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 DEPARTMENT OF CHMISTRY

ENGINEERING CHEMISTRY-II

E-NOTES
 SYLLABUS
10ACH02 ENGINEERING CHEMISTRY – II
UNIT I ELECTRO CHEMISTRY
Electrochemical cells – reversible and irreversible cells – EMF – measurement of
EMF– electrode potential – Nernst equation (problems) – reference electrodes –
Standard Hydrogen electrode -Calomel electrode – Ion selective electrode - glass
electrode and measurement of pH – electrochemical series – significance –
potentiomettic titrations (redox - Fe²+vs dichromate and precipitation – A+vs. CI-)
and conductometric titration (acid-base – HCI vs. NaOH).
UNIT II CORROSION AND CORROSION CONTROL
Chemical corrosion – Pilling – Bedworth rule – electrochemical corrosion – types –
galvanic corrosion – differential aeration corrosion – factors influencing corrosion –
corrosion control – sacrificial anode and impressed cathode current methods –
corrosion inhibitors – protective coatings – paints – constituents and functions –
metallic coatings – Hot dipping(Zn)-electroplating (Au) and electrolysis Plating (Ni).
UNIT III FUELS AND COMBUSTION
Fuels-Types-Calorific value – Coal – proximate and ultimate analysis-metallurgical
coke – manufacture by Otto-Hoffmann method – Petroleum refining– cracking –
catalytic cracking methods-knocking – octane number and cetane number – synthetic
petrol – Fischer Tropsch and Bergius processes – Gaseous fuels- water gas, producer
gas, CNG and LPG. Flue gas analysis – Orsat method – theoretical air for combustion
(problems).
UNIT IV PHASE RULE AND ALLOYS
Statement and explanation of terms involved – one component system – water system
– condensed phase rule – construction of phase diagram by thermal analysis – simple
eutectic systems (lead-silver system only) – alloys – importance of ferrous alloys –
nichrome and stainless steel – heat treatment of steel, non-ferrous alloys – brass and
bronze.
UNIT VANALYTICAL TECHNIQUES
Beer-Lambert‟s law (problems) – UV-visible spectroscopy and IR spectroscopy –
principles – instrumentation (problem & block diagram only) – estimation of sodium
by flame photometry - atomic absorption spectroscopy- principle – instrumentation
(block diagram only) -estimation of nickel by AAS.
TEXT BOOKS:
1. “Engineering Chemistry” , P.C.Jain and Monica Jain, Dhanpat Rai Pub, Co.,
New Delhi (2002).
2. “A text book of Engineering Chemistry”, S.S.Dara S.Chand & Co.Ltd.,
New Delhi (2006).
REFERENCES:
1. “Engineering Chemistry” , B.Sivasankar , Tata McGraw-Hill Pub.Co.Ltd,
New Delhi (2008).
2. “Engineering Chemistry”, B.K.Sharma Krishna, Prakasan Media (P) Ltd.,
Meerut (2001).
*************
 UNIT I ELECTROCHEMISTRY
Electrochemical cells – reversible and irreversible cells – EMF – measurement of
EMF– electrode potential – Nernst equation (problems) – reference electrodes –
Standard Hydrogen electrode -Calomel electrode – Ion selective electrode - glass
electrode and measurement of pH – electrochemical series – significance –
potentiomettic titrations (redox - Fe²+vs dichromate and precipitation – A+vs. CI-)
and conductometric titration (acid-base – HCI vs. NaOH).

Contents:

Electrochemistry
1. Nernst Equation
2. Ion selective electrode
3. Emf series / electrochemical series
4. Conductometric Titrations
5. Potentiometric Titrations
6. Reference Electrode ( SHE)/ Normal Hydrogen Electrode (NHE)
7. Secondary Reference Electrode (Saturated Calomel Electrode (SCE)
8. Measurement of emf of a cell

Ion Selective Electrode:

ION SELECTIVE ELECTRODE

Definition Construction Principle Representation Working Advantages Disadvantages Applications

Definition
It is defined as the ability to respond only to the activity of a particular ion and
develop a potential.
Eg. Glass Electrode

Glass Electrode
Construction
 It consists of thin walled glass bulb which have low melting point and high
electrical conductivity.
 It contain a platinum wire in 0.1 M HCl
Principle
A potential difference exists at the interface between glass (Na+ ions) and the
solution (H+ ions of solution). The magnitude of this difference of potential is given by
°
EG = E G + 0.0591 log [ H+]
°
EG = E G - 0.0591 log pH [ pH = -log [ H+] ]
Representation
Pt, 0.1M HCl/Glass

Working
Determination of pH of a solution using glass electrode
To determine the pH of a solution, the glass electrode is connected with the calomel
electrode.
From the emf, the pH of the solution can be calculated.
ECell = E Right - E left
°
= 0.2422- (E G - 0.0591 pH)
 °
pH = 0.2422- ECell - E G

0.05
Advantages
Construction easy, results accurate, not easily poisoned and equilibrium achieved
rapidly.

Disadvantages
 It can be used only for the solutions having pH - 0 to 10.
 Special electronic potentiometers are required.

Applications
 It is used to determine Ca2+ ion in boiler feed water, soil, milk, sea water etc.
 It is used in physiological investigations (Ca2+ ion is known to influence bone
formation, muscle contraction, cardiac expansion and contraction and nerve
conduction.

Emf Series / Electrochemical Series:

Definition
The arrangement of various metals in the order of increasing values of standard
reduction potential is called emf series.

Applications of Emf Series:

 Caculation of Standard emf of the cell
 Relative ease of Oxidation or Reduction
 Displacement of one element by the other
 Determination of equilibrium constant for the Reaction
 Hydrogen Displacement Behaviour
 Predicting Feasibility/ Spontaneity of the cell

1. Caculation of Standard emf of the cell

°
Using E , the standard emf can be calculated
° ° °
E Cell = E RHE - E LHE

2. Relative ease of Oxidation or Reduction

Standard Reduction Reaction

Potential
Positive Reduction
Negative Oxidation
 Eg. F ( + 2.87V) Reduction
Li ( - 3.01V) Oxidation

3. Displacement of one element by the other

Metal with more negative reduction potential can displace those metals with less
negative or positive potentials from the solution
°
Eg. E Cu2+/ Cu = + 0.34 V
°
E Zn2+/ Zn = - 0.76 V

4. Determination of equilibrium constant for the Reaction

Equilibrium constant can be calculated using the formula
°
WKT, G = RT ln K = 2.303 RT log K
°
Log K = - G
2.303 RT
°
= nFE
2.303 RT

5. Hydrogen Displacement Behaviour

Metal with negative reduction potential will displace hydrogen from the
solution
°
Eg. Zn + H2SO4 ZnSO4 + H2 ( E zn = -0.76 V)
°
Ag + H2SO4 No Reaction ( E Ag = +0.80 V)

6. Predicting Feasibility/ Spontaneity of the cell

Spontaneity depends on E° value
°
E - Positive ( Reaction Spontaneous)
°
E - Negative ( Reaction non Spontaneous)
°
E - Zero (Reaction Equilibrium)

Conductometric Titrations:

STRONG ACID – BASE TITRATION

Principle

Conductometric titrations are the titrations which involve the measurement of

conductance of a solution with the addition of another solution to get end point.
The change in conductance depends on
 The number of free ions in solution
 Nature of ions (size and mobility of ions)
(HCl Vs NaOH)

Burette NaOH
Pipette HCl
Cell Conductivity Cell
Reaction HCl + NaOH NaCl + H2O
Conductance
Point A High Conductance (Due to the presence of fast moving H+ ions)
Point B Complete neutralization of all H+ ions (Adding NaOH, conductance
decreases and reach the point B)
Point C Conductance begin to increase ( Due to the introduction of fast moving
OH- ions)
Advantage For more accurate end point, used for coloured solutions, dilute
solutions and weak acids
Disadvantage Less accurate when electrolytic concentration is high, only limited
number of redox titration can be carried out.

Graph

Potentiometric Titrations
Principle

It is a titration in which the end point is detected by measuring the change in

potential of a suitable indicator electrode (which responds to the change in concentration)
during the titration.
Redox Titrations ( Eg. Ferrous-Ferric System)
Indicator Electrode Platinum Foil
Reference Electrode Standard Calomel Electrode
Pipette Solution 20 ml of ferrous ion solution (Fe2+) and 20 ml of dilute sulphuric
Acid
Burette Solution Potassium dichromate (K2Cr2O7)
Cell SCE// Fe3+ - Fe2+/Pt
 K Cr O
Reaction 2 2 7
2+
Fe Fe3+ + e-

 A graph is plotted between emf against volume of K2Cr2O7.

 When K2Cr2O7 is added, concentration of ferric ion Fe3+ increases which in turn
gradually increases the potential.
 At end point the entire [Fe2+] converted [Fe3+], the emf suddenly increases.
 After the end point, there is no change in potential
 The end point is the point, where the slope of the curve is maximum.

Graph

Precipitation Titrations
( Eg: Silver Nitrate Vs Chloride ion)

Indicator Electrode Silver/Silver chloride electrode

Reference Electrode Standard Calomel Electrode
Pipette Solution 20 ml of Sodium chloride ion solution
Burette Solution Silver Nitrate Solution
Cell Ag/Ag+// Hg2Cl2, Cl-/ Hg
Reaction AgNO3 + NaCl AgCl + NaNO3

 A graph is plotted between emf and volume of AgNO3.

 At the beginning, as the salt (AgCl) is so sparingly soluble, the concentration of
Ag+ ion in solution progressively increases and soon it reaches a maximum value.
Hence the emf of the cell also increases.
 At end point – once all the chloride ions are precipitated, excess addition of AgNO3
rises the concentration of Ag+ ions in solution which in turn rises the emf very
rapidly.
 The end point is the point where the slope of the curve is maximum.

