bölen ouble

Co,
NON,GoK
Chapter 1
WATER CHEMISTRY AND POLLUTION
1.1 Water Chemistry
Water is a wonderful gift of the nature. Water is used for drinking, irrigation,
domestic and industrial purpose.
C
1.1.1. Sources of Water: X
Rain is the main source of the water. If it flows on the surface of the earth, it is called
Surface Water, and if it percolates into the ground, it is called Ground Water.
Surface Water. It may flow on the surface of the earth in the form of pond, lake,
canal, river or seawater.uesobioswitet bety
Ground Water: If the water percolates into the ground, it is called Ground Water.
It is in the form of well water andspring water.
The rainwater as soon as it comes into contact with the earth, it dissolves the
minerals present in the earth crust. Ifthe contact between the water and the earth
is more, salts dissolved in water are also more. In addition to the dissolved salts,
organic matter may also enter into the surface water. In fact surface water
contains more organic matter and less inorganic salts. On the other hand ground
water contains more inorganic salts and less organic matter. The various sources
of water and the impurities present in these sources are as follows:
1. Pond Water: It contains more organic matter, decaying leaves, parasites,
bacteria, virus etc.
2 Lake Water: lt also contains more organic matter, weeds etc.
3. Canal Water: Itcontain more turbid matter, decaying leaves, floating matter,
bacteria, virus, domestic and industrial effluents etc.

4. River Water: It contain suspended particles, turbid particles, uprooted trees

and dead animals during flood time, industrial as well as domestic efluents. The
religious beliefs like Kumbha Mela etc. also causes a lot of contamination. as a
large number of devotees take holy dip in the rivers.
5. Sea Water. It is highly concentrated with the salts (3.5%). Sodium Chloride
is the main salt (2.7%). The other salts are calcium bicarbonate, calcium chloride.
calcium sulphate, magnesium bicarbonate, magnesium chloride, magnesium
sulphate etc. Oil slicks also contaminate the sea water
1
 WATER CHEMISTRY AND POLLUTION

6. Well Water: It contain more dissolved salts and less organic matter. In
dustrial effluents are causing ground water pollution.
7. Spring Water. If the water comes out by itself due to hydrostatic pressure
then it is called spring water. It also has the same composition as well water.
A2(HARDNESS OF WATER,0M) k Otao
(Water that does not give immediate lather with soap is called hard water.
Hardness of water is due to dissolved salts like calcium bicarbonate, calcium
chloride, calcium sulphate, magnesium bi carbonate, magnesium chloride, magnesium
sulphate etc. Soap is a salt of higher fatty acids like sodium stearate, sodium
palmitate, sodium oleate etc. These fatty acids of soap are completely soluble
in water; but when these fatty acids react with hard water, calcium and magnesium salts
of hard water react with soap to form insoluble precipitate of calcium and magnesium
stearate or palmitate or oleate which is called scum tormation.s 1ofewnist S1T
20,H, CoONa +Ca *’ (C,,H,c00), Ca ! + 2Na' nseeson
Sodium stearate (soluble) Calcium stearate (insoluble)
20,,H COONa + Mgtt ’ (C,,H,CO0) Mg +2Na*nagro erom ziisinN
Sodium stearate (soluble) Magnesium stearate (insoluble)eaisinoo efh
Classification of Hardness : 1. Temporary hardness and 2. Permanent
hardness

11.2.1. Temporary hardness: It is due to bicarbonates of calcium and

magnesium and can be easily removed by boiling. On heating calcium bicarbonate is
converted into calcium carbonate, which is insoluble in water, and
magnesium
bicarbonate is converted into insoluble magnesium hydroxide.
Ca (HCO,) ,> CaCO, + HO+ CO,1em hcol oniub
elsmins bsets8 1
Mg(HCO),> Mg (OH), +2c0, t
11.2.2. Permanent Hardness: lIt is due to chlorides and
and magnesium. These salts are removed by
AMRU
sulphates of calcium
Lime-soda method. Zeolite method
and lon-exchange method.)
psnlgnoOd nulaenpsm etedalue muio6
 1.1.3. UNITS OF HARDNESS
Calcium Carbonate Equivalents: Hardness of water is expressed in calclurm
carbonate equivalents. The following equation is used to convert the hardness
causing salt into calcium carbonate equivalents.
Mass of hardness causing salt CaCO.
CaCO, equivalents = -X Mol. mass of 3

Molecular mass of that salt

(Molecular Mass of CaCO,3 is 100)

The units of Hardness are Parts per million, milligrams per liter, Degrees French
byb eM
and Degrees ClarkeoT911b1
1.1.3.1. Parts per million: ppm may be defined as the parts of calcium
carbonate equivalent hardness present per million parts of water:
1ppm =1 part CaCO, equivalent hardness for 10 parts of watere os
1.1.3.2. Milligrams per liter: mg/lt may be defined as the parts of milligrams
of calcium carbonate equivalent hardness present in one liter water. It is
equivalent to ppmlooic ouslegbau prinot eovb yleoo seROT e
eaon
1liter weight = 1 kg =10 mg. So mg/lt = p p m eEVDD e0Ree
1.1.3.3. Degrees French (°Fr) : It may be defined as the parts of calcium
carbonate equivalent hardness per one lakh parts of water.Snenenlo b
1degree French = 1part CaCO, equivalent hardness for 10 parts of water
4
WATER CHEMISTRY AND POLLUTION

io1.1.3.4. Degrees Clarke:lt may be defined as the parts of calcium carbonate

equivalent hardness present in 70000 parts of water. genisino0 noiuloe elni
1degree Clarke = 1part CaC0, equivalent hardness per 7x 10 parts of water
Seow bslliteib eil
11.4. Esti mation of Hardness of Water
Hardness of water can be estimated by Ethylene Diamine Tetra Acetic Acid
water
(EDTA) method. It is also called as Versenate method. In this method hard
Black-T (EBT)
is mixed with buffer pH-10 and one or two drops of Eriochrome
indicator. The color of water is changed to wine red due to the complex formation
EDTA blue color is
of EBT with calcium and magnesium. This on titration with
Complexes
obtained at the end point due to formation of Ca-EDTAand Mg -EDTA
magnesium ions
and liberation of free EBT (EBT is blue in color). Calcium and
react with EBT or EDTA individuallyl 0
Structure of EDTA

ovadl tel -ould asslo CH,CO0oloo ber eni edt 0oll

eHO0cH,O Vod bamua

-H,C -CH,NHaw bied eigmmee too S

H-N*

CH,COOH
-00CH,C
EDTAonr b i o o a arll natROh

Cat* +EBT ’ [Ca-EBT]

Mg ** +EBT ’ [Mg-EBT]
unstable wine red color

[Ca-EBT] + EDTA ’ [Ca-EDTA] + EBT

+ EBT
[Mg-EBT] + EDTA ’ [Mg-EDTA]
Stable Complex Blue color
following solutions are required for the estimation of hardness
Procedure: The
method
of water by EDTA 1.0 gm of pure, dry CaCO, in
Hard Water: Dissolve
1. Preparation of Standard evaporate the solution to dryness on a
dilute HCI and then
minimum quantity of
5
water bath. Then make up the solution to one liter with distilled water. Each ml of
this solution contains 1 mg of CaCO, equivalent hardness.
2. Preparation of EDTA solution: Dissolve 4 g of EDTA and 0.1g. of Mgcl, in 1
liter distilled water.
3. Preparation of EBT indicator. Dissolve 0.5 gof Eriochrome Biack-T indicator
in 100 ml alcohol.

4. Preparation of Buffer Solution:Add 67.5 g of NH,CI to 570 ml of concentrated

ammonium hydroxide solution and dilute it to 1 liter with distilled water.
Titrations are as follows
1. Standardization of EDTA solution: Measure 50 ml of standard hard water
into a conical flask. Add 5-10 ml of buffer solution and one or two drops of EBT
indicator. Awine red colored solution is obtained. Now rinse the burette with EDTA
and fill with EDTA solution. Titrate the solution of the conical flask with EDTA solu
tion till the wine red color changes to clear blue. Let the volume of EDTA con
sumed be V, ml.
2. Titration of sample hard water: Titrate 50 ml of sample hard water as above.
Let volume consumed is V, ml.
3. Titration of permanent hardness: Take 250 ml of water sample into a 500ml
beaker. Boil it, till all the temporary hardness is decomposed into CaCO, and
Mg (OH) p Filter the precipitate and make up the solution to 250 ml with distilled
water. Then titrate 50 ml of boiled water sample against EDTA as above. Let the
volume consumed be V, ml.
Calculations :
50 ml of Standard Hard Water = V, ml of EDTA
eltslene
50 x 1mg of CaCO, = V, ml of EDTA
1ml of EDTA = 50/ V, mg of CaCO,eq.
Now 50 ml of sample hard water = V, ml of EDTA
= V,x50/V, mg of CaCO, eq.
1000 ml of sample hard water = 1000VN, mg of CaCO, eq
Total hardness of water
u=1000V/V, mg/litaonota
= 1000 V/V, ppmowhop musn
6
WATER CHEMISTRY AND POLLUTION
EDTA.ResinavbeeiC
Now 50 ml of boiled water =V, ml of
entebteew è ast,eet io cro19ugn=V,x50 / V, mg of CaCO, eq.
1000 ml of boiled water = 1000 V,/ V, mg of CaCO,eq
Permanent hardness = 1000Vs/ V, ppmlicd srithdosio9
Temporary hardness = [Total hardness - permanent hardness]

