Module-3 and Module-4 Notes

Dept of Chemistry
MODULE-4
Green Chemistry and Alternative Energy Sources
Green Chemistry(UNIT-1)
Green Chemistry is defined as the “design of chemical products and processes to reduce or
eliminate the use and generation of hazardous substances.”
Principles of Green Chemistry

1. Prevent waste: Design chemical synthesis to prevent waste. Leave no waste to treat or clean
up.
2. Maximize atom economy: Design synthesis so that the final product contains the maximum
proportion of the starting materials. Waste few or no atoms.
3. Design less hazardous chemical synthesis: Design synthesis to use and generate substances
with little or no toxicity to either humans or the environment.
4. Design safer chemicals and products: Design chemical products that are fully effective yet
have little or no toxicity.
5. Use safer solvents and reaction conditions: Avoid using solvents, separation agents, or other
auxiliary chemicals. If you must use these chemicals, use safer ones.
6. Increase energy efficiency: Run chemical reactions at room temperature and pressure
whenever possible.
7. Use renewable feedstocks: Use starting materials that are renewable rather than depletable.
The source of renewable feedstocks is often agricultural products or the wastes of other
processes; the source of depletable feedstock is often fossil fuels (petroleum, natural gas, or
coal) or mining operations.
8. Avoid chemical derivatives: Avoid using blocking or protecting groups or any temporary
modifications if possible. Derivatives use additional reagents and generate waste.
9. Use catalysts, not stoichiometric reagents: Minimize waste by using catalytic reactions.
Catalysts are effective in small amounts and can carry out a single reaction many times. They
are preferable to stoichiometric reagents, which are used in excess and carry out a reaction only
once.
10. Design chemicals and products to degrade after use: Design chemical products to break
down to innocuous substances after use so that they do not accumulate in the environment.
11. Analyze in real time to prevent pollution: Include in-process, real-time monitoring and
control during synthesis to minimize or eliminate the formation of by-products.
12. Minimize the potential for accidents: Design chemicals and their physical forms (solid,
liquid, or gas) to minimize the potential for chemical accidents including explosions, fires,
and releases to the environment.
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Dept of Chemistry
Major Environmental pollutants:

The Major environmental pollutants are
1. Oxides of Carbon (COx).
2. Oxides of Sulphur (SOx).
3. Oxides of Nitrogen (NOX).
1. Oxides of Carbon (COx):

Types: Oxides of carbon are Carbon dioxide (CO2) and Carbon monoxide (CO).
Sources: The CO2 and CO are released into atmosphere from natural sources like volcanic eruptions
and Natural gases. The major sources of CO2 and CO are automobile exhaust gases due incomplete
combustion fuels. Other sources are thermal power plants, forest fire, blast furnace, combustion of coal
and Biomass burning.
Effects:
1. The CO2 is an green house gas that causes green house effect rising average temperature of
atmosphere.
2. During rainy seasons CO2 combines with rain water and produces weak carbonic acid
causing acid rains. This causes stone leprosy and damages forests.
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3. Breathing CO cause headache, dizziness, vomiting and chest pain

4. Breathing high concentrations of CO inhibits combination of oxygen and hemoglobin in blood
that supplies Oxygen to cells by formation of carboxyhemoglobin. This may lead to instant
death by asphyxia.
2. Oxides of sulphur (SOx):

Types: Oxides of sulphur are Sulphur dioxide (SO2) and Sulphur trioxide (SO3).
Sources: In volcanic eruptions, SO2 and SO3 gases are released into atmosphere are the natural sources.
The manmade source of SO2 is the combustion of fossil fuel in automobiles, thermal power plants.
Other sources are petroleum refineries, Sulphuric acid plant, Sulphide ore roasting plants and burning
of waste garbage.
Effects:
1. Causes acid rain by combination of SO2 and SO3 with moisture in the atmosphere by forming
H2SO3 and H2SO4.
2. Causes respiratory disorders.
3. Causes skin, eye irritations.
4. Causes corrosion to metallic structures.
5. Deteriorates the building and causes staining of Marbles – stone leprosy.
6. Effects plants and tree growth.
3. Oxides of Nitrogen (NOx):

Type: Oxides of Nitrogen are Nitrogen oxide (NO); Nitrogen dioxide (NO2); Nitrous oxide (N2O).
Sources: Automobile exhaust gases, thermal power plants, lightning, volcanic eruptions and
bacterial decomposition of nitrogen containing compounds, nitrogen fertilizers.
Effects:
1. Breathing causes damage to the respiratory tract, causes damage to pulmonary tissues.
2. Causes respiratory infections and asthma.
3. Acid rain by dissolving NOx in atmospheric moisture.
4. Secondary pollutant Peroxy Acetyle Nitrate (PAN) causes photochemical smog and
suppresses plant growth.
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Dept of Chemistry
Various Green Chemical Approaches:
The green chemical approaches for synthesis of various chemicals are,

1. Microwave Synthesis.
2. Bio catalyzed Reactions.
3. Solvent free reactions
1. Microwave Synthesis: Microwave synthesis is the technique of applying microwave radiation
to carry out chemical reactions. Microwave acts as high frequency electric fields and will
generates heat in any material containing mobile electric charges such as polar molecules in a
solvent or conducting ions in solid.
Microwave radiation has the appropriate frequency (0.3-30 GHz) to oscillate polar particles
and enable enough inter-particle interaction. Microwave synthesis involves electromagnetic
irradiation, where the sample is kept under microwaves which generate high temperature and
heated directly inside. Microwave radiation facilitates greener and quicker heating to prepare
materials because of lower energy requirements.
Example Microwave Synthesis:
i. Hydrolysis of Benzyl Chloride: Hydrolysis of Benzyl Chloride with water in

Microwave oven gives 97% yield of Benzyl Alcohol in 3 min. whereas conventional
method takes about 35 min.
Benzyl Chloride Benzyl Alcohol

ii. Oxidation of toluene: Oxidation of toluene to Benzoic Acid by conventional method takes
10 – 12 hr. But by microwave irradiation the reaction completed in 7 min. with 40% yield.
Toluene
Benzoic Acid
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Dept of Chemistry
2. Bio-catalyzed Reactions: “Bio-catalyzed reactions are defined as the use of natural substances as
catalysts such as enzymes, hormones, bio-molecules and proteins to perform chemical reactions
of organic compounds”. Enzymes are very efficient biocatalysts, present in every living organism
which carry out a wide range of chemical reactions, and also finds application as an important tools
used in green chemistry.
Examples of Bio-catalysts are Yeast, Zymase. Trypsin, Pepsin etc.
Example of Bio-catalyzed reactions:

i. Ethanol Fermentation: Yeast contains enzymes that metabolize the glucose to pyruvate and
the pyruvate breakdowns into ethanol and carbon dioxide.
Ethanol fermentation technique has been used in the production of beer, wine, and bread.
ii. Lactic Acid Fermentation: Lactic acid fermentation is used to convert lactose into lactic acid in
yogurt production using bacillus bacteria.
3. Solvent Free Reaction: Solvent-free refers to a substance that contains little or no solvent.
“Reactions carried out under solvents free or solid state conditions are referred as solvents
free reactions”.
Thermal process or irradiation with UV, microwave or ultrasound can be employed to bring
about the reaction.
Advantages and Conditions of Solvent-free Reactions:

1. Solvent-free reactions obviously reduce pollution and bring down handling costs due to
simplification of experimental procedure, work up technique and saving in labour. These would
be especially important during industrial production.
2. Often, the products of solid state reactions turn out to be different from those obtained in
solution phase reactions.
3. If two or more substrates are involved in the reaction, they are thoroughly ground together in
a glass mortar or co-crystallized and allowed to stay at room temperature or transferred to a
suitable apparatus and heated carefully in an oil bath or exposed to appropriate radiation until
the reaction is complete.
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Dept of Chemistry
4. More sophisticated reaction procedures are also adopted, if necessary. The progress of the
reaction can be monitored by TLC. In some cases, a small quantity of water or a catalyst may
be added. If it is a single-compound reaction, it is subjected to heat or radiation directly
Synthesis of Adipic Acid

