Engineering Chemistry

Dr. Saurav Prasad

Course Structure
Industrial and
Impurities of water Conducting
and its treatment polymers

Phase equilibria
and Alloys Energy sources

Electrochemistry & Energy conversion

Corrosion and storage
Course Plan
•** sessions
•N Assignment
•M Quizzes
•Practical / Theoretical project
Module 1: Session 1
Water Cycle: Processes?
C

D
E A

F
Water Resources
 Impurities in Water
Physical • Suspended Impurities
Impurities • Colloidal Impurities

• Bacteria
Bacteriological • Algae
Impurities • Fungi

• Dissolved Gases
Chemical • Dissolved Organic Salts
Impurities • Dissolved Inorganic Salts
Source of chemical impurities

US Department of the Interior

Impurities In Water
Physical • Suspended Impurities
Impurities • Colloidal Impurities

• Bacteria
Bacteriological • Algae
Impurities • Fungi

• Dissolved Gases
Chemical • Dissolved Organic Salts
Impurities • Dissolved Inorganic Salts
Water Hardness
• Hardness of water refers to the quantity of dissolved salts of certain
metal ions in water that reduces the tendency to form lather with soap.
• Hard water is “hard” to form lather or foam with.

?
Causes of Water Hardness
• Calcium (Ca2+ ), Magnesium (Mg2+) ions.

CaCO3 CaCl2
MgCO3 MgCl2
Ca(HCO3)2 CaSO4
Mg(HCO3) 2 MgSO4
How do Ca2+ and Mg get
2+ into water?
Limestone pavement

Limestone, mostly calcium

carbonate, does not dissolve in
pure water, BUT it does dissolve
in acid rain.

CaCO3 + H2CO3 Ca(HCO3)2

Carbonic
Ca2+
Calcium
Calcium Acid (acid Hydrogen
carbonate rain) carbonate HARD
Hard water and types of rock

Types of rocks across India. Water types?

• Hard water
• Soft water
Differences between Soft and Hard Water
Hard water Soft water
Does not produce lather with soap Produces lather with soap

Contains dissolved calcium and Does not contains dissolved calcium

magnesium salts and magnesium salts.

Cleansing action of soap is suppressed Cleansing action of soap is not

suppressed

Requires more material and time Does not require excess material and
time
 Temporary and Permanent Hardness
of Water
Temporary hardness Permanent hardness
Causes:
Causes: chlorides and sulphates
Calcium hydrocarbonate – Ca(HCO3)2 of Ca2+, Mg2+, Fe3+

e.g. CaCl2, MgSO4

Magnesium hydrocarbonate – Mg(HCO3)2

Removal: not by boiling the

Removal: boiling the water water

Ca(HCO3) 2 → CaCO3 + H2O + CO2 Sophisticated water treatment

methods

Mg(HCO3)2 → MgCO3 + H20 + CO2

 Disadvantages of Hard Water
Scale Formation
• CaCO3 formed upon boiling water with temporary hardness, is NOT
soluble in water.
• This calcium carbonate precipitates out, coating the insides of boilers,
kettles, pipes etc. It reduces the efficiency of any
heating element, using more
energy.

It can block pipes and damage

equipment.

Expensive to remove.
Disadvantages of Hard Water
Sludge Formation
• Salts such as MgCl2, CaCl2, MgCO3, MgSO4 etc. have
higher solubility in hot water than cold water.
• Get deposited in the ”cold” part of boilers.
• Soft and loose precipitates.

Poor conductor of heat.

Can combine with scale formation.

Removed by wire brush.

Disadvantages of Hard Water
Soap Scum Formation
• Calcium and magnesium ions react with soap to make calcium and
magnesium stearate.
2 C17H35COONa + CaCl2 → (C17H35COO)2Ca + 2 NaCl
(Sodium stearate) (calcium stearate)

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

(Magnesium stearate)

Lather is only formed once all

the Ca2+ /Mg2+ ions have been
precipitated.

Less bubbles, more soap!!!

Advantages of Hard Water
Some people still prefer it! Can you think of
any reasons why?

❖ Taste: some people prefer it

❖ It’s good for your teeth and bones
(Calcium ions)
❖ It can protect against heart problems
Degree of Hardness
Hardness is expressed in terms of equivalence of CaCO3:
highly insoluble (easy for precipitation) and molecular weight
of 100 (easier calculation).
For a particular hardness producing substance, say X,

Strength of X (mg/L) x 50
Hardness =
Chemical equivalent of X

NOTE: There may be no Calcium carbonate in the sample at all!!!

But we are expressing it as an equivalence.
Converting into CaCO3 equivalents
Example: Find multiplication factor for converting into CaCO3
equivalents for following salts and ions?
Ca(HCO3)2 CO2
Mg(HCO3)2 HCO3-
CaSO4 OH-
CaCl2 CO32-
MgSO4 H+
MgCl2 Mg(NO3)2
CaCO3 NaAlO2
MgCO3 FeSO4
Ca (HCO3)2 = 40 + 2 (1 + 12 + 48) = 162
Na = 23, Mg = 24, Al = 27 S = 32, Ca = 40, Fe = 56
Converting into CaCO3 equivalents
Example: Find multiplication factor for converting into CaCO3 equivalents for
following salts and ions?

