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Tech Engineering chemistry Question with answer complete material

WATER (UNIT-IV) PART-2

Q.No.5: Write a brief account of Zeolite process.
Answer: Zeolites are also known as Permutits;
Zeolites are mainly 2 types:
1. Natural zeolites are non-porous, eg. Natrolite- Na2O.Al2O3.4SiO2.2H2O.
2. Synthetic Zeolites are porous and possess gel structure. Sodium zeolites are generally used for
softening of water and are simply represented as Na2Ze, where ‘Ze’ stands for insoluble zeolite. In
the process, when hard water is passed through a bed of zeolite placed in an closed cylinder, the
hardness causing ions like Ca+2 and Mg+2 ions are taken up by the zeolite. Sodium salts are
released during the reaction, as byproduct.
Process: For softening of water by zeolite process, hard water is percolated at a specified rate
through a bed of zeolite, kept in a cylinder. The hardness causing ions like Ca+2, Mg+2 are
retained by the zeolite as CaZe and MgZe; while the outgoing water contains sodium salts.
The various reactions taking place may be
Na2Ze + Ca(HCO3)2  CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2  MgZe + 2NaHCO3
Na2Ze + MgCl2  MgZe + 2NaCl
Na2Ze + CaCl2  CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + 2Na2SO4

Na2Ze + CaSO4 CaZe + 2Na2SO4

Hence zeolite process removes the hardness of water effectively.

Regeneration: After some time, the Zeolite is completely converted into calcium and
magnesium zeolites and it ceases to soften water, i.e., it gets exhausted. At this stage, the supply of
hard water is stopped and the exhausted zeolite is reclaimed by treating the bed with a
concentrated Brine solution
(10% NaCl).
CaZe + 2 NaCl  Na2Ze + CaCl2
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MgZe + 2 NaCl  Na2Ze + MgCl2

Advantages:
a. It removes the hardness completely and water of about 10 ppm hardness is produced.
b. The equipment used is compact, occupying a small space.
c. No impurities are precipitated, so there is no danger of sludge formation in the treated water at
a later stage.
d. The process automatically adjusts itself for variation in hardness of incoming water.
e. It is quite clean
f. It requires less time for softening.
g. It requires less skill for maintenance as well as operation.

Disadvantages:
a. The treated water contains more sodium salts than in lime-soda process.
b. This method causes caustic embrittlement.
c. High turbidity water cannot be treated efficiently by this method.

Limitations:
1. If the supply of water is turbid, the suspended matter must be removed, before the water is
admitted to the zeolite bed. Otherwise the turbidity will clog the pores of zeolite bed, thereby
making it inactive.
2. If water contains large quantities of coloured ions such as Mn+2 and fe+2 they must be removed
first, because these ions produce magnesium and Ferrous zeolites. This cannot be easily
regenerated.
3. Mineral acids, if present in water, destroy the zeolite bed and therefore, they must be neutralized
with soda, before admitting the water to the zeolite softening plant.

Q.No.4: Write a brief account of Ion exchange process.

Answer: Ion exchange process also known as demineralization or de-ionization process. Ion-
Exchange resins are insoluble. Cross linked long chain organic polymers with a micro porous
structure, and the “functional Groups” attached to the chains are responsible for the ion-exchanging
properties.
In De-ionization process all the ions present in water are eliminated by using ion-exchange resins.
Basically resins with acidic functional group are capable of exchanging H + ions with other cations.
Resins with functional groups are capable of exchanging OH- ions with other anions.
Resins are classified as
1. Cation Exchange Resins
2. Anion Exchange Resins
1. Cation Exchange Resins: These are mainly styrene divinyl benzene co-polymers,
which on sulphonation or carboxylation. These are capable of exchanging their hydrogen
ions with cations in water.

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2. Anion Exchange Resins: Anion exchange resins are styrene-divinyl benzene or amine-
formaldehyde copolymers, which contains amino, quaternary ammonium or quaternary
phosphonium or tertiary sulphonium groups as an internal parts of the resin matrix. These
after treatment with dilute NaOH solution. Become capable of exchanging their OH- ions
with anions in water.

