Module-1:

WATER TECHNOLOGY

Engineering Chemistry
(CHY1701)

Dr. Kiran Kumar Tadi

Assistant Professor
Department of Chemistry
School of Advanced Sciences (SAS)
Vellore Institute of Technology, Chennai
Module 1: Water Technology

 Characteristics of Hard Water, Hardness

 Dissolved Oxygen (DO), TDS in water and their

determination

 numerical problems in hardness determination by EDTA

 Modern techniques of water analysis for industrial use

Disadvantages of hard water in industries

Distribution of Water
 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

 Classification of Impurities in Water
Water has different physical, chemical and biological Impurities
which can cause problems in both domestic and industrial
applications.
o Physical
- Inorganic such as clay, sand
- Organic such as oil globules, vegetable/animal matter
- Colloidal such as Fe(OH)3, Complex proteins, amines
o Chemical
- Anions such as Cl-, 𝑆𝑂42− , 𝐶𝑂32− , 𝐻𝐶𝑂3− , 𝑁𝑂3− of Ca & Mg
- Cations such as Ca2+, Mg2+, Na+, K+, Fe3+, Al3+
- Dissolved gases such as O2, N2, CO2, H2S, NH3
o Biological
- Microorganisms such as algae, fungi, bacteria
-(Pathogenic causing Malaria, diarrhoea, typhoid etc.)
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.

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 MicroSiemns/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, 𝑆𝑂42− , 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
 Hardness of Water
o Hardness of water is the characteristic of preventing lather
formation of water with soap. Generally salts like chlorides,
bicarbonates and sulfates of Ca2+, Mg2+ and Fe2+ make water hard.

o This hard water on treatment with soap which is stearic or palmitic

acid salts of sodium or potassium causes white precipitate formation
of calcium or magnesium stearate or palmitate.

o Thus the cause of hardness is the precipitation of the soap and

hence prevents lathering at first. When the hardness causing ions
are removed as insoluble soaps, water becomes soft and forms
lather.
 Types of Hardness
o Hardness of water is due to dissolved salts of mainly calcium
and magnesium as well as iron and other heavy metals.

o Hardness is two types:

a) Temporary :

- Due to the presence of dissolved bicarbonates of calcium and

magnesium and other heavy metals and carbonates of iron.
Hence it is also called as carbonate or alkaline hardness.

- Can be easily removed by boiling where CO2 gas gets expelled

removing

the hardness.
 Types of Hardness

Heat
Mg(HCO3)2 Mg(OH)2 + 2CO2
Insoluble Precipitate
b) Permanent:

- Due to the presence of dissolved chlorides and sulphates of

calcium and magnesium and other heavy metals. Also called as
non-carbonate or non-alakaline hardness.

- Can be removed through zeolite, Lime-soda, ion-exchange

processes.
Total hardness = Temporary hardness + permanent hardness
 Measurement of Hardness
o Hardness of water is measured in parts per millions (ppm.) as
calcium carbonate equivalents.

o Reasons for expressing hardness in CaCO3 equivalents:

- its molecular weight is 100 ; equivalent weight is 50.
o - it is the most common insoluble impurity in water and
therefore it is east to calculate its amount in water

o Units of hardness:
- parts per million in CaCO3 equivalents (1 mg/L is 1ppm.).
- if 146 mg/L of MgSO4 is present in water, the hardness of
water is 146 ppm. as MgSO4.

o When expressed in CaCO3 equivalents, the formula for conversion is:

mass of hardness causing substance
X 100
Mol. wt of hardness causing substance
 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 12
 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

13
Calcium carbonate equivalence conversion during
hardness calculation

Hardness Molecular Multiplication factor (in

producing weight 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

14
 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 Multiplication 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

15
 Examples of hardness calculations
2. A sample hard water contains,
8.1 mg/L Ca(HCO3)2 ; 7.5 mg/L Mg(HCO3)2; 13.6 mg/L CaSO4;
12.0 mg/L MgSO4 and 2.0 mg/L MgCl2.