Ca(HCO3)2 50/81 CO2 50/22

Mg(HCO3)2 50/73 HCO3- 50/61
CaSO4 50/68 OH- 50/17
CaCl2 50/55.5 CO32- 50/30
MgSO4 50/60 H+ 50/1
MgCl2 50/47.5 Mg(NO3)2 50/74
CaCO3 50/50 NaAlO2 50/82
MgCO3 50/42 FeSO4 50/76

Na = 23, Mg = 24, Al = 27 S = 32, Ca = 40, Fe = 56

Question
Example: A water sample contains 150 mg of
CaSO4 per litre. Calculate the hardness?

Answer:
Chemical equivalent of CaSO4 = 68

150 x 50
CaCO3 equivalent = mg/L =
68
110.29 mg/L
 Units of Hardness
1 ppm = 1 part by weight 1 mg/L = 1 mg of
Parts per 1 ppm = 1 mg/L Milligrams
of CaCO3 equivalent in CaCO3 equivalent
106 parts by weight of million per litre in one litre of
water. (ppm) (mg/L) water.

1 ppm = 0.1 °Fr

Units of
Hardness

Degree
French Clarke’s
(°Fr) Degree 1 °Cl = 1 part of CaCO3
1 °Fr =1 part of CaCO3
equivalent in 105 parts of (°Cl) equivalent in 70, 000 parts of
water.
water.
Degree of Hardness
Hardness Level ppm

Soft 0 - 17
Slightly Hard 17 - 60
Moderately Hard 60 - 120
Hard 120 - 180
Very Hard 180 and above
Source: Water Quality Association (WQA)
 Question
Q. Calculate the temporary, permanent, and total hardness of a
water sample, having the following analysis:
Express your answer in mg/L, ppm, oFr, and oCl.

Mg(HCO3)2 – 73 mg/L
Ca(HCO3)2 – 162 mg/L
CaSO4 – 136 mg/L
MgCl2 – 95 mg/L
CaCl2 – 111 mg/L
NaCl – 100 mg/L
 Question
Q. How many grams of MgCO3 dissolved per litre gives 124 ppm
of hardness?
Strength of MgCO3 (mg/L) x 50
Hardness =
Chemical equivalent of MgCO3

Strength of MgCO3 = 124 x (MgCO3 equivalence) ppm

CaCO3 equivalence

= 124 x (42/50) ppm = 104.16 ppm

= 104.16 mg/L
Hardness Measurement
• Useful test that provides a measure of the water quality to
be used for household and industrial purposes.

• Measure before having to deal with scale formation.

• EDTA Method
• O. Hehner’s Method
• Soap Titration Method
• Warta-Pfeifer Method
 Strategy
• If you are looking for “hardness”,
what are you actually searching
for…?
Metal ions!

• What’s the easiest way to

quantify the amount of metal
ions?
Precipitate them!
EDTA Method
• Complex formation titrations (Complexometric Method)

• Chelating or complexing agent in metal ion titrations is EDTA,

(ethylenediaminetetracetic acid).
• Tetraprotic acid
• Sodium salt of EDTA is used because of its high solubility.
• This causes the water to become softened, but the metal ions are not removed from
the water.
EDTA Method
M2+ + H2EDTA2- → [ M-EDTA ]2- + 2H+

EDTA, M2+, and M-EDTA are all soluble and colorless. No visible change…

Need a secondary indicator – some visible change.

Indicator:
Eriochrome Black T (EBT)
• EBT is a blue colored dye when alone in water and turns red when complexed with a Metal
ion.
• Works at pH 10 (add buffer NH4OH-NH4Cl)
• M-EBT + EDTA → M-EDTA + EBT
(red) (colorless) (blue)

Eriochrome black T
1st Step: The calcium ion coordinates with the indicator (Eriochrome Black T).

H2In- + Ca2+ ↔ CaIn- + 2H+

2nd Step: The EDTA chelates the calcium ion and releases the indicator.

EDTA (aq) + CaIn–(aq) → HIn2-(aq) + CaEDTA (aq)

EDTA

Water + EBT
Experiment:
• The hard water is buffered to a pH value of approx 10 using ammonia buffer
and a few drops of EBT are added, thus formed weak complex of metal ion
and EBT has wine-red colour.

• Add EDTA, which first combines with free metal ions and form colorless
metal-EDTA complex. After all ions have been consumed, next EDTA drops
displaces EBT from the metal-indicator complex. Thus freed EBT changes the
solution colour to blue.
Hardness Calculation

𝑇𝐻 𝑆𝑡𝑑
𝑉𝐸𝐷𝑇𝐴 𝑉𝑆𝐻𝑊
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 × 1000 × 𝑇𝐻 × 𝑆𝑡𝑑 𝑚𝑔/𝐿
𝑉𝑈𝐻𝑊 𝑉𝐸𝐷𝑇𝐴

𝑃𝐻 𝑆𝑡𝑑
𝑉𝐸𝐷𝑇𝐴 𝑉𝑆𝐻𝑊
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 × 1000 × 𝑃𝐻 × 𝑆𝑡𝑑 𝑚𝑔/𝐿
𝑉𝑈𝐻𝑊 𝑉𝐸𝐷𝑇𝐴

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠

0.28 g of CaCO3 was dissolved in HCl and the solution was made to one litre with distilled water. 100
ml of the above solution required 28 ml of EDTA solution on titration. 100 ml of the hard water sample
required 35 ml of the same solution on titration. After boiling 100 ml of this water, cooling and filtering
and then 10 ml EDTA solution was used on titration. Calculate the temporary and permanent hardness
of water.

