Engineering Chemistry

WINTER Semester
2021 –22

Instructor: Dr. Satyam Ravi

VIT Bhopal
Syllabus Structure

Impurities of Industrial and

water and its Conducting
treatment polymers

Phase equilibria
Energy sources
and Alloys

Energy
Electrochemistry
conversion and
- Corrosion
storage
 Course Plan

• 12-18 sessions

• N Assignments

• M Quizzes

• Practical / Theoretical project

Session 1
 C

D
E
A

Processes?
 Impurities In Water

Physical • Suspended Impurities

Impurities • Colloidal Impurities

• Bacteria
Bacteriological • Algae
Impurities • Fungi

• Dissolved Gases
Chemical • Dissolved Organic Salts
Impurities • Dissolved Inorganic Salts
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+ ) and Magnesium (Mg2+) ions.

CaCO3 CaCl2
MgCO3 MgCl2
Ca(HCO3)2 CaSO4
Mg(HCO3) 2 MgSO4
How do Ca2+ and Mg2+ get into water?

Limestone pavement

Limestone, 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
Types of rocks across India. Water types?

• Hard water
• Soft water
Differences b/w 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

magnesium salts calcium and magnesium salts.

Cleansing action of soap is Cleansing action of soap is not

suppressed suppressed

Requires more material and time Does not require excess material
and time
Temporary hardness
Causes: Calcium hydrocarbonate – Ca(HCO3)2
Magnesium hydrocarbonate – Mg(HCO3)2

Removal: boiling the water

Ca(HCO3) 2 → CaCO3 + H2O + CO2
Mg(HCO3)2 → Mg(OH)2 + 2 CO2

Permanent hardness
Causes: chlorides and sulphates of Ca2+, Mg2+, Fe3+
e.g. CaCl2, MgSO4

Removal: not by boiling the water

Sophisticated water treatment methods
 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
❖ It prevents the poisonous lead dissolved in drinking water.
 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
CaCO3 Equivalent =
Chemical equivalent of X

NOTE: There may be no Calcium carbonate in the sample at all!!! But we are
expressing it as an equivalence.
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

100 / 162 = 50 / 81
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

Units of Hardness
1 ppm = 1 part by weight of CaCO3 1 mg/L = 1 mg of CaCO3 equivalent
equivalent in 106 parts by weight of in one litre of water.
water.

Part per 1 ppm = 1 mg/L Milligrams

million per litre
(ppm) (mg/L)

1 ppm = 0.1 °Fr Units of

Hardness

Degree Clarke’s
French Degree
(°Fr) (°Cl)

1 °Fr =1 part of CaCO3 equivalent in 1 °Cl = 1 part of CaCO3 equivalent in

105 parts of water. 70, 000 parts of 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)

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 = 110.29 mg/L
68
 AAS analysis of a water sample determined the Ca2+ hardness to be 36 mg/L and the
Mg2+ hardness to be 16 mg/L. What is the total hardness expressed as CaCO3
equivalents?

36 mg Ca2+ * 50 g CaCO3 = 90 mg/L as CaCO3

20.05 g Ca2+

16 mg Ca2+ * 50 g CaCO3 = 66 mg/L as CaCO3

12.15 g Mg2+

Total hardness = 90 + 66 = 156 mg/L as CaCO3

Calculate hardness of all salts/ions → Type of substance → Type of hardness

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

• 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.
 M2+ + EDTA4- → [ 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:

Erichrome 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
• Excess EDTA causes a red to blue color change at near neutral pH.
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.

• Total hardness is thus determined:

o MEDTA x VEDTA = MUHW x VUHW

o Strength (gms/L) = MUHW x Molar mass of CaCO3
o Total hardness.
 Hardness Calculation

𝑇𝐻 𝑆𝑡𝑑
𝑉𝐸𝐷𝑇𝐴 𝑉𝑆𝐻𝑊
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 × 1000 × 𝑇𝐻 × 𝑆𝑡𝑑 𝑚𝑔/𝐿
𝑉𝑆𝐻𝑊 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
𝑉𝑆𝐻𝑊 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 × × = 150 𝑚𝑔/𝐿
100 28

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 350 − 150 = 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 𝑯𝑪𝑶−
𝟑 or mixture of 𝑂𝐻 and 𝐶𝑂3 or mixture of 𝐶𝑂3
− −2 −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 0 0 T

V2 = 0 T 0 0

V1 = V2 0 2P 0

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

V1 < V2 0 2P T – 2P
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
 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

 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 takes place 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 CaCO3, CaSO4, Mg (OH)2
MgCl2, and SiO2 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 lot of amount 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 in hot
water. 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 scale A boiler with 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.
 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 The high steam velocities.
o Very high water level in the boiler.
o Sudden steam demands leading to sudden drop of pressure in the steam line
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,

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

o Removing oil from boiler water also 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 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
Fe(OH)3, or 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

N2H4 + H2O + O2 → N2 + 2H2O

Mechanical Means: Mechanical deaeration involves, injecting hot feed-water, as a fine
spray, into a vacuum chamber heated externally by steam. The chamber is fitted with
perforated plates to provide large surface area. Large exposed surface, high temperature,
and low pressure reduces the solubility of the gas, the water free of dissolved oxygen is
collected at the bottom.
Water feed

Pr = 10-1 mbar

O2 To vacuum

Steam jacket

Perforated
plate

Deaerated
59
water
 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.