Graph
Reference Electrode ( SHE)/ Normal Hydrogen Electrode (NHE):
Construction
 It can be prepared by bubbling hydrogen gas of 1 atmospheric pressure over
platinised platinum.
 It is immersed in a solution of HCl (1M).
 Electrode potential is zero at all temperature.
Potential
E = 0V

Representation
Pt,H2 (1 atm) /H+ (1M); E = 0V

Reaction
H2(g) 2H+ + 2e-
2H+ + 2e- H2(g)

Secondary Reference Electrode

Saturated Calomel Electrode (SCE)

Construction
 Glass tube containing mercury at the bottom over which mercurous chloride
is placed
 Rest of the vessel is filled with saturated solution of KCl
 Bottom of the tube is sealed with a platinum wire
Potential E = + 0.2422V

Representation Hg, Hg 2Cl 2(s), KCl (Sat. Solution)

Reaction
 Cathodic Reaction: Hg 2Cl 2(s) + 2 e- 2 Hg(l) + 2 Cl-

Measurement of single Electrode Potential Zn using saturated calomel electrode

 Saturated calomel electrode is coupled with another Zn electrode
 E of Zn electrode < E of calomel electrode
Hg 2Cl 2(s) + 2 e- 2 Hg(l) + 2 Cl-
Ecell = E right - E l eft
Ecell = E cal - E Zn
E Zn = E cal - Ecell
= +0.2422 – 1.0025
= - 0.7603 volt

Measurement Of Emf Of A Cell:

Principle:
Poggendorff‟s Compensation Principle:
Emf of the cell is just opposed or balanced by an emf of standard cell (external emf)
so that no current flows in the circuit.

Diagram: (Refer Book)

Construction:
 Potentiometer consists of a uniform wire AB
 A Storage battery(K) is connected to the ends A and B of the wire through a
rheostat(R)
 Unknown emf (x) – connecting its
 Positive to Pole A
 Negative to Sliding contact (D) through galvanometer G.
 Sliding contact is free to move along the wire AB till no current flows through the
galvanometer.
 Emf of unknown cell is directly proportional to the distance AD
Ex AD
 Unknown cell (x) is replaced by a standard cell (s) in the circuit
 Sliding contact is again moved, till there is null reflection in the galvanometer
 Emf of the standard cell Es is directly proportional to the distance AD‟
Es AD‟
Emf of the unknown cell x = Length AD
Enf of the unknown cell s Length AD‟

Ex = AD
Es AD‟

Emf of the unknown cell = AD X Es

AD‟
 Part - A
1. What is single electrode potential?
2. What are reference electrodes?
3. What is secondary reference electrode?
4. Define emf of a cell.
5. Write the representation of Hydrogen electrode.
6. Define Redox reaction.
7. What is emf series?
8. Zn reacts with dilH2SO4 to give H2. But Ag does not. Why?
9. Define electrochemical cell. Give example.
10. What is salt bridge? Write its function.
11. What are electrolytic cells?
12. Write Nernst equation.
13. Define Helmholtz electrical double layer.
14. Explain oxidation and reduction potential of an electrode.
15. Write the representation of calomel electrode.
16. Suggest a method to determine the electrode potential of zinc.
17. Write the representation of glass electrode.
18. What are reversible cells?
19. What are irreversible cells?
20. (a) Write the cell reaction of Hydrogen electrode.
(b)What are the limitations of glass electrode?
(c)What are the merits of conductometric titrations?
PART – B ( 8 MARKS )
21. Derive Nernst equation for single electrode potential.
22. Describe the construction and working of calomel electrode with cell
reaction and diagram.
23. Describe glass electrode. How can it be used for determining the pH of the solution?
24. What is an irreversible cell? Explain the irreversibility taking a suitable example.
25. Describe the emf measurement of an electrochemical cell by poggendorff‟s balancing
method.
26. Explain the applications of electrochemical series.
27. Explain acid –base titrations conductometrically.
28. What is the principle of potentiometric titration? Discuss the redox titrations.
29. Explain the working and construction of hydrogen electrode. (SHE)
30. (a) Calculate the electrode potential of zinc dipped in 0.1M ZnSO4 at 25oC.
(b)Calculate the emf of iron –copper voltaic cell. Given the standard electrode potential
of copper and iron are +0.34 V and -0.44V respectively.
UNIT II CORROSION AND CORROSION CONTROL

Chemical corrosion – Pilling – Bedworth rule – electrochemical corrosion – types –

galvanic corrosion – differential aeration corrosion – factors influencing corrosion –
corrosion control – sacrificial anode and impressed cathode current methods –
corrosion inhibitors – protective coatings – paints – constituents and functions –
metallic coatings – Hot dipping(Zn)-electroplating (Au) and electrolysis Plating (Ni).

CONTENTS
Corrosion and Corrosion Control
1. Electrochemical or Wet Corrosion
2. Electroplating
3. Corrosion Control By Cathodic Protection
4. Corrosion Inhibitors
5. Differential Aeration Corrosion
6. Factors Influencing the Rate of Corrosion
7. Mechanism of Drying of Drying Oils
8. Electroless Plating

Corrosion and Corrosion Control

Dry or chemical corrosion:

Attack of metal surface by O2, Hydrogen sulphide, SO2, N2

3 Types of dry corrosion

Corrosion by O2 or Corrosion by H2 Liquid metal corrosion

Oxidation corrosion

I Corrosion by O2:
Direct attack of O2 at low or high temperature
Mechanism
i)Formation of metal ions

M oxidation M2+ + 2e-

ii) Oxygen changes to ionic form
½ O2 + 2e- O2-
iii) Metal – 0xide film formation

M + ½ O2 M2+ + O2- = MO
Growth of oxide film occurs perpendicular to metal surface (refer diagram on book)
 Nature of Oxide Film

Stable oxide layer Unstable oxide layer Volatile oxide layer

i) Adsorbed tightly to i) Occurs mainly on i) oxide layer volatiles easily
metal surface noble metals

ii) diffusion of oxygen ii) Metal oxide M+ O2 ii) no further corrosion

not take place occurs.
iii) No further corrosion Eg: Oxides of Pt, Ag Eg: MoO3
occurs
Eg: oxides of Al, Sn, Pb

Protective or non- protective oxide film

Pilling bed worth ratio: Ratio of volume of oxide formed to the volume of metal consumed.
I a) Volume of oxide layer formed < Volume of metal
 b) Oxide layer porous and non-protective
Eg: Oxides of alkali metals

II a) Volume of oxide layer formed > Volume of metal

b) Oxide layer non- porous and protective
Eg: Oxides of heavy metals

II Corrosion by H2

Corrosion by H2

H2 embrittlement ( ordinary temperature) Decarburization (high temp)

Fe + H2S FeS + 2H H2 2H

H + H H2 C + 4H CH4

Formation of cracks and blisters The process of decrease in

on metal surface due to high carbon content in steel is
pressure of H2 gas termed as decarburization of
steel

III Liquid metal corrosion

Occurs due to
a) Either dissolution of solid metal by a liquid metal (or)
b) Liquid metal may penetrate into the solid metal

Electrochemical or Wet Corrosion:

Wet corrosion occurs in two conditions

i) When two dissimilar metals are contact with each other
ii) When a metal is exposed to varying concentration of oxygen
Mechanism:
At Anode
Oxidation occurs
M M2+ + 2e-
At Cathode
Reduction occurs. Depends on nature of the environment

a) Acidic environment:
Hydrogen evolution occurs
2H+ + 2e- H2
b) Neutral environment:
Hydroxide ion formation takes place
½ O2 + 2e- + H2O 2OH-

Hydrogen Evolution Type:

All metals above H2 in electrochemical series undergo this type of corrosion
Example:
Iron metal in contact with HCl

At Anode:
Fe Fe2+ + 2e- (Oxidation)
At Cathode:
2H+ + 2e- H2 (Reduction)

Absorption of oxygen or Formation of hydroxide ion type corrosion:

Example:
Iron metal in contact with a neutral solution

At Anode:
Fe Fe2+ + 2e- (Oxidation)

At Cathode:
½ O2 + H2O + 2e- 2OH-
Net Corrosion reaction is
Fe2+ + 2OH- Fe(OH)2 (Reduction)

Electroplating:

Principle:
It is the process in which the coating metal is deposited on the base metal by
passing a direct current through an electrolytic solution containing the soluble salt of
coating metal.

Objectives:
On Metals:
i) To increase the resistance to corrosion.
ii) To improve the hardness
On Non-Metals:
i) To increase strength
ii) To preserve and decorate the surfaces of wood, glass, plastics etc.,
iii)
Process:
Object to be coated first treated with dil.Hcl or dil.H2SO4
Cathode Object to be coated
Anode Gold foil
Electrolyte AuCl3
Additives for strong and Glue, Gelatin
adherent coating
To improve brightness Brightening Agents
Optimum temperature 60oC
Optimum current 1 – 10 mA/cm2
Density
When current is passed gold dissolves in solution and deposits on the object

Various chemical reactions:

AuCl3 ionises as

AuCl3 Au3+ + 3Cl-

At Cathode:
Au3+ ions moves to cathode and deposits as Au metal

Au3+ + 3e- Au
At Anode:
Free chloride ions moves to the anode.

Au + 3Cl- AuCl3 + 3e-

Corrosion Control By Cathodic Protection

a) Sacrificial Anodic protection method:

The metal to be protected is made cathode. It is connected with more active
metal. Corrosion will concentrate only on the active metal. Thus original metal is
protected. Hence this process is known as sacrificial anodic protection method.
Applications:
i) Used for the protection of ships and boats.
ii) Protection of underground pipelines, cables from soil corrosion
iii) Calcium metal is employed to minimize soil corrosion.

b) Impressed current cathodic protection method:

The corroding metal is converted from anode to cathode. This is done by
applying a current in opposite direction of corrosion current.