𝑇𝐻 𝑆𝑡𝑑
𝑉𝐸𝐷𝑇𝐴 𝑉𝑆𝐻𝑊
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 × 1000 × 𝑇𝐻 × 𝑆𝑡𝑑 𝑚𝑔/𝐿
𝑉𝑈𝐻𝑊 𝑉𝐸𝐷𝑇𝐴

35 100
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 0.28 × 1000 × × = 350 𝑚𝑔/𝐿
100 28

𝑃𝐻 𝑆𝑡𝑑
𝑉𝐸𝐷𝑇𝐴 𝑉𝑆𝐻𝑊
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 × 1000 × 𝑃𝐻 × 𝑆𝑡𝑑 𝑚𝑔/𝐿
𝑉𝑈𝐻𝑊 𝑉𝐸𝐷𝑇𝐴

10 100
𝑃𝑒𝑟𝑚𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 0.28 × 1000 × × = 100 𝑚𝑔/𝐿
100 28

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 350 − 100 = 250 𝑚𝑔/𝐿

Alkalinity of water
• Hard water is generally associated with high alkalinity.

Alkalinity

CaMg(CO3)2 Ca2+ + Mg2+ + 2CO32-

Dolomitic Hardness
limestone

Hardness and alkalinity generally go hand-in-hand but they are NOT

the same.
 Alkalinity of water
• Alkalinity is defined as the ability to neutralize acids.

• Alkalinity of water is due to the presence of any of the ions 𝑶𝑯− , 𝑪𝑶−𝟐
𝟑 and 𝑯𝑪𝑶𝟑− or
mixture of 𝑂𝐻 − and 𝐶𝑂3−2 or mixture of 𝐶𝑂3−2 and 𝐻𝐶𝑂3− .

• 𝑂𝐻 − and 𝐻𝐶𝑂3− ions cannot be present together because they combine by reaction

𝑂𝐻 − + 𝐻𝐶𝑂3− → 𝐶𝑂3−2 + 𝐻2 𝑂

• No more than two of the three ions (𝑂𝐻 − , 𝐶𝑂3−2 and 𝐻𝐶𝑂3− ) can exist in the solution.
 Acid-base Titration
• If V1 is the volume of acid used from the start of the titration to the phenolphthalein end
point and V2 is the volume from the phenolphthalein end point to the methyl orange end
point, then the relation between V1 and V2 for a single component and mixture are listed in
the table below.

Relative Titrant Volume Constituent(s) in the sample

• V2 = 0 OH-
• V1 = V2 CO32-
• V1 = 0 HCO3-
• V1 > V2 OH- and CO32-
• V1 < V2 CO32- and HCO3-
Estimation of Alkalinity
NHCl x V1, HCl x 50 x 1000
Phenolphthalein Alkalinity, P = ppm
Vw
NHCl x (V1+V2)HCl x 50 x 1000
Total Alkalinity, T= ppm
Vw
Alkalinity due to
Volume (mL)
OH- CO32- HCO3-

V1 = 0, P = 0 0 0 T

V2 = 0, P = T T 0 0

V1 = V2, P = T/2 0 2P 0

V1 > V2 , P > T/2 2P - T 2T - 2P 0

V1 < V2, P < T/2 0 2P T – 2P

 Question
Q. 50 mL of a water sample required 10 mL of N/50 HCl using methyl
orange indicator but did not give any colouration with phenolphthalein.
What is the type and extent of alkalinity present in the solution?

V1 = 0, V2 = 10 mL

HCO3- only.

NHCl x (V1 + V2) x 50 x 1000

T= ppm
Vw

1/50 x (0 + 10) x 50 x 1000

= ppm
50

= 200 ppm
Question
100 mL of a water sample required 12 mL of N/50 HCl to phenolphthalein end point
and 15 mL of the acid to methyl orange end point. What is the type and extent of
alkalinity present in the solution?
V1 = 12 mL, V1+V2 = 15 mL

OH- + CO32- only.

NHCl x V1, HCl x 50 x 1000 NHCl x (V1+V2)HCl x 50 x 1000

P= ppm T= ppm
Vw Vw

1/50 x 12 x 50 x 1000 1/50 x 15 x 50 x 1000

P= = 120 ppm T= = 150 ppm
100 100

OH- = 2P – T = 240 - 150 = 90 ppm

CO32- = 2T – 2P = 300 – 240 = 60 ppm

 Tutorial 1
Q1. 50 mL of standard hard water containing 1 mg of pure CaCO 3 per mL consumed 20 mL of EDTA.
50 mL of water sample consumed 25 mL of same EDTA using EBT. Calculate the total hardness of
water sample in ppm.
Q2. 100 mL of water sample on titration with N/50 HCl requires 8.0 mL of the acid
to phenolphthalien end-point and 9.0 mL of the acid to methyl orange end point. Calculate the type
and extent of alkalinity present in the water sample.
Q3. 100 mL of water sample required 4 mL of N/50 H2SO4 for neutralization to phenolphthalien end
point. Another 16 ml of the same acid was used for further titration to methyl end-point. Determine
the type and amount of alkalinity.
Q4. 0.5 g of CaCO3 was dissolved in HCl and the solution was 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 required 15 mL of EDTA and after boiling and filtering required 10 mL of EDTA solution.
Calculate the hardness.
 Boiler Feed Water
• In industries, water is mainly required for cooling and steam generation purposes.
• Boiler is a heat exchanger which uses radiant heat and hot flue gases, liberated from
burning fuel, to generate steam and hot water for heating and processing loads.
• Water required to feed in boilers must be of high quality.