To calculate the hardness and express in CaCO3 equivalents:

Constituent Quantity Multiplication CaCO3 equivalents

(mg/L) factor (mg/L)
Ca(HCO3) 8.1 100/162 8.1 x 100/162 = 5.0
Mg(HCO3)2 7.5 100/146 7.5 x 100/146 = 5.14
CaSO4 13.6 100/136 13.6 x 100/136 = 10.0
MgSO4 12.0 100/120 12.0 x 100/120 =10.0
MgCl2 2.0 100/95 2.0 x 100/95 = 2.11

Temp. Hardness = 10.14 ppm P. Hardness = 22.10 ppm

Tot. Hardness =32.24 ppm 16

 Estimation of Water Hardness-EDTA Method
EDTA method:
o Ethylene diamine tetraacetic acid disodium salt (EDTA disodium
salt) is used as a strong complexing agent with Ca2+ and Mg2+ in
hard water.

o The structure of EDTA disodium salt is:

NaOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COONa

o Initially, Ca2+ and Mg2+ are treated with Eriochrome black T (EBT)
indicator using ammonia buffer (to maintain pH between 9-10) to
get an unstable complex of Ca2+ and Mg2+ formed with EBT.
pH 9-10
Ca2+/Mg2+ + EBT Ca2+/Mg2+ EBT
(unstable complex – wine red)
Contd….

On addition of EDTA, EBT gets replaced by EDTA since

EDTA forms a stronger complex with the metal ions.
This is indicated by the formation of a steel blue
coloured complex.
pH 9-10
Ca2+/Mg2+ EBT + EDTA Ca2+/Mg2+ EDTA + EBT
(Stable complex - Steel blue)

Metal-EBT Complex
Metal-EDTA Complex
 Procedure
o There are three major steps in the experimental procedure.
1. Standardization of EDTA
o First EDTA Solution is standardized using standard hard water
(1 mg/mL of CaCO3 equivalents is prepared as standard hard
water).
o For this, first known aliquot of Standard hard water is taken
and 10-15 mL of ammonia buffer is added to bring the pH
between 9-10.
o Then a few drops of EBT solution is added to form the unstable
complex giving wine red colour.
o This solution is titrated with the EDTA solution till the solution
turns to steel blue indicating the formation of stable EDTA-
Metal ion complex.
o This volume of EDTA is noted as V1.
 Procedure
2. Estimation of Total Hardness of Water Sample
o The above procedure is repeated with sample hard water of
unknown hardness.
o Volume of EDTA is noted as V2.

3. Estimation of Permanent Hardness of Water Sample

o Then sample hard water of 250 mL is taken and evaporated to
a volume of 50mL when the temporary hard salts settle down.
o The solution is filtered and washed thoroughly and made up
again to 250mL.
o From this solution, 50 mL is pipetted out and titrated in similar
manner as done with standard hard water.
o Volume of EDTA is noted as V3.
 Calculations
a) Total hardness:
Standardization of EDTA:
V1mL of EDTA is consumed by 50 mL of std. hard water
V1mL of EDTA = 50 mg of CaCO3
1 mL of EDTA = 50/V1 mg of CaCO3
Estimation of Total Hardness of Water Sample:
EDTA consumed by sample hard water = V2 mL
So, V2 mL of EDTA = 50/V1 x V2 mg of CaCO3
Hence, 50 mL of sample hard water contains 50/V1 x V2 mg of CaCO3

Therefore, 1 mL of sample hard water = 50/V1 x V2/50 mg

1000 mL of sample hard water = 50/V1 x V2/50 x 1000 mg/L
i.e. Total hardness of sample hard water = V2/V1 x 1000 mg of CaCO3
(ppm.)
Permanent hardness:
50 mL of sample hard water after removing temporary hardness consumed V3 mL of
EDTA.

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

Therefore, V3 mL of EDTA = 50/V1 x V3 mg of CaCO3 equiv.

50 mL of sample hard water after boiling contained 50/V1 x V3 mg of CaCO3 equiv.

Therefore, 1000 mL of sample hard water contains

= 50/V1 x V3/50 x 1000 mg/L CaCO3 equiv.

Permanent hardness = V3/V1 x 1000 mg/L CaCO3 equiv.