= 1000
 1.1.6 Municipal water treatment :
Municipalities have to supply potable water Potable water is the water, wno
IS tree from disease producing bacteria and safefor drinking. Drinking water must
De clear, colorless, odorless and pleasant to taste. It must be free from turoldy,
suspended impurities, toxic chemicals and excess dissolved salts and dsease
Causing bacteria. 80% of the diseases are water born diseases directly or
indirectlyyThe following steps are involved in the Municipal Water Treatment.
Screening 2. Sedimenttion, 4 Filtration and & Disinfection
Sedtw byaa
1.1.6.1. Screening : The raw water is passed through screens, have large number
of holes; which retain the floating matter
1.1.6.2. Sedimentation: It means simple settling. It is the process by which the
force of gravity acts on particles heavier than water and causes them to move
downwards and settle. For this pure water is kept in huge tanks, called sedimenta
tion tanks in which water moves very slowly. The time required for sedimentation
depends on the weight, size and shape of the particles and the viscosity and
frictional resistance of the water. It has been calculated that the settling rate at 0°C
is only 45% of the rate at 30°C. Consequently turbidity is more easily removed
during summer than in winter. Water is kept in sedimentation tanks from 4 to 12
hours. Sedimentation is of two typesol
1.1.6.2.1. Plain Sedimentati on : By plain sedimentation 70% of the suspended
particles are settled down. Finely divided matter and colloidal matter is not settled
by plain sedimentation.
18
 WATER CHEMISTRY AND POLLUTION

1.1.6.2.2. Sedimentation by coagulation: It is the process of removing fine

suspended matter and colloidal matter by adding coagulants like alum, aluminum
sulphate, ferrous sulphate,sodium aluminate etc. These coagulants on reaction with
water form a huge precipitate of respective hydroxides, which is called flocculent
precipitate. This precipitate settles downdue to gravitational force. In that course finely
divided suspended matter is trapped in the precipitate and settled down. Colloidal
particles are also settled as they carry negative charge and cations of coagulants
carry positive charge, charge neutralization takes place and settled down. Some
bacteria and color are also removed. The dosage of the coagulant depends upon the
turbidity and may be 5 to 100 mg/l. Each coagulant gives best results in a pH range,
which is affected by the mineral characteristics of the water.
Al, (SO,) , +3Ca (HCO)’ 2AI (OH), +3CaSO,+6 CO,‘
t NaAlO, +2 H,0 ’Al (OH), + NaOH
FeSO, +Mg (HCO),’ Fe (OH) 2+ MgSO, +2C0,
2

4Fe (OH) ,+0,+2H,0 ’4 Fe (OH),

1.1.6.3. Filtration: Filtration may defined as the process of passing awater
containing suspended matter through a suitable porous material in such a manner
so as to affectively remove the colloidal matter from the water. Filtration is mainly
a mechanical process. When water flows through a porous material many colloidal
particles are unable to pass through the interstices (or gaps) in the material because
of its size. Thus these particles are removed and clarification takes place. Filtration
e removes the colloidal matter and to some extent bacteria. True color is not re
- moved by the filtration. It can be removed by using the coagulants. Filters are of
two types: 1. Gravity filters and 2.Pressure filters
d 1.1.6.3.1. Gravity Filters: In these the water flows through by the gravity. These
filters are of two types a) Slow Sand Filters and b) Rapid Sand Filters
1.1.6.3.1.1. Slow Sand Filters : The filters are like large shallow tanks made of
2
concrete. At the bottom there is an under drain system through which the filtered
water goes to the storage tank. Gravel is placed in the tank above the under drain

d
system; on the gravel a bed of coarse sand and above it a layer of fine sand are
placed (Fig 1.6 ).
19
 POLLUTION
WATER CHEMISTRY AND

N U N N o o N s eiiem bobneqasa
uiule uls i aue euoe oieiglwe
111|0

Fine sand 30-60 cmirT eisiigiasa

Sedimented abregeue babivlb
waler Coarse sand 30-60 cms 9162sioitisg
Gravels

e15 iol03 brs tetosd

Fltered
eisw rli io 2Under drainST waterG
outlet
2i doW

(hO) sO8-02) IA
Fig.1.6. Sand Filter OAG oHSolAsM
HO)
As water percolates through the filter the colloidal particles are retained on the
top 5 to 10 cm layer of the fine sand. In fact, the layers of coarse sand and gravel
do not filter at all. They support the fine sand top layer, which retains the colloidal
matter. When the suspended matter has been deposited to such an extent that the
rate of filtration becomes very slow. Then a portion of the top layer is scrapped
and the bed is used again. After continued use of the bed fora tong time, it be
comes necessary to replace the top layer completely.
 nts. SUCh
potable
0 bacteria
.1.6.4.
Water,
water. and
Disinfection
which
croorganisms
The
is
hemicals free
from or
Sterilization:
pathogenic from
used

for
the
bacteriawater
killing It
is
the
and
athogenic and process
making
safe
for of
bacteria it
killing
drinking, safe
for
pathogenic
are
drinking.
is
calledcalled
 3. Chlorination It is mainly used for killing the disease causing bacteria. This method
is suitable for cosmopolitan cities. It is mixed with
water in chlorinator. It has a high tower with a num water Raw Concentrated
chlorine
ber of baffle plates. Water and proper quantity of inlet solution

concentrated chlorìne solutions are introduced at

Baffie
its top during their passage through the tower, they plates
get thoroughly mixed and the treated water is taken High tower
out from the bottom

Cl, +H,0’ HCl+HOCIotroiossoE&p

Germs+ HOCI > Germs are killed oscherio lo
Sterlized

Fig.1.7. Chlorinator
21
Advantages
1. Effective and economical
2. Storage requires little space
onitassld
3. Stable and does not deteriorate
oldnsbbisegvide9H noilpieo
4. Stable at high temperature anddifo
5. Produce no salts
Drawbacks : irritable to mucus
taste and odor and
causes unpleasant
1. Excess of chlorine pH 6.5 and less effective at higher pH
membrane 2.More effective at below
chlorination produces an unpleasant taste and odor in
Dechlorination: Over filtering the over chlorinated
qualities may be removed by
the water. These objectionable carbon. Objectionable qualities resulting trom
water through a bed of molecular
removed by the addition of small amount of sulphur
over chlorination may also be
dioxide or sodium sulphite or hypo. eiboe
po iatenwo tot eidsiiue
SO, +0l,+H,0 ’ H,SO, +HCI
Na,SO, +Cl,+H,0’ Na,sO,+2HCI
aaiuboiini veggodoRst8easdw
Break Point Chlorination:

Chlorine
Repidual

Polluted
P u rW
e ater

oBreak Point

Combined Chlorine Free Chlorine

Chlorine added

Fig 1.8Break Point ChlorinationDteo

of highly polluted
It is a specialized method of chlorination applied for the treatment and weeds. When
smell
Waterto remove the organic compounds, ammonia, color, -added chlorine
chlorine is added to the highly polluted water and a graph is plotted
o t e n o l o
WATER CHEMISTRY AND POLLUTION

against residual chlorine -first there is a gap in the curve as the chlorine added to
the water completely consumed to oxidize the organic matter and bacteria. After
that there is a proportionate increase in the curve and then it starts to decline
because the chlorine react with ammonia to form monochloro amine, dichloro amine
and trichloro amine. NCI, decomposes to give chlorine. So there is a sudden rise in
the curve and this point is known as break point and due to the peculiar nature of
the curveit is called break point chlorination. This point indicates at which free
residual chlorine begins to appear.ashiiy nleoistspshtog nuleesiog.
NH,+CI,’ NH,CIl +HCI9780Bgismsy Cldaslo4pe iovome beisluolso
E
NH,CI +CI, ’ NHCI, + HCIubog nie eve U: eniobeA isllaslU
NHCI,+CI, ’NCI, +HCI elooo prireiwe
2 NCI, ’ N,+3CI, s8sgslnsvbnalCh.
Advantages of Break point chlorination biT
S0
1. It oxidizes organic matter, ammonia and other reducing compounds.
2. It removes color in water
olien:laeol
3. lt destroys all disease producing bacteria1 lo
4 It removes both odor and taste from the water and SIOO STSW a
5 It prevents the growth of weeds in water.
4. Chloramine tablets: When chlorine and ammonia are mixed in the ratio of
2:1 by volume chloramines are formed.
Cl,+2 NH, ’NH,CI +HCI NH,CI +H,0 ’NH,+ HOCI o alee boilso
Chloramines are used for disinfection of water be Raw
cause its excess does not produce any irritating odour. water Ozone inlet
Army people for sterilization of drinking water use these Disinlecled
nalor oullat
tablets
Contact

Tourists may also use these tablets. Municipalities tank

distribute these tablets during the time of floods.