1. Conventional Method of Adipic Acid Synthesis:
Conventional method of Adipic Acid is synthesized using Benzene. Benzene is hydrogenated
using Ni-Al2O3 catalyst at 370–800 psi to Cyclohexane. Cyclohexane oxidized using Cobalt
catalyst to a mixture of Cyclohexanone and Cyclohexanol. This is then converted to Adipic
Acid using ammonium vanadate and nitric acid, with the help of a catalyst.
2. Green Route synthesis for Adipic Acid:

D-glucose is converted to 3-dehydroshikimate and Cis-Cis-muconic acid using E. coli,
which is further hydrogenated to Adipic acid using hydrogen gas.
COOH
Pt H2
E.Coli 50Psi (CH2)4
E.Coli
COOH
D-Glucose 3- dehydroshikimate Cis-Cis Muconic Acid Adipic Acid
Synthesis of Paracetamol
Paracetamol (acetaminophen) is widely used as an analgesic (pain reliever) and an antipyretic (for
reducing fever). The IUPAC name for paracetamol (acetaminophen) is N-(4-hydroxyphenyl)
ethanamide or N-(4-hydroxyphenyl) acetamide. Paracetamol (acetominaphen) is also known as N-
acetyl-p-aminophenol.
1. Conventional Method of Paracetamol Synthesis: Paracetamol (acetaminophen) can be

synthesized from phenol in three steps.
Step 1: Nitration of phenol:

Phenol (Hydroxybenzene) will react with sodium nitrate (an oxidizing agent) in the presence of
sulphuric acid to produce a mixture of structural isomers of nitro phenol.
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Dept of Chemistry
Step 2: Reduction of a Nitro group to an Amine:

In the reaction the nitro group of 4-nitrophenol the oxygen is removed and hydrogen is added
in presence of palladium catalyst to form 4-aminophenol, so the reaction is a reduction reaction.
Pd
4- Nitrophenol 4-Aminophenol
Step 3: Formation of an Amide:

The 4-aminophenol reacts with acetic anhydride to produce precipitate of amide paracetamol
(acetaminophenol).
Paracetamol
4-Aminophenol (Acetaminophen)
2. Green Route synthesis for Paracetamol:

A simpler synthesis by Hoechst-Celanese involves direct acylation of phenol with acetic
anhydride catalyzed by HF. Conversion of the Ketone to a Ketoxime with Hydroxylamine,
followed by the acid-catalyzed Beckmann rearrangement to give the amide
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Dept of Chemistry
Industrial applications of Green Chemistry:

➢ Synthesis of petroleum-based chemicals from biological and natural materials
➢ In production of new ways to make solar cells, fuel cells, and batteries for storing energy.
➢ To minimize or eliminate waste in the manufacture of chemicals and allied products.
➢ Green Technologies in the Pharmaceutical, Food, Paper, Polymer & Textile Industry.
➢ A range of Nano sized materials and composites can be produced by greener routes.
➢ In redesigning chemical products to reduce hazards waste..
Green fuel(UNIT-II)
Green fuels are bio-fuels obtained from plants and animal materials, natural sources and fuels
synthesized through green route.
2. Photo Electrocatalytic.
1. Photo Catalytic.
1. Hydrogen Production by Photo Electrocatalytic Water Splitting:

Photo electro catalytic hydrogen production is one of the most effective methods to split water
into oxygen and hydrogen at low operating temperatures and with very high efficiency and
storing it as chemical energy in the form of hydrogen.
In photo electro catalytic (PEC) water splitting, hydrogen is produced from water using sunlight
and specialized semiconductors called photo electrochemical materials. Photo electrochemical
material use light energy to directly dissociate water molecules into hydrogen and oxygen.
Sunlight
hʋ
1. Photo Anode.
2. Cathode with Electrocatalyst.
3. Ion Transfer Membrane.
1 3 2
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Dept of Chemistry
The light energy excites an electron in the semiconducting material (electrode). Thus
produced hole (h+) will react with the neighboring water molecule.
hʋ → 2 h+ + H2O → 2 H+ + ½ O2
These H+ ions formed will then bond with one other proton and combine with two electrons
to form hydrogen gas.
2 H+ + 2 e- → H2 (g)
The produced hydrogen can be used as the fuel in hydrogen fuel cell.
2. Hydrogen Production by Photo catalytic Water Splitting:

The photo catalytic production of hydrogen represents a fascinating way to convert and store
solar energy as chemical energy, in the form of renewable hydrogen, the ideal fuel for the
future.
Splitting of water molecules to get hydrogen by using a photo catalyst in presence solar energy
is called photo catalytic water splitting. This process can be more efficient if thephoto catalyst
is directly suspended in water so that the reaction takes place in one step.
The light energy excites an electron in the semiconducting photo catalytic material. Thus produced
hole (h+) will react with the neighbouring water molecule.
hʋ → 2 h+ + H2O → 2 H+ + ½ O2
The H+ ions combine to produce hydrogen at the surface of the Pt catalyst.
2 H+ + 2 e- → H2
The produced hydrogen can be stored as the fuel in hydrogen fuel cell.
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Dept of Chemistry
Application of Hydrogen in Fuel Cell:

“Fuel cells are electrochemical devices which convert chemical energy of a fuel and oxidant
directly into electrical energy through an electrochemical reaction without a combustion
process”. Fuel Cells are more efficient and environmental friendly than conventional electric power-
generation processes.
Anode : - Hollow porous carbon tube impregnated with Pt.

Cathode :- Hollow porous carbon tube, impregnated with
Oxides of Ag.
Fuel: Hydrogen.
Oxidant: Oxygen.
Electrolyte: KOH
Cell Reactions are

H2 (g) + 2 OH – 2 H2 O + 2 e – at anode.
½ O2 + H2O + 2e 2OH – – at cathode.

H2 (g) + ½ O2 (g) H2 O – Net cell reaction
This cell produces a voltage of about 1.15V
Methanol – Oxygen Fuel Cell [MeOH – O2 ]

Methanol fuel cell is an example of liquid fuel cell and widely preferred battery since methanol is
highly soluble in water, OH group is easily oxidisable and has low carbon content.
Construction and Working

In Methanol-Oxygen fuel cell anode is porous nickel electrode impregnated with platinum
and palladium catalyst, cathode is porous nickel electrode impregnated with silver. The electrolyte is
3.7M H2SO4 taken in polymeric membrane, which separates anode and cathode electrodes.
Fuel : Methanol dissolved in Water.Oxidant :
Oxygen or Air.
Electrolyte: 3.7M H2SO4.
Anode : Pt-Pd impregnated Nickel electrode.
Cathode : Ag impregnated Nickel electrode.
The methanol is supplied at anode oxidise into carbon dioxide and water. At cathode oxygen is reduced
to hot water sine the reaction is exothermic. Methanol – oxygen fuel cell generates a voltage of 1.21
volts.
Cell reactions
+
CH3 OH + H2 O CO2 + 6 H + 6e Anode
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Dept of Chemistry
+
1½ O2 + 6 H + 6e 3 H2 O Cathode
CH3 OH + 1½ O2 CO2 + 2 H2 O Net cell Reaction
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Dept of Chemistry
Applications of Methanol- Oxygen fuel Cell:

1. Ideal for smaller vehicles such as forklifts and mini transport vehicles..
2. Portable electronic gadgets such as mobile phones, digital cameras and laptops.
3. In emergency backup power systems and inverters.
4. In Military & Satellites since they have low thermal signatures and no toxic effluent.
5. To power devices such as unmanned aerial vehicles (UAV).
SOLAR ENERGY
“The term solar energy refers to various method of harnessing energy from the sunlight.”
Photovoltaic cells (solar cells)

“Photovoltaic cell (solar cell) is a device which converts photons (light energy) from sunlight in to electric
effect’’.
Construction of photovoltaic cell