Temporary hardness:

Temporary hardness = Total hardness – permanent hardness

 Temporary hardness calculation

Temporary hardness:

Temporary hardness = Total hardness – permanent hardness

V2 _ V3
X 1000 X 1000
V1 V1

V2 – V 3
= 1000 X
V1
 Dissolved Oxygen
Dissolved oxygen (DO) is the amount of oxygen dissolved in a given quantity of water at a
particular temperature and atmospheric pressure.
o DO depends on
• Aeration,
• Photosynthetic activity of the water,
• Respiration of animals and plants
• Speed of water flow
• Roughness of surface over which water flows
• Temperature of the water body

o Oxygen Demanding Wastes

- Chemical Oxygen Demand (COD)
The COD is a measure of the oxygen equivalent of that portion of organic matter in
a sample that is susceptible to oxidize.
- Biological Oxygen Demand (BOD)
BOD represents the quantity of oxygen required by bacteria and other micro-
organisms to oxidize organic matter present in the water over a period of 5 days.
o These are useful measures to check water quality
 DO by Winkler’s Method
Theory of Winkler’s Method:
o Oxygen in the water sample oxidizes iodide ion (I-) to iodine
(I2) quantitatively.
o The amount of iodine generated is then determined by titration
with a standard thiosulfate (S2O3-2) solution.
o The endpoint is determined by using starch as a visual
indicator.
o The amount of oxygen can then be computed from the titre
values
 DO Determination:

Winkler Method:
Technique: Iodometric Conversion
1 mole of O2 = 2 mole of I2 = 4 moles Na2S2O3
Procedure:
Water Sample Addition of MnSO4 followed by strong KOH solution
in a stoppered
bottle

Formation of MnO(OH)2 brown precipitation by DO

The dissolution Dissolved in (1:1) H2SO4

treated with KI solution

Oxidized KI solution liberates I2 Liberated I2 quantified by

Na2S2O3 titration
 Total Dissolved Solids (TDS)
Total dissolved solids (TDS) is the amount of particles dissolved in water. TDS comprise inorganic salts (mainly
cations of Ca, Mg, K, Na and anions of bicarbonates, chlorides and sulfates) and small amount of dissolved organic
matter.

o They come from

a) Organic sources (leaves)

b) Silt (granular material)

c) Industrial wastage and sewage as well as runoff from urban sources, fertilizers and pesticides

d) Inorganic materials such as rocks and air that may contain calcium bicarbonate, nitrogen, iron, sulphur and other
minerals

o A constant level of minerals, eg. Phosphorous, nitrogen and sulphur, is necessary for aquatic life.

o Concentration of dissolved solids should not be too high or too low which can affect the growth and leads to death of many
aquatic organisms.

o High concentration of dissolved solids reduces the clarity of water and can decrease the photosynthesis and raises the
water temperature.

o It can be determined taking a known amount (say 100 mL) of water and by evaporating the contents carefully to dryness.

o The residue (W/g) left after evaporation of the filtered sample shows the total dissolved solids present in that articular
water sample.
Contd…
TDS = (A-B) * 1000 *1000 mg/L
A= Weight of the evaporating dish + Filtrate
B = Weight of the evaporating dish on its own
o Recommended TDS for drinking water is 25-250 mg/L

o At any cost drinking water TDS should not exceed 500 mg/L

o TDS for distilled water will be 0.5-1.5 mg/L

o TDS ranges from 100-20,000 mg/L in river water and will be generally
higher in ground water

o Sea water will have 3500 mg/L of TDS

o Lakes and streams will have a TDS of 20-250 mg/L

Thermal Power Plant
 Problems of Hard Water for Domestic Use
a) Washing:
o Hard water, when used for washing purposes, does not lather
freely with soap.
o It produces sticky precipitates of calcium and magnesium soaps.
o Similar problem exists in bathing.

b) Cooking:
o Due to the presence of dissolved hardness producing salts the
boiling point of water is elevated.
o Consequently more fuel is and time are required for cooking.

