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U.R.BAGWAN
M.Sc



Water Technology and Nanomaterials :
Water Technology:
Introduction, sources and impurities of water;
boiler feed water, boiler troubles with disadvantages -scale and sludge formation, priming
and foaming, boiler corrosion(due to dissolved O2, CO2 and MgCl2).

Determination of DO, BOD and COD, numerical problems.
Sewage treatment:
Primary, secondary (activated sludge method) and tertiary methods.

Softening of water by ion exchange process.

Desalination of sea water by reverseosmosis & electrodialysis (ion selective).

Nano Materials :
Introduction,
properties (size dependent).
Synthesis- bottomup approach (sol-gel, precipitation, gas condensation, chemical vapour
condensation, hydro thermal & thermolysis processes).

Nano scale materials
nano crystals & clusters, nano crystalline, fullerenes, carbon nano tubes,
nano wires, nano rods, dendrimers & nano composites.





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U.R.BAGWAN
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WATER TECHNOLOGY
INTRODUCTION
Water is one of the most basic and essential component all life. Earth is covered with 72% of
water.Out of total water 97.2% in oceans , 2.1% in the form of ice, glaciers and 0.6% in the form
of under ground.0.01 % in the form of fresh water like rivers, lakes and other.Water gets
evaporated continiously from oceans,rivers and lakes into atmosphere as clouds and comes
down to earth surface in the form of rain. Water is essential for agriculture ,industrial
production ,power production and domestic purpose .Human body contains 65% of by weight
of water in the form of blood and other body fluids.
IMPURITIES IN WATER
The natural resources of water are rain ,river ,lakes ,ponds, well ,and sea. Impurities
present in the water is broadly classified into four different types a) Dissolved impurities b)
Suspended Impurities c)Dissolved gases d)Organic matter
a)Dissolved impurities:Dissolved imperities consist of bicarbonate , chlorides and sulphates of
calcium and sodium. Small amount of nitrates , nitrities , silicates ,ammonium and ferrous salts
are also present.
b) Suspended impurities :
The suspended matter may be inorganic or organic in nature.The inorganic materials include
small particles of sand ,clay silica, hydroxides of iron and aluminum derived from the erosion of
soil. Some of these have large particle size and therefore settle down readily. Others are fine
particles and colloidal in nature.These do not settle down easily. The organic suspensions are
decaying vegetable matter and are due to microorganisms.These are also present in colloidal
form.The presence of suspended matter ,particularly the colloidal particles , impart turbidity.
c)Dissolved gases: Most water sources contain dissolved gases like oxygen , carbon dioxide
,sulphur dioxide , ammonia and oxides of nitrogen .
d)Organic matter : It include decaying vegetable ,bacteria , microorganism .Water also gets
contaminated with sewage and human excreta due to which pathogenic bacteria are
introduced in water.
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Boiler feed water : A boiler is closed vessel in which water is converted into steam by
heating at high pressure.The water is used in boilers is called boiler feed water.Boiler requies
pure water ,if impurities are present in water following problems are observed. a) Scale and
sludge formation b)Priming and foaming c) Boiler corrosion.
a) Scale and sludge formation
When water is converted into steam , impurities concentrate and finally precipitate out. The
precipitation adheres to inner walls of boiler. If the precipitation is in the form of hard ,dense
and sticky coating it is called scale .If precipitation is inform greasy and loosely held mud , it is
called sludge.
SCALES: these are hard deposits which stick to inner surface of boiler and are difficult to
remove. The impurities like bicarbontes , hydroxides , sulphates ,phosphates , oxides of Ca ,Mg
and silica are responsible for scale formation .Formation of scales takes place due to
i) Due to increase in concentration of salt by evaporation.
Ii)Decrease in solubility of salt with increase in temperature For ex: CaSO4
iii)Precipitation of substance by chemical reaction.
For example
a) Calcium sulphate scale: The solubility 0 f CaSO4 decreases with increase in temperature.
Temperature will be higher at surface than the interior of the boiler. CaSO4 get saturated at the
surface and get deposited in the form of thin film. Due to continuous process a thick, hard,
multilayer scales are formed.
b)Calcium carbonate scale :Calcium bicarbonate decomposes into calcium carbonate in
presence of heat. It has low solubility and deposits in the form of scales.
SLUDGE : It is loose accumulation of suspended solids, found in the colder and less turbulent
sections of the boilers.It is formed by impurities which have greter solubility in hot water than
in cold water. The impurities like MgCl
2
, MgCO
3
,MgSO
4
, CaCl
2
are soluble in hot water but
precipitate out in cold water. Iron and silica are also commonly found in sludge. If sludge is not
removed periodically , it may settle down to form scale.
Harmful effects due to scale and sludge formation
1) Efficiency of boiler decrease
2)Scales and sludge do not conduct heat , hence wastage of fuel.
3)Over heating may lead to expansion of tubes called as bagging.
4) Bagging leads to cracking and seepage of water from boilers
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4) Colder parts of the boiler and distribution lines (pipes) may get blocked due to sludge .
2)PRIMING AND FOAMING
Priming: The steam produced in boiler , some time carry water droplets along with impurities.
This is called priming. The steam with water droplets is called wet steam. The impurities carried
by wet steam may adhere to blades of turbine , hence efficiency of turbine decreases. Primimg
occurs due to impurities present in water, improper construction of boilers, high level of water
in boiler and high steam velocity. Primming can be prevented by slow discharge of steam, proper
construction of boiler and by maintaining low water level.
FOAMING : It is the formation of persistent bubbles on the surface of boiler water. It fills up the
steam space of boiler.Foaming is caused by alkalis, oils, fats and other suspended oranic matter.
Foaming can be avoided by using antifoaming agents . Oil and grease can be removed by sodium
aluminates. Clay and suspended matter can be removed using coagulating agent.
BOILER COROSION
It is process in which boiler surface deteriorates (undergo destruction) due to attack by
impurities present in boiler feed water and environment .Corrosion in boiler occurs due to
a)Presence of dissolved oxygen
b) Presence of dissolved CO2
c) Presence of Magnesium chloride.
a)Presence of dissolved oxygen : Oxygen in feed water is main reason for boiler corrosion. It
reacts with iron at 350 -450
0
C to form ferrous hydroxide. It is further oxidized to ferric
hydroxide by dissolved oxygen. This process continuous until all dissolved oxygen is exhausted.
Fe +2H
2
O + O
2
2Fe(OH)
2