Method:
Negative terminal of the battery is connected to the metal. Positive terminal of
the battery is connected to an inert anode. Inert anode used are graphite, platinised
Titanium. The anode is buried in a “back fill” to provide electrical contact.
Applications:
Structures like tanks, pipelines, ships etc can be protected.

Corrosion Inhibitors:

Anodic inhibitors:
It prevents corrosion occurring at the anode. It forms an insoluble
compound with metal ions. These precipitate forms a protective film and prevents
corrosion.
Example:
Chromates, nitrates, phosphates of transition elements.

Cathodic inhibitors:
It prevents corrosion occurring at cathode.
In acidic solution:
Hydrogen evolution occurs.
2H+ + 2e- H2
Corrosion can be reduced by
i) Slowing the diffusion of H+ ions. This is done by adding amines, pyridines.
ii) Increasing over voltage. This is done by adding antimony and arsenic oxides.
In a neutral solution:
Formation of hydroxide ion occurs.
½ O2 + 2e- + H2O 2OH-

Corrosion can be reduced by

i) Eliminating O2. Done by adding Na2SO3, N2H4 etc.,
ii) Eliminating OH-. Done by adding Mg, Zn or Ni salts.
Vapour Phase inhibitors:
This readily vapourise and form a protective layer on the metal surface.
Example:
Dicyclohexyl ammonium nitrate, benzotriazole etc.,

Differential Aeration Corrosion:

This type of corrosion occurs when a metal is exposed to varying concentration of
O2 or any electrolyte on the surface of the base metal.
Example:
Metals partially immersed in water (or) conducting solution.

Mechanism:
Metal part which is above the solution is more aerated and hence becomes
cathodic.
Metal part which is inside the solution is less aerated and hence becomes anodic.
At Anode:
 Corrosion occurs
M M2+ + 2e-
At Cathode:
Hydroxide ions are produced.
½ O2 + 2e- + H2O 2OH-
Example:
Pipeline corrosion:
Pipelines passing from one type of soil example from clay(less aerated) to sand
(more aerated) undergo differential aeration corrosion.

Factors Influencing the Rate of Corrosion:

i) Nature of the metal

a) Position in emf series:
Metals above hydrogen in emf series undergo corrosion easily. Greater the
difference in their position faster is the corrosion rate.
b) Relative areas of the anode and cathode:
The rate of corrosion will be more when the cathodic area is larger.
c) Purity of the metal:
100% pure metal will not undergo corrosion. Higher the percentage of
impurity, faster is the rate of corrosion.
Example:
%Purity of Zinc 99.999 99.99 99.95
Corrosion Rate 1 2650 5000

d) Nature of corrosion product:

If the corrosion product is soluble in the medium, the corrosion rate will be
faster. If it is volatile, then also corrosion rate will be faster.
e) Nature of the surface film
If the surface film is porous and non-protective, it bring about further corrosion.
If the surface film is non-porous and protective, it prevents further corrosion.
f) Over voltage or over potential:
The over voltage of a metal in the corrosive environment is inversely
proportional to corrosion rate.
ii) Nature of the environment
a) Temperature:
The rate of corrosion is directly proportional to temperature.
b) Humidity:
The rate of corrosion will be more, when the humidity in the environment is high.
c) Presence of corrosive gases:
Acidic gases like CO2, SO2, H2S and fumes of Hcl, H2SO4 etc increases
corrosion
d) Presence of suspended particles:
 Particles like Nacl, (NH4)2SO4 with moisture increases corrosion.
e) Effect of pH:
The rate of corrosion will be maximum when the corrosive environment is acidic
i.e pH is less than 7.

Mechanism Of Drying Of Drying Oils:

Refer Book Page No: 3.5

Electroless Plating

Principle:
Electroless plating is a technique of depositing a noble metal on a
catalytically active surface of the metal to be protected by using a suitable reduging
agent without using electrical energy.

Metal ions + Reducing Agent Metal + Oxidised product

Process:

Step 1: Pretreatment and activation of the surface:

The surface to be plated is first degreased by using organic
solvents or alkali, followed by acid treatment.
Example:
The surface of stainless steel is activated by dipping in hot solution
of
50% dil.H2SO4

Step 2: Plating bath :

Nature of the Name of the Quantity(g/l) Function

compound compound
Coating solution NiCl2 20 Coating metal
Reducing agent Sodium 20 Metal ions reduced
Hypophosphite
Complexing agent Sodium succinate 15 Improves the quality
Buffer Sodium acetate 10 Control the pH
Optimum pH 4.5 -------------- ----------------
Optimum 93˚C -------------- ----------------
Temperature

Step 3: Procedure

The pretreated object is immersed in the plating bath for the required time.

At Cathode:

Ni2+ + 2e- Ni

At Anode:

H2PO2- + H2O H2PO3- + 2H+ + 2e-

Net Reaction:
 Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+

Applications:

1. Electroless Ni plating is extensively used in electronic appliances.

2. Electroless Ni plating is used in domestic as well as automotive fields.

UNIT – II PART - A

1. Define galvanic corrosion.

2. Give any three differences between chemical and electrochemical corrosion.
3. What is Pilling – Bedworth rule?
4. What is decarburization?
5. What is electroplating (or) electrodeposition?
6. State the basic design rules in controlling corrosion.
7. What are the characteristics of gold plating?
8. What is anodizing?
9. What is pitting corrosion?
10. What are the possible reaction at the of an aqueous corrosion cells?
11. How does the liquid metal cause corrosion in metals?
12. What is differential aeration corrosion?
13. Relate the rate of corrosion with temperature.
14. How does impressed current cathodic method carried out?
15. What are vapour phase inhibitors?
16. What is the function of extender in the paints?
17. What is metallic coating?
18. What are the functions of driers in the paint?
19. What is the role of pigment in paint? Give two examples.
20. Explain why magnesium corrodes faster when it is in contact with copper than
when it is in contact with Iron.

UNIT II PART - B
111.Discuss the mechanism of electrochemical corrosion.
112. Write notes on differential aeration corrosion.
113. Explain the control of corrosion by the use of sacrificial anode and by the
impressed current cathodic production.
114. What are corrosion inhibitors? Classify different types of inhibitors with example.
115. What is paint? What are the constituents and their function?
116.What is electroless plating? How is electroless Ni plating carried out?
117. How the hot dipping process (galvanizing) carried out?
118. Explain the mechanism of chemical corrosion.
119. What is electroplating? How copper plating carried out?
120. Write the mechanism of drying oil in paint industry .
UNIT III FUELS AND COMBUSTION
Fuels-Types-Calorific value – Coal – proximate and ultimate analysis-metallurgical
coke – manufacture by Otto-Hoffmann method – Petroleum refining– cracking –
catalytic cracking methods-knocking – octane number and cetane number – synthetic
petrol – Fischer Tropsch and Bergius processes – Gaseous fuels- water gas, producer
gas, CNG and LPG. Flue gas analysis – Orsat method – theoretical air for combustion
(problems).

CONTENTS

Fuels and Combustion

1. Synthetic Petrol
2. Otto Hoffmann‟s method
3. Flue gas Analysis
4. Producer gas
5. Water gas
6. Analysis of Coal
7. Refining of Petroleum

Fuels and Combustion

Synthetic petrol (Fischer-Tropsch process):

Synthetic Petrol :
Hydrogenation
Solid coal Liquid fuels ( Synthetic Petrol )
Fischer-Tropsch process :
12000c mixed with hydrogen
C + H2 O CO + H2 Mixture
coke steam Water gas

To remove H2S Passed through Fe2O3

To remove Organic sulphur Passed through Fe2O3 + Na2CO3

Purified gas
 Compressor (5-25 atm)

Converter ( 200 – 3000c)

Polymerisation

Condenser Mixture of saturated & Unsaturated

hydrocarbons

Crude oil

Gasoline Heavy oil

Cracking
Gasoline

Synthesis of Gasoline by Bergius Process:

Heavy oil H2 gas
Finely Powdered coal Paste Pumped into converter
Tin (or) 400 - 4500c
Nickel oleate 200 – 250 atm

Saturated Hydrocarbons

decomposition

Mixture of lower hydrocarbons

Condenser

Crude oil
 Gasoline Middle oil Heavy oil

H2 Fresh coal dust

Gasoline Recycled for making paste

Gasoline yield = 60% of the coal used

Ot t o Hoffman n ’ s met
h od : Significance :
i) Increase the thermal efficiency of the carbonization process
ii)Recover the valuable by-products
Process :
12000c
Coal in silica chamber Hot generators
( Length 10 - 12 m
Height 3 – 4 m
Wide 0.4 – 0.45 m )

1st & 4th 2nd & 3rd

Heated by hot flue gases Used for heating the incoming

air &gas mixture
Regenerative system of Heat economy :
For economical heating, direction of inlet gases & flue gases are changed
frequently
Recovery of by-products :
Liq.NH3 spray
Flue gas Tar & dust dissolves Ammonia is recovered
steam coil water spray

Naphthalene gets condensed NH4OH

cooled water spray
Petroleum spray
 Benzene gets condensed

Purifier packed with moist Fe2O3

H2S is retained

Coal gas (used as gaseous fuel)

Advantages :
 Recovery of valuable by-products
 Less carbonization time
 Regenerative system of heat economy

Proximate Analysis of Coal:

Determination of % of

Moisture content Volatile matter Ash content Fixed carbon

i) Moisture content :
, 100 – 1050c
1 g of air-dried coal Loss in weight of coal is calculated
1 hr, electric hot-air
oven