5, Ozone: Ozone is an excellent disinfectant, which
isproduced by passing silent electric discharge through
Fig.1.9.Ozone Sterilizer
cold and dry oxygen.ekeoetnib balb or
23
 Ozone O
ges: O,’

highly is
O,
+(0)
oves
unstable
and
Nascent
302

color,
Oxygen Silent
breaks
down
isodor
el
ectric
and
osl
rgealouno9 oxygen. WATER
liberating
nascent

CHEMISTRY

0,erit lan
AND

POLLUTION
1elswo(Fig.5.9)
 (b) operation,
down
e.g., adding
removable,
Na,HPO4,
The sodium (i)
main Phosphate
soft
disodium phosphate,
phosphates sludge

hydrogen conditioning
2Na,PO4
3CaCl, calcium
+ which
of
employed
phosphate reacts
and :
In
are magnesium with
high-pressure
(weakly 9

(a) : hardness
Ca,(P0,),
J+6NaCl ’
alkaline)
NaH,PO,,
phosphates,
boilers,
of
(c) ; water
Na,PO,sodium forming
scale
which
dihydrogen formation
trisodium can
non-adherent
be
removed can
phosphate
phosphate
be
avoided
and
(alkaline).
(acidic) by
bloweasily
by
;
 3 WIUCH Caii
sluage phosphate (NaPO,),
(iv) Calgon conditioning involves in adding calgon [sodium hexa meta
soluble complex conpound
to boiler water. It prevents the scale and sludge formation by forming
with CaSO4 Visakhanathe
Calgon
isvedoruraTisd a d o p s : i n u r sliod ot 2
2CaSO, +[NaP,O1sl
2Na+[Na,PeO,sl

Soluble mplex ion

+
GITA
2Na,SO4,o noit il
 1.1.5.3. lon -Exchange Process: This process is also called asdemineralization
process. lon exchangers are highly cross-linked organic polymers which posses
functional groups. Like exchanges like. Cation exchanger carry exchangeable cations
that exchanges cations of the hard water, similarly anion exchangers carry
exchangeable anions that exchange exchangeable anions of the hard water. The
exchangeable ions are also called as free ions or counter ions.

16
WATER CHEMISTRY AND POLLUTION

Process: When water containing dissolved salts of Cat* and Mgt* ions is passed
through a cation exchanger that carries exchangeable H ions; all the
Ca* and Mg** of the water are exchanged. When that water is passed cations Ike
through an
anion exchanger that carries exchangeablè OH ions, all the anions like Cl, SO,
and HCO, of the water are exchanged. The H+ ions released from the cation exchanger
and OH ions released from the anion exchanger combine to form water
Hard water in

ECation exchangar EAnion exchanger balsteneger

bed bed
inglainut
injector ’
Gravel Gavpl
ogvoguoEnector

To To
sink sink
L habnegeue
Acid Pump Soft watar/ Alkaline
regenerator Out regenerator

neuea9n Fig.1.5. Demineralization Processt

1.1.5.3.1. Cation Exchange Process
2RH +Ca" ’ R,Ca +2H*becest eineweaetae
2RH + Mg**>R,Mg +2H*
1.1.5.3.2. Anion Exchange Process2eenblene ioitasaoS0h
2R'OH +2CI ’2 R'CI +2OH
2R'OH+SO. R,SO,+20Hole covo wostwolelnst ot
H +OH > H,0
When all the H ions of the cation exchange resin and OH ions of the anion
exchange resin are exchanged with cations and anions of the hard water, then the
resins are unable to soften the hard water and that stage is called as exhausted.
Then resins are to be regenerated with proper acid and base(Fig.1.5).
Regeneration : Cation exchange resin is regenerated by 0.1 N HCI and anion
exchange resin by 0.1N NaOH solutions and excess acid and base are washed out with
distilled water. The resin beds after regeneration are used again for water softening.
17
 WATERCHEMISTRY AND POLLUTION
R,Ca +2H* >2RH +Ca**oto el R,Mg +2H>2RH
R'CI +OH> R'OH +CIaD R,'SO, +OH +Mg**noci/eoo
>2R'OH+SO,-so eiguOH
4

Advantages: The process may be used for highly acidic or alkaline waters and
hot water also. Both cations and anions are
the boilers for steam generation.
removed so it may be safely used in

Disadvantages:
regeneration.
The equipment is costly and costly chemicals are
needed for
Limitations: Turbid water cannot be treated as
Water containing Fet* and Mn+t ions should notthe pore of the resin is clogged.
be applied as these are not
regenerated.
 (2) Reverse osmosis : When two solutions of unequal concentrations are separated by a
semipermeable membrane (which selectively does not permit the passage of dissolved solute particles,
ie., molecules, ions, etc.), flow of solvent takes place from dilute to concentrated sides, due to
osmosis. If, however, a hydrostaticpressure in excess of osmotic pressureis applied on the concen
trated side, the solvent flow reverses, ie., solvent is forced to move from concentrated side to dilute
side across the membrane. This is the principle of reverse osmosis. Thus, in reverse osmosis (R.O.)
methods, pure solvent (tvater) is separated from its contaminates, rather than removing contaminants from
the water. This membrane filtration is sometimes also called "super-filtration" or "hyper
filtration",
o Method : In this process, pressure (of the order 15 to 40 kg cm) is applied to the sea
water/impure water (to be treated) to forceits pure water out through the semi-permeable mem
brane ;leaving behindthe dissolved solids (both ionic as well as non-ionic). The principle of reverse
osmosis, as applied for treating saline/sea water, is illustrated in Fig. 17.The membrane consists
of very thin films of cellulose acetate, affixed to either side of a perforated tube. However, more
recently superior membranes made of polynnethacrylate and polyamide polymers havecome into use.
Pressure

Piston

HuIuuu Fig. 17. Reverse osmosis cell.

water oStout
semi-permeable
membrane

Pure water
Pure water
out4CT
o1Advantages :(i) Reverse osmosis possesses adistinct advantage of removingionic as twell as non-ionic, colloidal
and high molecular weight organicmatter. (ii) It removes colloidal silica, which is not removed by demineralization.
(ip) The maintenance cost i_ almost entirely on the replacement of the semipermeable membrane. (in) The life
time of membran is quite high, about 2years. (v) The membrane can be replaced within afew minutes, thereby
providing nearly uninterrupted water supply. (u) Due to low capital cost, simplicity, low operating cost and
high reliablility, the reverse osmosis is gaining ground at present for converting sea water into drinking water
and for obtaining water for very high-pressure boilers.
 Water and its treatment
CHEM1001

Introduction – hardness of water – Causes of hardness - Types of hardness:

temporary and permanent – expression and units of hardness. Estimation of
hardness of water by complexometric method. Potable water and its
specifications. Steps involved in treatment of water – Disinfection of water by
chlorination and ozonization- industrial water treatment- Boiler feed water and
its treatment -internal conditioning– Calgon and Phosphate conditioning.
External treatment of water – Ion exchange process. Desalination of water –
Reverse osmosis.
 Introduction
1. Water is one of the most essential substance for existence
of life.
2. Nearly three-fourths of the earth's surface is covered with
water. Therefore, the earth is called as blue planet.
3. Even then out of the total amount of water, 97% is
blocked in the oceans, 2.1% in the polar ice caps and
glaciers and out of the remaining water is present deep in
the earth, which is inaccessible, leaving only around
0.003% of fresh water for domestic and other usage.
4. Water is a major constituent in living systems and
contributes to 55% - 85% of the total body weight.
5. Water is the only common substance found naturally in all
three physical states of matter.
• Sources of Water

• 1. Rainwater

• 2. Surface water- rivers, lakes, reservoirs etc.

• 3. Underground water – wells and springs

• 4. Sea water

▪ Properties of water
• Water is a transparent liquid which forms the world's streams,
lakes, oceans, and is the major constituent of all living organisms.
It can dissolve many substances and therefore is referred as a
universal solvent. Due to this property of water, it easily gets
contaminated, and its composition gets altered.
• It exists as a liquid over a wide range of temperature form 0°C to 100°C.

• It has the highest specific heat, due to which it warms up and cools down
very slowly without causing shocks of temperature jerks to the aquatic life.

• It is an excellent solvent for several nutrients.

• Due to high surface tension and cohesion it can easily rise through great
heights through the trunk even in the tallest of the trees.

• It has a high latent heat of vaporization. Hence, it takes a huge amount of

energy for getting vaporized. That’s why it produces a cooling effect as it
evaporates.
• It has an anomalous expansion behavior. Like all liquids, on cooling water contracts
but on further cooling below 4oC it expands and forms ice which is lighter. Due to this
property even in extreme cold regions, the lakes freeze only on the surface. Being lighter
the ice keeps floating where as the bottom waters remain at a higher temperature and
therefore, can sustain aquatic organisms even in extreme cold conditions.}

• Impurities in water:

• Suspended impurities Inorganic (clay, sand) organic (oil, plant and animal matter)

• Colloidal impurities- finely divided silica and clay

• Dissolved impurities – salts and gases

• Microorganisms – bacteria, fungi and algae

• Hardness of water and its types:

• Hardness of water: It is one of the characteristics of water which prevents lathering of

soap due to the presence of dissolved salts of Calcium, Magnesium, and other heavy
metals. It is of two types - Temporary Hardness and Permanent Hardness

• Temporary Hardness – It is due to the presence of dissolved bicarbonates of Calcium,

Magnesium, other heavy metals, and the carbonate of Iron in water. It is also known as
alkaline or carbonate hardness.