Fe(OH)
2
+ O
2
Fe
2
O
3
.3H
2
O
b) Presence of dissolved CO2: The dissolved CO
2
reacts with water to form carbonic acid.
Hence acidic condition leads to corrosion.The bicarbonate ions furnished by carbonic acid
combines with Fe to form iron bicarbonate . The Fe(HCO
3
)
2
decomposes to Fe(OH)
2
and
CO
2
.Thus the process continues
Fe(HCO
3
)
2
Fe(OH)
2
+ CO
2

c) Presence of Magnesium chloride.The salts like MgCl2 and FeCl2 undergo hydrolysis
producing mineral acids which leads to corrosion.
MgCl
2
+2H
2
O Mg(OH)
2
+2HCl
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M.Sc
FeCl
2
+2H
2
O Fe(OH)
2
+2HCl
DISSOLVED

OXYGEN
Oxygen in water is measured as dissolved oxygen(DO).It is expressed in mg/l or ppm. It
maintains the balance in water ecosystem. Oxygen is required for aquatic plants and animals
and also to prevent odors. Oxygen enters from atmosphere into water surface and also
produced by aquatic plants, algae, phytoplanktons during photosynthesis. Dissolved oxygen
can range from 0 to 18mg/l. Most natural water systems require 5 to 6 mg/l of O
2
to support
life in water. A high percentage of dissolved oxygen supports aquatic life. If dissolved oxygen
declines, aquatic plants and animals will die .There will be increase in worms and fly larvae and
also anaerobic respiration increases. DO analysis is key test to check on downstream water. If
organic waste such as animal waste is not properly treated and allowed to enter water body. It
decreases amount of dissolved oxygen.
Factors affecting dissolved oxygen 1)Water temperature 2)Aquatic plants 3)Stream Flow
4)Altitude/ atmospheric pressure 5) Human activities 6)Organic wastes.
DETERMINATION OF DISSOLVED OXYGEN (DO)
. BY WINKLER METHOD. (5MARKS)
Principle: In this method ,the given water sample is treated manganous sulphate and potassium
iodide .In alkaline medium O
2
oxidises Mn
+2
to Mn
+4
.On acidification Mn
+4
oxidises iodide and
liberates equivalent amount of iodine. The liberated iodine is titrated against standard sodium
thiosulphate solution using starch as indicator.
MnSO
4
+ 2KOH Mn(OH)
2
+K
2
SO
4