Loss in weight of the coal

% of Moisture in coal = x 100
Weight of air-dried coal

ii) Volatile Matter :

Muffle furnace, 7 min

Moisture removed coal Loss in weight of coal is noted
covered with lid 950 + 200c

Loss in weight of the coal

% of volatile matter in coal = x 100
Weight of moisture free coal
 iii) Ash content :
Moisture & volatile ½ hr
matter removed coal Loss in weight of coal is noted
without lid 700 + 500c

Loss in weight of the coal

% of ash content in coal = x 100
Weight of dried coal

iv) Fixed Carbon :

% of Fixed carbon in coal = 100 - % of ( Moisture content + Volatile matter

+ Ash content )

Significance of Proximate Analysis :

S.NO CONTENTS SIGNIFICANCE

i) Reduces Calorific value of coal
1 High Moisture
ii) Consumes more heat
High volatile i) Reduces Calorific value of coal
2
matter ii) Burns and produces high smoke
A good i) Reduces Calorific value of coal
High Ash
quality coal has 3 ii) Blocks the air supply through High
content
calorific value. the fuel For
High calorific More Fixed i) Greater calorific value
4
value, coal carbon ii)Helps in designing the furnace
must contain
1. Low Moisture content
2. Low Volatile matter
3. Low Ash content
4. More Fixed Carbon

Ultimate Analysis of Coal:

Determination of % of
 Carbon&Hydrogen Nitrogen Sulphur Ash Oxygen

i) Carbon & Hydrogen content :

O2
A known amount of coal Formation of CO2 & H2O
Combustion Apparatus

Reactions :

C + O2 CO2

H2 + ½ O2 H2O

KOH Tube :
 CO2 vapour is absorbed
 Increase in weight of the KOH tube = Weight of CO2
Anhydrous CaCl2 Tube :
 H2O vapour is absorbed
 Increase in weight of the CaCl2 tube = Weight of H2O
From the weight of CO2 & H2O,
% of Carbon & Hydrogen is calculated

ii) Nitrogen Content :

Kjeldahl’s method :
Con.H2SO4,
Powdered Coal Ammonium sulphate (clear solution)
K2SO4 Catalyst
NaOH
Std N/10 HCl
Neutralisation takes place NH3

Reactions :

2N + 3H2+H2SO4 (NH4)2SO4
(NH4)2SO4+2NaOH 2 NH3 + Na2SO4 +2 H2O
NH3 + HCl NH4Cl
 From the volume of HCl consumed,
% of Nitrogen is calculated

i) Sulphur Content :
Burnt in
A known amount of coal Sulphate
Bomb calorimeter
Extracted with water

Extract

BaCl2

Filtered, dried & weighed BaSO4

From the weight of BaSO4,

% of Sulphur is calculated

iv) Ash content :

Moisture & volatile ½ hr

matter removed coal Loss in weight of coal is noted
0
without lid 700 + 50 c

Loss in weight of the coal

% of volatile matter in coal = x 100
Weight of air-dried coal

v) Oxygen content :

% of Oxygen in coal = 100 - % of ( Carbon + Hydrogen + Sulphur

+ Ash content )

S.NO CONTENTS SIGNIFICANCE

i) Increases calorific value of coal
High Carbon &
1 ii) Helps in the classification of
Hydrogen
coal
2 High Nitrogen No calorific value
 i) Increase calorific value
High Sulphur
3 ii) It produces SO2 , SO3 and
content
corrosion takes place
i) Low calorific value
High Oxygen
4 ii) Increases moisture holding
content
capacity of coal

A good quality coal has High calorific value. For High calorific value, coal
must contain
1. High Carbon & Hydrogen content
2. Low Nitrogen content
3. Low Sulphur content
4. Low oxygen content

Flue gas Analysis:

Flue gas :

Mixture of gases like CO2 , CO, O2 etc

Orsat’s Apparatus : (Diagram Refer Book)

 It consists of horizontal tube
 At one end has U-tube containing fused Cacl2
 In other end has graduated burette with water reservoir

Working:
 3-way stop cock is opened
 Water and air is excluded from the burette
 3-way stop cock is connected to flue gas supply
 Flue gas is sucked into the burette and volume of flue gas is adjusted by
raising and lowering the reservoir
 3-way stop cock is closed

ABSORPTION
BULB REAGENTS
OF GASES
Potassium
1
hydroxide CO2
2 Alkaline Pyrogallol O2
Ammoniacal
3
Cuprous chloride
CO

Absorption of CO2
  The gas enters into the bulb – I where CO2 present in the flue gas is
absorbed by KOH
 Decrease in volume of flue gas in the burette indicates the volume of CO2
Absorption of O2
 The gas enters into the bulb – II where O2 present in the flue gas is absorbed
by alkaline Pyrogallol
 Decrease in volume of flue gas in the burette indicates the volume of O2

Absorption of CO
 The gas enters into the bulb – III where CO present in the flue gas is
absorbed by Ammoniacal Cuprous chloride
 Decrease in volume of flue gas in the burette indicates the volume of CO
Remaining gas in the burette after the absorption of the CO2 , CO & O2 is
Nitrogen

Significance :

 Gives an idea about the complete or incomplete combustion process

 Flue gas with more CO shows incomplete combustion and demand of oxygen
Flue gas with more O2 shows complete combustion and excess of oxygen

Producer gas:

Constituents Percentage (%)

CO 30
N2 51 - 56
H2 10 – 15
CO2+CH4 rest

Calorific value : 1300kcal/m3

Construction:
 It consists of tall steel vessel lined with refractory bricks
 It has cup and cone feeder at the top and a water gas exit

Manufacture :

Air + steam
Red hot coke Producer gas
11000c
Zones present :

i) Ash Zone :
  Lowest zone contains ash
 Air and steam is preheated
ii) Combustion or Oxidation Zone :
 Zone next to ash zone
 Exothermic reactions take place
 Temperature of the bed reaches around 11000c

C + ½ O2 CO

C + O2 CO2
iii) Reduction Zone :
 Middle zone
 Endothermic reactions take place
 Temperature of the coke bed falls to 10000c
iv) Distillation or Drying zone
Uppermost layer of the coke bed
Tempertaure : 400 - 8000c
Uses :
i) As a reducing agent in Metallurgy
ii) For heating muffle furnace
Water gas:

CONSTITUENTS PERCENTAGE(%)
CO 41
H2 51
N2 4
CO2+CH4 REST

Calorific value : 2800kcal/m3

Construction:
It consists of tall steel vessel lined with refractory bricks
It has cup and cone feeder at the top and a water gas exit
Manufacture :
Air & steam passed alternatively
 Red hot coke Water gas
900 – 1000 c0

Various Reactions :

Endothermic reactions
H = +VE
i) Step 1 : Steam is passed through the red hot coke to produce CO & H2
( Temperature falls)
C + H2O CO + H2

ii) Step 2 : Air is blown to raise the temperature (1000˚C)

C + O2 CO2
Uses :
ii) In the synthesis of ammonia
ii)In the synthesis of gasoline in Fischer Tropsch Process

Refining of Petroleum:

Crude oil : Mixture of oil, water and unwanted impurities

Step-1
Crude oil Separation of water by Cottrell‟s process
Flow between two
highly charged
electrodes water removed crude oil

CuO

Purified crude oil CuS

4000c, Iron retort

Oil is vaporized
Fractionating column

Fractions having higher boiling point condense at lower trays

Fractions having Lower boiling point condense at higher trays
 Straight run gasoline

( Refer book Page – 4.18 for various fractions , composition and uses)
UNIT III PART - A
21. Define carbonization.
22. What is cracking? Give example.
23. What is knocking? Write the chemical structure.
24. Define leaded petrol.
25. Define cetane number.
26. Define octane number.
27. What are LPG and CNG? Give the composition.
28. Define GCV and NCV.
29. What is coalification?
30. Name the important of calorific values.
31. Name the various methods of proximate analysis.
32. What is meant by the term „Fixed Carbon‟?
33. All coking coals are caking coals. But all caking coals are not coking coals. Why?
34. What is meant by refining of petroleum?
35. What is producer gas?
36. Define the calorific value of fuel?
37. What is water gas?
38. Calculate the volume of air (volume % of O2 in air = 21). Require for complete
combustion of 1 litre of CO.
39. Give the Dulong‟s formula for the calculation of GCV & NCV.
40. What are the molecular mass and the density of the air?
UNIT – III PART - B
131. Explain the proximate analysis of coal. Give its significance.
132. Discuss the principle steps in to refining of crude petroleum.
133. Describe the Otto – Hoffman method of coke manufacture and the recovery of
various byproducts.
134.What is water gas? How it is manufacture? Give the various chemical reactions..
135.Explain physiochemical principles involved in the manufacture of producer gas.
136.Describe the manufacture of synthetic petrol by Bergius process.
137.Explain the Flue gas analysis by Orsat apparatus with neat diagram.
138.Explain the fixed bed catalytic cracking of gasoline.
139.Discuss the manufacture of synthetic petrol by Fischer – Tropsch method.
140.Explain the moving bed catalytic cracking of gasoline
UNIT IV PHASE RULE AND ALLOYS
Statement and explanation of terms involved – one component system – water system
– condensed phase rule – construction of phase diagram by thermal analysis – simple
eutectic systems (lead-silver system only) – alloys – importance of ferrous alloys –
nichrome and stainless steel – heat treatment of steel, non-ferrous alloys – brass and
bronze.
CONTENTS

Phase Rule and Alloys

1. Water system
2. Pb-Ag System
3. Thermal analysis
4. Non-ferrous alloys

Phase Rule

Water system:

Water exists in three possible phases namely solid, liquid and vapour.