 Caustic Embrittlement
• 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
This also causes embrittlement of boiler
Na2CO3 + H2O → 2 NaOH + CO2
parts like rivets, bends and joints, which are
under stress and are also called stress
corrosion

Fe + 2 NaOH ----> Na2FeO2+ H2

3Na2FeO2 + 4H2O ------> Fe3O4+ H2+ ????

Sodium Ferrate

Na2CO3
When there is a minute crack on the wall of the
BFW boiler NaOH gets enriched in the minute crack and
reacts with Fe to form Sodium Ferrate which results
in the corrosion of boiler wall
Crack NaOH

Boiler wall
8/7/2023
made of Fe 63
 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.
• Boiler waters containing Na2SO4 or Na3PO4 block capillaries, thereby preventing the
infiltration of caustic soda solution to these.
• However, 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.
• The process increased the pH value of the treated water, thereby
corrosion of the distribution pipes is reduced.
• 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 15 ppm, 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
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

8/7/2023 83
 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 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 a concentrated solution of sodium chloride
through it.
 Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

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

SO-3H+ SO-3H+ CH2NR+3OH- CH2NR+3OH-

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

SO-3H+ SO-3H+ 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

8/7/2023 Soft water 90

Process of softening

Reactions occurring at Cation exchange resin

2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+

Reactions occurring at Anion exchange resin

2 ROH- + SO42- (hard water) R2SO42- + 2 OH-

2 ROH- + Cl- (hard water) R2Cl- + 2 OH-
Advanced ion exchange softening-
Precautions
At the end of the process
1. Best applied for additional softening following lime-
H+ + OH- H2O soda softening, or
Softening water that is not too hard to begin with,
say <10 PPM

2. Ion exchange should not be used when the

concentration
of Fe, Mn, or the combination exceeds 0.3 mg/L

3. Ion exchange should not be used on raw or wash

8/7/2023 waters containing (high) dissolved oxygen 91
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
8/7/2023 94
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.

• 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.
 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].
Settlement (Sedimentation):

• The flocculated water is pumped into the bottom of large settlement

tanks and rises up slowly (allows maximum settlement to take
place atthe bottom of the tank) to the surface where clear water is
collected in channels

• The suspended particles settle to the bottom.

• Approximately 90% of particles are removed in settlement stage.

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.

Filters
 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 vegetative 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, distances, 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,
ClO2 gas.
 Bleaching Powder
• CaOCl2 + H2O → Ca(OH) 2 + Cl2
• Cl2 + H2O → HCl + HOCl Hypochlorous Acid
• HOCl → HCl + [O]

Chlorine Gas
• Cl2 + H2O → HCl + HOCl
• HOCl + H2O → H3O+ + OCl- Hypochlorite Ion
• OCl- → Cl- + [O]

• Hypochlorous (HOCl) and hypochlorite ions are strong chemical oxidants,

and kill microbes.
• Over chlorination (> 0.2 ppm) produces bad odour & taste in water.
Dechlorination removes excess chlorine from water.
 Ozonation

• Ozone can be produced by passing high

voltage electric current through a stream
of air in a closed chamber. Raw Hard
Water
O inlet
3O2 → 2O3. 3

O3 → O2 + [O] Sterilized water Sterilizing

Chamber

• Nascent oxygen is a powerful oxidizing

agent which removes the organic matter
& kills the bacteria.

• Ozone removes colour, odour & taste

from water.
Filtration tank

Fine sand

Coarse sand
Water
feed Gravel

Filtered
Water

8/7/2023 111
 Desalination
• Processes that remove some amount of salt and other minerals from Water.
• Brackish Water: contain 3.5 % salts & salty taste. Unfit for drinking

Commonly used methods:

• Electrodialysis
• Reverse Osmosis
Electrodialysis
Reverse Osmosis

Reverse Osmosis
 Direction of Osmosis

Direction of Reverse Osmosis

Salt Water
Pure water

H2 O Na+ Cl-
Piston H2O
H2O Na+ Cl-
H2O H2O
Na+ Cl- Na+ Cl-
H2O
H2O H2O
H2O
Na+ Cl-

Semi permeable
membrane

Figure: Purification of water by RO Method

Pure H2O
© S. Arockiasamy, VITC