Photovoltaic cell consists of p-n junction obtained by sandwiching thin wafers of p-type and n-
type silicon semiconductors, which forms p-n junction at the interface of two semiconductors. At the
interface of p-n junction, an electric field is created that causes the electrons to jump from
semiconductor to the surface and make them available for electric circuit.
p-type n-type
p-n junction
Photo voltaic cell has two electrical contacts, one in the form of a metallic grid on top of n-
type semiconductor, serves as negative terminal and the other is a layer of noble metal at the bottom
of p-type conductor, serves as positive terminal. Both the terminals are connected to a battery or
application. The top surface of n-type semiconductor between grids is coated with anti-reflection layer
which increases the amount of light transmitted to semiconductor.
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Dept of Chemistry
Working of photovoltaic cell

When photo voltaic cell is exposed to sunlight, electrons absorb photon energy (E = hν) and drift across
the junction and move towards n- type and hole towards the p- type. As the electron moves in one direction
(towards negative terminal), the hole moves in the opposite direction (towards positive terminal). Thus
sufficient electron pressure is built up at n- type and electrons move through circuit causing flow of electric
current through the circuit in opposite direction.
Applications of photo voltaic cell

1. Street light in rural areas.
2. Operating electronic gadgets
3. In the field of space & satellites.
4. Portable and emergency power supplies.
5. Water treatment & pumping.
6. Lighthouses and offshore drilling rig operations.
7. Operating water pumps for domestic and agricultural purpose.
8. Electric fencing for security.
9. In Transport and automobile industry.
Dept of Chemistry
MODULE-5
Water Chemistry(UNIT-1)
Natural Sources of Water
1. Rain Water.
2. River Water.
3. Lake Water.
4. Sea Water.
5. Underground Water.
1. Rain water: Probably rain water is purest form of natural water. But due to dissolution of
atmospheric gasses, it is slightly acidic in nature. This small amount of acidity does not cause
any damage and is necessary to dissolve the minerals in earth soil to make them available to
plants and animal life.
2. River water: contains various dissolved minerals of the soil such as chlorides, sulphates,
bicarbonates of calcium, magnesium and iron etc. it also contain the organic matter and
suspended impurities due to decomposition of plants.
3. Lake water: more or less has a constant chemical composition. It is usually contains less
amount of dissolved and higher quantities of organic matter.
4. Sea water: is the most impure form of natural water. It contains an average of 3.5% of
dissolved salts, out of which about 2.6% is sodium chloride.
5. Underground water. Spring and well water are the natural underground water. Due to
filtration action of soil, it has clear appearance, but contains more of the dissolved salts and
less organic impurities.
Impurities in water: Water usually contaminated by various types of impurities. The impurities
in water largely depend upon the source. The major impurities of water are,
1. Suspended solids
2. Dissolved solids
3. Dissolved gases
4. Biological impurities.
1. Suspended solids: Suspended or colloidal impurities are the extremely fine particles such as
clay, silt, silica, salts of iron, magnesium, are inorganic suspensions and peat, algae, weeds,
protozoa, microorganisms are organic suspensions. These fine particles impart turbidity and colour
to the water. These impurities can be removed by filtration, sedimentation or by coagulation
process.
2. Dissolved solids: Dissolved solids are soluble impurities present in water, such as bicarbonates,
sulphates, chlorides of calcium, magnesium and sodium salts. And also small amounts of nitrate,
nitrites, silicates and iron salts.
3. Dissolved gases: All natural waters contain CO2 and O2 as dissolved gases. Some waters have
H2S, SO2, NH3 and oxides of nitrogen as dissolved gases. Dissolved gases impart a foul odour to
the water.
4. Biological Impurities: Biological impurities are pathogenic bacteria, microorganisms, which
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are main cause of water borne diseases. E.g. Algae, Fungi, viruses, parasites, worms andpathogenic
bacteria, such as coliforms, typhoid bacillus, faecal streptococcus, etc.
Potable water:
Water that is fit for human consumptions and meets the stringent microbiological and chemical
standards of quality to prevent waterborne diseases and health risks from toxic chemicals is
called potable water.
1. It should be clear,
2. It should be colourless,
3. It should be odourless,
4. It should be free from toxic chemicals and heavy metals.
5. It should be free from pathogenic microorganism.
6. Palatable taste.
WHO Drinking Water Specifications

Parameters Standard limits as per WHO guidelines (mg/L)
pH 6.5 – 8.5
Total Dissolved Solids 300
Calcium 75 – 200
Sulphates 200 – 400
Chloride 250
Magnesium 30
Nitrate 50
Nitrite 3
Fluoride 1.5
Mercury, Arsenic, Lead 0.001
Dissolved Oxygen 5.0 – 8.0
Residual Chlorine 0.2 – 1.5
Hardness of Water:
Hardness of water is the lather producing capacity of water with soap. It is due to the presence of
salts like bicarbonates, chlorides and sulphates of Ca & Mg. The unit of Hardness is ppm or
mg/ liter of CaCO3.
Hardiness of water is classified into two types Temporary Hardness and Permanent Hardness.
1. Temporary Hardness: Temporary Hardness of water is caused by the presence of

bicarbonates of calcium and magnesium. It can be removed easily by simple methods like
boiling or by addition of simple chemical substances such as lime.
2. Permanent Hardness: Permanent hardness of water is caused by the presence of chlorides
and sulphates of calcium and magnesium. It cannot be removed by simple methods like boiling
etc. Instead advanced methods like ion exchange process can be used to remove the permanent
hardness.
Total hardness of water is the sum of both temporary and permanent hardness.
Total hardness of water is determined by complexometric titration by titrating known volume of the
water sample against standard disodium salt EDTA solution with the aid of Eriochrome Black-T
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indicator.
Determination of Total Hardness of a sample of water using disodium salt of EDTA By

Complexometric Method.
Theory: The total hardness is determined by titrating a known volume of the water sample against
ethylenediamine tetra acetic acid (EDTA) using Eriochrome Black-T indicator. EDTA is a hex dentate
ligand and forms a weak complex with Ca2+ and Mg2+ ions. The molecule represented as H4Yhas two
easily replaceable hydrogen atoms in its molecule.
Procedure:
Part A: Preparation of standard solution of disodium salt of EDTA

Weigh accurately to 0.1 mg (4th decimal place) the weighing bottle containing around .5g of crystals
of disodium salt of EDTA using electronic balance (m1 g). Transfer the crystals carefully into a funnel
placed over a 250 cm3 volumetric flask and find the weight of the emptied weighing bottle (m2g). Wash
the funnel with ion exchange water and remove the funnel. Dissolve the crystals by gently swirling the
flask (add a few drops of ammonia if the crystals do not readily dissolve). Dilute withion exchange
water and make upto the mark. Stopper and invert the flask several times so that a homogeneous
solution results. Calculate the molarity of the Na2EDTA salt solution.
Part B: Determination of total hardness of water sample

Transfer 25.0 cm3 of the given hard water sample into a clean 250 cm3 conical flask using a pipette.
Add 5 cm3 of NH3 - NH4Cl buffer solution and a pinch of Eriochrome Black-T indicator. Titrate against
EDTA solution till the colour of the solution changes from wine red to clear blue. Repeat the
experiment for agreeing values.
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Observations and Calculations(REFER CLASS NOTES)

Weight of weighing bottle + Na2EDTA crystals = m1g
Tare weight of weighing bottle = m2 g
Weight of Na2EDTA crystals transferred = (m1 - m2) g
= ‘Z’
Volume of Na2EDTA solution required to react with 25 cm3 of water sample = ‘X’ cm3
1000 cm3 of 1 M Na2EDTA 100g of CaCO3 (Molecular mass of CaCO3 = 100)
25 cm3 of the Hard Water sample contains 'a' g of CaCO3