Curve OA

 Vaporization curve
 Equilibrium between water and water vapour
 Water Water vapour
 F=1; Univariant.
 Beyond the critical temperature only water vapour will exist
Curve OB
Sublimation curve
Equilibrium between ice and vapour.
Ice Vapour
 F=1, Univariant
 Beyond the absolute zero only ice will exist.

Curve OC

 Melting point curve

 Equilibrium between ice and water
 Ice Water
 F=1, Univariant
 OC inclined towards Pressure indicates melting point of ice
decreases with increase in pressure
Triple point
  Three phases are in equilibrium at this point.
 Equilibrium between solid, water and vapour.
 Ice(s) Water(l) vapour(g)
Curve OB1
  Vapour pressure curve
 Metastable equilibrium will exist.
 Super – cool water vapour
Areas

AOC-Water
BOC-Ice
AOB-Vapour
F=2
(OR)

Curve Name Equation Comp Phase Degree of IMPORTANT POINTS

Area onent freedom
Point
OA Vapourisati Water Vapour 1 2 1 a)Extend upto temp 374oc
on curve of b)Beyond this temperature
water Vapour exist.
OB Sublimation I ce Vapour 1 2 1 a)curve OBextend upto – 27
curve of ice b)Below this temperature ice
exist.
OC Melting I ce Water 1 2 1 a)OC inclined towards press
point curve axis.
of ice b)Melting point of ice
decreases with increase of
pressure.
O(Tripl Triple point I ce Water 1 3 0 a)at point O Temp -0.0075oc
e point) Vapour pressure-4.58mm
Curve Vapour Super coolwater 1 2 1 a) Super cooled water-water
OB‟(Me pressure cooled below 0oc with out
ta curve of Vapour formation of ice converted to
stable Super water.
eq) cooled
water.
Area AOC - 1 1 2 -
Water
BOC - I ce
AOB -
Vapour

Pb-Ag System:

It is a type of two component system,

 a. A binary system consisting of two substances, which are completely
miscible in the liquid state, but completely immiscible in the solid state
is known as eutectic system.
b. They do not react chemically.
c. Lead silver system is an example of simple euctectic system.
d. Condensed phase rule is used.
Curve AO
 Freezing point curve of Ag.
 Point A is the melting point of pure Ag (961oC)
 Curve AO is the melting point depression of Ag by the addition of
Pb.
 Along this curve AO, solid Ag and the melt are in equilibrium.
Solid Ag Melt
1
 F =1; Univariant.

Curve BO

 Freezing point curve of Pb.

 Point B is the melting point of Pure Pb (327 oC)
 Curve Bo is the melting point depression of Pb by the addition of Ag.
 Along this curve BO, solid Pb and the melt are in equilibrium.
Solid Pb Melt
 F1 = 1; Univariant.

Point O

 Called as Eutectic point.

 Curves AO and BO meet at Point O at a temperature of 303 oC, where
three phase are in equilibrium.
Solid Pb + Solid A Melt
 F1 =0, non-variant.
 At point O, the composition of Pb is 97.4% and 2.6% of Ag.
 Below this point, the eutectic compound and the metal solidify.
Areas

 Area above the line AOB has a single phase (molten Pb+Ag)
 F1 = 2; Bivariant.
 Area below the line AO (solid Ag + liquid melt), below the line BO
(solid Pb+ liquid melt) and below the point O (Eutectic compound +
Solid Ag or Solid Pb) has two phases.
 F1 = 1; Univariant.

Applications of Pattinson’s process for the desilversation of Argentiferous Lead:-

  The Argentiferrous Pb, consisting of a very small amount of Ag (Say
0.1% )
 It is heated to a T above its melting point, so that the system has only
one liquid phase represented by the point P.
 It is then allowed to cool.
 The T falls down along the line PQ.
 As soon as the point q is reached, Pb is crystallized out and the solution
contains considerable amount of Ag.

 On further cooling, more and more Pb is separate out and the amount of
Ag increases until the point O is reached.
 At the point O, the percentage of Ag rises to 2.6%.
 The process of increasing the composition of Ag in the alloy is done by
this method.
Uses

 Suitable alloy composition can be predicted.

 Used in preparing solders and joining two metal pieces together.

(OR)

(Studied at constant Pressure, Vapour phase ignored)

CURVE NAME EQUATION COMPO PHASE DEGRE IMPORTANT POINTS

AREA NENT E OF
FREED
OM
Curve Freezing Solid Melt 1 a)Point A-Melting point
AO point of Ag 2 2 of pure Ag(961oc)
Silver b)Curve OA-Melting
point depression of Ag
by successive addition of
Pb
Curve Freezing Solid Melt 2 2 1 a)Point B-Melting point
BO point of Pb of pure Pb(3270c)
Lead b)Curve OB-Melting
point depression of Pb by
successive addition of Ag
Point O Eutectic Solid + Solid Pb 2 3 0 a)Eutectic
Point Ag Temperature(3030c)
b)Composition-97.4%Pb
Melt 2.6% Ag
c) Below this eutectic
point metal solidify.
 Area a)Above Molten Pb+ Ag 2 1 2
the line
AOB
b)Below Solid Ag +Liquid 2 2 1
line AO melt
c)Below Solid Pb +Liquid 2 2 1
line AO melt
d)Below Eutectic
point O compound + 2 2 1
Solid Ag or Solid
Pb

APPLICATION OF PATTINSONS PROCESS

Argentiferous Lead (small amount of silver)

Heated above its melting point

System consist only the Liquid phase (point P)

Cooling

Reaches the point q (Pb crystallised out containing increasing amount of Ag)

Further cooling

More and more Pb separated along line BO

Point O reached (percentage of Ag = 2.6%)

Thermal analysis

 It is a study of the cooling curves of various compositions of a system

during solidifications.
  It indicates the composition of the solid.
 From this, shape of the freezing point curves for any system can
be
determined.
For a pure substance

 A pure substance in the fused state is allowed to cool slowly

and the T is noted at different time interval.
 The graph is drawn between Temperature and time.
 At the initial, the rate of cooling is continuous.

 When it reaches the Point b, solid begins to appear.

 Now, the Temperature remains constant until the liquid metal is
fully solidified.
 This process is completed at the point c.
 The line „bc‟ represents the equilibrium between the solid and
the liquid melt.
 After the point c, there is a fall in Temperature along the curve
cd.

For a mixture

 If a mixture of two substances in the fused state is allowed to

cool slowly, the cooling curve is obtained.
 The rate of cooling is continuous as in the pure substance.
 When it reaches the point b one substance begins to solidify out
of
the melt.
 It is indicated by a break and the rate of cooling is different.
 On further cooling at the break point c the second compound
also begins to solidify.
 Now the T remains constant until the liquid melt is
completely solidified, which forms the line cd.
 After the break point d cooling of solid mass begins.
 The T of the horizontal line gives the eutectic point or eutectic
temperature.
 The experiment is repeated for various compositions of A and B.

Non-Ferrous Alloys

Refer Book
UNIT – IV PART - A
1. State Gibbs phase rule
2. Define a phase
3. Define a component as applied to phase rule
4. Define variance (or) degree of freedom as applied to phase rule
5. What is a phase diagram?
6. What is maximum number of phases and degree of freedom permissible in a one
component system?
7.What is meant by a triple point in a phase diagram?
8.Define eutectic point in a phase diagram?
9.State the condensed phase rule.
10.Under what circumstance is condensed phase rule applied?
11.What is the condition for two substances to form a eutectic mixture?
12.With respect to phase diagram ,explain the terms solidus and liquidus.
13.Give one example each for the formation of a (i).simple eutectic point (ii).triple point
14.Mention two applications of phase diagram
15.Give the names and number of phase ,components and degree of freedom in the closed
system
(i).CaCO3(s) ------CaO(s) + CO2(g)
(ii) Ice (s)--------- water(l)----------- vapour (g)
(iii) A Mixture of N2 and CO2 (gases) contains 50% each at 300 C and 780 mm Hg
pressure .
16.In the dissociation of ammonium chloride in vacuum the following reaction occurs.
NH4Cl (s) <--------- NH3 (g) + HCl(g)

How many components and phases are in this system?

17. What is Stainless steel?
18. What are brasses? Mention their applications
19. What is nichrome? Mention it‟s applications
20.What is the purpose of heat treatment of steel?