• 2C17H35COONa + Ca (HCO3)2 → (C17H35COO)2Ca↓ + 2NaHCO3

• Soap Scum

• It can be removed by boiling water.

• It can be removed by boiling water.

• Ca (HCO3)2 → CaCO3↓ + H2O + CO2↑

• Mg (HCO3)2 → Mg (OH)2↓ + 2 CO2↑

• It can be determined by titration with HCl using methyl orange as an indicator.

• Permanent Hardness – It is caused by dissolved Chlorides and Sulphates of Ca, Mg, Fe

and other heavy metals. It is also known as non-carbonate or non alkaline hardness.

• It cannot be removed by simple boiling method but needs special external treatment
techniques like Lime Soda method, Ion Exchange method, and zeolite process.

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

• Total hardness = Temporary hardness + Permanent hardness

• Causes of Hardness:

• Hard Water is very dangerous to health of human beings. It causes many diseases in humans.
It also disturbs the industries. It is not safe to drink, also for other domestic purposes.

1. In some areas of the country hard water is caused by a high mineral content, which are
generally calcium and magnesium. This hardness is largely due to groundwater that flows
over or through limestone.

2. The hardness in water is caused by polyvalent metallic ions from sedimentary rocks, seepage,
and runoff from soils containing the two principal ions Calcium and magnesium
• As this water moves through soil and rock, it dissolves very small amounts of minerals and
holds them in solution.
• The degree of hardness becomes greater as the amount of divalent or multivalent cations
dissolved in the water increases.
• Types of water:

1) Soft water

2) Hard water

• Soft water: Water which easily lathers with soap is called soft water. It
does not contain dissolved Ca and Mg salts.

• Hard Water: It does not produce lather with soap, instead forms a white
curdy precipitate (scum). The scum is produced due to the presence of
dissolved Ca and Mg salts.

• Soap – Na or K salts of long chain fatty acids C17H35COOH

• Soap – Na or K salts of long chain fatty acids C17H35COOH

• 2C17H35COONa + CaCl2 → (C17H35COO)2Ca↓ + 2NaCl

Soap Scum

• 2C17H35COONa + MgSO4 → (C17H35COO)2Mg↓ + Na2SO4

Soap Scum

• Advantages of hard water

1. Calcium in water helps to produce strong teeth and bones,

2. hard water coats lead pipes with layer of insoluble CaCO3, thus preventing dissolution
of toxic lead in drinking water.
• Disadvantages of Hard Water

• Hard Water is very dangerous to health of human beings. It causes many diseases in humans. It
also disturbs the industries. It is not safe to drink, also for other domestic purposes.

1. Cleansing action of soap and detergents is suppressed and results in excess wastage of soap as seen in
textile, laundry, and domestic sectors.

2. Hard water can cause digestive problems and

3. leads to fuel wastage because of elevation in its boiling point.

4. The dissolved salts in hard water react with costly dyes and chemicals used in textile and paper industry
which affects the shades of fabric and smooth finish of papers.

5. Hard water forms undesirable products during the manufacture of drugs in pharmaceutical industry.
6. In industry it causes boiler troubles during steam generation.

7. Hard water problems are often the cause of dry skin and hair after bathing and preventing soap from
lathering on your skin.

8. The dissolved minerals are also primarily responsible for the build-up of scale in pipes and water
heaters, causing numerous problems in the laundry, kitchen, and bath.

9. They are also common essential mineral constituents of food. Excess intakes of calcium and
magnesium can increase the risks of osteoporosis, nephrolithiasis, colorectal cancer,
hypertension and stroke, coronary artery disease, insulin resistance and obesity.

Hard Water containing these ions can be treated at primary level for household purposes.
• Point-of-entry ion exchange (water softener) devices are used in some households to remove
hardness (calcium, magnesium) and iron from water.
EXPRESSION AND UNITS OF HARDNESS
• The expression of hardness producing salts usually expressed in terms
of an equivalent amount of CaCO3.
• Calcium Carbonate is chosen as a standard because:
• i. Its molecular weight (100) and equivalent weight (50) is a whole
number, so the calculations in water analysis can be simplified.
• ii. It is the most insoluble salt that can be precipitated in water
treatment.
• The conversion of the hardness causing salts into CaCO3 equivalents
can be achieved by using the following formula:
• Degree of Hardness = The weight of hardness causing salts × 100
(Molecular weight of CaCO3)
• Molecular weight of hardness causing salts
• Units of Hardness:

• Parts per million(ppm)

• It is defined as parts of CaCO3 equivalent hardness per 106 parts of water.

• E.g.: 2ppm means 2 parts of CaCO3 equivalent hardness per 106 parts of water.

• Milligram per liter(mg/lit)

• It is defined as the no. of milligrams of CaCO3 equivalent hardness per liter of water.

• E.g.: 1mg/L means 1mg of CaCO3 equivalent hardness per liter of water.

• Degree Clarke’s (0Cl)

• It is defined as the no. of grains of CaCO3 equivalent hardness per gallon of water.

• 1 grain = 1/7000 lbs or pounds

• 1 gallon = 10 lbs

• It is defined as the no. of parts of CaCO3 equivalent hardness per 70000 parts of water.

• E.g.: 10Cl = 1grain of CaCO equivalent hardness per gallon of water

• It is defined as the no. of parts of CaCO3 equivalent hardness per 70000 parts of water.

• E.g.: 10Cl = 1grain of CaCO3 equivalent hardness per gallon of water

• Degree French (0Fr)

• It is defined as the no. of parts of CaCO3 equivalent hardness per 105 parts of water.

• E.g.: 10Fr = 1part of CaCO3 equivalent hardness per 105 parts of water

• Milliequivalents per liter (meq/L):

• It is defined as the no. of milliequivalents of CaCO3 equivalent hardness per liter of water.

• E.g.: 1meq/L means 1meq of CaCO3 equivalent hardness per liter of water.

1ppm =1mg/lit =0.10Fr = 0.07 0Cl= 0.02 meq/L

• Determination of hardness By Complexometric Method /
EDTA Method

• Principle: The determination of hardness is carried out by

titrating water sample with Sodium salt of Ethylene Diamine
Tetra Acetic Acid (EDTA) using Eriochrome Black-T as an
indicator
• and keeping the pH of the water at 9.0 - 10.0.
• The end point is the change in colour from wine - red to
blue, when the EDTA solution complexes the calcium and
magnesium salt completely.
• (Ca2+ or Mg2+) + EBT → [Ca – EBT] (or) [Mg – EBT]
• Hardness-salts indicator unstable complex (wine red)

• [Ca – EBT] (or) [Mg – EBT] + EDTA → [Ca – EDTA] (or)

• [Mg – EDTA] + EBT stable complex

• Chemicals Required:
• i. Preparation of standard hard water (0.01M): Dissolve 1g of pure,
dry CaCO3 in minimum quantity of dil.HCl and then evaporate the
solution to dryness on a water bath. Dissolve the residue in distilled
water to make 1 Litre solution. Each ml of this solution thus contains
1mg of CaCO3 equivalent hardness.

• ii. Preparation of EDTA solution: Dissolve 4 g of pure EDTA crystals +

0.lg MgCl2 in 1 Litre of distilled water.

• iii. Preparation of Indicator (EBT): Dissolve 0.5 g of Eriochrome

Black−T in 100mL alcohol.
• iv. Preparation of Buffer solution: Add 67.5g of NH4Cl to 570 ml of
Con. Ammonia solution and then dilute with distilled water to 1 Litre.
• Strength of standard hard water sample (CaCO3 solution) M1

•=
• Weight of CaCO3 × 1000
• Mol. wt of CaCO3 X 1000 =
• 1 gm × 1000 = 0.01 M
• 100 X 1000
• 1. Standardization of EDTA solution: Rinse and fill the burette with EDTA
solution. Pipette out 20 ml of standard hard water (M1) in a conical
flask. Add 4ml of buffer solution and 2 drops of EBT indicator.
• Titrate with EDTA solution till wine-red colour changes to clear blue. Let
volume used by ‘X’ ml.

• M1 V1 = M2 V2 Where,
• M1 = Molarity of Standard Hard water (0.01M), V1 = Volume of Standard
Hard water (20 ml),

• M2 = Molarity of EDTA, V2 = Volume of EDTA (Xml).

• 2. Determination of Total Hardness: Rinse and fill the burette with
EDTA solution. Pipette out 20 ml of sample water (V3) in a conical
flask. Add 4 ml of buffer solution and 2 drops indicator. Titrate with
EDTA solution till wine-red colour changes to clear blue. Let volume
used by ‘Y’ ml.
• M2 V2 = M3 V3 Where, M2 = Molarity of EDTA, V2 = Volume of EDTA
(Yml).
• M3 = Molarity of sample water, V3 = Volume of Sample water (20 ml).

