UNIT – I WATER AND ITS TREATMENT

1. What are boiler compounds? Give an example with their action. (May 2001)
The chemicals added inside the boilers to remove scale forming substances are called
boilers compounds. Examples : Sodium carbonate and sodium phosphate.
CaSO4 + Na2CO3  CaCO3 + Na2SO4
3CaSO4 +2Na3PO4  Ca3(PO4)2 + 3Na2SO4

2. What are the requirements of the boiler feed water? (Jan 2018)
S.No. Specifications Disadvantages
1 Boiler feed water should have zero Scale and Sludges will be produced, which
hardness. prevent efficient heat transfer.
2 It must be free from dissolved It leads to boiler corrosion.
gases like O2, CO2.
3 It Should be from suspended Produces wet steam.
impurities.
4 It should free from dissolved salts Produces caustic embrittlement, which causes
and alkalinity. brittleness of parts.

3. What is meant by “Reverse Osmosis”? (A.U. June 2007) (Jan 2018)

If pressure in excess of osmotic pressure is applied on the higher concentration side, the solvent flows
from higher concentration to lower concentration. The process is called reverse osmosis. Example, salt
water is taken as higher concentration and water is taken as solvent. If the pressure is applied on the salt
water, the water flows from salt to water side.

4. What is calgon conditioning? (A.U. June 2005,Jan 2010 )

Calgon is sodium hexa meta phosphate Na 2[Na4(PO3)6].This substance interacts with calcium ions
forming a highly soluble complex and thus prevents the precipation of scale forming salt
2CaSO4+Na2[Na4(PO3)6  Na2[Na4[Ca2(PO3)6]+2Na2SO4.

5.Write the principle of EDTA method.

The amount of hardness causing ions can be estimated by titrating the water sample against EDTA
using EBT at a pH of 8 to 10. In order to maintain pH, buffer solution is added. When the EBT is added
to the water sample it forms wine red colour weak complex with Ca 2+, Mg2+ ions.
(Ca2+,Mg2+) + EBT  (Ca,Mg - EBT)

When this solution is titrated against EDTA, it replaces the indicater from the weak complex form
stable EDTA complex. The end point is the change of colour from wine red to steel blue.
(Ca,Mg - EBT) + EDTA  (Ca,Mg - EDTA) + EBT

6. What is meant by carbonate and non carbonate hardness?

Carbonate hardness : This is due to the presence of bicarbonate of calcium and magnesium.
Non – carbonate hardness : This is due to the presence of chlorides of sulphates of calcium and
magnesium.

7. What is desalination? Name any four methods of converting sea water into fresh water.
The process of removing common salt from the sea water is known as desalination. The water
containing dissolved salts with a peculiar salty or brackish taste is called brackish water. The various
desalination process are (a)distillation, (b)freezing, (c)reverse osmosis and (d)electrodialysis
8. Differentiate between sludge and scale.
S.No. Sludge Scale
1 It is a soft, loose and slimy precipitate It is hard, adherent coating formed on the
formed in the boiler during steam inner walls of the boiler during steam
generation. generation.
2 The main sludge forming substances are The main scale forming substances are
CaCl2, MgCO3, MgCl2, MgSO4 Ca(HCO3)2, CaSO4, Mg(OH)2

9. Soft water is not demineralised water whereas demineralised water is soft water justify.
Softening involes removal of only hardness causing ions whereas demineralization involves removal
of all the ions present in water. Hence, the above statement is justified.

10. What is blow down operation? (A.U. June 2009)

It is a process of removing a portion of concentrated water by fresh water frequently from the boiler
during steam production.

11. Name some of the membranes employed in reverse osmosis process. State the advantages of this
process.
Membranes : Cellulose acetate, Cellulose butyrate.
Advantages: 1. It removes ionic, non ionic and colloidal impurities. 2. The water obtained can be used
for high pressure boilers.

12. Why calgon conditioning is better than phosphate conditioning?

Calgon conditioning results in highly soluble salt whereas phosphate conditioning results in sludge
formation which needs further disposal.

13. What are boiler compounds?

Substances which are added directly into the boiler to treat scale causing substances are called boiler
compounds.

14. List out the units by which hardness can be expressed.

Mg/lit, ppm, French degree, clark’s degree and calcium carbonate equivalence.

15. How hardness of a sample can be detected?

(i) with soap: Hard water gives white precipitate
(ii) with EBT: At pH 9-10 hard water gives wine red colour.