c) Drinking:
o Hard water causes bad effect on our digestive system.
o The possibility of forming calcium oxalate crystals in urinary tracks
is increased (Kidney stones).
 Problems of Hard Water for Industry
Paper Industry:
The presence of calcium and magnesium has impact on the properties and
quality of paper and their products
Textile industry :
Hard water cause much of the soap to go as waste.
During dyeing process, calcium and magnesium salts present in water make
the quality of the shades very poor.
Sugar industry :
If nitrates, sulphates of calcium and magnesium are present, they cause
hindrance to crystallization of sugar
Concrete making :
Water containing chlorides and sulphates, if used for concrete making, affects
the hydration of the cement and the final strength of the hardened concrete.
In steam generation in boilers:
If the hard water is fed directly to the boilers, which led to the many problems
such as
Formation of scales which corrodes the boiler, wastage of fuel etc.
Contd…

1. Scale and Sludge formation:

a) Sludges:
o Soft, loose, slimy precipitates are sludge
~~~~ o Can be easily scrapped off with a wire brush
~~~~~~~~
~~~~ ~ ~
~~ ~ ~ ~~~~
~ ~ o Forms in comparatively colder portions of the
~~~~~~~~~ ~
~~~ ~ ~~ ~~
~~~~ boiler such as bends etc.
~~~~ ~~~~
~ ~~~~~
~~ ~~
~ ~ ~ ~ ~~~~
~ o Formed because of MgCO3, MgCl2, CaCl2, MgSO4
~~~~~~~
~~~~ Mg(OH)2,(more soluble in hot water)
Heat

b) Scales: o Dissolved salts deposit because of continuous

evaporation of water concentration of salts
x increases
x o These are hard and stick strongly to the walls
x
o Difficult to be removed even with a hammer and
chisel.

Heat o Formed because of CaCO3, CaSO4, CaSiO3, MgSiO3

33
Examples of Sludge and Scale

34
 Scales
o Scales are the main source of boiler troubles.
Scale are mainly formed by decomposition of calcium bicarbonate

Ca(HCO3)2 CaCO3 + H2O +CO2

o Dissolved magnesium salts undergo hydrolysis forming magnesium

hydroxide precipitate which forms a soft type of scale
MgCl2 + 2 H2O Mg(OH)2 + 2 HCl

o 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.

o Scales reduce the thermal conductivity and if there is a crack on the scale,
it may lead to differential heating and increases the possibility of boiler
explosion.

35
 2. Priming and Foaming
a) Foaming:
o Foaming is the production of persistent foam or bubbles in boilers
which do not break easily.
o This is because of presence of oils which reduce the surface
tension of water.
o Can be avoided by adding anti-foaming agents like caster oil or
removing oil from the boiler feed water by adding sodium
aluminate.

b) Priming:
o Along with steam, some particles of water are carried (wet steam)
which is called priming.
o This is because of large amounts of dissolved salts, high steam
velocities, sudden boiling, improper boiler design, sudden increase
in steam production rate.
o Priming can be avoided by maintaining low water level in boilers,
avoiding rapid steam generation, efficient softening, installing
mechanical steam purifiers.
 3. Caustic Embrittlement

o Caused by using highly alkaline water in boiler

o When water is softened by lime-soda process, free Na2CO3 is present in softened

water.

o In high pressure boilers, this Na2CO3 decomposes to NaOH and CO2

Na2CO3 + H2O 2 NaOH + CO2

o This NaOH makes the water caustic.

o This NaOH flows through minute cracks present in the boiler by capillary action.

o As water is boiling it evaporates and the conc. of NaOH increases.

o This caustic soda attacks the boiler and forms sodium ferroate.

o This makes the boiler parts brittle (embrittlement).

Concentration cell representation of caustic embrittlement
Caustic attack on boiler parts can be represented as:
+ _
Iron at Conc. NaOH Dil. NaOH Iron at
rivettes, soln. soln. Plane
bends, surfaces
Joints etc.

o The iron in contact with dil. NaOH becomes cathode and the iron in contact
with conc. NaOH becomes anode.

o The anodic part slowly dissolves and corrodes.

o Caustic embrittlement can be avoided by adding:

a) sodium phosphate (Softening agent)

b) tannin or lignin (Blocks hair line cracks)

c) sodium sulphate (Blocks hair line cracks)

 4. Boiler Corrosion