• Total Hardness = M3 × Molecular weight of CaCO3 (100) × One Litre

(1000ml) = M3 × 105 ppm
• 3. Determination of Permanent Hardness: Take 100 ml of sample
water in 250 ml beaker. Boil it to remove temporary hardness to
about half of its volume and cool to room temperature, filter through
filter paper to remove insoluble salts. Make up the volume to the
original 100ml by adding distilled water. Now Pipette out 20 ml of this
solution (V4) in a conical flask. Add 4 ml of buffer solution and 2
drops indicator. Titrate with EDTA solution till wine-red colour
changes to clear blue. Let volume used by ‘Z’ ml
• . M2 V2 = M4 V4
• Where, M2 = Molarity of EDTA, V2= Volume of EDTA (Z ml). M4 =
Molarity of Permanent hard water, V4 = Volume of Permanent hard
water (20 ml)
• Permanent Hardness = M4 × Molecular weight of CaCO3 (100) × One
Litre (1000ml) = M4 × 105 ppm
• 4. Determination of Temporary Hardness:
• Temporary Hardness = Total Hardness - Permanent Hardness
• Problem-1: 50 ml of standard hard water containing 1 gram of pure CaCO3
per liter consumed 20 ml of EDTA. 50 ml of hard water consumed 25 ml of
same EDTA solution EBT indicator.
• Calculate the total hardness of water sample in ppm.
• Solution:
• Strength of standard hard water sample (CaCO3 solution) M1=
• Weight of CaCO3 × 1000
• Mol. wt of CaCO3 X 1000 = 1 gm × 1000 = 0.01 M

100X 1000
• Strength of EDTA solution M2 = V1 M1 =50 × 0.01 = 0.025 M
• V2 20
• V1 = Volume of standard hard water (50 ml), M1 = Strength of standard hard
water (0.01M) V2 = Volume of EDTA solution (20 ml), M2 =Strength of EDTA
solution =?
• Calculation of Total hardness
• M3 = V2 M2 = 25 × 0.025 = 0.0125 M
• V3 50
• V2 = Volume of EDTA solution (25 ml), M2 =Strength of EDTA solution=
0.025M
• V3 = Volume of sample hard water (50 ml), M3 = Strength of sample hard
water =?
• Total Hardness = 0.0125 × 105 ppm = 0.0125 × 100 (Mol. Wt of CaCO3) ×
1000 (ml)ppm = 1250 ppm.
• Problem-2:
• 0.28 grams of CaCO3 were dissolved in HCl and the solution was
made upto one litre with distilled water. 100 ml of the above solution
required 28 ml of EDTA solution on titration. 100 ml of hard water
sample consumed 33 ml of same EDTA solution EBT indicator.
• 100 ml of this water after boiling cooling and filtering required 10 ml
of EDTA solution in titration.
• Calculate the permanent and temporary hardness of water sample in
ppm.
• Strength of standard hard water sample (CaCO3 solution) M =
• Weight of CaCO3 × 1000
Mol. wt of CaCO3 X 1000
Strength of EDTA solution M2 = V1 M1 = 100 × 0.0028 = 0.01 M
V2 28

V1 = Volume of standard hard water (100 ml), M1 = Strength of

standard hard water (0.0028M)
V2 = Volume of EDTA solution (28 ml), M2 = Strength of EDTA
solution=?
• Calculation of Total hardness
• M3 = V2 M2 = 33 × 0.01 = 0.0033 M
• V3 100
• V2 = Volume of EDTA solution (33 ml), M2 = Strength of EDTA
solution (0.01M)
• V3 = Volume of sample hard water (100 ml), M3 = Strength of sample
hard water =?
• Total Hardness = 0.0033 × 105 ppm =
• 0.0033 × 100 (Mol. Wt of CaCO3) × 1000 (ml)ppm = 330 ppm
• Calculation of Permanent hardness M4 = V2 M2 = 10 × 0.01 = 0.001
M V4 100
• UNIT-1 9
• V2 = Volume of EDTA solution (10 ml), M2 = Strength of EDTA
solution (0.01M) V4 = Volume of sample hard water after boiling
cooling and filtering (100 ml) M4 = Strength of sample hard water
after boiling cooling and filtering =?
• Permanent Hardness = 0.001 × 105 ppm = 0.001 × 100 (Mol. Wt of
CaCO3) × 1000 (ml)ppm = 100 ppm
• Calculation of Temporary hardness = Total hardness - Permanent
hardness
• = 330 – 100 = 230 ppm
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UNIT 2 Chemical Bonding and Electrochemical Energy Systems 9 Hours
Valence Bond theory, Orbital Hybridization, Molecular Orbital (MO) diagram, Highest Occupied Molecular Orbital
(HOMO)-Lowest Unoccupied Molecular Orbital (LUMO), Bond order, Band structure,
Battery Technology: Basic concepts, battery characteristics, classification of batteries,
Important applications of batteries, Classical batteries-dry/Leclanche cell, Modern batteries-zinc air, Lead-acid storage
battery, lithium cells- Lithium-ion cell, Li MnO2 cell. Fuel cells- Introduction - classification of fuel cells – hydrogen
and oxygen fuel cell, propane, and oxygen fuel cell- Merits of fuel cell. Renewable energy sources – Types of renewable
energy sources. Semiconductors: Definition, types of semiconductors: doping- n type and p – type semiconductors and
applications. - Solar cells: Introduction, harnessing solar energy, Photovoltaic cells, solar water heaters.
 Valence
Valence Bond Theory (VBT) is a by Heitler Bondlater
and London Theory
extended by Pauling and Slatter used to explain the bondin
molecules. It focuses on how atomic orbitals overlap to form chemical bonds.
Postulates of Valence Bond Theory
1.Atomic Orbital Overlap:
Postulate: A chemical bond forms when atomic orbitals on adjacent atoms overlap. The greater the overlap, the stronge
the bond.
Explanation: Atomic orbitals, which are regions of space around an atom where electrons are likely to be found, combin
to form a bond when they come close to each other. This overlap allows electrons to be shared between atoms.
Example: In a hydrogen molecule (H₂), each hydrogen atom has a 1s orbital. When two hydrogen atoms come together,
their 1s orbitals overlap to form a σ-bond (sigma bond).

Textbook of engineering chemistry by Jain and Jain, internet

2. Hybridization:
Postulate: Atomic orbitals on the same atom can mix or hybridize to form new orbitals that are oriented in specific
directions to make bonds with other atoms.
Explanation: Hybridization helps to explain the geometry of molecules and the formation of bonds. For example,
the mixing of one s orbital and three p orbitals on a carbon atom results in four sp³ hybrid orbitals, which form
tetrahedral shapes.
Example: In methane (CH₄), carbon undergoes sp³ hybridization. The four sp³ hybrid orbitals form sigma bonds
with hydrogen atoms, resulting in a tetrahedral molecular shape.
3. Directional Bonding:
Postulate: Bonds are directional because they form from the overlap of specific orbitals. This directionality affects
the geometry of the molecule.
Explanation: The shape of a molecule is determined by the orientation of the overlapping orbitals and the
arrangement of the bonded atoms.
Example: In water (H₂O), the oxygen atom undergoes sp³ hybridization, but only two of the hybrid orbitals form
bonds with hydrogen atoms, while the other two hold lone pairs of electrons. This results in a bent or V-shaped
geometry.
Localized Electron Model:
•Postulate: Electrons are localized between two atoms in a bond and do not delocalize over the molecule.
•Explanation: In VBT, bonding electrons are considered to be shared between specific pairs of atoms rather than being
spread out over the entire molecule.
•Example: In the ethene (C₂H₄) molecule, each carbon forms three sigma bonds and has a pi bond above and below
the plane of the molecule, localized between the carbon atoms.
Examples
1.Hydrogen Molecule (H₂):
1. Each hydrogen atom has one 1s orbital. When two hydrogen atoms come together, their 1s orbitals overlap to
form a sigma bond, resulting in a stable H₂ molecule.
1.Methane (CH₄):
1. The carbon atom undergoes sp³ hybridization, creating four
equivalent sp³ hybrid orbitals. These orbitals overlap with the 1s
orbitals of four hydrogen atoms to form four sigma bonds, resulting
in a tetrahedral geometry.
2.Water (H₂O):
1. The oxygen atom undergoes sp³ hybridization, forming four sp³
hybrid orbitals. Two of these orbitals overlap with the 1s orbitals of
two hydrogen atoms to form sigma bonds. The remaining two
orbitals hold lone pairs, leading to a bent molecular shape.
3.Ethene (C₂H₄):
1. Each carbon atom undergoes sp² hybridization, resulting in three
sp² hybrid orbitals and one unhybridized p orbital. The sp² hybrid
orbitals form sigma bonds with hydrogen atoms and the other
carbon atom. The unhybridized p orbitals on each carbon overlap
side-by-side to form a pi bond, resulting in a double bond between
the carbon atoms.
 Limitations of VBT