Therefore, 106 (1 million cm3) of Hard Water sample contains
= ............ g of
Total hardness of the water sample =...........................ppm or mg/litre of CaCO3
Result: Total Hardness of the water sample is found to be--------------------------------------- ppm of CaCO3.
Important Note:
Hardness type Hardness causing ions Hardness causing salts
Temporary Bicarbonates of Ca & Mg Ca (HCO3)&Mg (HCO3)
Permanent Chlorides and Sulphates of CaSO4, MgSO4, CaCl2&MgCl2

Ca & Mg
Total Hardness Bicarbonates, Chlorides and Ca (HCO3),Mg (HCO3), CaSO4, MgSO4,
Sulphates of Ca & Mg CaCl2&MgCl2
Amounts equivalent to CaCO3 (mg/Lit) =

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Numerical Problems on Hardness of Water

1. A sample of water is found to contains following dissolving salts in milligrams per liter
Mg(HCO3)2 = 73, CaCl2 = 111, Ca(HCO3)2 = 81, MgSO4 = 40 and MgCl2 = 95. Calculatetemporary,
permanent hardness and total hardness.
Solution:
Name of the Amount of the Molecular weight
Amounts equivalent to
hardness causing hardness causing of hardness
CaCO3 (mg/Lit)
salts salts(mg/Lit) causing salts
Mg(HCO3)2 73 146
Ca(HCO3)2 81 162
CaCl2 111 111

MgSO4 40 120
MgCl2 95 95
Temporary hardness= Mg(HCO3)2+ Ca(HCO3)2= 50 + 50 = 100mg/Lit.

Permanent hardness = CaCl2 + MgSO4 + MgCl2 = 100 + 33.3 + 100 = 233.3mg/Lit.
Total hardness = Temporary hardness + Permanent hardness
= 100 + 233.3
Total hardness = 333.3mg/Lit or ppm of CaCO3
2. Calculate the temporary and permanent hardness of water sample containing

Mg(HCO3)2= 7.3mg/L, Ca (HCO3)2= 16.2mg/L, MgCl2= 9.5mg/L, CaSO4=13.6mg/L).
Solution:
CaCO3 (mg/Lit)
Mg(HCO3)2 7.3 146
Ca(HCO3)2 16.2 162
MgCl2 9.5 95
CaSO4 13.6 136
Temporary hardness= Mg(HCO3)2+ Ca(HCO3)2= 5 + 100 = 15mg/Lit.

Permanent hardness = MgCl2 +CaSO4 = 10 + 10 = 20mg/Lit.
= 15 + 20
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Total hardness = 35 mg/Lit or ppm of CaCO3
3. A sample of water is found to contains following dissolving salts in milligrams per litre
Mg(HCO3)2 = 16.8, MgCl2 = 12.0, MgSO4 = 29.6 and NaCl = 5.0. Calculate temporary
and permanent hardness of water.
Solution:
CaCO3 (mg/Lit)
Mg(HCO3)2 16.8 146
MgCl2 12.0 95
MgSO4 29.6 120
NaCl does not contribute any hardness to water

NaCl 5.0
hence it is ignored.
Temporary hardness= Mg(HCO3)2= 11.50 mg/Lit.

Permanent hardness = MgCl2 +MgSO4 = 12.63 + 24.66 = 37.29 mg/Lit.
= 11.50 + 37.29
Total hardness = 48.79 mg/Lit or ppm of CaCO3
4. 100 ml of a sample of water required 15.0 ml of 0.01 M EDTA for titration using
Eriochrome Black-T indicator. In another experiment, 100 ml of the same sample was
boiled and the precipitate was removed by filtration. The filtration required 8.0 ml of
0.01 M EDTA using Eriochrome Black-T indicator. Calculate (i) the total hardness (ii) permanent
hardness (iii) bicarbonate hardness in terms of mg/lit of CaCO3.
Solution:
Volume of EDTA consumed before boiling = 15 ml
Volume of EDTA consumed after boiling = 8 ml
Molarity of EDTA = 0.01 M
Volume of water sample taken = 100 ml
Total Hardness of the water sample:
Total Hardness = ppm of CaCO3 equivalent
= ppm of CaCO3 equivalent

Total Hardness= 150 ppm of CaCO3
Permanent Hardness of the water sample:

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Permanent Hardness = ppm of CaCO3 equivalent

Permanent Hardness= 80 ppm of CaCO3
Temporary Hardness of the water sample:

Temporary hardness= Total hardness − Permanent hardness
= 150 − 80 = 70 ppm
Temporary hardness = 70 ppm of CaCO3
5. In an estimation of hardness of water by EDTA titration, 250 ml of a sample of water

required 15ml of 0.025 M EDTA solution to get the end point. Calculate the hardness of
water.
Solution:
Volume of EDTA consumed = 15 ml
Volume of water sample taken = 250 ml
Total Hardnessof the water sample:

Total Hardness = 150 ppm of CaCO3
6. 200 ml of water sample requires 30 ml of 0.02 M EDTA with NH4Cl – NH4OH buffer and
EBT indicator. Another 200 ml of water sample was boiled and the precipitate was
removed by filtration.100 ml of this boiled sample (filtrate) requires 5 ml of 0.02 M EDTA
following the same procedure. Calculate temporary, permanent and total hardness of
water.
Solution:
Volume of water sample taken before boiling= 200 ml (For Total hardness)
Volume of water sample taken before boiling= 100 ml (For Permanent hardness)

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Permanent Hardness = 100 ppm of CaCO3

= 300 − 100 = 200 ppm
Temporary hardness = 200ppm of CaCO3
7. 50 ml of sample water consumed 15 ml of 0.02 M EDTA before boiling and 5 ml of the

same EDTA consumed after boiling. Calculate temporary, permanent and total hardness
of water.
Solution:
Volume of water sample taken before boiling= 50 ml (For Total hardness&Permanenthardness)


Permanent Hardness = 200 ppm of CaCO3

= 600 − 200 = 400 ppm
Temporary hardness = 400ppm of CaCO3
Dept of Chemistry
BOD – Biological Oxygen Demand

BOD is defined as the “amount of oxygen required by microorganisms for the biological oxidation of the organic
matter Present in one liter waste water at 200 C for a period of 5 – days under aerobic conditions.”
COD Value is always greater than BOD; Because COD is the amount of Oxygen required for oxidation
of both inorganic and organic matter. Whereas BOD is the amount of Oxygen required for biological
oxidation of only organic matter.
COD – Chemical Oxygen Demand

COD is defined as the “amount of oxygen required for chemical oxidation of organic and inorganic matter present in
one liter waste water by a strong oxidizing agent.”
Determination of Chemical Oxygen Demand (COD) of Waste water
Theory: Chemical Oxygen Demand is a measure of the oxygen equivalent of organic and inorganic
materials in a water sample that can be oxidized by a strong chemical oxidant. This parameter is
important for industrial waste studies. COD is expressed as milligrams of Oxygen required to oxidise
impurities present in 1000 cm3 of Waste water.
Procedure:
Back Titration: Pipette out 25 cm3of the Waste water sample into a 250 cm3 conical flask . Add
25.0 cm3 of standard Potassium dichromate solution using a different pipette followed by one test tube
of 1:1 Sulphuric acid (containing Silver Sulphate) with constant shaking of the contents of the flask.
Add boiling chips to the flask. Attach a reflux condenser and reflux the mixture for half an hour and
cool. Wash the condenser with ion exchange water and transfer the washings to the flask. Add 2-3
drops of Ferroin indicator and titrate against the standard Ferrous Ammonium Sulphate solution until
the colour changes from blue green to reddish brown.
Blank Titration: Transfer 25 cm3of Potassium dichromate solution using a pipette. Add one test tube
of 1:1 sulphuric acid (containing silver Sulphate) followed by 2 or 3 drops of Ferroin indicator and
titrate against the Ferrous Ammonium Sulphate solution until the colour changes from blue green to
reddish brown. Repeat for concordant values.
Observations and CalculationsREFER CLASS NOTES)