o Decay of boiler material by chemical or electrochemical attack by
surrounding environment.
o Reasons for boiler corrosion are:
a) Dissolved oxygen
b) Dissolved carbon dioxide
c) Acids from dissolved salts
a) Dissolved oxygen (DO):
2 Fe + H2O + O2 2 Fe(OH)2

2 Fe(OH)2 + O2 2 Fe2O3.2H2O (Rust)

o DO can be removed by adding calculated qty. of sodium sulphite or
hydrazine or sodium sulphide:
2 Na2SO3 + O2 2 Na2SO4
N2H4 + O2 N2 + 2H2O
Na2S + 2O2 Na2SO4

o DO can be removed by mechanical aeration also

 4. Boiler Corrosion
b) Dissolved CO2:
o Dissolved CO2 forms carbonic acid which corrodes the boiler slowly.
CO2 + H2O H2CO3
o CO2 is removed by adding calculated quantity of ammonia:

2NH4OH + CO2 (NH4)2CO3 + H2O

It is also removed by mechanical aeration along with oxygen.
c) Acids from dissolved salts:
o Dissolved magnesium salts hydrolyse to form acids:

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

o This acid reacts with boiler and corrodes:
Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl

o Small quantity of magnesium salts will large amount of boiler corrosion

 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
41
Additional Information
on Boiler troubles
 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.

43
 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

44
 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

45
 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

46
 Prevention of scale formation
• Internal Treatment
• Colloidal Conditioning
• Phosphate conditioning
• Carbonate conditioning
• Calgon conditioning
• Treatment with sodium aluminate
• External Treatment
• The treatment includes efficient ‘softening of water’
• Removing hardness-producing constituents of water

47
 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.

Colloidal Conditioning:
In low-pressure boilers, scale formation can be avoided
by adding substances

Kerosene, tannin, agar-agar : non-sticky and loose deposit

Blow-down operations - removal
Phosphate Conditioning: High-Pressure boilers
Sodium phosphate Optimum pH – 9.5 to 10.5
NaH2PO4
3CaSO4+ 2Na3PO4 -----------Ca3 (PO4)2 ↓+ 3 Na2SO4
Na2HPO4
3CaCl2+ 2Na3PO4 -----------Ca3 (PO4)2 ↓+ 6NaCl
Na3PO4

Carbonate Conditioning: Low-Pressure boilers

Sodium carbonate
CaSO4+ Na2CO3----------- CaCO3 + Na2SO4

Calgon Conditioning:
Sodium hexa meta phosphate
Na2 [Na4 (PO3)6] ↔2Na+ + [Na4 (PO3)6]2-
2CaSO4+ [Na4 (PO3)6]2- →[Ca2 (PO3)6]2- + 2Na2SO4

Treatment with sodium meta aluminate:

NaAlO2 +2H2O →NaOH+Al[OH]3↓

MgCl2 +2NaOH →2NaCl+Mg(OH)2↓

 Caustic Embrittlement
• Its a kind of boiler corrosion, caused by using highly alkaline
water in the boiler
Na2CO3 + H2O 2NaOH +CO2

Minutes 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
+ __

Iron at Conc. Dil. Iron at

stressed NaOH NaOH plane
parts solution solution surfaces

50
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

 Boiler Corrosion
• It’s a decay of boiler material by chemical or electro-
chemical attack by its environment

(1) Dissolved oxygen in water at high temperature attack boiler material.

Fe + 2H2O + O2 Fe(OH)2

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

Removal of dissolved oxygen

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

Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4

52
 Removal of dissolved oxygen by de-aeration

Water spraying in a perforated plate-fitted tower, heated from sides

and connected to Vacuum pump. High temperature, low pressure
and large exposed surface reduces dissolved oxygen in water

53
 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
54
Priming
• When a boiler is steaming rapidly some particles of the liquid water are carried
along with the steam. Its called priming.

– Presence of large amount of dissolved solids

– Sudden boiling
– Improper boiler design

Foaming
• It is the production of persistent foam or bubbles in boilers, which do not break
easily. It is due to the presence of oil.

• Priming and foaming occur together

Priming can be avoided by

Fitting mechanical steam purifier

avoid rapid change in steaming rate

Foaming can be avoided by

adding anti-foaming agent like castor oil
Removing oil from boiler water by adding compounds like sodium aluminate
55