2Mn(OH)
2
+O
2
2MnO(OH)
2 (BROWN)
(Manganic oxide)
2MnO(OH)
2
+ 2H
2
SO
4
2Mn(SO
4
)
2
+6H
2
O
2Mn(SO
4
)
2
+ 4 KI 2MnSO
4
+2 K
2
SO
4
+ I
2

2I
2
+ 4Na
2
S
2
O
3
2Na
2
S
4
O
6
+ 4NaI

Procedure : 250ml of water sample taken in a bottle. Add 2ml of MnSO
4
solution and 3ml of
alkaline iodine solution.The bottle is stoppered and shaken well for 10-15minutes and allowed
to stand for 2 minutes for precipitate to settle. Then 1ml of conc H
2
SO
4
is added, stoppered and
shaken well to dissolve the MnO
2
precipitate.100ml of the solution are is pipetted out from the
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bottle into conical flask and titrated with standard Na
2
S
2
O
3
solution using starch as indicator till
the violet color disappears.
Normality of the dissolved oxygen =N
1

Volume to water sample =V
1
ml
Normality of Na
2
S
2
O
3
soution = N
2
Volume of Na
2
S
2
O
3
solution consumed =V
2
ml

N
1
V
1
=N
2
V
2

Normality of dissolved oxygen = N
2
V
2

. V
1
Mass of oxygen dissolved per /dm
3
=Normality Equivalent massof oxygen
= N
1
8 = A g/l
= A 1000 = A mg/l or ppm

SEWAGE
Sewage is the waste material which comes from different sources. Sewage may be broadly
classified into
1)Domestic sewage
2)industrial Sewage

1)Domestic sewage : Domestic sewage is the liquid wastes from residences ,institutions ,
business buildings , kitchens, baths and laboratories . They contain organic wastes, pathogenic
bacteria ,plant mineral, pesticides ,detergents and other waste material.
2) Industrial Sewage: Industrial sewage is from industrial establishments such as chemical
plants,fertilser factories ,tanneries ,refineries ,textiles etc. They contain acids, oils,toxic
chemicals ,metals non biodegradable compounds.etc

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In recent years use of chemicals in high scale and disposing in improper
way by industries has created many environmental problems. Sewage treatment is done to
avoid its harmful effects on environment. Sewage treatment involves breaking down of
complex molecules of organic wastes into simple molecules by bacteria
Bacterial degradation of organic matter is of two types.
a)Aerobic degradation involves degradation of organic waste by bacteria in presence of
oxygen and producing harmless productssuch as carbon dioxide and water.
b)Anaerobic degradation involves degradation of organic waste by bacteria in absence of
oxygen and producing ahrmful end products such as methane ,hydrogen sulphide and ammonia

BIOLOGICAL OXYGEN DEMAND (BOD)

Defination :Biological oxygen demand (BOD) is defined as the amount of oxygen required by
microorganisms to oxidise the organic wastes present in one litre of waste water under
aerobic conditions at 20
0
C over a period of 5 days
BOD is expressed in mg/l or ppm.The amount of organic matter present in the water is
measured interms of amount of dissolved oxygen required by micro organisms to oxidise the
organic matter.This is called as BOD.Higher value of BOD of particular water sample indicates
that water is having more amount of organic waste.Increase in temperature also leads to high
BOD value.
Measurement of BOD: The BOD value of water sample determined by measuring dissolved
oxygen (DO) using winkler method.The DO of water sample placed in BOD bottle is
determined.The bottle is sealed and incubated in dark for 5 days at 20
0
C .After the end of
incubation again the DO is measured. The difference in DO value gives the oxygen consumed by
microrganisms to oxidise the organic waste.
Significance of BOD: Its important to know the BOD of sewage before disposing into rivers or
lakes because ,dissolved oxygen content in water will be decreased by the sewage.If the BOD of
sewage is high ,fishes and other aquatic plants will die.In such cases sewage is diluted with
required amount of clean water and then left in water bodies. Bod gives following information.
1)Polluting power of sewage or its nuisance value.
2)The load of organic matter on the sewage treatment plants .
3)The amount of clean diluting water required for disposal of sewage.

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CHEMICAL OXYGEN DEMAND (COD)
Defination: COD is defined as the amount of oxygen consumed to oxidise organic and inorganic
waste present in 1 litre of water by using strong oxidisng agent like K
2
Cr
2
O
7

It is expressed in mg/l or ppm.COD is always greater than BOD, because COD involves oxidation
of both biodegradable and non-biodegradable matter.