If used untreated then it may lead to following problems:

o Scale and Sludge Formation.
o Priming and Foaming
o Boiler Corrosion
o Caustic Embrittlement
Scale And Sludge Formation
• In boilers, water is converted into steam. When water containing impurities is used
for generating steam, the concentration of the dissolved salts increases.
• If dissolved salts precipitate in the form of loose, non adherent, slimy precipitates, it
is called sludge.
• If the precipitates form hard, adhering coating on the inner walls of the boilers, it is
called scales.
• Salts responsible for the formation of scales and sludge are CaCO 3, CaSO4, Mg
(OH)2, MgCl2, etc.
• Sludge can be removed easily but scale formation is more dangerous.
Sludge
Slimy loose precipitate
called sludge suspended
in water

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.,
 Sludge
Sludge are formed by the substances having greater solubilities in hot water than in the cold water e.g.
MgCO3, MgCl2, CaCl2, MgSO4 etc.
Disadvantages of Sludge Formation
• Poor conductor of heat so it tends to waste a lot of heat. So boilers require more heat.
• Decrease the efficiency of the boilers.
• Slows down the water circulation as it cause choking of pipes.

Prevention of Sludge Formation

• By using soft water.
• By frequently carrying out the cleaning operations.

Removal of Sludge removed by scrapping off with a brush.

 Scale
Causes:
• Decomposition of bicarbonates: When water containing bicarbonates is heated in the boiler, the bicarbonates
present are converted into insoluble CaCO3.
Ca (HCO3)2 → CaCO3 + CO2 + H2O
• Hydrolysis of Mg Salts: Dissolved magnesium salts undergo hydrolysis forming precipitates of Mg(OH)2.

MgCl2 + 2H2O → Mg(OH)2 + 2HCl

• CaSO4 is less soluble in hot water so it forms hard scale on the heated portions of the boiler. CaSO4 is the
main cause of scale formation in high pressure boilers.

• Silica Salts like calcium silicate, magnesium silicate are completely insoluble. So they form hard scale on
inner boiler surface and are very difficult to remove.
 Disadvantages:
Heating Heating Scale

H2Ovap H2Ovap

Heating Heating

A boiler without A boiler with

scale scale

Wastage of Fuel: Because of low thermal conductivity of the scales, more heat is supplied
to the boiler to maintain the supply of steam leading to wastage of fuels.
 Scale
Disadvantages:

• Bagging: The distortion of boiler material is known as bagging. The superheating of the
boiler leads to the distortion of the boiler material. Due to overheating, it causes thinning of
the boiler material.

• Danger of Explosion: The uneven expansion of the scale may lead to the cracking of the
scale.
Scale
Removal:
• Soft scales are removed with the help of scrapper or wire brush.

• Brittle or hard scales can be removed by giving thermal shocks i.e. heating the boiler
and suddenly cooling with cold water.

• Scales can also be dissolved in certain chemicals and hence can be removed along with
water.
For e.g. CaCO3 scales can be dissolved by using 5-10% HCl. Similarly EDTA
can also be used to dissolve the salts of Ca, with which it forms soluble complexes.
 Boiler Feed Water
• In industries, water is mainly required for cooling and steam generation purposes.
• Boiler is a heat exchanger which uses radiant heat and hot flue gases, liberated from
burning fuel, to generate steam and hot water for heating and processing loads.
• Water required to feed in boilers must be of high quality.

If used untreated then it may lead to following problems:

o Scale and Sludge Formation.
o Priming and Foaming
o Boiler Corrosion
o Caustic Embrittlement
 Priming
• Steam formed due to the extremely rapid boiling of water in the boiler carries away some water droplets with
it. Formation of this wet steam is called priming.
• Refers to the propulsion of water into the steam drum by extremely rapid boiling of water at the heating
surfaces.
• If steam contains 1.5% moisture, its steam quality will be reported as 98.5% (percentage by weight of
steam).
 Priming
• Causes
o Large amount of dissolved salts & high steam velocities.
o Very high water level in the boiler.
o Faulty boiler design.
o Presence of suspended and dissolved impurities in water.
• Prevention
o Controlling rapid change in steaming velocities.
o By blowing off sludge or scale regularly
o Ensuring efficient softening.
o Proper boiler design.
o Filtration of the boiler-water carried over to the boiler.
Foaming
• Foaming : Foaming is the formation of small
persistent bubbles at the surface of water in the
boiler.
• Bubbles are formed due to the difference in
concentration of solute and the bulk of the liquid.
• Any material which lowers the surface tension of
the water will collect at the interface and thus
increase the foaming.
• The substances which increase the viscosity of the
surface film also increase foam forming tendency.
 Foaming
• Prevention

o Adding antifoaming chemicals: Chemicals, such as polyamide antifoamers.