In ion-exchange process, hard water is allowed to pass through cation exchange resins, which
remove Ca+2 and Mg+2 ions and exchange equivalent amount of H+ ions. Anions exchange resins
remove bicarbonates, chlorides and sulphates from water exchange equivalent amount of Oh ions.
Thus by passing hard water through cation hardness is observed by the following reactions.

Cation Exchange Resins

2RH+ + Ca+2 - R2Ca+2 + 2H+
2RH+ + Mg+2  R2Mg+2 + 2H+ (RH+ = cation exchange resin)
Anion Exchange Resins
R’OH + Cl+2  R’Cl- + OH-
2R’OH- + SO4-2  R2SO4-2 -2 + 2OH-
2R’OH + CO -32  R’2 CO-32 + 2OH- (R’OH = anion exchange resin)

H- And OH- ions, thus released in water from respective cation and anion exchange columns, get
combined to produce water molecules.
H+ + OH-  H2O
The water coming out from the exchanger is ion free i.e., free from anions and cations. Thus water of
zero hardness is obtained.

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REGENERATION: When cation exchanger losses capacity of producing H+ ions and exchanger
losses capacity of producing OH- ions, they are said to be exhausted. The exhausted cation exchanger
is regenerated by passing it through dilute sulphruric acid.
R2Ca+2 + 2H+  2RH+ + Ca+2
The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.
R2SO4-2 + 2OH  2R’OH- + SO

Merits of Ion-exchange process:

a. The process can be used to soften highly acidic or alkaline water.
b. It produces water of very low hardness (2 ppm)
c. So it is very good for treating water for use in high-pressure boilers.
Demerits of Ion-exchange process:
a. The equipment is costly and more expensive chemicals are needed.
b. If water contains turbidity, the output of the process is reduced. The turbidity must be below 10
ppm; else it has to be removed by coagulation and filtration.

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Q.No.6 : What are Boiler troubles? Write short notes on scale & sludge formation and
caustic embrittlement?
Answer: BOILER TROUBLES: In treatment of water complete elimination of all the
impurities is not possible. The impurity that gives rise to certain troubles will be removed to certain
extent. In modern pressure boilers and laboratories, water purer than the distilled water is required.
Some of the boiler troubles caused by the use of unsuitable water are..
1. Carryover – Priming and Foaming
2. Scale formation
3. Boiler corrosion and
4. Caustic embrittlement
Carryover – Priming and Foaming
a. Priming: it may defined as the violent or rapid boiling of water occurring in the boiler which
results in carrying out of water with steam in in the form of a spray.
When a boiler is producing steam rapidly, some particles of liquid water are carried along with
the steam. This process of wet steam formation is called priming.
Priming mainly caused due to very high water level. The presence of large amount of dissolved
solids, high steam velocities, sudden increase in steam production rate. Sudden steam demand
which leads to sudden boiling, presence of excessive foam filling the foam spare, and due to faulty
boiler design.
priming can be controlled by proper boiler design, fitting mechanical steam purifier, avoiding
rapid change in steam-rate, proper evaporation and adequate heating surfaces, uniform distribution
of fuel and providing anti priming pipes, keeping the water level low and avoid sudden steam
demands. Efficient softening and filtration of the boiler feed water.
b. Foaming: Foaming is the formation of small but stable bubbles above the surface. The main
reason for foaming is being presence of fatty acids and other impurities.
Foaming can be controlled by using anti-foaming chemicals, removal of concentrated boiler
water and replacing it by fresh feed water. Removing oil from boiler water by adding
compounds like sodium aluminate.

SLUDGE FORMATION IN BOILERS:

In boilers, because of continuous evaporation of water, the concentration of salts increase
progressively and after the saturation point is reached, precipitate form on the inner walls of boiler.
SLUDGE: Sludge is a soft, loose and slimy precipitate formed within the boiler. It is formed at
comparatively colder portions of the boiler and collects in the area where flow rate is slow.
These are formed by substances which have greater solubilities in hot water than in cold-water.
Eg. MgCO3, MgCl2, CaCl2, MgSO4.