EXPERIMENTAL METHOD
Principle: Water sample is made to react with acidified K
2
Cr
2
O
7
in presence of Ag
2
SO
4
and
HgSO
4
. The un reacted K
2
Cr
2
O
7
is made to react with ferrous ammonium sulphate solution.The
amount of K
2
Cr
2
O
7
consumed to oxidize the water sample corresponds to COD of water sample.

3CH
2
O + 16H
+
+ Cr
2
O
7
2
4Cr
+3
+CO
2
+ 11 H
2
O
Procedure : Take water sample in conical flask .Add 10cm
3
of 0.25N K
2
Cr
2
O
7
and 30cm
3
of of
6N H
2
SO
4
.Now add 1g Ag
2
SO4 as a catalyst and 1g of HgSO
4
to avoid interference of chloride
ions.Attach a reflux condenser and gently reflux the contents for two hours .Cool and titrate the
excess K
2
Cr
2
O
7
against ferrous ammonium sulphate solution using frroin as indicator till the
bluish green color turns to reddish brown.Let the volume FAS consumed be Aml .Now carry out
the blank titration by taking distilled water in place water sample. Let the volume of FAS
consumed be B ml
Calculation:
Volume of K
2
Cr
2
O
7
required to react with water sample in terms of FAS V
2
= (BA) ml
Normality of FAS = N
2

COD of water sample = N
1
Volume of water sample = V
1
N
1
V
1
= N
2
V
2

= N
2
(BA)
. V
1

mass/dm
3
= N
1
Equivalent mass of O
2

= N
1
8 g/l
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= N
1
8 1000 mg/l or ppm

SEWAGE TREATMENT
Sewage contains pathogenic bacteria ,organic, inorganic and suspended impurities. If left
untreated in water bodies .It causes death of aquatic plants and animals.Sewage treatment is
done to reduce BOD level and to remove other impurities. Sewage treatment is done in three
steps.
1)Primary treatment.
2) Secondary treatment.
3) Tertiary treatment.

1) Primary treatment.
It involves removal of floating and suspended impurities.These impurities are removed by
passing sewage water through bar screens and mesh screens in which impurities get filtered.
Sand ,broken glass pieces are removed by passing sewage water slowly through grit chamber.
Here heavy material settels down due to gravity.Oil and grease are removed by passing
compressed air to form froth which floats on water and skimmed off.Suspended particles are
removed my coagulation method (sedimentation process) by addiing coagulating agents like
alum , FeSO
4
.

2) Secondary treatment (Biological treatment )
Waste water after sceondary treatment is mixed with activated sludge in aeration tank
.Activated sludge is mixture containg microrganism and bacteria. Air is blown for several hours
from the bottom of the tank ,to bring good contact between bacteria and organic wastes.
Under sunlight and oxygen bacteria oxidises (aerobic oxidation) organic matter.The purified
water and sludged is sent to a tank in which sludge settles down.A part of sludge is used to
purify fresh sewage and remaining is used as fertilisers. Purified water is collected separately
and chlorinated to remove bacteria and finally discharged into running water or used for
watering plants.This method operates at 90-95% efficiency of BOD treatment. If the treated
water contains a high concentration of phosphates ,heavy metals , colloidal impurities and non
degradeble organic compounds , the water is sent to tertiary treatment.



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U.R.BAGWAN
M.Sc






3) Tertiary Treatment
Phosphates are removed by adding lime to form calcium phosphate.Heavy metals are removed
by treating with S
-2
ions to form insoluble sulphides. Water is also treated with activated
charcoal where impurities get adsorbed. Colloidal particals if not removed in sceondary method
is now removed by adding alum to reduce BOD level
WATER POLLUTION
Water pollution is contamination of water with foreign material. With rapid globalization and
industrialization water bodies are unlawfully used to dump waste material.Water bodies are
contaminated with, pathogenic bacteria, organic wastes , pesticides, heavy metals ,radioactive
wastes, industrial wastes and heat. Water suitable for drinking purpose is called as potable
(safe) water .Water for drinking purpose should be soft, clear and odorless , free from
pathogenic organisms ,free from any harmful foreign material and should be of good taste.
DESLAINATION OF WATER
The process of removal of dissolved salts from sea (or brackish) water to make it usable is
called desalination of water. Desalination is expensive process usually applied in countries
where there are no sources of fresh water. Salt water is desalinated to produce fresh water
suitable for human consumption or irrigation. There are three grades of water based on the
level of dissolved salts.
a) Fresh water contains less than 1000mg/l of dissolved salts.
b) Brackish water is one whose salinity lies between fresh water and sea water. It contains
1000 35,000mg/l of dissolved salts
c) Sea water contains more than 35,000mg/l of salts.
Desalination of water is done by
a)Reverse Osmosis b) Electro dialysis
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REVERSE-OSMOSIS (5 MARKS)
Defination: The process of demineralization of water by passing water under pressure
greater than osmotic pressure through semi permeable membrane is called as Reverse
Osmosis .It is commonly referred to as RO.
Pressure greater than OP