PART - B
1. Discuss briefly the Silver-Lead system with the help of Phase Diagram and its
application (8 marks)
2. Explain the importance of thermal analysis and reduced Phase rule.(8 marks)
3. State Gibb‟s Phase rule.Explain the terms involved in it with suitable examples.(8
marks)
4. What is meant by Phase Diagram?With the help of the Phase diagram,explain triple
point and eutectic point.(8 marks)
5. Discuss different heat treatment methods and their effect on steel.(8 marks)
6. Discuss the importance and purpose of making alloys.(8 marks)
7. What do you mean by Ferrous alloys?Discuss various types of stainless steel and
Nichrome.(1+5+2=8 marks)
8. What do you mean by non-ferrous alloys?Tabulate the various types of brasses ,their
composition and uses.(1+7=8 marks)
9. Explain various types of Bronzes.(8 marks)
10. Determine the F,C and P for the following systems.
(i) Na2SO4.10 H2O(s) -<------------ Na2SO4(s) + 10 H2O(g)
(ii) N2(g)+O2(g) -<------------ 2NO(g) (closed system)
(iii)PCl5(g) -<------------ PCl3(g) + Cl2(g) (2+2+4=8 marks)
11. Distinguish between Brasses and Bronzes.Mentoin and Explain various types of case
hardening process.(2+6=8 marks)
12.What are limitations and advantages of Phase rule? (8 marks)
13.Explain the application of phase rule to one component system with neat phase diagram
( 8 marks)
14.Comment on the following.
(i) Fusion curve of ice has a negative slope whereas the sublimation curve has a
positive slope
(ii) Triple point is an invariant system (4 + 4 = 8 marks)
15.Explain the following with one example each. (2+2+2+2 = 8 marks)
(i) Eutectic Point
(ii) Eutectic mixture
(iii) Condensed system
(iv) Triple point
 UNIT V ANALYTICAL TECHNIQUE
SYLLABUS
Beer-Lambert‟s law- UV-Visible spectroscopy and IR spectroscopy-principles-instrumentation
(problem & Block diagram only) - Estimation of Sodium by flame photometry- atomic absorption
spectroscopy- principle- instrumentation-estimation of nickel by AAS
**********

Contents:
 Introduction to spectroscopy

 Beer-Lambert Law

 Visible and Ultraviolet (UV) Spectroscopy

 Infrared Spectroscopy

 Flame Emission Spectroscopy

 Atomic Absorption Spectroscopy

Spectroscopy

Introduction

Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic

radiation by atoms or molecules (or atomic or molecular ions) to qualitatively or
quantitatively study the atoms or molecules, or to study physical processes. The interaction
of radiation with matter can cause redirection of the radiation and/or transitions between
the energy levels of the atoms or molecules. A transition from a lower level to a higher
level with transfer of energy from the radiation field to the atom or molecule is called
absorption. A transition from a higher level to a lower level is called emission if energy is
transferred to the radiation field or non radioactive decay if no radiation is emitted.
Redirection of light due to its interaction with matter is called scattering, and may or may
not occur with transfer of energy, i.e., the scattered radiation has a slightly different or the
same wavelength.

Absorption

When atoms or molecules absorb light, the incoming energy excites a quantized structure
to a higher energy level. The type of excitation depends on the wavelength of the light.
Electrons are promoted to higher orbitals by ultraviolet or visible light, vibrations are
excited by infrared light, and rotations are excited by microwaves.
An absorption spectrum is the absorption of light as a function of wavelength. The
spectrum of an atom or molecule depends on its energy level structure, and absorption
spectra are useful for identifying of compounds.

Measuring the concentration of an absorbing species in a sample is accomplished by

applying the Beer-Lambert Law.

Emission

Atoms or molecules that are excited to high energy levels can decay to lower levels by
emitting radiation (emission or luminescence). For atoms excited by a high-temperature
energy source this light emission is commonly called atomic or optical emission and for
atoms excited with light it is called atomic fluorescence) or molecular fluorescence For
molecules it is called fluorescence if the transition is between states of the same spin and
phosphorescence if the transition occurs between states of different spin.

The emission intensity of an emitting substance is linearly proportional to analyte

concentration at low concentrations, and is useful for quantitating emitting species.

Scattering

When electromagnetic radiation passes through matter, most of the radiation continues in
its original direction but a small fraction is scattered in other directions. Light that is
scattered at the same wavelength as the incoming light is called Rayleigh scattering. Light
that is scattered in transparent solids due to vibrations (phonons) is called Brillouin
scattering. Brillouin scattering is typically shifted by 0.1 to 1 cm-1 from the incident light.
Light that is scattered due to vibrations in molecules or optical phonons in solids is called
Raman scattering. Raman scattered light is shifted by as much as 4000 cm-1 from the
incident light.

Introduction

The energy levels of atoms are quantized and have definite, discrete energies. The energies
are measured relative to the energy required to remove an electron, which is called the
ionization potential of the atom. The figure shows the energy levels for the H atom.
Transitions between energy levels that involve the absorption or emission of light is the
field of spectroscopy.
H atom energy levels

Ground State of a Diatomic Molecule

Morse potential energy function

Vibrational energy levels given by

Selection rule

Beer-Lambert Law

Introduction

The Beer-Lambert law (or Beer's law) is the linear relationship between absorbance and
concentration of an absorbing species. The general Beer-Lambert law is usually written as:
A = a( ) * b * c
where A is the measured absorbance, a( ) is a wavelength-dependent absorption
coefficient, b is the path length, and c is the analyze concentration. When working in
concentration units of molarities, the Beer-Lambert law is written as:
A= *b*c
where is the wavelength-dependent molar absorption coefficient with units of M-1 cm-1.

Instrumentation

Experimental measurements are usually made in terms of transmittance (T), which is

defined as:
T = I / Io
where I is the light intensity after it passes through the sample and Io is the initial light
intensity. The relation between A and T is:
A = -log T = - log (I / Io).

Absorption of light by a sample

Modern absorption instruments can usually display the data as transmittance, %-

transmittance, or absorbance. An unknown concentration of solution can be determined by
measuring the amount of light that a sample absorbs and applying Beer's law. If the
absorption coefficient is not known, the unknown concentration can be determined using a
working curve of absorbance versus concentration derived from standards.

Derivation of the Beer-Lambert law

The Beer-Lambert law can be derived from an approximation for the absorption coefficient
for a molecule by approximating the molecule by an opaque disk whose cross-sectional
area, , represents the effective area seen by a photon of frequency w. If the frequency of
the light is far from resonance, the area is approximately 0, and if w is close to resonance
the area is a maximum. Taking an infinitesimal slab, dz, of sample:
Io is the intensity entering the sample at z=0, Iz is the intensity entering the infinitesimal
slab at z, dI is the intensity absorbed in the slab, and I is the intensity of light leaving the
sample. Then, the total opaque area on the slab due to the absorbers is * N * A * dz.
Then, the fraction of photons absorbed will be * N * A * dz / A so,

dI / Iz = - * N * dz

Integrating this equation from z = 0 to z = b gives:

ln(I) - ln(Io) = - *N*b

or - ln(I / Io) = * N * b.

Since N (molecules/cm3) * (1 mole / 6.023x1023 molecules) * 1000 cm3 / liter = c

(moles/liter)

and 2.303 * log(x) = ln(x)

then - log(I / Io) = * (6.023x1020 / 2.303) * c * b

or - log(I / Io) = A = *b*c

where = * (6.023x1020 / 2.303) = * 2.61x1020

Typical cross-sections and molar absorptivities are:

(cm2) (M-1 cm-1)

absorption - atoms 10-12 3x108
molecules 10-16 3x104
infrared 10-19 3x10
Raman scattering 10-29 3x10-9

Limitations of the Beer-Lambert law

The linearity of the Beer-Lambert law is limited by chemical and instrumental factors.
Causes of nonlinearity include:

deviations in absorptivity coefficients at high concentrations (>0.01M) due to

electrostatic interactions between molecules in close proximity
scattering of light due to particulates in the sample
fluorescence or phosphorescence of the sample
changes in refractive index at high analytic concentration
shifts in chemical equilibrium as a function of concentration
non-monochromatic radiation, deviations can be minimized by using a relatively
flat part of the absorption spectrum such as the maximum of an absorption band
stray light.

Ultraviolet and Visible Absorption Spectroscopy (uv-vis)

Introduction

UV-vis spectroscopy is the measurement of the wavelength and intensity of absorption of

near-ultraviolet and visible light by a sample. Ultraviolet and visible light are energetic
enough to promote outer electrons to higher energy levels. UV-vis spectroscopy is usually
applied to molecules and inorganic ions or complexes in solution. The uv-vis spectra have
broad features that are of limited use for sample identification but are very useful for
quantitative measurements. The concentration of an analyte in solution can be determined
by measuring the absorbance at some wavelength and applying the Beer-Lambert Law.

Instrumentation

The light source is usually a hydrogen or deuterium lamp for uv measurements and a
tungsten lamp for visible measurements. The wavelengths of these continuous light sources
are selected with a wavelength separator such as a prism or grating monochromator.
Spectra are obtained by scanning the wavelength separator and quantitative measurements
can be made from a spectrum or at a single wavelength.
Schematic of a single beam uv-vis spectrophotometer

Dual-Beam uv-vis Spectrophotometer

Introduction

In single-beam uv-vis absorption spectroscopy, obtaining a spectrum requires manually

measuring the transmittance (see the Beer-Lambert Law) of the sample and solvent at each
wavelength. The double-beam design greatly simplifies this process by measuring the
transmittance of the sample and solvent simultaneously. The detection electronics can then
manipulate the measurements to give the absorbance.

Instrumentation

Schematic of a dual-beam uv-vis spectrophotometer

Visible And Ultraviolet (Uv)

Spectroscopy:

Principle

Transition of valency electrons with in a molecule or ion from a lower

electronic energy level (ground state)E1 & to higher electronic energy level (excited
state)E0.
Amount of energy = E1 _ E0 = h
 Instrumentation

Radiation source (Hydrogen (or) deuterium lamps.

Monochromators - Disperse the radiation

Cells a)sample b) reference (analysis)

Uniform
Inert to solvents
Transmit light

Detector (converts radiation into current)

Recording system. (signal received)

Working:

Radiation source (Hydrogen (or)deuterium lamps.

Monochromators - Disperse the radiation

½ of a beam pass through to transparent cell
Other ½ pass through cell cotains solvents

Cells a)sample b) reference (analysis)

Compare the intensities of two beams.

Intensity of sample beam < Intensity of reference beam

Graph plotted wavelength Vs absorption of light.

Applications:

 Predicting relationship between different groups:

a) between two or more c-c multiple bonds
 b) between c-c & c-o double bonds
c) between c-c double bonds & aromatic benzene ring.
d) Structure of several vitamins.
 QUALITATIVE ANALYSIS
- for aromatic compounds
- comparing UV absorption spectrum of sample with known compounds.

 DETECTION OF IMPURITES
- impurities present intense band
appear

 QUANTITATIVE ANALYSIS
- using Beer‟s law A = - log T = log I0 / It = ЄC x
- Plotting graph between absorbance vs concentration

 DETERMINATION OF MOLECULAR WEIGHT

- Compound converted in to suitable derivative and determined.