Castor oil spreads on the surface of water and prevents foaming.

o Oil and grease can be removed by addition of coagulants such as sodium

aluminate, ferrous sulphate etc.
Disadvantages of Priming and Foaming
• Priming and foaming are often used synonymously.
• These are highly objectionable because water is contaminated by them.
• Impurities with the steam goes to super heaters or turbine blades, where they get
deposited as the water evaporates.
• These deposits reduce their efficiency by hindering the flow of steam.
• Dried salts may be deposited on the engine valves decreasing their life.
• Water in the steam may lead to corrosion in the super heaters.
• Height of the water column cannot be judged properly due to foaming, thereby
making the maintenance of the boiler pressure difficult.
 Boiler Feed Water
• In industries, water is mainly required for cooling and steam generation purposes.
• Boiler is a heat exchanger which uses radiant heat and hot flue gases, liberated from
burning fuel, to generate steam and hot water for heating and processing loads.
• Water required to feed in boilers must be of high quality.

If used untreated then it may lead to following problems:

o Scale and Sludge Formation.
o Priming and Foaming
o Boiler Corrosion
o Caustic Embrittlement
 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

• In general, corrosion occurs, if Fe of the boiler material combines with the water molecules to form
ferrous hydroxide, which reacts with oxygen to form rust.

Fe2+ + 2H2O → Fe(OH) 2 + 2H+

4Fe(OH) 2 + O2 → 2 [Fe2O3. 2H2O]
[ Rust ]
Boiler Corrosion
Disadvantages:
• Shortening of boiler life
• Leakages of the joints and rivets
• Increased cost of repairs and maintenance

Main reasons for boiler corrosions are:

o Presence of dissolved oxygen.
o Presence of dissolved carbon dioxide.
o Presence of Mineral Acids.
Dissolved Oxygen
• When water containing dissolved oxygen is heated in the boiler, evolved free gas with high
temperature of boiler attacks the boiler material.
2 Fe + 2H2O + O2 → 2Fe(OH)2
4Fe(OH)2 + O2 + 2H2O → 2 [Fe2O3. 2H2O]

Removal of dissolved Oxygen:

Chemical Means: Oxygen can be removed by adding calculated amounts of certain chemicals such as
Na2SO3, Na2S and N2H4.

2 Na2SO3 + H2O + O2 → 2 Na2SO4 + H2O

N2H4 + H2O + O2 → N2 + 3H2O

Dissolved Oxygen

Mechanical Means: Mechanical deaeration Water feed

involves, injecting hot feed-water, as a fine spray,

Pr = 10-1 mbar
into a vacuum chamber heated externally by
O2
steam. The chamber is fitted with perforated To vacuum

plates to provide large surface area. Large

Steam jacket
exposed surface, high temperature, and low
pressure reduces the solubility of the gas, the
water free of dissolved oxygen is collected at the Perforated
plate
bottom.

Deaerated
water
62
Dissolved CO2
• CO2 is formed by the decomposition of dissolved bicarbonates at high temperature of boiler.
Mg (HCO3)2 → MgCO3 + CO2 + H2O.

• CO2 forms carbonic acid in presence of water which has slow corrosive effect on boiler
material.
CO2 + H2O → H2CO3 Carbonic acid

Removal of dissolved CO2:

Chemical means: By addition of calculated amount of NH4OH.
2 NH4OH + CO2 → (NH4)2CO3 + H2O

Mechanical means: Similar process as discussed in removal of oxygen.

 Presence of Acids
• Free mineral acids, present in boiler water, reacts with iron material in
the following way
Fe + 2HCl → FeCl2 + H2

FeCl2 + 2H2O → Fe(OH)2 + 2HCl

Fe(OH)2 + O2 → 2[Fe2O3.2H2O]

• Thus a small amount of HCl may lead to corrosion to a great extent.

• If the water is acidic, calculated amount of alkali is added to neutralize

it.
 Boiler Feed Water
• In industries, water is mainly required for cooling and steam generation purposes.
• Boiler is a heat exchanger which uses radiant heat and hot flue gases, liberated from
burning fuel, to generate steam and hot water for heating and processing loads.
• Water required to feed in boilers must be of high quality.

If used untreated then it may lead to following problems:

o Scale and Sludge Formation.
o Priming and Foaming
o Boiler Corrosion
o Caustic Embrittlement
Caustic Embrittlement
• Type of boiler corrosion due to high alkaline water in the boiler.

• Boiler material becomes brittle due to accumulation of caustic substance.

• During the softening of water by lime-soda process a slight excess of Na2CO3 is

used for the complete removal of calcium and magnesium salts.

• In low pressure boilers, treatment with Na2CO3 is quite satisfactory but in high
pressure boilers the free Na2CO3 present forms NaOH as
Na2CO3 + H2O→ 2NaOH + CO2
 Caustic Embrittlement
Na2CO3 + H2O → 2 NaOH + CO2
This also causes embrittlement of boiler
parts like rivets, bends and joints, which are
Fe + 2 NaOH ----> Na2FeO2 + H2 under stress and are also called stress
corrosion
3Na2FeO2 + 4H2O ------> Fe3O4+ 4H2+ 6NaOH

Sodium Ferroate

Na2CO3

BFW
When there is a minute crack on the wall of the
Crack boiler NaOH gets enriched in the minute crack and
NaOH
reacts with Fe to form Sodium Ferroate which
8/18/2023 Boiler wall results in the corrosion of boiler wall 67
made of Fe
Caustic Embrittlement
Prevention of Caustic Embrittlement:

• Using sodium phosphate as softening reagent instead of sodium carbonate.

