CHY 1701 – Engineering

Chemistry

Module – I
Water Technology

Dr. M. Akhila Maheswari

Cabin: SJT 611B
akhila.maheswari@vit.ac.in
akhila.maheswari@gmail.com
1
 Contents
• DO and its determination
• Characteristics of hard water – hardness
• Numerical problems in hardness
determination by EDTA
• Disadvantages of hard water in industries

2
 Water

“Without food, human can survive for number of days, but

water is such an essential that without it one cannot
survive”.
“Water is nature’s most wonderful, abundant and useful
compound yet, is also the most misused one”.

3
Distribution of water

4
Deep Ground Water No pathogens, rich in
dissolved solids
carbonates & sulphates Ca
and Mg or Fe
Shallow Ground Variable bacteriological
water quality, soluble materials
including toxic metals of
As, Zn & Cu
Upland Lakes & Bacteria levels usually low,
Reservoirs rich in organic & inorganic
matters, pH adjustment
required
Rivers, Canals & Low Significant Bacterial levels,
land Reservoirs suspended solids &
dissolved constituents
 Impurities in water

Physical Biological
Temperature, Microorganisms
Dust Bacteria
Clay Chemical
Fungi
Sand Algae
Other suspended Acid rain
Dissolved CO2 Pathogens
particles
Minerals
Dissolved salts
Synthetic organic compounds
Radioactive substances
Oxygen demanding wastes
Plant nutrients
Effect of impurities on water

• Bad taste, colour & odour

• Hardness, corrosiveness, staining
• Decrease in DO level
• Increase in BOD/COD
• Causes various diseases and
infections
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases

Hardness

Alkalinity
Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2
Magnesium Carbonate other suspended matter H2 S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

8
 Total Dissolved Solids
Total Dissolved Solids (TDS) are the total amount of mobile charged
ions, including minerals, salts or metals dissolved in a given volume of
water, expressed in units of mg per unit volume of water (mg/L), also
referred to as parts per million (ppm).

Total dissolved solids (TDS) is a measure of the combined content of all

inorganic and organic substances contained in a liquid in molecular,
ionized or micro-granular (colloidal sol) suspended form.

Generally, the operational definition is that the solids must be small

enough to survive filtration through a filter with two-micrometer
(nominal size, or smaller) pores.

Total dissolved solids are normally discussed only for freshwater systems,
as salinity includes some of the ions constituting the definition of TDS.

The principal application of TDS is in the study of water quality for

streams, rivers and lakes, although TDS is not generally considered a
primary pollutant (e.g. it is not deemed to be associated with health
effects). 9
TDS continued---

Primary sources for TDS in receiving waters are agricultural and

residential runoff, leaching of soil contamination and point source
water pollution discharge from industrial or sewage treatment plants.

The most common chemical constituents are calcium, phosphates,

nitrates, sodium, potassium and chloride.

The chemicals may be cations, anions, molecules or agglomerations

on the order of one thousand or fewer molecules, so long as a soluble
micro-granule is formed.

More exotic and harmful elements of TDS are pesticides arising from
surface runoff.

Water can be classified by the amount of TDS per liter:

•Fresh water < 1000 mg/L TDS
•Brackish water 1000 to 10,000 mg/L TDS
•Saline water 10,000 to 30,000 mg/L TDS
•Brine > 30,000 mg/L TDS
10
 DO (Dissolved Oxygen)

• Number of molecules of O2 dissolved in one litre of water –

Expressed as mg/L (ppm).
• One of the best indicators to understand the health of the water
body and life sustaining ability.
• Most life supporting water systems – 4-6 mg/L of DO
• Factors affecting DO levels
– Water temperature
– Organic waste
– Aquatic plant populations
– Water flow
– Altitude (atm. Pressure)
– Human activities

11
DO levels

12
DO vs Aquatic life

13
14
 DO determination - Winkler’s method
• Iodometric titration
• Redox chemistry is involved
• Sources of error – presence of nitrites and hydrogen
sulphide in the water sample.