Limited Explanation of Molecular Orbitals: VBT focuses on the overlap of atomic orbitals and does not provide a
detailed description of the bonding in terms of molecular orbitals.
Difficulty in Predicting Bonding in Complex Molecules: VBT has limitations in predicting the bonding and
electronic structure of larger, more complex molecules and materials.
No Explanation for Magnetic Properties: VBT does not account for the magnetic properties of molecules, such as
paramagnetism or diamagnetism, which arise from unpaired electrons and their arrangement. Example: The
paramagnetism of oxygen (O₂), which has unpaired electrons, is not explained by VBT. Molecular Orbital Theory
offers a better explanation by describing the electron distribution in molecular orbitals.
Resonance Structures:VBT does not adequately explain resonance, where a molecule is represented by multiple
Lewis structures. Example: The resonance in the nitrate ion (NO₃⁻) involves delocalization of electrons, which is not
fully captured by VBT. Resonance Theory helps in understanding this concept better
Molecular Orbital Theory (MOT)
The Molecular Orbital Theory (MOT) provides a quantum mechanical model for describing the electronic structure of
molecules. It explains how atomic orbitals combine to form molecular orbitals that span the entire molecule. Here are the
key postulates of MOT:
1. Atomic Orbitals Combine to Form Molecular Orbitals
•When atoms come together to form a molecule, their atomic orbitals overlap to form new molecular orbitals.
•These molecular orbitals are distributed over the entire molecule, rather than being confined to individual atoms.
2. Linear Combination of Atomic Orbitals (LCAO)
•Molecular orbitals are formed by the linear combination of atomic orbitals (LCAO). This means that atomic orbitals
from different atoms are mathematically added together to form bonding and antibonding molecular orbitals.
3. Types of Molecular Orbitals: Bonding and Antibonding
•Bonding molecular orbitals are formed when atomic orbitals combine constructively (in-phase), leading to an increase
in electron density between the nuclei. This lowers the energy of the system and stabilizes the bond.
•Antibonding molecular orbitals are formed when atomic orbitals combine destructively (out-of-phase), leading to a
decrease in electron density between the nuclei and the formation of a node. This raises the energy and destabilizes the
bond.
4. Number of Molecular Orbitals
•The number of molecular orbitals formed is equal to the number of atomic orbitals combined. For example, when two
atomic orbitals combine, one bonding and one antibonding molecular orbital are formed.
5. Electron Filling of Molecular Orbitals
•Electrons fill the molecular orbitals in order of increasing energy, according to the Aufbau principle.
•Each molecular orbital can hold a maximum of two electrons with opposite spins (following the Pauli exclusion principle).
•Electrons prefer to occupy degenerate (equal-energy) orbitals singly before pairing, in accordance with Hund's rule.
6. Bond Order
•Bond order is calculated as the difference between the number of electrons in bonding and antibonding orbitals, divided by
two: Bond order=(number of bonding electrons−number of antibonding electrons) \ 2
•A positive bond order indicates a stable bond, while a bond order of zero means no bond is formed.
7. Molecular Orbitals Extend Over the Entire Molecule
•Unlike in the valence bond theory, where bonds are localized between two atoms, MOT describes molecular orbitals as
being delocalized over the entire molecule. This is especially important in explaining the properties of molecules like
benzene, where electrons are spread over several atoms (delocalization).
8. Energy Levels of Molecular Orbitals
•Bonding molecular orbitals are lower in energy than the parent atomic orbitals, while antibonding molecular orbitals
are higher in energy.
•The energy difference between bonding and antibonding orbitals influences the stability of the molecule and its
reactivity.
9. HOMO and LUMO
•HOMO (Highest Occupied Molecular Orbital): The highest-energy molecular orbital that contains electrons.
•LUMO (Lowest Unoccupied Molecular Orbital): The lowest-energy molecular orbital that is empty.
•The energy gap between the HOMO and LUMO is critical in determining the reactivity of a molecule, especially in
reactions like photochemistry and catalysis.
10. Magnetism
•MOT can explain the magnetic properties of molecules. Molecules with unpaired electrons in their molecular orbitals
are paramagnetic, while those with all paired electrons are diamagnetic.
•For example, MOT explains why oxygen (O₂) is paramagnetic due to two unpaired electrons in its antibonding molecular
orbitals.
These postulates form the basis of the molecular orbital theory and provide a more detailed and accurate description of
the electronic structure and bonding in molecules than the valence bond theory.
Formation of Molecular Orbitals:
When atomic orbitals combine, two types of molecular orbitals are formed:
•Bonding Molecular Orbitals: Lower energy, increase stability.
•Antibonding Molecular Orbitals: Higher energy, decrease stability and are denoted with an asterisk (e.g.,
σ∗\sigma^*σ∗).
Energy Level Ordering:
The relative energy levels of molecular orbitals depend on the type of molecule. For homonuclear diatomic molecules
(molecules consisting of two identical atoms), such as O₂, N₂, or F₂, the order of molecular orbitals can vary.
In general, the energy ordering for molecular orbitals formed from 2s and 2p atomic orbitals (for diatomic molecules
like N₂ or O₂) is as follows:
For Molecules with Atomic Number 𝑍<8 (e.g., Li2,B2,C2,N2):
Energy Ordering:σ1s<σ∗1s<σ2s<σ∗2s<π2px=π2py<σ2pz<π∗2px=π∗2py <σ∗2pz

For Molecules with Atomic Number 𝑍≥8Z≥8 (e.g., O2,F2,Ne2O 2 ,F 2 ,Ne 2):
Energy Ordering: σ1s<σ∗1s<σ2s<σ∗2s<σ2pz<π2px=π2py<π∗2px=π∗2py <σ∗2pz

σ orbitals are symmetrical about the internuclear axis. π orbitals have electron density above and below the
internuclear axis. Bonding orbitals (without asterisk) are lower in energy. Antibonding orbitals (with asterisk) are
higher in energy.
• Electron Filling Rules:
Aufbau Principle: Electrons fill molecular orbitals starting from the lowest energy level.
Pauli Exclusion Principle: Each orbital can hold a maximum of two electrons with opposite spins.
Hund’s Rule: Electrons occupy degenerate orbitals (orbitals of the same energy, such as π\piπ orbitals) singly before
pairing.

Conditions for effective overlapping of AO’s

➢ Nearly same energies and symmetry

➢ Same sign on AO’s
➢ Maximum overlapping of electron clouds of AO’s

Bonding & Antibonding Molecular orbital

Bonding Molecular orbital Antibonding Molecular orbital
Addition overlap - AO’s of same sign Subtraction overlap - AO’s of opposite sign
overlap overlap

Magnitude - higher than individual AO’s Magnitude - lower than individual AO’s

Electron density in overlapped region- max Electron density in overlapped region- min

Makes bond stable Makes bond unstable

Energy- less than AO’s Energy- more than AO’s

Electron in BMO Contributes to attraction Electron in ABMO Contributes to repulsion

Sigma and Pi Molecular orbitals
 MO Diagrams
➢ Aufbau principle
➢ pauli's exclusion principle
➢ totalling the electrons in combining atoms and distribution in
molecular orbitals in increasing order of energies
➢ atomic orbitals of combining atoms shown on extreme left and
right
➢ molecular orbitals shown in middle portion
➢ atomic orbitals of same energy shown at same level
➢ bonding molecular orbitals causes low energy and higher
Bond strength
➢ antibonding molecular orbitals have higher energy and small
ball strength
➢ sequence 1-7,8-10
➢ bond order
Upto N2 σ1s<σ∗1s<σ2s<σ∗2s<π2px=π2py<σ2pz<π∗2px=π∗2py <σ∗2pz

From O2 σ1s<σ∗1s<σ2s<σ∗2s<σ2pz<π2px=π2py<π∗2px=π∗2py <σ∗2pz

Molecular orbital electronic configuration

Configuration = σ1s2

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 2-0/2 = 1

2

Stability: Stable
Configuration: σ1s2<σ∗1s2

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 2 -2 / 2 = 0

2

Stability: unstable
Configuration of Li2 = σ1s2<σ∗1s2<σ2s2
Bond order = no. of electrons in BMO - no. of electrons in ABMO = 4-2/2 = 1
2
Stability: Stable
Configuration of Be2 = σ1s2<σ∗1s2<σ2s2<σ∗2s2

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 4 – 4/ 2 = 0

2
Stability: not stable
 C2

Configuration = σ1s2<σ∗1s2<σ2s2<σ∗2s2<π2px2=π2py2

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 8-4/2 = 2

2
Stability: Stable
 N2

Configuration = σ1s 2 <σ∗1s 2 <σ2s 2 <σ∗2s 2 <π2px 2 =π2py 2 <σ2pz 2 <π∗2px=π∗2py <σ∗2pz