Osmosis is the movement of solvent (water) molecules from higher concentration
to lower concentration through semi permeable membrane. When salt water and pure water
are separated by semi permeable membrane a difference in concentration of salt arises. This is
called chemical potential. Salt water shows greater chemical potential than pure water. To
equalize the chemical potential water molecules from pure water diffuse through semi
permeable membrane into salt water , this is called as osmosis and the pressure with which
molecules are diffusing is called osmotic pressure (OP).

Osmosis can be reversed by applying pressure on saline water.
The applied pressure should be greater than osmotic pressure. The amount of pressure
required depends on concentration of the salt water. Concentrated salt water requires more
pressure to overcome osmotic pressure(OP). Sea water exerts an osmotic pressure of about
240psi and brackish water exerts less OP value. Reverse osmosis is done applying pressure in
the range of 410 psi to 540 psi. A reverse osmosis unit consists of a membrane, a vessel and
high pressure pump. The semi permeable membranes are generally made up of cellulose
acetate or nylon which allows on water molecules to pass through.


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Softening of water by Ion exchange process (6 Marks )
Ion exchange process is one in which there is a reversible exchange of ions between solid
phase and solution phase. If an aqueous solution containing B
+
cations is placed in contact with
solid exchanger A
+
X
--
. Following reaction takes place.

B
+
+ A
+
X
--
X

B
+
+ A
+

Ionexchange resins are polymers of high molecular mass and with porous cross linked
structure.Ion exchange property arises due to presence of acidic or basic group in resins. The
acidic group (sulphonic or carbonyl) exchange H
+
ions for cations (Ca
+2 ,
Mg
+2
). The basic group
(amino) exchange OH

ions for anions (SO
4
-2
,Cl

)


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.

Cation Exchange Resins
2RH
+
+ Ca
+2
2RCa
+2
+ 2H
+

2RH
+
+ Mg
+2
2RMg
+2
+ 2H
+
(RH
+
= cation exchange resin)


Now water is passed through anion exchange resins which
remove bicarbonates, chlorides and sulphates ,fluoride and nitrate from water and exchange
equivalent amount of OH

ions.
.
Anion Exchange Resins
ROH + Cl


R Cl

+ OH-
2ROH
-
+ SO4
-2
2RSO4
-2
+ 2OH- (ROH = anion exchange resin)


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Regeneration of resin

When cation exchanger looses capacity of producing H+ ions and anion exchanger
Looses capacity of producing OH
--
ions, they are said to be exhausted. The exhausted cation
exchanger is regenerated by passing it through dilute HCl or H
2
SO
4
The exhausted anion
exchanger is regenerated by passing a dilute solution of NaOH.

Advantages of ion exchange process
1)The process is completed in a few seconds
2)Ion exchange resin can be easily regenerated.
3)Water of 1 to 2 ppm purity could be obtained.

ELECTRODIALYSIS (5MARKS)

Principle : Electrodialysis process is based on the principle that ions migrate towards oppositely
charged electrodes when an emf is applied.

The direction of ions are made specific by using ion selective membranes.
Cation membrane(C) allows only cations to pass through it and anion selective membrane (A)
allows only anions to pass through it.The process of decreasing the concentration of salt in
saline water using ion selective membranes under the influence of an applied field is called
electrodialysis.

An electrodialysis cell consists of series of alternative cation and anion membranes
( C & A) as shown in figure. The anode is placed near the anion permeable membrane. The
cathode is placed near cation permeable membrane.A suitable emf is applied and it depends
upon concentration of salt in water.Under the influence of the applied emf, Na
+
ions move
through the cation permeable membrane (C) and anion Cl

ions move through anion


permeable membrane. The net result is decrease in concentration of salt content in CA
compartment and increase in salt concentration in AC compartment .The fresh water formed
at CA compartment is collected. The concentrated salt solution (brine) is discharged through
outlet.









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M.Sc






+ C A C A C A

Na
+
Na
+
Na
+


Cl

Cl

Cl