 DISSOCIATION CONSTANTS OF ACIDS AND

BASES PKa = pH + log [HA]/ [A-
]

 STUDY OF TAUTOMERIC EQUILIBRIUM

- from the strength of the respective absorption bands
- eg. Keto & enol form
-
 STUDYING KINETICS OF CHEMICAL REACTION
- Change in concentration of a product or a reactant with time.

 DETERMINATION OF CALCIUM IN BLOOD SERUM

Ca (its oxalate) redissolving in H 2SO4 treating Dil.
Ceric sulphate solution absorption of solution (315 nm)

Infrared Absorption Spectroscopy (IR)

Introduction

IR spectroscopy is the measurement of the wavelength and intensity of the absorption of

mid-infrared light by a sample. Mid-infrared light (2.5 - 50 µm, 4000 - 200 cm-1) is
energetic enough to excite molecular vibrations to higher energy levels. The wavelength of
IR absorption bands are characteristic of specific types of chemical bonds, and IR
spectroscopy finds its greatest utility for identification of organic and organometallic
molecules.

Mechanism of IR absorption

The transition moment for infrared absorption is:

R = < Xi | u | Xj dt >
where Xi and Xj are the initial and final states, respectively, and u is the electric dipole
moment operator:
u = uo + (r-re)(du/dr) + ... higher terms.
uo is the permanent dipole moment, which is a constant, and since < Xi | Xj > = 0, R
simplifies to:
R = < Xi | (r-re)(du/dr) | Xj >
The result is that there must be a change in dipole moment during the vibration for a
molecule to absorb infrared radiation.

Examples of infrared active and inactive absorption bands in CO2

There is no change in dipole moment during the symmetric stretch vibration and the 1340
cm-1 band is not observed in the infrared absorption spectrum (the symmetric stretch is
called infrared inactive). There is a change in dipole moment during the asymmetric stretch
and the 2350 cm-1 band does absorb infrared radiation (the asymmetric stretch in infrared
active). A related vibrational spectroscopic method is Raman spectroscopy, which has a
different mechanism and therefore provides complementary information to infrared
absorption.

Infrared Absorption Spectrometers

Introduction
This document describes dispersive and Fourier-transform spectrometers that are used in
infrared absorption spectroscopy.

Dispersive infrared spectrometers

Common light sources are tungsten lamps, Nernst glowers, or glowbars. Dispersive IR
spectrometers use a grating monochromator to select wavelengths and are commonly used
when a single wavelength is desired to monitor the kinetics of a reaction or as a GC or LC
detector.

Schematic of a dispersive IR absorption spectrometer

Infrared Absorption Bands

Introduction

IR absorption spectroscopy uses mid-infrared light (2.5 - 50 µm, 4000 - 200 cm-1) to detect
specific types of chemical bonds in a sample for identification of organic and
organometallic molecules.

Table of characteristic IR bands

Group Bond Appox. Energy (cm-1)

hydroxyl O-H 3610-3640

amines N-H 3300-3500

aromatic rings C-H 3000-3100

alkenes C-H 3020-3080

alkanes C-H 2850-2960

nitriles C=-N 2210-2260

carbonyl C=O 1650-1750

amines C-N 1180-1360

Infrared Spectroscopy - Vibrational

Spectroscopy:

Principle

Absorption of energy by a molecule in the infrared region and transition

occur between vibrational levels.

Instrumentation
Radiation source (Nichrome wire, Nernst glower)

Heated electrically 1200- 20000C

Monochromator

Allow light of required wavelength

Sample cell ( Transparent to IR radiation)

IR Detector ( Photo conductivity cell, Thermocouple, Pyroelectric detector)

Convert thermal radiant energy
Into electrical energy

Recorder (records the signal)

Working
Radiation emitted by source
 2 identical beams
1 beam other beam
Sample cell reference cell
(less intense)
Combine

Oscillating signal detector recorder

Applications of IR Spectroscopy

 Identity of the compound can be established

Particular group of atoms – characteristic absorption band.

 Detection of functional groups

functional groups absorb IR energy nearly same wavelength.

 Testing purity of sample

Pure sample - Sharp, well resolved absorption bands
Impure sample - Broad , poorly resolved absorption bands

 Study of progress of a chemical reaction

Examining IR spectra at different time intervals

 Determination of shape or symmetry of a molecule

For non- linear molecule = 3n- 6
For linear molecule = 3n-5

 To study tautomerism
Keto-enol ( C=O,OH), lacto-lactum(-NH), Mercapto-thioamide(C= S)
Groups show a characteristic absorption band.

 Industrial applications
a) Determination of structure of chemical products
b) Determination of molecular weight
c) Crystallinity.

Flame Photometry (Or) Flame Emission Spectroscopy:

Intensity of emitted light is measured, when metal is introduced in to the flame.

Wave length of colour tells what the element is
Intensity of colour tells how much the element is
 Principle:

Evoporation Vapourisation Dissociation

M+X- MX MX
Thermal Excitation h Emission
X+ M M* M (ground state)
(excited state)

Instrumentation

BURNER - Flame excitation unit

MIRROR -Radiation is emitted: to increase amount of radiation concave mirror used
SLITS - Entrance slits: Permit radiation
Exit slit : Prevent entry of interfering lines

MONOCHROMATOR (OR) PRISM (OR) GRATING (OR)FILT

- Allows the light of required wavelength

DETECTOR – Measures the intensity of radiation

-Converts radiation in to electric current.
AMPLIFIER - Record the current.

Working

Air + Sample solution + Fuel gas mixture

Burnt in burner

Radiation emitted
Passed
Lens,Filter, Detector, Amplifier,Recorder.

Expt carried out for series of std.solutions

Graph plotted between concentration and intensity of emitted light.

Applications of Flame Photometry

1. ESTMATION OF SODIUM BY FLAME PHOTOMETRY

 Instrument is switched on.

Air & gas supply regulated

Distilled water is sent.

Warmed for 10 mins

Instrument adjusted for zero degree

Sodium produces yellow emission at 589 nm, the instrument is set

Readings are noted for a series of std NaCl solution.

Graph plotted between concentration and intensity of emitted light.

Straight line is obtained.
Intensity of
emitted
Light ……………..
.
.
.
.
Unknown concentration

Concentration (mgs/lit)
2. Determination Of Elements :

QUALITATIVE ANALYSIS QUANTITATIVE ANALYSIS

Element max Colour of flame Elements in group I & II (Alkali & Alkaline
Ca 422nm Brick red earth metals.
K 766nm Red Transition elements such as Cu, Fe,Mn
Na 586nm Yellow
Li 670nm Scarlet red

3. Other Applications :

 Medicine, Agriculture, Plant science

 Analysis of biological fluids, tissues
  Soil analysis
 Industrial & natural waters
 Petroleum products
 Cement,glass,metallurgical products

Atomic-Absorption Spectroscopy (AA)

Introduction

Atomic-absorption (AA) spectroscopy uses the absorption of light to measure the

concentration of gas-phase atoms. Since samples are usually liquids or solids, the analyte
atoms or ions must be vaporized in a flame or graphite furnace. The atoms absorb ultraviolet
or visible light and make transitions to higher electronic energy levels. The analyte
concentration is determined from the amount of absorption. Applying the Beer-Lambert law
directly in AA spectroscopy is difficult due to variations in the atomization efficiency from
the sample matrix, and nonuniformity of concentration and path length of analyte atoms (in
graphite furnace AA). Concentration measurements are usually determined from a working
curve after calibrating the instrument with standards of known concentration.

Schematic of an atomic-absorption experiment

Instrumentation

Light source
The light source is usually a hollow-cathode lamp of the element that is being measured.
Lasers are also used in research instruments. Since lasers are intense enough to excite atoms
to higher energy levels, they allow AA and atomic fluorescence measurements in a single
instrument. The disadvantage of these narrow-band light sources is that only one element is
measurable at a time.

Atomizer
AA spectroscopy requires that the analyte atoms be in the gas phase. Ions or atoms in a
sample must undergo desolvation and vaporization in a high-temperature source such as a
flame or graphite furnace. Flame AA can only analyze solutions, while graphite furnace AA
can accept solutions, slurries, or solid samples.

Flame AA uses a slot type burner to increase the path length, and therefore to increase the
total absorbance (see Beer-Lambert law). Sample solutions are usually aspirated with the gas
flow into a nebulizing/mixing chamber to form small droplets before entering the flame.

The graphite furnace has several advantages over a flame. It is a much more efficient atomizer
than a flame and it can directly accept very small absolute quantities of sample. It also
provides a reducing environment for easily oxidized elements. Samples are placed directly in
the graphite furnace and the furnace is electrically heated in several steps to dry the sample,
ash organic matter, and vaporize the analyte atoms.

Light separation and detection

AA spectrometers use monochromators and detectors for uv and visible light. The main
purpose of the monochromator is to isolate the absorption line from background light due to
interferences. Simple dedicated AA instruments often replace the monochromator with a
bandpass interference filter. Photomultiplier tubes are the most common detectors for AA
spectroscopy.

Atomic Absorption Spectroscopy:

Principle

When the light of the required wavelength is allowed to pass through a flame,having
atoms of the metallic species, part of that light will be absorbed by the ground state
gaseous atoms.
Absorption concentration of the atom in the flame.

Instrumentation

Radiation source (eg) Hallow cathode lamp

Emit stable,
Intense radiation

Chopper (rotating shutter)

Breaks the steady light from lamp
 Nebulisation liquid sample
Of liquid
Sample droplets

Burner or flame (total consumption burner, premixed burner)

Convert liquid sample into gaseous state
Convert molecule into atomic vapour
Monochromators (prisms, gratings)
Select a given absorbing line from the spectral lines
Emitted from the cathode lamp.