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DIS-ADVANTAGES:
a. As the sludge’s are poor conductor of heat they cause loss of heat.
b. The working of the boiler is disturbed because of chocking of pipes by the sludge.
PREVENTION:
a. By using well softened water.
b. By drawing off a portion of concentrated water frequently.

SCALES: Scales are hard, adhering precipitates formed on the inner walls of the boilers. They
stick very firmly on to the inner wall surface and are difficult to remove with chisel and hammer.

causes of scale formation: Following are the causes

a. decomposition of calcium bicarbonate:
Ca(HCO3)2  CaCO3 + H2O + CO2
In low pressure boilers, CaCO3 causes scale formation.
In High pressure boilers, CaCO3 becomes soluble.
CaCO3 + H2O  Ca(OH)2 + CO2
b. Decomposition of calcium sulphate:
The solubility of CaSO4 in water decreases with rise of Temperature. In super heated water
CaSO4 is insoluble.
This is the main cause in high-pressure boilers.
c. Hydrolysis of Magnesium salts:
Dissolved Magnesium salts undergo hydrolysis forming Mg(OH)2 precipitate.
MgCl2 + 2H2O - Mg(OH)2 + 2 HCl
Mg(OH)2 so found by hydrolysis of Magnesium salts is a soft type of scale.
d. Presence of Silica: Silica present in small quantities deposits as silicates like CaSiO3 and
MgSiO3. These are very difficult to remove.
Disadvantages:
a. wastage of fuel: The scale formation causes decreases of heat transfer. As a result over heating
is required this causes consumption of fuel.
b. danger of Explosion: The hot scale cracks because of expansion and water suddenly comes in
contact with overheated Iron plates. This causes in formation of large amount o steam
suddenly. This results high pressure causing boiler to burst.
PREVENTION:
a. External treatment: Efficient softening of water is to be carried out.
b. Internal treatment: Suitable chemicals are added to the boiler water either to precipitate or to
convert the scale into compounds.

Boiler Corrosion: The chemical or electro chemical eating away of metal by its environment in a
boiler is known as boiler corrosion. The main reason for this problem is the presence of excess of
oxygen in water. It can be prevented by mechanical deaerator, pre-heating and chemical treatment.

a. Dissolved oxygen: Water usually contains about 8 ml of dissolved oxygen per liter at room
temperature. Dissolved oxygen in water, in presence of prevailing high temperature, attacks boiler
material:
2Fe + 2H2O + O2  2Fe(OH)2
4Fe(OH)2 + O2  2[ Fe2O3.2H2O]

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Removal of dissolved oxygen: 1. By adding calculated quantity of sodium sulphite or hydrazine or

sodium sulphide.
2Na2SO3 + O2  2Na2SO4
N2H4  N2 + 2H2O
Na2S + O2  Na2SO4
Hydrazine is an ideal internal treatment chemical for the removal of dissolved oxygen. It reacts with
oxygen, forming nitrogen and water. Nitrogen is harmless. Recently Azamina 8001-RD a poly organic
compound, has been employed for degassing of water.

b. Dissolved carbon dioxide: carbon dioxide is carbonic acid,

CO2 + H2O  H2CO3
This has a slow corrosive effect on the boiler material. Carbon dioxide is also released
inside the boiler, if water used for steam generation contains bicarbonate,
Heat
Mg(HCO3)2  MgCO3 + H2O + CO2
Removal of carbon dioxide:
1. By adding calculated quantity of ammonia,
2NH4OH + CO2  (NH4)2CO3 + H2O
2. By mechanical – aeration process along with oxygen.
c. Acids from dissolved salts: Water containing dissolved magnesium salts liberates acids on
hydrolysis.
MgCl2 + 2H2O  Mg(OH)2 + 2HCl
The liberated acid reacts with iron in chain – like reactions producing HCl again and again.
Fe + 2HCl  FeCl2 + H2
FeCl2 + 2H2O  Fe(OH)2 + 2HCl
Consequently, presence of even a small amount of MgCl2 will cause corrosion of iron to a
large extent.