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 10-4/2 = 3

2
Stability: Stable
Configuration = σ1s2<σ∗1s2<σ2s2<σ∗2s2<π2px2=π2py2<σ2pz2<π∗2px1=π∗2py1

Bond order = no. of electrons in BMO - no. of electrons in ABMO = 10-6/2 = 2

2

Stability: Stable
Molecular Orbital Theory (MOT) :
In molecular orbital theory, atomic orbitals combine to form molecular orbitals. These molecular orbitals can either
be bonding, anti-bonding, or non-bonding, depending on how the atomic orbitals interfere (constructively or
destructively).
•Bonding orbitals: Result from constructive interference, where electrons are more stable.
•Anti-bonding orbitals: Result from destructive interference, where electrons are less stable.
•Non-bonding orbitals: Don’t participate in bonding but still house electrons.
HOMO and LUMO :
1.HOMO (Highest Occupied Molecular Orbital): This is the molecular orbital that is fully occupied by electrons and
has the highest energy level among the filled orbitals. Electrons in the HOMO are the most reactive because they are
the highest-energy electrons that can be donated in chemical reactions (e.g., during bonding or in electron transfer
processes).
2.LUMO (Lowest Unoccupied Molecular Orbital): This is the lowest energy molecular orbital that does not contain
any electrons. The LUMO is the orbital that can accept electrons. When a molecule absorbs energy (like light in UV-
Vis spectroscopy), electrons can be excited from the HOMO to the LUMO.
Why Are HOMO and LUMO Important?
•Electronic Transitions: When molecules absorb light, electrons are often promoted from the HOMO to the
LUMO. The energy difference between these two orbitals corresponds to the wavelength of light absorbed.
•Chemical Reactivity
•Band Gap in Semiconductors
•Visualization in MOT:
When using MOT diagrams:
•The HOMO is the last filled orbital, while
•The LUMO is the first unfilled orbital.
The energy gap between the HOMO and LUMO can be visualized as the vertical space between the highest
filled level and the lowest empty level in the molecular orbital energy diagram.
Example: Molecular Oxygen (O₂)
1. Molecular Structure:
Oxygen (O₂) is a diatomic molecule where two oxygen atoms are bound together by a double bond. The bonding in O₂
consists of:
•One sigma (σ) bond.
•One pi (π) bond.
In addition to bonding molecular orbitals, there are also anti-bonding orbitals, where electrons are less stable.
2. Molecular Orbitals in O₂:
Oxygen has a total of 12 valence electrons (6 from each oxygen atom). These electrons fill the molecular orbitals formed
from the overlap of atomic orbitals.
The molecular orbital diagram of O₂ is important because it shows both bonding and anti-bonding orbitals:
•The bonding orbitals include σ(2s), σ(2p), and π(2p) orbitals.
•The anti-bonding orbitals include σ*(2s) and π*(2p) orbitals.
When the electrons are filled into the molecular orbitals, the π*(2p) anti-bonding orbital is partially filled, leading to
some interesting electronic properties.
3. HOMO and LUMO in O₂:
•HOMO: In the case of molecular oxygen, the HOMO is the highest occupied molecular orbital. In O₂, this is the
π(2p) anti-bonding orbital*. Because the π*(2p) orbital is anti-bonding and partially occupied, molecular oxygen has
unpaired electrons, making it paramagnetic (it is attracted to magnetic fields).
• The HOMO in O₂ is higher in energy than in many other diatomic molecules because of this anti-bonding
character.
•LUMO: The LUMO is the σ(2p) anti-bonding orbital*, which is the next available orbital that can accept electrons.
This orbital is empty and higher in energy than the π*(2p) orbital.
4. Energy Transition:
When O₂ absorbs energy, it can excite an electron from the HOMO (π*) to the LUMO (σ*). This type of electronic
transition requires a specific amount of energy that corresponds to the energy gap between the HOMO and LUMO.
Example 2: Nitrogen (N₂)
1. Molecular Structure:
Nitrogen (N₂) is a diatomic molecule, just like O₂, but with some significant differences in terms of its electronic
configuration and reactivity.
•N₂ has a triple bond between two nitrogen atoms, consisting of one sigma (σ) bond and two pi (π) bonds.
2. Molecular Orbitals in N₂:
•The molecular orbitals in N₂ are formed similarly to O₂, with both bonding and anti-bonding orbitals. However, the
electrons are arranged differently due to the difference in total electron count.
•The important molecular orbitals in N₂ are:
• Bonding orbitals: σ(2s), σ(2p), and π(2p).
• Anti-bonding orbitals: σ*(2s) and σ*(2p).
Unlike O₂, N₂’s anti-bonding π*(2p) orbital is completely unoccupied, meaning all electrons are paired in bonding orbitals.
3. HOMO and LUMO in N₂:
•HOMO: The HOMO in N₂ is a bonding π(2p) orbital, which is fully occupied.
•LUMO: The LUMO is the σ(2p) anti-bonding orbital*, which is empty.
Battery Technology:
A battery is a device that stores chemical energy and converts it into electrical energy. It consists of one or more
electrochemical cells, each having two electrodes: the anode (negative) and the cathode (positive). During discharge,
electrons flow from the anode to the cathode through an external circuit, while ions move internally through the
electrolyte, generating electrical power.
Important Battery Characteristics:
1.Capacity: The amount of charge a battery can store, measured in ampere-hours (Ah). It determines how long the
battery can power a device.
Suppose you have a battery that delivers 2 amperes (A) for 5 hours
Capacity (Ah)=2 A×5 hours=10 Ah
1.Voltage: The potential difference between the electrodes, measured in volts (V), which depends on the cell
chemistry.
2.Energy Density: The amount of energy a battery can store per unit mass or volume, measured in watt-hours per
kilogram (Wh/kg) or watt-hours per liter (Wh/L).
Gravimetric Energy Density or Volume Energy Density
Suppose you have a battery that stores 500 watt-hours (Wh) of energy and has a mass of 2 kilograms
(kg).Energy Density=500 Wh2 kg=250 Wh/kg
3. Power Density: The rate at which energy can be delivered per unit mass, measured in watts per kilogram (W/kg).
Power Density= Power (W)/Mass (kg)
4. Cycle Life: The number of complete charge and discharge cycles a battery can undergo before its capacity
significantly degrades.
5. Efficiency: The ratio of energy output to energy input, usually measured as Coloumbic efficiency (percentage).
6. Self-discharge: The rate at which a battery loses charge when not in use.
Electrochemical cells: An electrochemical cell is a device which can produce electrical work in the surroundings. It
may used to perform two functions
(1) It converts chemical energy into electrical energy .
(2) (2) it converts electrical energy into chemical energy.
Electrochemical cells/ Batteries are three types
Primary cells:- These cells have only one cycle (Discharge Cycle)
i. These cells convert chemical energy into electrical energy.
ii. After some time the cell is discharged
iii. These are not chargeable as the products of electrochemical reactions are consumed in secondary reactions.
Ex. : Leclanche cell, Bichromate cell.
Secondary Cells:-These cells have two cycles- discharge cycle and charge cycle.
In the first cycle the cell acts as a galvanic cell. The chemical energy is converted into electrical energy and the cell is
discharged.
2. In the second cycle the cell is an electrolytic cell. So, electrical energy is converted into chemical energy and charging
take place.
3. These cells are recharged because the products of electrode reactions are not consumed in the secondary reactions
Ex. Lead storage Battery, Alkaline storage Battery.
Fuel Cells: These are the cells in which
1. Chemical energy of fuel gases H2, CH4, C2H6 etc., converted into electrical energy.
2. These are the primary galvanic cells and have only discharge cycle.
3. Efficiency of the conversion from a fuel to electrical energy is 70%. In a fuel cell. It is only 20% in case of conversion
of chemical energy into thermal, followed by mechanical and finally electrical energy.
Applications of Batteries:
•Smartphones: Power portable communication and computing devices.
•Laptops: Provide mobility for computing without a constant power source.
•Electric Vehicles (EVs): Supply energy for propulsion in cars, bikes, and buses.
•Medical Devices: Power pacemakers, hearing aids, and portable medical equipment.
•Renewable Energy Storage: Store solar and wind energy for later use.
•Remote Controls: Power wireless control devices for TVs, AC units, etc.
•Watches and Wearables: Enable long-term use of smartwatches, fitness trackers.
•Uninterruptible Power Supplies (UPS): Backup power for critical systems during outages.
•Drones: Provide energy for flight and control systems.
•Flashlights: Supply portable light sources in emergency and outdoor settings.
The Leclanché cell, commonly known as a dry cell, is a primary (non-rechargeable) battery. Its main features include:
1.Electrodes:
1. Anode: Zinc, which serves as the container and the negative terminal.
2. Cathode: Manganese dioxide (MnO₂), mixed with carbon powder to improve conductivity.
2.Electrolyte: A paste of ammonium chloride (NH₄Cl) or zinc chloride (ZnCl₂), instead of a liquid, which prevents leakage
and makes the battery more portable.
3.Voltage: Typically provides about 1.5 V per cell.
4.Compact Size: Suitable for portable devices like flashlights, clocks, and remote controls.
5.Low Cost: Inexpensive to manufacture, making it widely used for general household purposes.
6.Moderate Energy Density: Sufficient for low to moderate power demands in small devices.
7.Short Lifespan: Limited by self-discharge and the degradation of materials over time, especially in continuous use.
8.Non-rechargeable: Once depleted, it cannot be recharged and must be replaced.
Zinc-Air Battery: Used in hearing aids, blood glucose meters, pagers
1.Anode: Made of zinc (gel or powder) that gets oxidized during discharge.
2.Cathode: A porous air electrode with a catalyst (carbon, silver, or platinum) that allows oxygen from the air to enter and react.
3.Electrolyte: An alkaline solution, usually potassium hydroxide (KOH) or sodium hydroxide (NaOH), allowing ion movement.
4.Separator: A permeable membrane that prevents direct contact between the electrodes while allowing ion flow.
5.Air Access Hole: Allows oxygen to enter through small openings, activating the battery.
6.Casing: A protective metal or plastic housing for all components.
Operation:
•Zinc is oxidized at the anode, releasing electrons.
•Oxygen is reduced at the cathode, completing the electrochemical reaction.
•The battery generates power as oxygen from the air reacts with zinc.
Anode reaction
Zinc reacts with hydroxide ions to form zincate ions:
Zn + 4OH– → Zn(OH)42– + 2e–
Cathode reaction
Oxygen reacts with water to form hydroxide ions:
O2 + 2H2 O + 4e– → 4(OH)–
Zincate decay
Zincate decays into zinc oxide and water:
Zn(OH)42– → ZnO + H2 O + 2(OH)-
The zinc-air battery has a theoretical voltage of 1.65 volts, but the actual voltage is typically between 1.35 and 1.4 volts
Advantages of Zinc-Air Battery:
1.High Energy Density: Offers a higher energy-to-weight ratio compared to many other batteries.
2.Cost-Effective: Zinc is abundant and inexpensive, making these batteries relatively affordable.
3.Environmentally Friendly: Contains fewer toxic materials and is easier to recycle.
4.Stable Voltage Output: Provides a steady voltage throughout its discharge cycle.
5.Long Shelf Life: Can remain inactive for a long period when sealed from air.
Limitations of Zinc-Air Battery:
1.Non-Rechargeable: Most zinc-air batteries are not rechargeable, limiting reuse.
2.Air Sensitivity: Performance can be affected by environmental factors such as humidity and CO₂.
3.Limited Power Output: Not suitable for high-power applications.
4.Short Active Life: Once exposed to air, they degrade faster compared to other batteries.
5.Slow Discharge Rate: Not ideal for applications requiring a rapid energy release
Lithium-ion (Li-ion) Cells
Construction:
• Anode: Typically made of graphite.
• Cathode: Made of lithium metal oxides (e.g., LiCoO2, LiMn2O4).
• Electrolyte: A lithium salt (e.g., LiPF6) dissolved in an organic solvent.
• Separator: A porous polymer membrane that prevents short-circuiting by
keeping the anode and cathode apart while allowing ion flow.
• Cell Reactions:
Lithium Manganese Dioxide (Li-MnO2) Cells
Construction:
• Anode: Made of lithium metal.
• Cathode: Made of manganese dioxide (MnO2).
• Electrolyte: A lithium salt (e.g., LiClO4) dissolved in an organic solvent.
• Separator: A porous membrane that separates the anode and cathode while allowing ion flow.