Detectors (photo multiplier tube)

Photon strikes
Electric current (emf) produced
Amplifier

Recorder (chart recorder) signal recorded.

Working
  Radiation passes through a flame.
 Metallic compounds are decomposed into the atoms
 Atoms absorb a fraction of radiation
 Unabsorbed radiations from flame pass through monochromator
 Unabsorbed radiations is led into detector
 Output is amplified & recorded.

Quantitative Estimation of Nickel

Operating parameters
Wave length 232.0 nm
Light source Hollow cathode lamp (Ni)
Flame type Nitrous oxide-acetylene flame

Step I
Preparation of standard stock Ni solution
Dissolved in 1:1
HNO3
1 gm nickel nitrate (Ni(NO3)2 Diluted to 1 litre with
1%HNO3

Step II
Standard calibration curve
 Seris of standard solutions of Ni are prepared by appropriate dilution.
 Sprayed one by one into flame
 Absorbance measured
 Graph plotted between absorbance & concentration.
Step III
Determination of unknown concentration

 Unknown solution of Ni is aspirated (spray) into flame.

 Absorbance ,Concentration of unknown sample is measured.

Comparison Of Flame Emission & Atomic Absorption

Spectroscopy:

FLAME EMISSION ATOMIC ABSORPTION

SPECTROSCOPY SPECTROSCOPY
1. Purpose Measurement of intensity of Measurement of intensity of
emitted light absorbed light
2. Principle
3. Block Diagram
4. Radiation Source Nil Hollow Cathode Lamp-
Glass tube containing noble
gases made of noble metal
5. Chopper Nil Rotation wheel-breaks the
steady light convert into
alternate current into
alternate current.
6. Burner It should evaporate the It should evaporate the
solvent, decomposes the solvent, decompose the
solid and exite the atom solid and exite the atom.
Convert liquid into gaseous
and then to gaseous state.
7. Nebulisation Nil Formation of small droplets
from liquid
8. Monochromator Allows only the required Allows only the required
wavelength wavelength
9. Detector Convert light into electric Convert light into electric
current current
10.Meter/Amplifier Amplifies the current Amplifies the current
11. Recorder Signals are recorder using Signals are recorder using
12. Working chart(given
Air recorder
pressure) chart recorder
Radiation from the hollow
13. Application produce suction.
Estimation of sodium- cathode lamp
Estimation of is
Nickel –
passed
14.Calibration graph Air+Sample
Sodium solution+
produce yellowFuel Standard
through the flame. Atoms
solutions are
15.Limitation burnt
emission
1.Not in the
used λ=589
burner.
sofor nm
Theis set absorb
determining prepared
1. radiation from
and readings
It is limited only to the
are
emitted
in
all the radiation
instrument.
metal atoms and isStandard
passed
inert flame. Calibration
noted.
metals.2.TheDoes
unabsorbed
not graph isis
provide
through
solutions the
aremirror,
preparedfilter,
and passed
drawn through
between
gases.2. Only liquid samples information on chemical the mirror,
concentration
detector,
readings
must amplifier
are
be used. noted. and filter,
form of detector, amplifier and
the metal.
finally
Calibration Unit-V
recorder
graph is drawn finally recorder
between concentration and
81. What is atomic spectroscopy?
intensity of emitted light
82. What is molecular spectroscopy?
and straight line is obtained.
83. What are absorption and emission
From thespectrums?
calibration graph
84. State Beer-Lambert‟s law.the unknown concentration is
85. Find out the absorbance ornoted.
optical density of a solution if the
transmittance of a solution is 18.5%.
86. What is colorimetry?
87. What is the principle of colorimeter?
88. What is the principle of flame photometry?
89. What is the principle of UV-visible spectroscopy?
90. What are chromophores and auxochrome?
91. What are bathochromic and hypsochromic shifts?
92. What are hyperchromic and hypochromic shifts?
93. What are stretching and bending vibrations?
94. What is the fingerprint region?
95. What is hollow cathode lamp?
 96. What are the various types of electronic transitions?
97. Give the frequency region of Infrared spectrum?
98. How to calaculate the number of vibrational modes for different types of molecules?
99. Write any two advantages of AAS.
100. (a) What is the basic principle of AAS?
(b)What are the components of UV Visible spectrophotometry?
(c) What are the important processes that occur in the flame emission spectroscopy?
(d) Can a colorless compound be estimated using colorimetry? Give example.
(e)Give the limitations of Beer-Lamberts law.
(f)Differentiate AAS and Flame emission spectroscopy.

Unit-V PART - B
141. Derive Beer- Lambert‟s law and write the limitations of its.
142. Explain the principle and instrumentation of flame photometry.
143 Explain the working and instrumentation of UV spectroscopy
144. Explain the principle and instrumentation of IR spectroscopy
145. Estimation of nickel by AAS
146. How will you estimate the sodium by flame photometry?
147. Estimation of Iron by colorimetry.
148. Discuss the principle and working of AAS
149. What is colorimetry? Name the components of colorimeter and their function.
150. (a) Write briefly the applications of IR and UV-Visible spectroscopy.
(b).A solution shows a transmittance of 20% when taken in a cell of 2.5cm thickness.
Calculate it‟s concentration if molar absorption coefficient is 12000dm3mol-1cm-1
(c ). A solution of thickness 2cm transmits 40% incident light. Calculate the
concentration of the solution .Given that ε = 6000 dm3mol-1cm-1

Engineering Chemistry II

Expected Types of Questions based on Topics

Electrochemistry
Nernst Equation - Problems
Ion selective electrode
Emf series / electrochemical series
Conductometric Titrations
Potentiometric Titrations
Reference Electrode ( SHE)/ Normal Hydrogen Electrode (NHE)
Secondary Reference Electrode (Saturated Calomel Electrode (SCE)
Measurement of emf of a cell

Corrosion and Corrosion Control

Electrochemical or Wet Corrosion
Dry Corrosion
 Electroplating
Corrosion Control by Cathodic Protection
Corrosion Inhibitors
Differential Aeration Corrosion
Factors Influencing the Rate of Corrosion
Constituents of Paints

Fuels and Combustion

Otto Hoffmann‟s method
Flue gas Analysis
Producer gas
Water gas
Synthetic Petrol
Analysis of Coal
Refining of Petroleum
Calorific Value and air required for complete combustion of fuels - Problems

Phase Rule and Alloys

Water system
Thermal analysis
Pb-Ag System
Heat Treatment Alloys
Non-ferrous alloys

Analytical Techniques
Colorimetry
Flame Emission Spectroscopy
B.E./B.Tech. DEGREE EXAMINATION, JUNE 2010.
Second Semester (REGULATION 2008)

CY2161-ENGINEERING CHEMISTRY-II

Time: Three hours Maximum: 100 marks

PART A — (10 X 2 = 20 Marks)

1. How will you predict the spontaneity of any redox system using emf?
2. Define a reference electrode with an example.
3. Using chemical equations,state the mechanism of corrosion of iron in weakly
alkaline solution.
4. Give the principle of electro-deposition.
5. Distinguish between coal and coke.
6. What are the advantages of compressed natural gas?.
7. How many phases and components are present in the following system?
CaC03(s)-->CaO(s)+CO2(g).
8. Give the percentage composition of bronz.
9. Calculate the concentration in ug/ml of a solution of organic compound whose molecular mass is
211.2,in 0.1 M HCL giving an absorbance at its lamtamax 281 nm of 0.62 in a 4cm cell.The major
absorptivity at 281 nm is 5372 mole^-1cm^-1.
10. Calculate the number of modes of vibrations for the following molecules : (a)CH4,(b)CO2.

PART B - (5 X 16=80 Marks)

11.i. Differentiate reversible and irreversible cells.Illustrate with examples.

ii. Describe the construction of a saturted calomel electrode.Write its electrode reaction.
Or
12. Give a detailed account of conductometric titrations.

13.i. When does the electrochemical corrosion occur?Describe the mechanism of electrochemical
corrosion.
ii. Write a brief note on cathodic protection methods.
Or
14.i. What are the constituents and their functions in paints?
ii. Explain the main objectives of electro plating.Give an account of the method used in electroplating
of gold.

15.i. How is proximate analysis of coal carried out?What are its significances?.
ii. What is cracked gasoline?How is it obtained?.
Or
16.i. How is flue has analysis carried out using Orsat's apparatus?What are its significances?.
ii. What is synthetic petrol?How is it obtained?.

17.i. State phase rule and explain the terms involved.

ii. Draw and explain the phase diagram of two components system with an example.
Or
18.i. What are the objectivities of heat treatment?Discuss the different methods of heat treatment of
steel.
ii. What are alloys?Write the chemical composition and uses of (1)heat tretable stainless steel and
(2)non-heat treatable stainless steel.

19.i. State Beer-Lambert's law.Mention its applications and limitations.

ii. Explain the instrumentation of IR spectrometer with block diagram .
Or
20.
i. Explain briefly the principle of a flame photo meter.A sample solution is found to contain KCL and
NaCl.How will you determine the amount of NaCl alone present in the solution using a flame
photometer?
ii. Compare: Flame photometry and Atomic absorbtion spectroscopy.
iii. Write a short note on carbon nano tubes.
22. A solution taken in a curve of thickness 1cm transmits 40% incident light.
Calculate the concentration of the solution given that the molar extinction coefficient is
5000dm3 mol-1cm-1.
Given: % T = 40%; T = 0.40 ; x = 1 cm
A = - log T
= - log 0.40
= 0.3980
We know A = Cx
C = A/ x
= 0.3980 / 5000x 1
Concentration = 7.96x 10 -5 mol dm-3