Caustic Embrittlement: The formation of brittle and incrystalline cracks in the boiler shell is
called caustic embrittlement.
It is a type of boiler corrosion and the main reason for this, is the presence of alkali-metal
carbonates and bicarbonates in feed water and also the presence of sodium sulphate.
In lime-soda process, it is likely that, some residual Na2CO3 is still present in the softened water.
This Na2CO3 decomposes to give NaOH and CO2, due to which the boiler water becomes
“Caustic”.
Na2CO3+ H2O  NaOH + CO2
This caustic water flows inside the boiler and causes some minutes hair-cracks, by capillary action.
On evaporation of water, the dissolved caustic soda increases its concentration which attacks the
surrounding area, thereby dissolving Iron of boiler as Sodium ferroate.
This causes embrittlement of boiler parts such as bends, joints, reverts etc, due to which the boiler
gets fail. Caustic cracking can be explained by considering the following concentration cell:

Iron at bends,
+
| Concentrated | Dilute NaOH solution |- Iron at plane surfaces
joints, reverts etc, NaOH solution

Therefore, caustic embrittlement can be prevented.

 By maintaining the pH value of water and neutralization of alkali.
 By using Sodium Phosphate as softening reagents, in the external treatment of boilers.

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 Caustic embrittlement can also be prevented by adding Tannin or Lignin or Sodium

sulphate which prevents the infiltration of caustic-soda solution blocking the hair-cracks.
Q.No. 7: Write a brief account of internal treatment of water.
Answer: INTERNAL TREATEMENT:
Internal treatment of boiler water is carried out by adding proper chemicals to precipitate the scale
forming impurities in the form of sludge and to convert the scale forming chemicals into compounds
which will stay in dissolved form in water. This process is mainly used as a corrective treatment to
remove the slight residual hardness and also sometimes to remove the corrosive tendencies in water.
Some of the internal treatment methods used for the removed of scale formation in boilers are.
.COLLODIAL CONDITIONING: The addition of organic substances such as Kerosene, tannin, Gel
etc., to the surface in low pressure boilers may prevent the scale formation. These substances gets
coated over the scale forming precipitates and gives a loose and non-sticky precipitates which can be
removed by using blow-down operation.
PHOSPHATE CONDITIONING: The addition of sodium phosphate in hard water reacts with the
hardness causing agents and gives calcium and magnesium phosphates which are soft and non-adhere
and can be removed easily by blow-down operation. In this way, scale formation is removed in high-
pressure boilers.
3CaCl2 + 2 Na3PO4  Ca3(PO4)2 + 6NaCl

CARBONATE CONDITIONING: In low-pressure boilers, scale-formation can be avoided by

adding sodium carbonate to boiler water, when CaSO4 is converted into calcium carbonate in
equilibrium.
CaSO4 + Na2CO3  CaCO3 + Na2SO4
Consequently, deposition of CaSO4 as scale doesn’t take place and calcium is precipitated as loose
sludge of CaCO3 which can be removed by blow-down operation.
CALGON CONDITIONING: Involves in adding calgon to boiler water. it prevents the scale and
sludge formation by forming soluble complex compound with CaSO4.
Calgon = Sodium hexa Meta phosphate = (NaPO3)6
Na2 [Na4 (PO3)6] ==== 2Na+ + [Na4P6O18]-
2CaSO4 [ Na4P6O18]-2 [Ca2P6O18]-2 + 2Na2SO4
SODIUM ALUMINATE: Sodium aluminate gets hydrolyzed yielding NaOH and a gelatinous
precipitate of aluminum hydroxide.
Thus NaAlO2 + 2H2O  NaOH + Al (OH)3
The sodium hydroxide, so-formed, precipitates some of the magnesium as Mg (OH)2, i.e.,
MgCl2 + 2NaOH  Mg (OH)2 + 2NaCl
The flocculent precipitate of Mg (OH)2 plus aluminum hydroxide, produced inside the boiler, entraps
finely suspended and colloidal impurities, including oil drops and silica. The loose precipitate can be
removed by pre-determined blow-down operation.