Normality of FAS solution = 'Z
Volume of FAS required in Back Titration = 'Y' cm3
Volume of FAS required in Blank Titration = 'X' cm3
Volume of FAS equivalent to the oxidisable impurities = (X - Y) cm3
1000 cm3 of 1 N FAS solution = 1 equivalent of Oxygen = 8 g of oxygen.
(X - Y) cm3 of 'Z' N FAS solution = 8(X-Y)Z = ................... g of Oxygen
1000
1000 cm3 of Waste water sample = 8(X - Y)Z =.................. g of Oxygen
25
COD of Waste water sample = 8000 (X - Y)Z = .............. mg of Oxygen
25
Result: COD of the Waste water sample is found to be mg of Oxygen/dm3
Dept of Chemistry
Important Statements to be Remembered:
1000 cm3 of 1.0 N FAS Solution = 1 equivalent of oxygen = 8g of oxygen

1000 cm3 of 1M solution of K2Cr2O7 = 48 g of Oxygen
Numerical problems on Chemical Oxygen Demand

1. 25ml of the waste water sample was mixed with 25ml of acidified K2Cr2O7 and refluxed. The
unreacted K2Cr2O7 required 10.2ml of FAS. In a blank titration 25ml of acidified K 2Cr2O7
required 25.4 ml of FAS. The strength of FAS is 0.1N, calculate COD of waste water.
Solution:
Volume of waste water Sample: 25ml
Volume of FAS required for unreacted K2Cr2O7(y): 10.2ml ( Back Titter Value)
Volume of FAS required for 25ml K2Cr2O7(x): 25.4ml(Blank Titter Value)
Normality of FAS: 0.1N
Volume of FAS required to react with 25ml of waste water sample =(x-y)
=(25.4-10.2)ml
= 15.2ml
1000ml of 1.0 N FAS Solution = 1 equivalent of oxygen = 8g of oxygen
15.2 ml of 0.1 N FAS solution = 15.2 x 0.1 x 8 = 0.01216 g of Oxygen

1000
25ml of waste water sample = 0.01216 g of Oxygen.
1000ml of waste water sample = 1000 x 0.01216 = 0.4864 g of Oxygen

25
COD of waste water sample = 0.4864 g of oxygen per liter
= 0.4864 x 1000 mg 0f oxygen per liter
Result: COD Of waste water sample is 486.4 mg of oxygen per liter
Dept of Chemistry
2. In a COD test 28.1cm3 and 14.0 cm3 of 0.05N FAS solution were required for blank and
sample titration respectively. The volume of test sample used is 25 cm3,. calculate COD of the
sample
Solution:
Volume of FAS required for unreacted K2Cr2O7 (y): 14.0ml ( Back Titter Value)
Volume of FAS required for 25ml K2Cr2O7 (x): 28.1ml (Blank Titter Value)
Normality of FAS: 0.05
=(28.1-14.0)ml
= 14.1ml
1000ml of 1.0 N FAS Solution = 1 equivalent of oxygen = 8g of Oxygen
14.1 ml of 0.05N FAS solution = 14.1 x 0.05 x 8 = 0.00564 g of Oxygen

1000
1000ml of waste water sample = 1000 x 0.00564= 0.2256 g of Oxygen

25
= 0.2256 x 1000 mg of Oxygen per liter
Result: COD Of waste water sample is 225.6 mg of Oxygen per liter
3. Calculate COD of the effluent sample when 25 cm3 of the effluent sample requires 8.5 cm3
of 0.001M K2Cr2O7 solution for complete oxidation.
Solution:
Volume of effluent (Waste Water Sample) = 25cm3.
Volume of K2Cr2O7 required for compete oxidation of 25cm3 effluent =8.5 cm3
Molarity of K2Cr2O7 = 0.001
8.5 cm3 of 0.001M solution of K2Cr2O7 = 48x0.001x8.5 = 0.000408g of Oxygen

1000
25 cm3 of effluent =0.000408g of Oxygen
1000 cm3 of effluent = 0.000408x1000 = 0.01632 mg of Oxygen per liter

25
Result: COD Of waste water sample is 16.32 mg of Oxygen per liter.

Dept of Chemistry
4. Calculate COD of the effluent sample when 20cm3 of the effluent sample requires 7.8 cm3
of 0.002M K2Cr2O7 solution for complete oxidation.
Solution:
Volume of K2Cr2O7 required for compete oxidation of 20cm3 effluent = 7.8 cm3
7.8 cm3 of 0.002 M solution of K2Cr2O7 = 48x0.002x 7.8= 0.0007488g of Oxygen

1000
20cm3 of effluent =0.0007488g of Oxygen
1000 cm3 of effluent = 0.0007488x1000 = 0.03774g of Oxygen per liter

20
= 0.03774x 1000 mg of Oxygen per liter
Result: COD Of waste water sample is 37.74 mg of Oxygen per liter
5. 50ml of an industrial effluent is allowed to react with 100ml of K2Cr2O7 solution. The unreacted
K2Cr2O7 consumed 25ml of 0.05N FAS solution. The blank titration of the same consumed
35ml of FAS. Calculate COD of effluent.
Solution:
Volume of effluent Sample: 50ml
Volume of FAS required for unreacted K2Cr2O7 (y): 25ml ( Back Titter Value)
Volume of FAS required for 25ml K2Cr2O7 (x): 35ml (Blank Titter Value)
=(35-25)ml
= 10ml
10 ml of 0.05N FAS solution = 10 x 0.05 x 8 = 0.0004 g of Oxygen

1000

50
COD of waste water sample = 0.008g of oxygen per liter
Result: COD Of waste water sample is 8 mg of Oxygen per liter
6. In COD experiment 20 cm3 of waste water sample consumes 30 cm3 of 0.01 M K2Cr2O7 for
oxidation of impurities. Calculate COD value of water sample.
Solution:
Volume of K2Cr2O7 required for compete oxidation of 20cm3 effluent = 30 cm3
Dept of Chemistry
30 cm3 of 0.01M solution of K2Cr2O7 = 48x0.01x30= 0.0144g of Oxygen

1000
1000 cm3 of effluent = 0.0144g x1000 = 0.72 mg of Oxygen per liter

20
Result: COD Of waste water sample is 720 mg of Oxygen per liter
7. In a COD experiment 25 cm3 of polluted water was allowed to react with 25 cm3of K2Cr2O7.
The K2Cr2O7 left over after oxidizing the impurities require 11.5 cm3 0.025 N FAS solution. In
a blank titration, 25 cm3 of K2Cr2O7 solution was consumed 18.5 cm3 of 0.025 N FAS solution.
Calculate COD of Waste water.
Solution:
Volume of FAS required for unreacted K2Cr2O7 (y): 11.5ml ( Back Titter Value)
Volume of FAS required for 25ml K2Cr2O7 (x): 18.5ml (Blank Titter Value)
=(18.5-11.5) ml
= 7.0 ml
7.0 ml of 0.05N FAS solution = 7.0 x 0.025 x 8 = 0.0014 g of Oxygen

1000

25
COD of waste water sample = 0.0056g of oxygen per liter
Result: COD Of waste water sample is 56 mg of Oxygen per dm3.
8. 50 cm3 of industrial sewage has consumed 11.5 cm3 0.04 N K2Cr2O7 solution for complete
oxidation organic and inorganic impurities. Calculate COD of industrial sewage.
Solution:
Volume of K2Cr2O7 required for compete oxidation of 25cm3 effluent = 11.5 cm3
11.5 cm3 of 0.04M solution of K2Cr2O7 = 48x0.04x 11.5= 0.02208g of Oxygen

1000
1000 cm3 of effluent = 0.02208x1000 = 0.4416g of Oxygen per liter
50
Dept of Chemistry