15
16
 Calculation - DO

1 mole of O2 = 2 moles of I2 = 4 moles of Na2S2O3

1 mole of Na2S2O3 = ¼ mole of O2 = 8 g of O2
1mL of 1N Na2S2O3 = 8 mg of O2
‘V’ mL of ‘N1’N Na2S2O3 = 8 x V x N1

DO of water sample = 8 x Vol. of Na2S2O3 consumed x Normality of Na2S2O3 x 1000

Volume of water sample taken

DO of the water sample is expressed in mg/L (ppm)

17
 Biological Oxygen Demand
Biological oxygen demand (BOD) is the amount of dissolved oxygen
needed by aerobic biological organisms in a water body to break down
organic material present in a given water sample at certain
temperature over a specific time period.
The BOD value is most commonly expressed in milligrams of oxygen
consumed per litre of sample for the biologically oxidizable impurities
during 5 days of incubation at 20 °C and is often used as a robust
surrogate to determine the degree of biodegradable organic pollution
in water.
BOD is similar in function to COD, in that both measure the amount of
organic compounds in water. However, COD is less specific, since it
measures everything that can be chemically oxidized, rather than just
levels of biologically active organic matter.

18
 Chemical Oxygen Demand (COD)
Chemical oxygen demand (COD) test is commonly used to
indirectly measure the amount of organic compounds in water.

Most applications of COD determine the amount of organic

pollutants found in surface water (e.g. lakes and rivers) or
wastewater, making COD a useful measure of water quality.

The chemical oxygen demand determines the

amount of oxidizable organic pollutants found in
surface water, making COD a useful measure of
water quality.

It is expressed in milligrams per litre (mg/L), which indicates the

mass of oxygen consumed per litre of solution.

The basis for the COD test is that nearly all organic compounds
can be fully oxidized to carbon dioxide with a strong oxidizing
agent under acidic conditions. The amount of oxygen required to
oxidize an organic compound to carbon dioxide, ammonia, and
19
water.
 COD Estimation

The COD is determined by refluxing the sample in the presence of

excess K2Cr2O7, which serves as oxidizing agent. The solution is
acidified with H2SO4, and Ag2SO4 is added as a catalyst to speed the
oxidation of low-molecular-weight fatty acids.

Mercuric sulfate, HgSO4, is added to complex any chloride that is

present, thus preventing the precipitation of the Ag+ catalyst as AgCl.

After refluxing for 30 min, the solution is cooled to room temperature,

and the excess Cr2O72- is determined by a back titration, using ferrous
ammonium sulphate as the titrant and ferroin as the indicator.

Since it is difficult to completely remove all traces of organic matter

from the reagents, a blank titration must be performed.

The difference in the amount of FAS needed to titrate the blank and the
sample is proportional to COD.

20
 Calculation
COD of water (mg/L) = (A-B) x M x 8 x 1000
V

A = FAS used for Blank (mL)

B = FAS used for sample (mL) = unreacted dichromate
M = Molarity of FAS
V = Volume of water sample (mL)

21
 Hard Water
What’s hard water?

Practically speaking, measurement of:

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

Hardness as calcium carbonate

mg/L (ppm)

Soft 0-17
Moderately hard (Medium) 60-120
Hard 120-180
Very hard 180 & over

22
 Why be concerned about Hard Water?

• Originally, water hardness was defined as the measure of

the capacity of the water to precipitate soap

• Hard water does cause soap scum, clogs pipes and clogs
boilers as lime scale

23
 Disadvantages of Hard water
Domestic Use Industrial Use
✓ Washing ➢ Textile industry
do not lather with soap, silky (wastage of soap, precipitates of Ca
& Mg adhered to the fabric- which
precipitates of Mg and Ca
don’t produce the exact shades)
C17H35COONa + H2O C17H35COOH + NaOH
➢Sugar Industry
Lather
C17H35COOH + C17H35COONa
(water containing sulphates,
✓ Bathing nitrates, alkali carbonates etc.
Cleansing quality of soap is poor causes difficulties in sugar
crystallization)
✓ Cooking
elevated boiling point; more fuel for ➢Concrete making
cooking (hydration of cement as well as
concrete strength)
✓ Drinking
bad effect in digestive ➢Pharmaceutical Industry
system; possibility of forming calcium (May produce undesirable
oxalate crystals in urinary tracks substance)
 Hard water and soap

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

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

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

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

25
 Hardness of Water

• Hardness in Water is characteristic that prevents the

‘lathering of soap’ thus water which does not produce lather
with soap solution readily, but forms a white curd is called
hard water.