Q. No.8: Write a short note on Reverse osmosis & electrodialysis.

Desalination of Brackish water: The process of removing common salt from the water is known
as desalination. The water containing dissolved salts with a peculiar salty taste is called brackish
water. Sea water, containing on an average about 3.5% salts, comes under this category. Brackish
water is totally unfit for drinking purpose. Commonly used methods for the desalination of
brackish water is: 1. Reverse Osmosis & 2. Electrodialysis.

1. Reverse Osmosis: Osmosis is the phenomenon by virtue of which flow of solvent takes place from
a region of low concentration to high concentration when two solutions of different concentrations are
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separated by a semi-permeable membrane. The flow continues till the concentration is equal on both
the sides. The driving force for osmosis is osmotic pressure. How ever, if a hydrostatic pressure in
excess of osmotic pressure is applied on the concentrated side, the flow of solvent reverses as it is
forced to move from concentrated side to dilute side across the membrane. This is the basis of reverse
osmosis.

For practical purposes, semi-permeable membrane based on thin films of cellulose acetate,
polymethyl acrylate and polyamide polymers are used. A pressure of the order of 15-40 kg/cm2 is
applied for separating the water from its contaminants. The process is also known as super or hyper
filtration.
Advantages:
a. Colloidal SiO2 can be removed by reverse osmosis which even cannot be removed by
demineralization.
b. It is simple and reliable process.
c. Capital and operating expenses are low.
d. The life of the semi-permeable membrane is about 2 years and it can be easily replaced within
a few minutes, thereby nearly uninterrupted water supply can be provided.

2. Electrodialysis: Electrodialysis is based on the fact that the ions present in saline water migrate
towards their respective electrodes, through ion-selective membrane under the influence of applied
emf.

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The unit consists of electrodes and thin and rigid ion-selective membranes which are
permeable to either cation or anion. The anode is placed the anion-selective membrane while the
cathode is placed near the cation-selective membrane. Under the influence of fixed functional groups,
which carry positive charge, inside the membrane. Similarly, a cation selective membrane is based on
polystyrene resin embedded with negatively charged functional groups such as RSO3- or RCOO- and
is permeable only to cations,
Under the influence of an applied emf across the electrodes the cations move towards the cathodes
through cation selective membrane and anions move towards the anode through anion selective
membrane the net result is the depletion of ions in the central compartment while it increases in the
two side compartments. Desalinated water is periodically drawn out from the central compartment
while the concentrated brackish water.
Advantages of desalination by electrodialysis:
 This process is economical as per the capital cost and operational expenses are
concerned.
 The unit is compact and the method is best suited.

1. Calculate the quantities of lime and soda required in kgs for softening 10,000 lit of water using 82 ppm of NaAlO2 as
coagulant. Analysis of water was as follows:
Cacl2 = 111 ppm; Mg(HCO3)2 = 146ppm; NaCl = 58.5ppm; KCl = 74.5ppm; Dissolved CO2 = 44ppm. (At. Wt of Na = 23, Mg
= 24, K = 39, Ca = 40 and Al = 27)
Ans.
S.No. Constituent Amount(ppm) MF * CaCO3 equivalent
1. CaCl2 111 100/111 100
2. Mg(HCO3)2 146 100/146 100
3. NaCl 58.5
4. KCl 74.5 Do not contribute
5. CO2 44 100/44 100
6. NaAlO2 82 100/164 50

We have to consider atomic weight of metal ion.