16. What are the salts responsible for temporary hardness of water? (May 2019)
The salts responsible for temporary hardness are bicarbonates of calcium and magnesium. Ca(HCO3)2
and Mg(HCO3)2

17. Mention the indicator used in EDTA titration. What is the end point? (May 2019)
Indicator used in EDTA titration: Erichrome Black-T (EBT)
End point: Change of colour from wine red to steel blue
 PART-B
1. Explain the EDTA method of estimation of hardness of water. (Jan 2009)

Procedure:
(i) Standardisation of EDTA solution:
Pipette out 20 ml of standard hard water into a clean 250 ml conical flask. Add 5 ml of
buffer solution and 4-5 drops of EBT indicator and titrate against EDTA solution taken in
the burette. The end point is the change of colour from wine red to steel blue.
Let the volume of EDTA consumed be V1 ml

(ii) Estimation of total hardness of water sample:

Pipette out 20 ml of the given hard water sample into a clean 250 ml conical flask and
titrate it against EDTA as before.
Let the volume of EDTA consumed be V2 ml

(iii) Estimation of permanent hardness of water sample:

Take 100 ml of the given hard water sample in a 250 ml beaker and boil it for 15 minutes.
During boiling temporary hardness gets removed. Cool and filter the solution and make
up to 10 ml in a standard flask by adding distilled water.
Pipette out 20 ml of the made up solution into a clean 250 ml conical flask and titrate it
against EDTA as before.
Let the volume of EDTA consumed be V3 ml
Calculation
 2. Write a note on scale and sludge formation. Add the drawbacks of
scale formation. (May 2019)
S. No. Sludge Scale

1. A loose, slimy and non-adherent S hard and adherent coating

precipitate
2. MgCO3, MgCl2, MgSO4 and CaCl2 Ca(HCO3)2, CaSO4, Mg(OH)2

3. Poor conductors of heat and decreases the Decreases the efficiency of boiler, crack
efficiency of boiler developed leads to explosion
4. Prevention: Using HCl, H2SO4
Using softened water
By blow-down operation Internal and external treatment, by
applying thermal shocks, scrapers, wire
brush, etc.
Drawback of scale formation:
1. Wastage of fuels
The heat transfer from boiler to inside water in not efficient because of the low thermal
conductivity of scales. Overheating is done to provide steady supply of heat to water which
causes wastage of fuel.The wastage of fuel depends on the thickness and nature of the scale,
which is shown in the table

2. Decrease in efficiency – due to the deposition of scales in the valves and condensers of the
boiler and choke.
3. Boiler explosion Sometimes due to overheating the thick scales may crack and causes sudden
contact of high heated boiler material with water. This causes formation of a large amount of
steam and high pressure is developed which may lead to explosion.

3. What is Zeolite? Explain how water can be treated using zeolite. (May
2015)
Zeolite (or) Permutit Process

Hydrated sodium aluminosilicate – Na2O.Al2O3.xSiO2.yH2O; x = 2 – 10, y = 2 – 6, Natrolite –

Na2O.Al2O3.3SiO2.2H2O
Natural zeolites are green sand and are usually non-porous.
Permutit – artificial zeolite, porous.

Sodium zeolite – Na2Ze which exchange Na+ ions with the hardness producing
ions like Ca2+, Mg2+ in water.
 Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3

Mg(HCO3)2 + Na2Ze MgZe + 2NaHCO3

CaSO4 + Na2Ze CaZe + Na2SO4

MgSO4 + Na2Ze MgZe + Na2SO4

CaCl2 + Na2Ze CaZe + 2NaCl

MgCl2 + Na2Ze MgZe + 2NaCl

The sodium salts formed in the above reactions remain dissolved in the softened
water and do not impart any hardness.

Regeneration
Sodium zeolite gets exhausted due to its conversion into Ca and Mg zeolites.
Regeneration is done by percolating 10% brine solution through the exhausted
zeolite. The Ca and Mg zeolites are converted back into sodium zeolite.
CaZe + 2NaCl Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze + MgCl2

Advantages of the process

 Water obtained by this process will have a residual hardness between7 and 15 ppm.
 The method is cheap, because the regenerated zeolite can be used again.
 This process does not produce any sludge and hence a clean process.
 The equipment is compact and occupies less space.

Disadvantages of the process

 The process exchanges only calcium and magnesium ions with sodium ions and hence
the softened water contains more sodium and also more of dissolved salts.
 It does not remove the acidic ions such as bicarbonate and carbonate and remain as
sodium salts contributing to the alkalinity and causes boiler corrosion.
 The water containing turbidity and suspended impurities cannot be treated by this method
because turbidity clogs the pores of the zeolite bed.
 The process cannot tolerate acidity or alkalinity as the zeolite disintegrates.
 The process is not very efficient for treating water containing large quantities of Fe 2+ and
Mn2+ ions as these ions convert sodium zeolite into their respective zeolites which are
difficult to be regenerated.
4. What is ion exchange process? How demineralisation is done using ion
exchanger? (May 2019)

Demineralization or Ion Exchange Process

This process removes almost all the ions present in water.Soft water does not contain hardness
producing Ca2+ and Mg2+ ions but it may contain other ions like Na+, K+, Cl-, SO42-. Every soft
water is not demineralized water whereas every demineralized water is soft water.
Ion exchangers are resins with a long chain, cross-linked, insoluble organic polymers with a
microporous structure. The functional groups attached to the chains are responsible for the ion
exchanging properties.

