness is caused by the presence of dissolved

bicarbonate of calcium, magnesium and other heavy metals and the
carbonate of ion.
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.

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 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 +

2Na 2SO
Sodium 4
stearate Magnesium stearate
Hardness
(sodium soap) (Insoluble)

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 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

• Clarke's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water
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• Degrees French (oFr)
1o Fr = 1 part of CaCO3 eq per 105 parts of water
 CACO3 EQUIVALENT HARDNESS

Mass of hardness Molecular weight of

producing substance
X 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
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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
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 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

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Tot. Hardness =71.5 ppm
SOME WEBSITES FOR YOUR REFERENCE

water-softening.org website

The Salt Guru on water softening

http://www.feedwater.co.uk/boiler-water-treatment.php

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INTERESTING FACTS ABOUT WATER
Roughly 70 percent of an adult’s body is made up of water.
At birth, water accounts for approximately 80 percent of an
infant’s body weight.

Drinking too much water too quickly can lead to water

intoxication. Water intoxication occurs when water dilutes
the sodium level in the bloodstream and causes an imbalance
of water in the brain.

Water intoxication is most likely to occur during periods of

intense athletic performance.
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INTERESTING FACTS ABOUT WATER
While the daily recommended amount of water is eight cups per
day, not all of this water must be consumed in the liquid form.
Nearly every food or drink item provides some water to the body.

Soft drinks, coffee, and tea, while made up almost entirely of

water, also contain caffeine. Caffeine can act as a mild diuretic,
preventing water from traveling to necessary locations in the body.

Pure water (solely hydrogen and oxygen atoms) has a neutral pH of

7, which is neither acidic nor basic.
Water dissolves more substances than any other liquid. Wherever it
travels, water carries chemicals, minerals, and nutrients with it.

Somewhere between 70 and 75 percent of the earth’s surface 22

is covered with water. Much more fresh water is stored under the
ground in aquifers than on the earth’s surface.
ESTIMATION OF HARDNESS BY EDTA METHOD
- READ LAB MANUAL (EXPT.NO.1)

ESTIMATION OF TOTAL DISSOLVED SOLIDS (TDS) – -

- REFER ENGINEERING CHEMISTRY
BY O G PALANNNA, MC GRAW HILLS
PUBLICATIONS

23
 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
6. In Steam generation in
stain 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. 24

Certains food don’t cook soft
and also gives unpleasant
taste
 BOILER FEED WATER

A boiler is a device for generating steam, which consists of two principal

parts:

1) The furnace, which provides heat, usually by burning a fuel

2) The boiler proper, a device in which the heat changes water into steam.

The steam or hot fluid is then recirculated out of the boiler for use in
various processes in heating applications.

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AN INDUSTRIAL BOILER

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 BOILER TROUBLES
Proper treatment of boiler feed water is an important part of operating and
maintaining a boiler system.

As steam is produced, dissolved solids become concentrated and form

deposits inside the boiler.

This leads to poor heat transfer and reduces the efficiency of the boiler.

Dissolved gases such as oxygen and carbon dioxide will react with the metals
in the boiler system and lead to boiler corrosion.

In order to protect the boiler from these contaminants, they should be

controlled or removed.

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 BOILER TROUBLES DUE TO HARD WATER

Slimy loose precipitate

1. Scale and Sludge 1. Sludge called sludge suspended in
water
2. Priming and Foaming

3. Caustic embrittlement

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,
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e.g. MgCl2, CaCl2, MgSO4 etc.,
 1. Scale
Hard adherent coating on
inner walls of boiler

water

Boiler
wall

Scale is formed by salts that have limited solubility but are not totally insoluble in boiler water.
These salts reach the deposit site in a soluble form and precipitate.

They 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. 29

Deposits will cause the temperature of the metal to increase until overheating, metal softening,
blistering and failure occurs
 REASONS FOR FORMATION OF SCALE

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

But in high pressure boilers it is

Ca(HCO3)2 CaCO3 + H2O + CO2 soluble by forming Ca(OH)2
Calcium bicarbonate Calcium Carbonate (scale)

2. Presence of CaSO4 in high pressure boilers

To C Solubility of CaSO4
4. Presence of SiO2
15 3200 ppm
230 15 ppm
It forms insoluble hard adherent
Super heated water Insoluble (scale) CaSiO3 and MgSiO3 as scales

3. Presence of MgCl2 in high temperature boilers

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

Magnesium chloride scale

A low-pressure fire-tube boiler can usually tolerate high feed-

water hardness
All impurities must be removed from water used in some 30
modern, high-pressure boilers.
 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

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

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BOILER PRESSURE AND PERMISSIBLE
LIMITS OF TDS

TOTAL DISSOLVED ALKALINI

BOILER PRESSURE
SOLID TY
(PSI)
( TDS) (PPM)

0 - 300 3500 700

301-450 3000 600
451-600 2500 500
601-750 2000 400
751-900 1500 300
901-1000 1250 250
1001-1500 1000 200
1501-2000 750 150
ABOVE 2000 500 100
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http://www.hacschem.com
 Thickness of scale & Fuel consumption

Thickness of scale
Increases in fuel consumption
due to this scale

1) 1/2 mm 2%

2) 1 mm 4%

3) 2 mm 6%

4) 4 mm (1/8 ") 10 %

5) 8 mm (1/4") 20 %

6) 16 mm (1/2 ") 40 %

7) 30 mm (1") 80 %

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WHAT PROBLEMS DOES SCALE CAUSE?
Increased Energy Costs
The scale acts as insulation,
dramatically reducing heating
or cooling efficiency and adding
to your energy costs.