• By adding liquids or tannin to boiler water. These block up the hair cracks thus
prevent the infiltration of NaOH.
• It is preferable to use Na3PO4 instead of Na2SO4. It is over 300 times as effective as
Na2SO4 in suppressing embrittlement.
Prevention/Treatment of Scale
• The scale formation can be minimized by subjecting the boiler feed water to
certain treatments

Water
Softening

External Internal
Treatment Treatment

Zeolite Lime-soda Ion-exchange Colloidal Carbonate Phosphate Calgon

Process Process Process Conditioning Conditioning Conditioning Conditioning

• External treatment: treatment of water before its entry into the boiler.

• Internal Treatment: treatment of water in the boiler itself.

 Internal Treatment

The methods used for internal treatment of water are:

1. Colloidal Conditioning
2. Carbonate Conditioning
3. Phosphate Conditioning
4. Calgon conditioning
 Colloidal Conditioning

• Scale formation can be reduced by introducing colloidal substances

like kerosene, tannin, glue, agar etc. to the boiler water.

• These substances act as protective coatings.

• They surround the minute particles of scale forming salts and

prevent their coalescence and coagulation.

• Hence, the salts remain as loose, non-sticky deposits in the form of

sludge, which can be removed by simple 'blow down operation’.
Carbonate Conditioning
• Scale forming salts like CaSO4 present in water are
precipitated as insoluble CaCO3 by the addition of sodium
carbonate.

CaSO4 + Na2CO3 → CaCO3 + Na2SO4

• The lose and slimy precipitate (sludge) of CaCO3 formed is

removed by blow-down operation.
 Phosphate Conditioning
• Hardness causing salts are converted into non-adherent and easily removable
soft sludge of their phosphates by treating them with sodium phosphates.

3MCl2 + 2Na3PO4 → M3(PO4) 2 + 6NaCl

3MSO4 + 2Na3PO4 → M3(PO4) 2 + 6NaSO4

where M = Ca2+ and Mg2+

• Calcium can be properly precipitated at a pH of 9.5 or above. Therefore, the

choice of phosphate salt depends upon the alkalinity of boiler-feed water.
NaH2PO4 (acidic in nature) → used for highly alkaline water.
Na2HPO4(weakly alkaline in nature) → used for moderate alkaline water
Na3PO4 (Alkaline in nature) → used for low pH (acidic) water
Calgon Conditioning

• Calgon is the commercial name of sodium hexametaphosphate.

• Ca2+ from the scale forming salts is trapped by the phosphate
and forms complex, which is soluble in water and remains in the
dissolved form without causing any harm to the boiler.

Na2[Na4(PO3)6] → 2Na+ + [Na4(PO3)6]2-

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

External Treatment

Lime Soda Process

Zeolite Process

Ion Exchange Process

LIME-SODA PROCESS

• The soluble calcium and magnesium salts in water are chemically

converted into insoluble compounds.

• Done by adding calculated amounts of lime Ca(OH)2 and soda

Na2CO3.

• Resulting calcium carbonate CaCO3 and magnesium hydroxide

Mg(OH)2 get precipitated and are filtered off.
LIME-SODA PROCESS

Permanent Hardness:
• 𝐶𝑎𝐶𝑙2 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 ↓ + 2𝑁𝑎𝐶𝑙
• 𝑀𝑔𝑆𝑂4 + 𝐶𝑎(𝑂𝐻)2 → 𝑀𝑔(𝑂𝐻)2 ↓ + 𝐶𝑎𝑆𝑂4
• 𝐶𝑎2+ + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 ↓ + 2𝑁𝑎+

Temporary Hardness:
• 𝐶𝑎(𝐻𝐶𝑂3 )2 + 𝐶𝑎(𝑂𝐻)2 → 𝐶𝑎𝐶𝑂3 ↓ +2𝐻2 𝑂
• 𝑀𝑔(𝐻𝐶𝑂3 )2 + 2𝐶𝑎(𝑂𝐻)2 → 𝐶𝑎𝐶𝑂3 ↓ +𝑀𝑔(𝑂𝐻)2 ↓ +2𝐻2 𝑂
COLD LIME-SODA PROCESS

• Calculated quantity of chemicals (lime and soda) is mixed with

water at room temperature.

• At room temperature, the carbonates of metal ions are precipitated

as fine powder and settle down very slowly.

• Coagulants (Like Alum, aluminum sulphate, sodium aluminate, etc.)

are added to grow the size of carbonates and settle down quickly.
Schematic Diagram of Cold Soda Lime Softener
 Continuous lime soda softener

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

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2
 HOT LIME-SODA PROCESS

• Involves treating water with softening chemicals at temperature of 90 to 100 °C.

• Since hot process is operated at a temperature close to the boiling point of the
solution, so
o the reaction proceeds faster;

o the softening capacity of hot process is increased to many fold;

o the precipitate and sludge formed settle down rapidly and hence, no
coagulants are needed;

o Viscosity of softened water is lower, so filtration of water becomes much

easier. This in-turn increases the filtering capacity of filters.
Schematic Diagram of Hot Soda Lime Softener
Advantages of LIME SODA Process

• It is a very economical
• If this process is combined with sedimentation via coagulation, lesser
amounts of coagulants shall be needed.
• Besides the removal of hardness, the quantity of minerals in the water are
reduced.
• To certain extent, iron and manganese are also removed from the water.
Disadvantages of LIME SODA Process

• For efficient and economical softening, careful operation and skilled supervision
is required.