The following two types of resins are used for demineralization process:

Cation exchange resins and Anion exchange resins

Cation exchange resins – possess acidic group such as –COOH or –SO3H groups.
Cations in hard water are exchanged with H+ ions of these resins. This resin may be represented
as RH2.
examples: sulphonated coal, sulphonated polystyrene

Anion exchange resins – possess basic groups such as OH- or NH2- group. Anions
in hard water are exchanged with –OH ions of this resins. It may be represented as
R’(OH)2.
examples – cross-linked quaternary ammonium salts, urea-formaldehyde resin.

Hard water is first passed through the cation exchange resin. The cations like
Na+, K+, Ca2+, Mg2+, etc. in hard water get exchanged with H+ ions of the resin.
 RH2 + CaCl2 RCa + 2HCl

RH2 + MgSO4 RMg + H2SO4

RH + NaCl RNa + HCl

The water coming out from this column is acidic in nature.

The water is then passed through the anion exchange resin which exchanges the anions like Cl -,
SO42-, HCO3- with OH- ions of the resin.

R'(OH)2 + 2HCl R'Cl2 + 2H2O

R'(OH)2 + H2SO4 R'SO4 + 2H2O

The water coming out from this column is completely free from both cations and anions. H + and
OH- ions combine to produce water molecule.
+ _
H + OH H2O

The water coming out from the second column is neutral and is free from all ions.It is known as
deionised or demineralised water.

Regeneration of resins
The exhausted cation exchange resin is regenerated by percolating a dilute HCl solution
through it.
RCa + 2HCl RH2 + CaCl2
RNa + HCl RH + NaCl
The exhausted anion exchange resin is regenerated by percolating dilute NaOH
solution through it.

R'Cl2 + 2NaOH R'(OH)2 + 2NaCl

Advantages
 The hardness of water can be reduced to about 2 ppm and hence it is suitable for
use in high pressure boilers.
 Highly acidic or highly alkaline water can be softened by using this process.

Limitations

 The resin used in the process are quite expensive.

 If water contains turbidity, the efficiency of the process is reduced.
 Water containing Fe and Mn cannot be treated because they form stable product
 with the resins.

5. Explain internal conditioning. (Jan 2018)(May 2019)

Internal Treatment or Internal Conditioning

It involves adding chemicals directly to the water in the boilers for removing dangerous scale
forming salts. This method is used to convert scale or sludge which can be removed by blow-
down operation.
Phosphate conditioning
Scale formation can be avoided by adding sodium phosphate. It is used in high pressure boilers.
The phosphate reacts with calcium and magnesium salts to give soft sludges of calcium and
magnesium phosphates.
3CaSO4 + 2Na3PO4 Ca3(PO4)2 + 2Na2SO4

Calgon conditioning
Calgon is sodium hexa meta phosphate, Na2[Na4(PO3)6]. This interacts with calcium ion
forming a highly soluble complex and thus prevents the precipitation of scale forming salt.
2CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2Na2SO4
Calgon highly soluble
complex

The complex Na2[Ca2(PO)3]6 is soluble in water and there is no problem of sludge disposal. So
calgon conditioning is better than phosphate conditioning.

Colloidal conditioning
The colloidal conditioning agents are kerosene, agar-agar, gelatin, glue, etc. They are used in
low pressure boilers. The colloidal substance converts scale forming substances like CaCO3,
CaSO4 into a sludge which can be removed by blow-down operation.

6. Define desalination. How saline water is converted into drinking water?

(Jan 2018)
Desalination or Desalting
Desalination – The process of removal of dissolved salts (NaCl) from water.
Brackish water – Water containing high concentration of dissolved salts.
Water quality is usually graded as
Fresh water : less than 1000 mg/L of dissolved salts
Brackish water : 1000 – 35000 mg/L of dissolved salts
Sea water : greater than 35000 mg/L of dissolved salts.
Reverse osmosis
 Osmosis – when two solutions of different concentrations are separated by a semi-permeable
membrane, solvent flows from a region of lower concentration to a region of higher
concentration. This process is a natural process.

Osmotic pressure - the excess pressure applied on the concentrated solution side to prevent
osmosis. This natural process can be reversed by applying a pressure higher than the osmotic
pressure of the order 15 – 40 kg/cm2 on the high concentrated side. The solvent flow is reversed
i.e., solvent flows from higher concentrated side to lower concentrated side. This process is
called reverse osmosis. Membranes used are cellulose acetate, cellulose butyrate, etc.,
Advantages
 The water obtained by this process is used for high pressure boilers
 Due to low capital and operating cost and high reliability this process is used for
converting sea water into drinking water.
 The life time of the membrane is high and it can be replaced within a short time.
 It also removes ionic, non-ionic and colloidal impurities.