• Type of Hardness

– Temporary or Carbonate Hardness

– Permanent Hardness or non-carbonate Hardness.

26
 Types of Hardness

Temporary Hardness (or) Permanent Hardness (or)

carbonate hardness noncarbonate hardness
-Dissolved bicarbonate salts of Ca - presence of chlorides and
and Mg and other heavy metals such sulphates of Ca, Mg and
as iron other heavy metals)
-Can be removed easily by boiling - Can’t be removed by simple
boiling
Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 Mg(OH)2 + 2CO2

 Temporary Hardness (Alkaline hardness)
– Temporary Hardness is caused by the presence of dissolved
bicarbonate of calcium, magnesium

It is mostly destroyed by more boiling of water, when bicarbonates

are decomposed yielding insoluble carbonates.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Calcium bicarbonate Calcium Carbonate

Mg(HCO3)2 Heat Mg(OH)2 + 2CO2

Magnesium Bicarbonate Magnesium hydroxide

Permanent Hardness (Non-alkaline hardness)

Non-Carbonate Hardness is due to the presence of chlorides,
sulfates of calcium, Magnesium

Permanent hardness cannot be removed by boiling

28
HOW TO EXPRESS
HARDNESS OF WATER ?
 CaCO3 equivalent hardness

Mass of hardness X Molecular

producing substance weight 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

30
 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 31
1oFr = 1 part of CaCO3 equivalent hardness per 105 parts
1 ppm = 1 part per 10,00,000 parts of water
1o cl = 1 part per 70,000 parts of water

1 ppm = 0.07 o cl = 0.1o Fr Problem:

1 o cl = 1.42o Fr = 14.2 ppm
1 o Fr = 0.7 o cl = 10 ppm
If the hardness of water is
210.5 ppm Calculate its
hardness in o cl.
1 ppm = 0.07 o cl
210.5 ppm = 0. 07 × 210.5
= 14.735o cl
Calcium carbonate equivalence conversion during hardness
calculation

Hardness Molecular Multiplication factor

producing weight (in terms of CaCO3
substance equivalence)
Ca(HCO3)2 162 100/162 or 50/81
Mg(HCO3)2 146 100/146 or 50/73
CaSO4 136 100/136 or 50/68
CaCl2 111 100/111 or 50/55.5
MgSO4 120 100/120 or 50/60
MgCl2 95 100/95 or 50/47.5
CaCO3 100 100/100 or 50/50
MgCO3 84 100/84 or 50/42
CO2 44 100/44 or 50/22
HCO-3 61 100/61 or 50/61
OH- 17 100/17 or 50/17
CO32- 60 100/60 or 50/30

33
 Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, Ca(HCO3)2 = 20 ppm, MgSO4
=24.0mg/L and KOH = 1 ppm. Calculate the temporary, permanent and total
hardness of the water sample.

Solution
Step 1 conversion in to CaCO3 equivalent

Constituent quantity Conversion Hardness

present factor
Mg(HCO3)2 16.8 mg/L 100/146 16.8 *100/146 = 11.5ppm
MgCl2 19.0 mg/L 100/95 19.0*100/95 = 20ppm
20.0*100/162 = 12.3 ppm
Ca(HCO3)2 20 ppm 100/162
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculation

Temp. Hardness = 23.8 ppm P. Hardness = 40 ppm

Tot. Hardness =63.8 ppm

34
Example 1. How many grams of FeSO4 dissolved per litre gives 210.5
ppm of hardness?
(Fe = 56, S = 32, O = 16, Ca = 40, C = 12).