Result: COD Of waste water sample is 441.6 mg of Oxygen per liter.
9. 20ml of sewage sample was reacted with 25cm3 of K2Cr2O7 solution and the unreacted
K2Cr2O7 requires 9.0 cm3 of N/4 FAS solution. Under similar conditions, in blank titration
15.0 cm3 of FAS was require for 25 cm3 of K2Cr2O7. Calculate the COD of the sample.
Solution:
Volume of waste water Sample: 20 cm3
Volume of FAS required for unreacted K2Cr2O7 (y): 9.0 cm3 ( Back Titter Value)
Volume of FAS required for 25 cm3 K2Cr2O7 (x): 15.0ml (Blank Titter Value)
Normality of FAS: N/4 = 0.25
=(15.0 – 9.0) cm3
= 6.0 cm3
3
1000 cm of 1.0 N FAS Solution = 1 equivalent of oxygen = 8g of Oxygen
6.0 cm3 of 0.25N FAS solution = 6.0 x 0.25 x 8 = 0.012 g of Oxygen

1000
20 cm3 of waste water sample = 0.012 g of Oxygen.
1000 cm3 of waste water sample = 1000 x 0.012= 0.6 g of Oxygen

20
Result: COD Of waste water sample is 600 mg of Oxygen per dm3
Methods of Chemical Analysis
Volumetric Analysis:
The volumetric analysis is quantitative analytical method of estimation of unknown substances.
In this method unknown concentration of a substance in a solution is estimated by adding exactly the
same number of equivalents of known concentration solution. It is also called as titrimetric analysis.
Basic principles of volumetric (titrimetric) analysis:

Volumetric analysis is based on the law (principle) of chemical equivalent which states that “the
substances react in the proportion of their equivalent weights”.
i.e., one gram equivalent of an acid would be neutralised by one gram equivalent of the base.
1 gram equivalent of HCl (36.46g) = 1 gram equivalent of NaOH (40.0g)
1000 cm3 of 1N solution of HCl = 1000 cm3 of 1N solution of NaOH
Thus, Volume of acid x Normality of acid = Volume of base x Normality of base
V HCl x N HCl = V NaOH x N NaOH

Dept of Chemistry
Requirements of volumetric analysis:

1. The reaction between analyte and titrant must be quantitative, with a high equilibrium
constant.
2. The reaction must be rapid. If the reaction is slow, the time of determination is extended,
possibly leading to an inaccurate determination.
3. The reaction should proceed stoichiometrically, in order to calculate the amount of analyte
present.
4. The exact concentration of the titrant must be known.
5. Only one specific reaction should occur between the titrant and the analyte. There should be
no side reaction.
6. The endpoint of the reaction should be detectable precisely with the help of an indicator.
Standard Solution: The solution whose concentration or strength is known is called a standard
solution. The strength of a solution is expressed in Normality, Molarity, Molality, Mole fraction and
ppm.
There are two types of standard solution namely,

1. Primary standard solution
2. Secondary standard solution.
1. Primary standard solution: The substance whose standard solution can be prepared directly by
dissolving a known weight of the substance in fixed volume of the solution is known as primary
standard solution.
A Primary standard is a chemical substance that remains stable for a long period of time and
its solution and is not affected by atmospheric CO2.
Ex: Silver nitrate solution, Potassium dichromate solution, Potassium hydrogen phthalate
solution, etc.
Requirements of primary standard solution:
1. The substance used must be available in pure form and should be non toxic.
2. It should not be hygroscopic (ability to absorb moisture) or deliquescent (turns to solution).
3. It should have high molecular weight or equivalent weight so as to minimize the weighing
error.
4. It should be readily soluble in water.
5. It should be stable and should be easily available at modest cost.
2. Secondary standard solution. The substance whose standard solution can be standardized with
the help of primary standard solution is known as secondary standard solution. A secondary
standard substance cannot be used for preparing the standard solution by direct weighing.
A secondary standard is a chemical substance that does not remain stable for a long period of
time and its chemical composition changes due to absorption of atmospheric CO2.
Ex: NaOH, HCl, KMnO4, FeSO4, etc.
Units of Standard Solution: The strength of solution is expressed in Normality,

Molarity,Molality, Mole fraction and ppm.
Normality (N): Normality of a solution is defined as the number of gram equivalents of the
solute present in one liter of the solution.
Dept of Chemistry
Molarity (M): Molarity of a solution is defined as the number of gram moles of the solute
present in one liter of the solution.
Molality (m): Molality of a solution is defined as the number of gram moles of the solute
dissolved in 1kg (1000grams) of the solvent.
Mole fraction ( X): The ratio of the number of moles of one component (solute) of a
Solution to the total number of moles representing all of the components in a mixture.
Number of Moles of Solute
Mole fraction of solute (X) =
Total Number of Mole of Solution
Number of Moles of Solute (A)

Mole fraction of solute (XA) =
Total Number of Mole of Solution (A+B)
Number of Moles of Solute (B)

Mole fraction of solute (XB) =
Total Number of Mole of Solution (A+B)
Parts Per Million (ppm): One part per million (ppm) is one part of solute per one million parts
of solvent or 10-6. It can be explained as one milligram of substance dissolved in one liter of
water (mg/l) or 1 milligram of substance present in one kilogram of other substance (mg/kg).
Dept of Chemistry
Instrumental methods of analysis(UNIT-2)

Colorimetry:
Theory: It is a chemical analysis through measurement quantity of light absorbed by a colored solution.
The basic law which relates the light absorbed with the chemical analysis is the Beer – Lamberts’ law.
Beer’s law: It states that “the intensity of a monochromatic light decreases exponentially as the concentration
of the absorbing medium (substance) increases arithmetically”.
Mathematically it can be expressed as,
It = Io e−kc
where ‘c’ is the molar concentration of the sample solution.
Lambert’s law: It states that “The intensity of the emitted light decreases exponentially as the thickness of
the absorbing medium (substance) increases arithmetically”.
Mathematically it can be expressed as,
It = Io e−kt
where ‘t’ is the thickness of the absorbing medium.
Beer – Lamberts’ law: This is the combination of Beer’s law and Lambert’s law.
Beer – Lambert’s law states that absorbance of light by the coloured solution is directly proportional to the
molar concentration of the solution and the thickness of the medium.
A = log Io = ct
It
Instrumentation: The essential parts of a photoelectric colorimeter are shown schematically below.
Dept of Chemistry
1. Source – Light
2. Filter- To filter undesired radiations , it allows radiations of a definite wave length range to
pass through it and reach the sample
3. Cuvette- Sample Holder
4. Photocell- To receive the transmitted light
5. Recorder – to record the absorbance in nm
Application of colorimetry:
Procedure: A series of standard Cu2+ ions (2, 4, 6, 8, 10ml) are taken and colour in each of the solution is
developed by the addition of aqueous ammonia. Then the absorbance values of the standard solutions are
measured against a reagent blank using a colorimeter at a wavelength range corresponding to maximum
absorbance against concentration. The test solution in which the concentration of Cu2+ ions is to be determined
is also treated withammonia to develop colour and its absorbance is measured. From the calibration curve, the
concentration of Cu2+ ions in the solution can be determined.
Advantages of colorimetry:
i) Colorimetry gives more accurate results at low concentrations than the corresponding titrimetric or
gravimetric procedure.
ii) The method is simple and rapid.
POTENTIOMETRY
Determination of concentration of ionic solution by measuring the emf is referred to as potentiometry.
Titration in which the end point is detected by measuring the change in potential of a suitable electrode during the
titration. The electrode which responds to the change in concentration of the ion in the solution is called the indicator
electrode. The indicator electrode is combined with the reference electrode to form the cell and the e.m.f of the so
formed cell is measured during the titration
Dept of Chemistry
Instrumentation:
Potentiometric method consist of Potentiometer and two electrodes in which one electrode is indicator
electrode (eg Platinum electrode) and reference electrode
Instrument used- potentiometer or pH meter.
Magnetic stirrer: It is used to maintain the uniform concentration after each addition.
Applications:
Redox titrations - Redox titrations are also carried out potentiometrically. The indicator electrode used is an
inert metal such as platinum and calomel electrode is used as the reference electrode. The electrodes are
immersed in the solution containing the oxidized and reduced forms of the same species.
As the redox reaction proceeds, the ratio of the concentrations and hence the potential changes more rapidly in
the vicinity of the end point of the titration. This may be followed potentiometrically and a plot of change in
potential against volume is characterized by a sudden change of potential at the equivalence point.
Advantages of potentiometry:
i) Potentiometric titrations can be carried out in coloured solutions where indicators cannot be used.
ii) By potentiometry, it is possible to determine the end point in the titrations of very weak acids or very
weak bases.
Dept of Chemistry
CONDUCTOMETRY
Theory: Measurement of conductance can be employed to determine the equivalence point in acid-base
titrations. In conductometric titrations, there is a sudden change in conductance of the solution after the
equivalence point. Hence, the equivalence point is determined graphically by plotting conductance against titre
values.
Instrumentation: A simple arrangement of conductometric titration is depicted in figure.
Conductivity cell:
A conductivity measuring cell is fitted with a pair of platinum electrodes (1-cm square surfaces spaced 1-cm
apart).
Conductivity meter: To display the reading during titration.
Magnetic stirrer: It is used to maintain the uniform concentration after each addition.
Applications:
Conductometric titrations can be employed to locate the equivalence point of various acid-base
titrations. Some of the examples are discussed below.
1) Titration of strong acid and a strong base (HCl against NaOH):