74
Lime required = ---- [Mg2+ + CO2 + NaAlO2]
100
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74
= ---- [100 + 100 + 50] = 185 mg/lit.
100

So for 10000 lit = 10000 X 185 = 1850000 mg = 1.85 kg

106
Soda required = ---- [Ca2+ + Mg2+]
100
106
= ---- [100 + 100] = 212 mg/lit
100
For 10000 lit = 10000 X 212 = 2120000 mg = 2.12 kg.
2. Calculate the lime and soda needed for softening 50,000 litres of water containing the
following salts: CaSO4 = 136 mg/lit; MgCl2 = 95 mg/lit; Mg(HCO3)2 = 73 mg/lit; Ca(HCO3)2=
162 mg/lit. Given that the molar mass of Ca(HCO3)2 is 162 and that of MgCl2 is 95.
Ans:

S.No. Constituent Amount MF CaCO3

(mg/lit) equivalent
1. CaSO4 136 100/136 100
2. MgCl2 95 100/95 100
3. Mg(HCO3)2 73 100/146 50
4. Ca(HCO3)2 162 100/162 100

Lime required = 74
---- [ Ca(HCO3)2 + 2 Mg (HCO3)2 + MgCl2]
100
74
= --- [100 + 2 x 50 + 100 + 100]
100

74 400
= --- x ---- = 296 mg/l
100 1

For 50000 lit of water: 50000 x 296 = 14.8 Kg of lime required.

106
Soda required = ---- [CaSO4 + MgCl2]
100

106 200
= ---- x ---- = 212 mg/l
100 1

For 50000 lit of water: 50000 x 212 = 10.6 kg of soda required.

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DIFFERENCES between lime-soda and zeolite process

S.NO LIME-SODA PROCESS PERMUTIT/ZEOLITE

1 Water treatment plant occupies more area Water treatment plant occupies less area.
or place.

2 Water after treatment has lesser dissolved Water after treatment has much more dissolved
solids. solids.

3 This method of water treatment plants is This method of water treatment plants is more
not much expensive and material used is expensive and material used for softening is
cheap. expensive.

4 Operation expenses are higher Operation expenses are low

5 The cost incurred on softening of water is
high.
6 It cannot operate in under pressure.
7 It can be used for treating acidic water
also.
8 There is a problem of settling, coagulation
and removal of sludge.
The cost incurred on softening of water is low.
It can even operate in under pressure.
This method of softening the water is not used for
treating acidic water.
There is no problem of settling, coagulation and
removal of sludge.

9 It is not possible. This method can be made automatic.

10 In order to meet the changing hardness of Control test comprises only in checking the
incoming water, frequent control and hardness of treated-water.
adjustment of reagents is needed.

11 Residual hardness is low about 15 to 50 Residual hardness is low about 10 to 15 ppm

ppm

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12 It is not good for boilers It is not good for boilers

13 Skilled persons required It required less skill for maintenance as well as

operation

DIFFERENCES between lime-soda and ion-exchange process

S.NO LIME-SODA PROCESS ION-EXCHANGE/RESIN

1 Water treatment plant occupies more area Water treatment plant occupies less area.
or place.

2 Water after treatment has lesser dissolved Water after treatment free from dissolved
solids. solids

3 This method of water treatment plants is This method of water treatment plants is more
not much expensive and material used is expensive and material used for softening is
cheap. expensive.

4 Operation expenses are higher Operation expenses are higher

5 The cost incurred on softening of water is
high.
6 It cannot operate in under pressure.
7 It can be used for treating acidic water
also.
8 There is a problem of settling, coagulation
and removal of sludge.
The cost incurred on softening of water is high
It can even operate in under pressure.
It can be used for treating acidic and alkaline
water also.
There is problem of turbidity.

9 It is not possible. This method can be made automatic.

10 In order to meet the changing hardness of Control test comprises only in checking the
incoming water, frequent control and hardness of treated-water.
adjustment of reagents is needed.

11 Residual hardness is low about 15 to 50 Residual hardness is low about 0 to 2 ppm

ppm

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12 It is not good for boilers It is very good for treating water for use in high
pressure boilers.
13 Skilled persons required It required less skill for maintenance as well as
operation

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