Solution. FeSO4 = CaCO3

(56 + 32 + 64 = 152g) =100g
100 ppm of hardness = 152 ppm of FeSO4

210.5 ppm of hardness = 152 × 210.5 = 319.9 ppm of FeSO4

100
= 319.9 mg/L or 0.319 g/L of FeSO4
Example 2. Calculate the temporary hardness and permanent hardness of a
sample water containing Mg(HCO3)2 = 7.3 mg/L ; Ca(HCO3)2 = 16.2 mg/L ; MgCl2
= 9.5 mg/L; CaSO4 = 13.6 mg/L (atomic weight of Mg and Ca are 24 and 40
respectively, Cl and S are 35.45 and 32 respectively)

Solution: Conversion into CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 7.3mg/L 100/146 7.3 × 100/146 = 5mg/L

Ca(HCO3)2 = 16.2mg/L 100/162 16.2 × 100/162 = 10mg/L

MgCl2 = 9.5mg/L 100/95 9.5 × 100/95 = 10 mg/L

CaSO4 = 13.6/L 100/136 13.6 × 100/136 = 10mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (5 + 10) mg/L = 15 mg/L or 15 ppm

Permanent hardness, due to MgCl2 and CaSO4

= (10 + 10) mg/L= 20mg/L or 20 ppm

Total hardness = Temporary hardness + Permanent hardness

Example 3. Calculate the temporary hardness and total hardness of a sample
water containing Mg(HCO3)2 = 73 mg/L ; Ca(HCO3)2 = 162 mg/L ; MgCl2 = 95
mg/L; CaSO4 = 136 mg/L (atomic weight of Mg and Ca are 24 and 40
respectively, Cl and S are 35.45 and 32 respectively)

Solution: Calculation of CaCO3 equivalent:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2 = 73mg/L 100/146 73 × 100/146 = 50mg/L

Ca(HCO3)2 = 162mg/L 100/162 162 × 100/162 = 100mg/L

MgCl2 = 95mg/L 100/95 95 × 100/95 = 100 mg/L

CaSO4 = 136/L 100/136 136 × 100/136 = 100mg/L

Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2

= (50 + 100) mg/L = 150 mg/L or 150 ppm

Total hardness, = (50 + 100 + 100+100) mg/L= 350 mg/L or 350 ppm

Permanent hardness = Total hardness - Temporary hardness

 EDTA method: Hardness
• Complexometric titration.
• Pipette solution: water sample
EBT
• Titrant: EDTA (Strong complexing agent)
• Condition for titration: pH-9-10 – Ammonia-ammonium chloride
buffer added.
• Indicator: Eriochome Black – T (EBT)
• End point: wine red to steel blue
Colorless

Ca2+ Color of Ca-EBT

Color of free EBT

EDTA
Colorless 38
Ca-EDTA Complex
EDTA forms permanent complex with Ca2+ and Mg2+ present in the hard water

EDTA: Colorless solution

Eriochrome Black T

EBT is blue in a buffered solution at pH 10, it turns red when Ca2+

ions were added

The characteristic blue end-point is reached when sufficient EDTA is

added and metal ions is chelated by EDTA, leaving the free indicator
molecule
 Experiment
1. Preparation of EDTA solution (0.01 M)
i.e. dissolve 3.72 g of sodium salt of EDTA crystals in 1 litre of
distilled water

2. Preparation of standard Hard Water

a. Dissolve 1.0 g of pure, dry CaCO3 in small quantity of conc.
HCl and evaporate the solution to dryness
b. Dissolve the residue in distilled water (1 litre)
1ml of this solution contains 1 mg of CaCO3 equ. hardness

3. Preparation of buffer solution

Add 67.5 g of NH4Cl to 570 ml of conc. Ammonia soln. and dilute
with distilled water to 1 litre

4. Preparation of indicator
Dissolve 0.5 g of EB-T in 100 ml alcohol
 5. Standardization of EDTA solution

Burette - EDTA solution (0.01 M)