Cell Reactions:
1.Discharge Reaction:
1. Anode: Li→Li+ + e−
2. Cathode: MnO2​+ Li+ +e− → LiMnO2
Since Li-MnO2 cells are non-rechargeable, they do not have a
charge reaction.
Hydrogen-Oxygen (H2-O2) Fuel Cell
Construction:
1.Anode: Made of a porous material, often coated with a catalyst like platinum.
2.Cathode: Also porous and coated with a catalyst, typically platinum or a similar material.
3.Electrolyte: Can be a polymer electrolyte membrane (PEM) or an alkaline solution like potassium hydroxide (KOH).
Advantages:
a. Fuel cells are quite efficient and can operate on a riety of hydrocarbon fuels and produce almost no objectionable
emissions.
b. It takes little time to go into operation
c. It produces electric current directly from the reaction of the fuel and oxidizer without going through the wasteful
intermediate conversion of chemical energy into heat.
Applications:
a. Application to power generation in space and remote locations. Power supply for communication systems and spacecraft
b. Its advantage is that it produces water in addition to energy in remote locations and space and that water is used for
drinking purposes.
c. This source power is used in transportation like electric mobiles, electric locomotives, etc., which do not contaminate the
atmosphere with harmful combustion of gases
d. Fuel cells are widely and efficiently employed for power generation, which is used for industrial and domestic purposes.
Propane-Oxygen (C3H8-O2) Fuel Cell
• Anode:
• Made of a porous material, typically coated with a catalyst such as nickel.
• Facilitates the oxidation of propane.
• Cathode:
• Porous and coated with a catalyst, often a metal oxide.
• Facilitates the reduction of oxygen.
• Electrolyte:
• Usually a solid oxide material like yttria-stabilized zirconia (YSZ).
• Conducts oxygen ions from the cathode to the anode.
Definition of Renewable Energy Sources
Renewable energy sources are energy sources that are naturally replenished on a human timescale. They are derived
from natural processes that are continuously replenished, such as sunlight, wind, rain, tides, waves, and geothermal
heat12.
Important Types of Renewable Energy Sources
1.Solar Energy:
• Source: Sunlight.
• Usage: Photovoltaic cells convert sunlight directly into electricity; solar thermal systems use sunlight to produce
heat.
• Advantages: Abundant, sustainable, and reduces electricity bills.
2.Wind Energy:
• Source: Wind.
• Usage: Wind turbines convert the kinetic energy of wind into electrical energy.
• Advantages: Clean, cost-effective, and can be used in various locations.
1.Hydropower:
• Source: Flowing water.
• Usage: Dams and turbines convert the energy of flowing water into electricity.
• Advantages: Reliable, efficient, and provides flood control and water supply benefits.
2.Geothermal Energy:
• Source: Heat from the Earth’s interior.
• Usage: Geothermal plants convert heat from the Earth into electricity and provide direct heating.
• Advantages: Stable, sustainable, and low emissions.
3.Biomass Energy:
• Source: Organic materials (plants, agricultural waste, etc.).
• Usage: Biomass is burned or converted into biofuels to produce energy.
• Advantages: Reduces waste, can be carbon-neutral, and supports agricultural economies.
4.Ocean Energy:
• Source: Tides, waves, and ocean thermal gradients.
• Usage: Tidal and wave energy converters harness the energy of ocean movements; Ocean Thermal Energy
Conversion (OTEC) uses temperature differences in ocean water.
• Advantages: Predictable and vast energy potential.
5.Hydrogen Energy:
• Source: Hydrogen gas.
• Usage: Hydrogen fuel cells convert hydrogen into electricity, with water as the only byproduct.
• Advantages: High energy content, clean, and versatile.
Semiconductors are materials with electrical conductivity between that of conductors (like metals) and insulators (like glass).
Types of Semiconductors
1.Intrinsic Semiconductors:
1. Definition: Pure semiconductors without any significant impurities.
2. Examples: Silicon (Si), Germanium (Ge).
3. Properties: Conductivity is low and depends on temperature.
2.Extrinsic Semiconductors:
1. Definition: Semiconductors doped with impurities to enhance conductivity.
2. Types:
1. N-type: Doped with elements that add extra electrons (e.g., phosphorus in silicon).
2. P-type: Doped with elements that create “holes” or positive charge carriers (e.g., boron in silicon).
P-type Semiconductors:

Doping Element: Typically doped with trivalent elements like boron (B).
Charge Carriers: The primary charge carriers are “holes,” which are the absence of electrons in the crystal lattice.
Mechanism: When a trivalent atom replaces a silicon atom in the lattice, it creates a deficiency of one electron, resulting in a
hole. These holes can move through the lattice, allowing current to flow.
Behavior: In an electric field, holes move towards the negative terminal, contributing to electrical conductivity.

N-type Semiconductors:
Doping Element: Typically doped with pentavalent elements like phosphorus (P).
Charge Carriers: The primary charge carriers are free electrons.
Mechanism: When a pentavalent atom replaces a silicon atom, it provides an extra electron that is free to move through the
lattice.
Behavior: In an electric field, these free electrons move towards the positive terminal, contributing to electrical conductivity.
Photovoltaic cells are semiconductors made of silicon, cadmium sulphate,
gallium arsenide which absorbs photons from sunlight and creates electron
hole pairs (+ve and –ve charges). The difference in energy level between the
valence band and conduction band electrons is overcome by photon energy,
and potential is produced by charge-collecting front and back electrodes.

•The n-type layer is thin and transparent, while the p-type layer is thick.
•The magnitude of the electromotive force is directly proportional to the
intensity of the incident radiation.
•Solar cells are made of a sandwich of n-type and p-type silicon.

Light absorption: When sunlight hits the solar cell, photons are absorbed by
the semiconductor material.
•Electron-hole pair creation: The photons' energy is transferred to electrons in
the lower p-type layer, which causes them to jump across the junction into the
upper n-type layer. This process creates electron-hole pairs, with electrons
being negative charges and holes being positive charges.
•Electric field: The oppositely charged ions in the depletion zone create an
internal electric field that prevents electrons from filling holes.
•Current flow: When the n-type and p-type layers are connected by a metallic
wire, electrons flow through the wire, creating an electric current.
Solar Water Heater
1.Components:
• Collector to capture solar energy.
• Insulated storage tank for hot water.
2.Working:
• Solar energy heats the absorber panel.
• Heat transfers to riser pipes beneath the panel.
• Water in riser pipes heats up and moves to the storage tank.
• Recirculation through the absorber panel increases water temperature up to 80°C on sunny days.
3.System: The entire setup, including the collector, storage tank, and pipelines, is called a solar hot water system.
REFERENCES:
•Atkins, P., & Friedman, R. (2011). Molecular Quantum Mechanics.
•McQuarrie, D. A., & Simon, J. D. (1997). Physical Chemistry: A Molecular Approach.
Levine, I. N. (2013). Quantum Chemistry (7th Edition).
Jensen, F. (2017). Introduction to Computational Chemistry.
•Molecular Orbital Theory for Diatomic Molecules - UC Berkeley Chemistry Lecture Notes.
•"Electrochemical Systems" by John Newman and Karen E. Thomas-Alyea –
•"Batteries in a Portable World" by Isidor Buchmann
•Wikipedia articles and ChatGPT.
•"Chemistry of Batteries" (Journal Articles) –Journal of Power Sources or Electrochimica Acta.
•Online Educational Resources such as:
•Battery University (batteryuniversity.com)
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