During the titration of a strong acid (HCl) with a strong base (NaOH), the reaction taking place is,
Na+ + OH− + H+ + Cl− → Na+ + Cl− + H2O
In this case, the conductance first falls, due to replacement of highly mobile H+ (mobility 350 −1m−1) by
the added cation (mobility 40 – 80 −1m−1). After the equivalence point, the conductance rapidly rises with
further additions of strong base and is due to increase in the concentration of OH − ions (mobility 198 −1m−1).
The plot of conductance versus volume of the base added gives two straight lines. The point of intersection of
the two straight lines gives the neutralization point.
Dept of Chemistry
2) Titration of weak acid with a strong base (CH3COOH with NaOH):

In case of this, the conductance will be initially low due to poor dissociation of the weak acid. When a
strong base is added to the acid, the salt formed is highly ionized and the conductance increases. On complete
neutralization of the acid, further addition of base leads to an increase in the number of more mobile OH− ions.
Hence, conductance increases sharply. Thus a plot of conductance against volume of the base added gives two
straight lines as shown in the figure.
3) Titration of a mixture of strong acid and a weak acid with a strong base
(HCl and CH3COOH with NaOH):
One of the important features of the conductometric titration is that, it permits the analysis of a mixture
of a strong acid and a weak acid (e.g., HCl+CH3COOH) with a strong base (NaOH). Upon adding strong base
to the mixture of acids, the conductance falls initially until the strong acid is neutralized completely, due to the
replacement of highly mobile H+ ions of the HCl by less mobile Na+ ions. The weakacid remains un dissociated
in the presence of a strong acid. Once the strong acid is completely neutralised, the weak acid begins to dissociate
and gets neutralized. This results in increase in conductance as the weak acid gets converted into its salt. When
the neutralization of the weak acid is complete, there is sharp increase in conductance due to the ions of the
strong base. The plot of conductance versus the volume of the titrant is shown below.
Dept of Chemistry
where, V1 = volume of base required to neutralize HCl
V2 = volume of base required to neutralize HCl and
CH3COOHV2 −V1 = volume of base required to
neutralize CH3COOH
Advantages of conductometry:
i) Mixture of acids can be titrated more accurately by conductometric titration.
ii) Accurate in dilute solutions as well as in more concentrated solutions.
iii) It can be employed with coloured solutions.
iv) Very weak acids which cannot be titrated potentiometrically in aqueous solutions can
be titratedconductometrically with relative ease.
FLAME PHOTOMETRY
Theory: The principle of flame photometry is atomic spectra arising due to the emission of light of
different wavelengths when atoms are excited in a flame. Such spectra consist of emission lines
characteristic of the elements present in a sample. Lithium, sodium, potassium, calcium and a few other
elements impart characteristic colours to the flame. For example, sodium salt solution introduced into
the flame emits light around 569 nm in the yellow-orange region of the spectrum. The intensity of line
emitted is proportional to the concentration and is measured by a flame photometer.
Instrumentation:
Air is passed into the atomizer through a compressor at a given pressure. This causes reduced
pressure at the tip of the capillary in the atomizer and the solution of the analyte is drawn in to the
atomizer through the capillary. Here, the solution mixes with the air as a fine mist and passes through
spoilers where bigger droplets are blocked. The mist passes in to the flame of the burner and burns. The
radiations emitted pass first through an eye piece lens of the spectrometer and then through the filter
which transmits only the radiation characteristic of the element under test. The radiation finally falls on
the phototube detector. The detector displays the emission intensity.
Applications:
1. It is applicable for the determination of sodium & potassium in water, soil extract, plant material.
2. It is applicable for the determination of sodium & potassium in cement, glasses, blood serum.
3. It is applicable to the determination of Lithium, cesium, calcium, barium, strontium etc.,.
Estimation of sodium content in the given sample of water

Dept of Chemistry
• Transfer 2, 4, 6, 8, and 10 cm3 of standard sodium chloride/KCl solution into different 50 cm3
volumetricflasks ,make up to the mark using distilled water.
• Set the instrument to read zero with distilled water. Place each of the standard solutions in
the suctioncapillary & set the instrument to read 2,4,6,8 & 10 respectively.
• Dilute the given unknown solution up to the mark & shake well. Record the reading of unknown.
• Calibration curve: Plot a graph of Emission intensity against volume of sodium chloride.
• Using calibration curve volume of unknown solution can be determined.
Most likely questions and scheme of answers.

1. What are sources of water and impurities? Write a brief note on sources and
impurities ofwater.
2. What is potable water and its characteristics? List out WHO Drinking Water
Specifications.
3. What is hardness of water? Explain Determination of Total Hardness of a
sample of waterusing disodium salt of EDTA By Complexometric Method.
4. What is chemical oxygen demand? Explain Determination of Chemical
Oxygen Demand(COD) of Waste water.
5. What is Volumetric analysis? Explain basic principle and requirements.
6. Define the following units of standard solution.
i) Molarity ii) Normality iii) ppm.
7. Explain the theory, instrumentation and applications of flame photometry.
8. Explain the theory and instrumentation of conductometry.
9. Explain the theory and instrumentation of Potentiometry.
10. Explain the theory and instrumentation of colorimetry.
Dept of Chemistry
Model Question Paper-1 with effect from 2021 (CBCS Scheme)
First Semester Engineering Degree

Examination Subject Title 21CHE12/22
TIME: 03 Hours Max. Marks: 100
Note: Answer any FIVE full questions, choosing at least ONE question from each
MODULE.
MODULE 1 Marks
a Define Single Electrode Potential. Derive Nernst equation for single electrode 7
potential.
Q.1 b Describe the construction and working of calomel electrode 6
c Explain the construction and working of Li-ion battery, mention its 7
applications.
OR
a Distinguish between primary, secondary and reserve batteries. 6
b Explain construction and working of glass electrode. 7
Q.2 For the cell, Fe/Fe (0.01M)//Ag + (0.1M)/Ag write the cell reaction and
2+
c calculate the emf of the cell at 298K, if standard electrode potentials of Fe 7

and Ag electrodes are -0.44V and 0.8 V respectively.
MODULE 2
a Define metallic corrosion? Describe the electrochemical theory of corrosion 7