50 ml of 10-15 ml of few drops of

Conical Flask - std. hard + ammonia + EB-T
water buffer indicator

Volume of EDTA consumed = V1 ml

6.Estimation of total Hardness

50 ml of 10-15 ml of few drops of

Conical Flask - sample + ammonia + EB-T
hard water buffer indicator

Volume of EDTA consumed = V2 ml

7.Estimation of permanent Hardness

50 ml of 10-15 ml of few drops of

Conical Flask - boiled + ammonia + EBT indicator
sample buffer
hard water
Volume of EDTA consumed = V3 ml

Boiled water preparation:

250mL of Hard water – boiled it – reduced the volume about 50mL
Bicarbonates are decomposed to insoluble CaCO3 and Mg(OH)2
Filter, wash the precipitate with distilled water – collect the filtrate –
make up to 250mL

50mL of boiled water + EDTA

 Calculation: Estimation of Total Hardness

50ml of standard hard water = V1 mL of EDTA

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

50ml of given hard water = V2 mL of EDTA

= V2 X 50 / V1 mg of CaCO3 eqvt.

1mL of Given hard water = V2 X 50 / V1X 50 mg of CaCO3 eqvt.

1000mL of Given hard water = 1000 V2 / V1 mg of CaCO3 eqvt.

Total Hardness of water = 1000 V2 / V1 mg/L

= 1000 V2 / V1 ppm
 Calculation: Estimation of Permanent Hardness
50ml of boiled water = V3 mL of EDTA

= V3 X 50 / V1 mg of CaCO3 eqvt.

1mL of boiled water = V3 X 50 / V1X 50 mg of CaCO3 eqvt.

1000mL of boiled water = 1000 V3 / V1 mg of CaCO3 eqvt.

Permanent Hardness of water = 1000 V3 / V1 mg/L

= 1000 V3 / V1 ppm

Temporary Hardness of water = [Total – Permanent] hardness

= 1000{(V2-V3)/V1} ppm
Disadvantages of hard water in industries

46
 Boiler troubles due to Hard Water

1. Scales and sludges

2. Caustic embrittlement
3. Priming and foaming
4. Boiler corrosion
 Scale & Sludge Formation in Boilers

In boilers
– Concentration of the dissolved salts increases progressively when water
evaporates during continuous steam generation. When their
concentration reaches saturation point, the salts gets precipitated
probably on the inner walls of the boiler.

If the precipitate is
- Soft, Loose, slimy precipitate - Sludge
- Hard, adhering crust/coating on the inner walls of the boiler- Scale
 Sludge Scale
Hard adhering
coating to the
Loose precipitate
suspended in water
Boiler wall inner walls of the
boiler

water

Heat Heat
 Sludge
Slimy loose
precipitate called
sludge suspended in
water

wate
r
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.,

Remedy: Sludges can be removed using wire brush or mild acid

51
Disadvantages of sludges Prevention
• Poor conductor of heat – wastage of
energy •By using soft water

• If sludge formed along with the scale, •Frequent blowdown operation

sludge get entrapped within scale and
both gets deposited as scale

• Excessive sludge formation disturbs

the working condition of the boiler
 Scale
Hard adherent coating on
inner walls of boiler

water

Boiler
wall

Scales are hard substances which sticks very firmly to the inner
surfaces of the boiler wall.
Scales are difficult to remove even with the help of a hammer
and chisel.
Examples: CaSO4, CaCO3, Mg(OH)2 53
 Formation of Scales
Decomposition of calcium bicarbonate

• Scales are the main source of boiler troubles. Scale composing

chiefly of calcium carbonate is soft and is the main cause of scale
formation in low-pressure boilers.

Scale (low pressure boilers)

• But in high-pressure boilers, CaCO3 is soluble.

CaCO3+ H2O Ca(OH)2 (Soluble) + CO2

54
 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.

Gypsum is composed of calcium sulfate (CaSO4)

and water (H2O), i.e. Calcium Sulphate Dihydrate
(CaSO4.2H2O) 55
 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.
56
 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
57
 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

58
 Caustic embitterment
❖Formed by highly alkaline water in the boiler.

❖Excess sodium carbonate (Lime soda process) used up for removing hardness
can also result in the formation of NaOH in high pressure boilers.