• Disposal of large amounts of sludge (insoluble precipitate) poses a problem.

However, the sludge may be disposed off in raising low-lying areas of the city.

• This can remove hardness only up to 30 ppm to 15 ppm (HLS) and 60 to 50 ppm
(CLS), which is not good for boilers.
Zeolite Process
• Hydrated sodium alumino silicate
minerals: Na2O. Al2O3. xSiO2 .yH2O
where x = 2-10 and y = 2-6.

• Zeolite is capable of exchanging

reversibly its sodium ions with
hardness-causing ions in water.

Micro pores
 Schematic Diagram of Zeolite Softener

• Hard water is percolated at

a specified rate through a
bed of zeolite; kept in a
cylinder.

• The Hardness causing ions

(𝐶𝑎2+ , 𝑀𝑔2+ etc.) are retained
by the zeolite as CaZe and
MgZe; while the outgoing
water contains sodium salts.
Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through the zeolite
bed at a specified rate. The hardness causing ions such as Ca2+, Mg2+ are retained by the
zeolite bed as CaZe and MgZe respectively; while the outgoing water contains sodium salts.
The following reactions takes place during softening process
To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

Ca2+
To remove permanent hardness

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4
Regeneration of Zeolite Bed

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

Used 10% brine Regenerated Washings
Zeolite solution Zeolite drained
 Zeolite softener Construction of Zeolite Softener

Hard water
in

Hard water
Ca Cl2
spray

NaCl
NaZe Zeolite bed Na Ze
Gravel

Injector

CaCl2
Softened
To sink water
NaCl storage

8/18/2023 88
Zeolite Process
ADVANTAGES:

• The hardness is removed almost completely

• Equipment occupying a small space

• Requires less time

DISADVANTAGES:

• Treated water contains more sodium salts than in lime soda process

• The method only replaces 𝐶𝑎2+ 𝑎𝑛𝑑 𝑀𝑔2+ ions by 𝑁𝑎+ ions; leaves all the
anions.
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 chain is responsible for the “ion-exchange” properties.

• Modern ion exchange resins are man-made materials which exchange or

‘swap’ ions that cause hardness (Ca2+, Mg2+) with ions that do not cause
hardness (Na+).
 ION EXCHANGE PROCESS

• The hard water is passed through a

cation exchange resin.

• The resins used are complex sodium

compounds and represented as RNa.

• The Ca2+ and Mg2+ ions in the hard

water swap with the Na+ ions in the
resin:

• 2RNa(s) + Ca2+(aq) → R2Ca(s) + 2Na+(aq)

• Eventually the resin loses all of its Na+

ions and it needs to be regenerated by
passing sodium chloride solution
through it.
Structure of Cation and Anion exchange resins

Cation exchange resin (acidic/ styrene-divinyl Anion exchange resin (basic/ styrene-divinyl
benzene copolymer) benzene or amine-formaldehyde copolymer)

- CH – CH2 – CH – CH2 – CH – CH2 - - CH – CH2 – CH – CH2 – CH – CH2 -

SO3H SO3H CH2NR+3OH- CH2NR+3OH-

-CH – CH – CH- -CH – CH – CH-
-CH2 - CH CH – CH2- -CH2 - CH CH – CH2-

SO3H SO3H CH2NR+3OH-

CH2NR+3OH-
 Ion exchange purifier (or) softener
Hard
water

Gravel
2Cl- 4H+ SO 2-
bed
Cation exchange Resin Anion exchange Resin
4
Ca2+ 2Cl- Mg 2+
SO42-
Injector
4H+
Injector
4OH-

Acid solution for Wastages to

regeneration of sink
Alkaline solution
resin Wastages to
for regeneration
sink of resin
pump

8/18/2023 Soft water 93

 ION EXCHANGE PROCESS

Process of softening Advanced Ion Exchange Precautions:

Reactions occurring at Cation exchange resin

1. Best applied for additional softening following lime-
2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+ soda softening, or Softening water that is not too
2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+
hard to begin with, say <10 PPM

2. Ion exchange should not be used when the

Reactions occurring at Anion exchange resin
concentrationof Fe, Mn, or the combination exceeds
0.3 mg/L
2 ROH- + SO42- (hard water) R2SO42- + 2 OH-
2 ROH- + Cl- (hard water) R2Cl- + 2 OH- 3. Ion exchange should not be used on raw or wash
waters containing (high) dissolved oxygen
At the end of the process

H+ + OH- H2 O
8/18/2023 94
 Regeneration Process
Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) 2 RH+ + Ca2+ (CaCl2, washings)

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH) 2 ROH- + SO42- (Na2SO4, washings)

Advantages
1. The process can be used to soften highly acidic or alkaline waters
2. It produces water of very low hardness of 2ppm. So the treated waters by this method can be used in high
pressure boilers
Disadvantages
1. The setup is costly and it uses costly chemicals
2. The water should not be turbid and the turbidity level should not be more than 10ppm
Deionisation
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 exchange
resin
c Mixed bed Mixed
a deionizer a resin bed
a
c a cc Cation exchange
resin

Demineralised
water
Distillation:
• Involves boiling the water and then cooling the vapour
• ALL dissolved and suspended solids and dissolved liquids are removed from the water
• not used on a large scale to soften water due to the expense involved in boiling the water
Specification of Drinking Water

• Primary Standards: Primary standards specify the maximum

contaminant levels of various dissolved minerals based on their
effect on human health. (toxic substances)

• Secondary Standards: vary from place to place depending upon

the taste, odour, colour and hardness of water etc. and do not
have any anticipated effect on the health. (less toxic species)
Requisites of Drinking Water
• Free from objectionable minerals.