Increased Pumping Costs and

Wear
Scale reduces the internal bore
of pipework, which causes
impaired flow

Overheating and Hot-Spots

Because scale is an insulator, it
can cause hot spots to form on
heat transfer surfaces as heat is
not conducted away fast 34
enough, leading to overheating.
Major benefits of boiler water treatment:

Save energy losses or stabilizes fuel consumption

Increase life of your boiler

Ensures optimum heat transfer

Reduces unnecessary shutdown / maintenance bills

Saves frequent acid cleaning cost

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II. Priming and foaming

Foaming
It is the production of continuous foam or
bubblers in boilers. It is due to the presence
of substance like oil in boiling water.

Priming
Foaming It is the process in which some particles of
Normal bubble liquid water are carried along with the
steam. It is then called as wet steam and
the process of formation of wet steam in
boilers is called priming.

Priming is due to the

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

Disadvantages of Priming and foaming 36

 III. Caustic embrittlement

It is caused due to the presence of caustic soda (NaOH) in boiler feed

water.

NaOH is introduced into water by the use of sodium carbonate used

for removal of permanent hardness.

Na2CO3 + H2O → 2 NaOH + CO2

2NaOH + Fe Na2FeO2 + H2
Sodium ferroate
Treatment for caustic embrittlement

By using sodium phosphate as softening agent instead of sodium

carbonate 37
By adding tannin or lignin to boiler water which blocks the hair cracks
Removal of foaming

By adding anti-foaming agents like castor oil

Avoiding priming

By maintaining low water levels in boilers

Controlling the boiling rate and hardness level of water
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 2Fe(OH)2

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O] 38

Ferrous Rust
hydroxide
 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 Sodium Water
DO feed
sulphite sulphate

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

Steam
jacket
2. By mechanical deaeration

Perforate
d plate

39

Deaerated
water
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

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 DISSOLVED OXYGEN
It is the amount of free oxygen in water. It is
required for the aquatic species like Fish and
other microorganisms.
: While DO is essential for aquatic animals,
it is harmful to the boiler material, inducing
corrosion. (Refer: Boiler troubles-Boiler Corrosion
due to oxygen)
Using DO, organic matters in water can be
converted to Carbon dioxide and water as
given below. 41
CH2O + O2 CO2 + H2O
 NITRIFICATION
DO is also used in nitrification process in water
bodies

O2 O2
NH3 NO2 NO3
AMMONIA NITRITE NITRATE

Aeration of water bodies can be done to reduce oxygen

demand or to remove ammonia.
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APPLICATIONS OF DO ANALYSIS

In BOD Analysis

Water Treatment Processes

Plant Effluent Treatments

Receiving Stream

43
Maximum D.O. Concentrations in Water (Saturation)

Temperature Max. Concentration

0C
mg/L
0 14.6
4 13.1
8 11.9
12 10.8
16 10.0
20 9.2
24 8.5
28 7.9 44
30 7.6
 SAMPLE COLLECTION

Sample Atmosphere
21 %
0 to 10 mg/L
210,000 mg/L

45
SAMPLE COLLECTION

46
SAMPLE COLLECTION

47
 Do Not AERATE Sample

NO YES

Do Not Splash Sample in Air

or 48

Let Air Circulate in Sample

Procedure

49
 Winkler’s Method
Iodometric Method
Mn SO4 + 2 KOH Mn(OH)2 + K2SO4

2 Mn(OH)2 + O2 2 MnO(OH)2

MnO(OH)2 + 2 H2SO4 MnSO4

+ 2H2O+[O]

2 KI + H2SO 4 + [O] K2SO4 + H2 O + I2

2Na2S2O3 + I2 Na2S4O6 + 2NaI

Starch + I2 Blue colored complex

50
 Procedure

1 mL
Alkaline
KI Solution

1 mL
Manganous
51
Sulfate
Stopper
Mix Well

Allow
Floc
to Settle 52
 Settle
Repeat Mixing
Again

Contact and Time 53

White - No Dissolved Oxygen

54
 Sulfamic
Acid

1 mL
Sulfuric
Acid

55
Mix
 Measure
100 mL

Iodine
Solution
56

Free IODINE released in relation to D.O. in Sample

 Titration
Sodium Thiosulfate (Thio) OR Phenylarsene Oxide (PAO)

57
End Point Indicator

Starch 58
 Clear

Blue
59
D.O. =
Volume of thio × Normality of thio × 8 × 1000

Volume of water sample

Y ml x 0.**** N x 8 x 1000
= ---- mg/L
100

60
Outline Of Winkler Dissolved Oxygen Procedure

Add
1 mL Yellow
MnSO4 Soln. To Add
Carefully Brown 1 mL
and
Collect Floc, Mix By H2SO4
1 mL
Sample D.O. Present Inverting Repeat and
Alkali-iodide-azide
In 300 mL and Mixing Mix
Reagent
BOD Bottle Allow To and
Settle Settling

White
Floc, 61
No D.O.
Titration of Iodine Solution

Titrate
With
THIO Titrate
to
Clear
Pour
100 mL Add
Into Flask Starch
Indicator

Reddish- Pale Blue Clear

Brown Yellow

62
63
Thank You

64