❖NaOH has better mobility and can percolate into fine cracks present in boiler
walls.
Na2CO3 + H2O → 2 NaOH + CO2

❖ NaOH gets concentrated in the fine cracks present in the boiler walls.

❖ A concentration cell corrosion is established between the conc. NaOH and

dilute NaOH solution in contact with boiler walls.

❖ Concentrated NaOH region behaves as anode thus resulting in corrosion of

boiler leading to the formation of sodium ferroate.
59
 Corrosion by Caustic Embrittlement
• Its a kind of boiler corrosion, caused by using highly
alkaline water in the boiler
Na2CO3 + H2O 2NaOH +CO2

Minute 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
ANODE CATHODE

Iron at Conc. Dil. Iron at

stressed NaOH NaOH plane
parts solution solution surfaces
60
 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
Lignin – derived from
wood
 Priming and foaming
Foaming
It is the production of continuous foam or
hard bubblers in boilers. Foaming is due to
the presence of substance like oil in
boiling water.
Foaming
Normal bubble
Priming
It is the process in which some particles
in water are carried along with the
steam. The resulting process is called as
wet steam or carry over. The process of
formation of wet steam in boilers is
called as priming.
Priming
Carry over bubble
Priming can be avoided by Causes of Priming
Fitting mechanical steam
purifier 1. Presence of dissolved salts
avoid rapid change in steaming rate
2. High velocity steam due to
Foaming can be avoided by sudden boiling
Removing oil from boiler water
by adding compounds like sodium 3. Improper boiler design 63
aluminate
 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

Three major causes of boiler corrosion are

1. Corrosion due to dissolved O2
2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts

64
 Dissolved oxygen – a nuisance for boiler
material

Dissolved oxygen in water at high temperature attack boiler material.

Fe + H2O + ½ O2 Fe(OH)2

Fe(OH)2 + O2 [Fe2O3.nH2O]
(Ferrous hydroxide) (Rust)

Removal of DO – Chemical method

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

Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4
 Removal of DO – By mechanical deaeration
Water feed

It comprises of a tall stainless

tower with different layers capped
with baffles to facilitate multiple
O2 To vacuum
equilibration.

The entire chamber is Steam jacket

vacuumized and also maintained
at high tempt using perforated
heating plates on the walls.
Perforated plate
Principle: High T and low P
favors lower solubility of
gases in water (Henry’s and
Deaerated water
dalton’s law)
 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 67
 Prevention of scale formation
• External Treatment
– The treatment includes efficient ‘softening of water’
– Removing hardness-producing constituents of
water

• Internal Treatment

– Phosphate conditioning
– Calgon conditioning

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 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.
Internal conditioning methods to prevent scale formation

1. Phosphate conditioning – addition of phosphate compound

2. Carbonate conditioning – addition of carbonate compound

3. Calgon conditioning – addition of sodium hexa meta

phosphate

4. Colloidal conditioning – spreading of organic compounds

like tannin, agar gel

5. Sodium Aluminate – removes oil, Mg salts and silica

6. Complexometric method – using EDTA

1. Phosphate conditioning – For High-Pressure boilers

Scale formation can be prevented by adding sodium

phosphate to the boiler water which reacts with the hardness
producing ions and forms easily removable phosphate salts
of respective ions

3CaCl2 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

Calcium Sodium calcium phosphate
chloride phosphate (non adherent and can be
removed by blow down method)
pH
Na3PO4 (Alkaline)
Optimum pH to precipitate Ca
is pH 9.5 – 10.5 Na2HPO4 (Weakly alkaline)
NaH2PO4 (Acidic)
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 2. Carbonate conditioning

CaSO4 (Boiler water) + Na2CO3 CaCO3 + Na2SO4

Calcium Sodium calcium
sulfate carbonate carbonate
(non adherent
loose and soft
ppt and can be
removed by
blow down
method)

Caution: Excess Na2CO3 can result in caustic embrittlement

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 3. Calgon conditioning

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

Calgon – sodium hexa meta phosphate

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

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

Calgon tablets are used in the cleaning of

washing machine drums

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