Q.3 taking iron as an example.
b Explain: (i) Differential metal corrosion & (ii) Water-line corrosion 6
c What is electroplating? Explain the electroplating of chromium 7
OR
a What is meant by metal finishing? Mention (any five) technological 6
importance of metal finishing.
Q.4 b What is electroless plating? Explain the electroless plating of copper. 7
c Explain the factors affecting the rate of corrosion (i) Nature of corrosion 7
product, (ii) Ratio of anodic to cathodic areas & (iii) pH
MODULE 3
a Explain the synthesis and application of Polyurethane. 7
Q.5 b Describe the mechanism of conduction in Polyaniline and factors influencing 7
conduction in organic polymers.
c Explain any two size dependent properties of nanomaterials 6
OR
a What are nanomaterials? Explain the synthesis of nanomaterial by sol gel 7
process.
Q.6
b Write a note on Fullerenes. Mention its applications. 6
c Explain the synthesis, properties and application of Polylactic acid. 7
Dept of Chemistry
MODULE 4
a With suitable example explain microwave synthesis and bio catalyzed 7
reactions
Q.7 b Explain the synthesis of Adipic acid by conventional route from Benzene and 7
green route from Glucose.
c Describe the construction and working of Methanol –Oxygen fuel cell. 6
OR
a Describe the hydrogen production by photo catalytic water splitting method. 7
Q.8 b Explain the synthesis of Paracetamol by conventional and green route from 7
phenol.
c Explain the construction and working of photovoltaic cells. 6
MODULE 5
a Explain the theory, instrumentation and applications of flame photometry. 7
b Write the principles and requirement of titrimetric analysis. 7
Q.9 In a COD test, 30.5 cm3 and 15.5 cm3 of 0.05 N FAS solutions are required
c for blank & sample titration respectively. The volume of test sample used was 6
25 cm3. Calculate the COD of the sample solution.
OR
a Explain the determination of hardness of water by EDTA method. 7
Q.10 b Define the following units of standard solution. 6
i) Molarity ii) Normality iii) ppm
c Explain the theory and instrumentation of potentiometry. 7
Dept of Chemistry
Model Question Paper-2 with effect from 2021 (CBCS Scheme)
First Semester Engineering Degree

Examination Subject Title 21CHE12/22
TIME: 03 Hours Max. Marks: 100
Note: Answer any FIVE full questions, choosing at least ONE question from each
MODULE.
MODULE 1 Marks
a Define Single Electrode Potential. Obtain the expression for single electrode 7
potential.
Q.1 b What are ions Selective Electrodes? Explain construction and working of 7
glass electrode
c Write briefly the recycling of Li-ion battery by direct recycling method 6
OR
a Explain the construction, working and applications of Li-ion batteries. 6
Q.2 b Explain the experimental determination of P H using glass 7
c Calculate the single electrode potential of Cu electrode at 27oC when the 7
standard potential of Cu is 0.34V and [ Cu2+] 0.1M
a Explain the following factors which affecting the rate of corrosion i) Ratio of 7
anodic and cathodic areas ii) nature of corrosion product
Q.3
b What is anodizing? Explain the process of anodizing of Al 6
c What is electroless plating? Distinguish between electro and electroless 7
plating.
OR
a What is meant by metal finishing? Mention (any five) technological 6
importance of metal finishing.
2
A thick steel sheet of area 400 cm is exposed to air near the ocean. After a
one year period it was found to experience a weight loss 375 g due to corrosion.
Q.4 b 7
If the density of the brass is 7.9g/cm2 calculate the corrosion
penetrating rate in mpy and mm/y ( given K= 534 in mpy and 87.6 in mm/y)
c What is cathodic protection? Explain sacrificial anode and impressed 7
voltage methods of cahtodic protection
MODULE 3
a What are polymer composites? Explain the synthesis and application of 7
Kevlar fibre
Q.5 b What are conducting polymers? Explain the various factors influencing the 7
conduction in organic polymers.
c Briefly explain the carbon nanotubes with properties and applications. 6
Dept of Chemistry
OR
a Explain optical and electrical properties of nanomaterials. 7
b What are nanomaterials? Explain the synthesis of nanomaterials by 6
Q.6 precipitation method
c What are Biodegradable polymers? Explain the properties and applications of 7
Polylactic acid.
MODULE 4
a Briefly explain any six basic principles of green chemistry. 6
Q.7 b Explain the following i) Phase transfer catalyst ii) Solvent free reaction 7
c With a neat diagram explain the production of Hydrogen by Photocatalytic 7
method
OR
a Describe the hydrogen production by photo electrocatalytic method. 7
Q.8 b Explain the synthesis of Paracetamol by conventional and green route from 7
phenol.
c Explain the construction and working of photovoltaic cells. 6
MODULE 5
a Explain the theory, instrumentation and applications of flame photometry. 7
b Write the principles and requirement of titrimetric analysis. 7
Q.9 In a COD test, 30.5 cm3 and 15.5 cm3 of 0.05 N FAS solutions were
c consumed for blank & sample titration respectively. The volume of testsample 6
used was 25 cm3. Calculate the COD of the sample solution.
OR
a Explain the determination of hardness by EDTA method. 7
Q.10 b Define the following units of standard solution. 6
i) Molarity ii) Normality iii) ppm
c Explain the theory and instrumentation of potentiometry. 7
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Dept of Chemistry

Green Chemistry and Alternative Energy Sources

Principles of Green Chemistry

Major Environmental pollutants:

1. Oxides of Carbon (COx):

3. Breathing CO cause headache, dizziness, vomiting and chest pain

2. Oxides of sulphur (SOx):

3. Oxides of Nitrogen (NOx):

Various Green Chemical Approaches:

The green chemical approaches for synthesis of various chemicals are,

Example Microwave Synthesis:

i. Hydrolysis of Benzyl Chloride: Hydrolysis of Benzyl Chloride with water in

Benzyl Chloride Benzyl Alcohol

Example of Bio-catalyzed reactions:

Advantages and Conditions of Solvent-free Reactions:

Synthesis of Adipic Acid

2. Green Route synthesis for Adipic Acid:

D-Glucose 3- dehydroshikimate Cis-Cis Muconic Acid Adipic Acid

1. Conventional Method of Paracetamol Synthesis: Paracetamol (acetaminophen) can be

Step 1: Nitration of phenol:

Step 2: Reduction of a Nitro group to an Amine:

Step 3: Formation of an Amide:

2. Green Route synthesis for Paracetamol:

Industrial applications of Green Chemistry:

1. Hydrogen Production by Photo Electrocatalytic Water Splitting:

2. Hydrogen Production by Photo catalytic Water Splitting:

The H+ ions combine to produce hydrogen at the surface of the Pt catalyst.

Application of Hydrogen in Fuel Cell:

Anode : - Hollow porous carbon tube impregnated with Pt.

Cell Reactions are

½ O2 + H2O + 2e 2OH – – at cathode.

This cell produces a voltage of about 1.15V

Methanol – Oxygen Fuel Cell [MeOH – O2 ]

Construction and Working

Fuel : Methanol dissolved in Water.Oxidant :

Electrolyte: 3.7M H2SO4.

Anode : Pt-Pd impregnated Nickel electrode.

Cathode : Ag impregnated Nickel electrode.

CH3 OH + 1½ O2 CO2 + 2 H2 O Net cell Reaction

Applications of Methanol- Oxygen fuel Cell:

Photovoltaic cells (solar cells)

Construction of photovoltaic cell

Working of photovoltaic cell

Applications of photo voltaic cell

WHO Drinking Water Specifications

1. Temporary Hardness: Temporary Hardness of water is caused by the presence of

Determination of Total Hardness of a sample of water using disodium salt of EDTA By

Part A: Preparation of standard solution of disodium salt of EDTA

Part B: Determination of total hardness of water sample

Observations and Calculations(REFER CLASS NOTES)

25 cm3 of the Hard Water sample contains 'a' g of CaCO3

Temporary Bicarbonates of Ca & Mg Ca (HCO3)&Mg (HCO3)

Permanent Chlorides and Sulphates of CaSO4, MgSO4, CaCl2&MgCl2

Amounts equivalent to CaCO3 (mg/Lit) =

Numerical Problems on Hardness of Water

CaCl2 111 111

Temporary hardness= Mg(HCO3)2+ Ca(HCO3)2= 50 + 50 = 100mg/Lit.