• pH value ranging from 6.5 to 8.5.

• Total dissolved solids should be less than 500 ppm.

• Free from pathogenic microorganisms.

• Suspended matter should not exceed 10 ppm.

• Free of Fe & Mg, permissible limit being 0.3 mg/L and 0.05 mg/L resp.

• Free from objectionable dissolved gases like H2S.

• Clear, odourless and should have pleasant taste.

Water Treatment for Domestic/Municipal
Purpose

Disinfection by
Raw Water Storage & For removal of
Chlorination/ozone
from Source Distribution /UV rays Pathogenic bacteria

For Removal For removal of

Screening of Floating Filteration Colloidal matter &
Matter Microorganisms

For Removal Coagulation & For removal of

Sedimentation of insoluble Fine particles
Sedimentation
impurities
Screening:
Water is first passed through a wire mesh to remove any floating debris –
twigs, plastic bags etc.
Sedimentation:
Process of allowing water to stand undisturbed in big tanks for 2-8 hours

so that the suspended particles settle down at the bottom.

Coagulation:
• Fine particles of clay & silica doesn’t settle down by sedimentation.
• A coagulant is added, which entraps the fine particles of clay & silica
making bigger particles which settle down easily.
• Most commonly used coagulants: Alum [K2(SO4)3. Al2 (SO4)3. 24H2O],
sodium aluminate [NaAlO2] and ferrous sulphate [FeSO4. 7H2O].
Filtration:
• The water, from top of settlement tanks, is allowed to fall through beds of graded sand and gravel.

• These filter beds remove any remaining suspended solids.

• The sand acts just like a sieve or filter paper in removing the suspended solids.
Filter

Concrete Tank
3 ft. Fine Sand

1 ft. Coarse Sand

8 ft. Gravel Sand

Sedimented Water
Under drain channel

Filtered
Water

Rapid gravity filter

• Particles removed are in the range of 0.1 to 100 mm.

Filtration tank

Fine sand

Coarse sand
Water
feed Gravel

Filtered
Water
Disinfection:
• Process of destroying pathogenic bacteria and
microorganisms is known as sterilization or disinfection.

• Physical disinfection techniques include boiling and

irradiation with ultraviolet light.

• Chemical disinfection techniques include adding

chlorine, bromine, iodine, and ozone to water.

• Chemicals used for disinfecting are known as

disinfectants.
Sterilization (boiling):

• Boiling kills bacterial cells, but spores, viruses, and some

protozoa may survive long periods of boiling.

• Boiling is an effective method for small batches of water

during water emergencies.

• Boiling is prohibitively expensive for large quantities of

water.
UV radiation:
• Ultraviolet radiation is an effective and relatively safe
disinfection method, but is relatively expensive and not
widely used.

• UV light disrupts DNA of microbial cells, preventing

reproduction.

• Specific wavelengths, intensities, flow rates, and

retention times are required.
Chlorine disinfection:

• Chlorination is a cheap, effective, relatively harmless (and therefore

most popular) disinfection method.

• Chlorine is added to water in following forms: Chlorine gas/liquid,

bleaching powder (CaOCl2)/hypochlorites (NaOCl), tablets, chloramines.
Bleaching Powder • Hypochlorous (HOCl) and hypochlorite
• CaOCl2 + H2O → Ca(OH) 2 + Cl2 ions are strong chemical oxidants, and kill
• Cl2 + H2O → HCl + HOCl Hypochlorous Acid microbes.
• HOCl → HCl + [O] • Over chlorination (> 0.2 ppm) produces bad
odour & taste in water. Dechlorination
removes excess chlorine from water.
Chlorine Gas
• Cl2 + H2O → HCl + HOCl
• HOCl + H2O → H3O+ + OCl- Hypochlorite Ion
• OCl- → Cl- + [O]
Ozonation
• Ozone can be produced by passing high
voltage electric current through a stream
of air in a closed chamber.

3O2 → 2O3. Raw Hard

Water
O inlet
3
O3 → O2 + [O]
Sterilized water Sterilizing
• Nascent oxygen is a powerful oxidizing Chamber

agent which removes the organic matter

& kills the bacteria.

• Ozone removes colour, odour & taste

from water.
 Desalination
• Processes that remove some amount of salt (mainly sodium chloride) and other
minerals from Water.
• Brackish Water: contain 3.5 % salts & salty taste. Unfit for drinking

Commonly used methods:

• Electrodialysis: ions are pulled out of the salt water by passing electric current.
• Reverse Osmosis
Electrodialysis
Reverse Osmosis

Reverse Osmosis
Reverse Osmosis Direction of Osmosis

Direction of Reverse Osmosis

Salt Water
Pure water
Apply a
hydrostatic
H2O Na+ Cl-
pressure in Piston H2O

excess of H2O
H2O
Na+ Cl-
H2O
osmotic Na+ Cl- Na+ Cl-
H2O
pressure H2O
Na+ Cl-
H2O H2O

Semi permeable
membrane

Figure: Purification of water by RO Method

Thank you!