Chemisty - II - NOL

V.S.
Saravanaman
Annapoorana
Lninccrin Collcc
Salcm
Ft6ltFFRlt6
CHFHl3TRY-ll
www.Vidyarthiplus.com
Engineering Chemistry-II
Department of Chemistry, Annapoorana Engineering College, Salem 2
Unit-I
Electrochemistry
Galvanic (or) Voltaic (or) Electrochemical cell
It is a device that produces electrical energy at the expense of chemical energy
produced in a reaction.
A cell consists of two half cells or electrodes.
A half-cell or electrode contains a metal rod dipped in an electrolytic solution.
Electrolytic cell: It is a cell in which electrical energy brings about a chemical
reaction.
Electrochemical cell: It is a device that produces electrical energy at the expense of
chemical energy produced in a reaction.
Differences between electrolytic cell and electrochemical cell.
Electrolytic Cell Electrochemical cell
1. Electrical energy brings about a
chemical reaction.
2. Anode is positively charged.
3. Cathode is negatively changed.
4. Electrons move from anode to
cathode through external circuit.
5. The extent of chemical reaction at the
electrode is governed by Faradays
laws of electrolysis.
6. The amount of electricity passed is
measured by a coulometer.
7. One electrolyte and two electrodes of
the same element are generally used
in these cells.
1. Electrical energy is produced at the
expense of chemical energy.
2. Anode is negatively charged.
3. Cathode is positively charged.
4. Electrons move from cathode to
anode through external circuit.
5. The emf of the cell depends on
concentration of electrolyte and
nature of the metal electrode.
6. The emf of the cell is measured by a
potentiometer.
7. Two different electrolytes and two
different electrodes are often used.
Electrochemical (or) galvanic cell: Daniel cell is a typical galvanic or
electrochemical cell. The cell consists of a zinc rod dipped in ZnSO
4
solution. The
two solutions are interconnected by a salt bridge. The electrodes are connected by a
wire through a voltmeter.
When the cell produces current, oxidation occurs at anode and reduction at
cathode.
Zn Zn
2+
+ 2e
(at anode)
Cu
+2
+ 2e
Cu (at cathode)
Zn + Cu
2+
Zn
2+
+ Cu (net cell reaction)
Daniel cell is represented as
Zn |ZnSO
4
||CuSO
4
| Cu
(IM) (IM)
The Standard emf of the cell is 1.1 volt.
Representation of a galvanic cell
A galvanic cell has two electrodes namely anode and cathode. The following
points are kept in view when a cell is represented:
1) Anode is written on the left hand side and cathode on the right side.
2) The electrode and the electrolyte are separated by a vertical line to denote the
phase boundaries. The physical state is indicated in bracket. For anode, the
electrode is written first and then the electrolyte. (e.g)
Pt |H
2
(g) |H
+
(1M)
(1atm)
Zn |ZnSO
4
(1M)
For cathode, the electrolyte is written first and then the electrode (e.g.)
CuSO
4
(1M)| Cu
3) Concentrations of electrolytes and pressures of gases are mentioned.
cathode.
Zn Zn
2+
+ 2e
(at anode)
Cu
+2
+ 2e
Cu (at cathode)
Zn + Cu
2+
Zn
2+
Zn |ZnSO
4
||CuSO
4
| Cu
(IM) (IM)
Pt |H
2
(g) |H
+
(1M)
(1atm)
Zn |ZnSO
4
(1M)
CuSO
4
(1M)| Cu
cathode.
Zn Zn
2+
+ 2e
(at anode)
Cu
+2
+ 2e
Cu (at cathode)
Zn + Cu
2+
Zn
2+
Zn |ZnSO
4
||CuSO
4
| Cu
(IM) (IM)
Pt |H
2
(g) |H
+
(1M)
(1atm)
Zn |ZnSO
4
(1M)
CuSO
4
(1M)| Cu
4) Direct contact between the electrolyte solutions is indicated by a single vertical line
(|).
If they are connected through a salt bridge two vertical parallel lines (||) are
used.
For example, Daniel cell with a salt bridge is represented as follows:
Zn |ZnSO
4
||CuSO
4
| Cu
(1M) (1M)
5) When emf is mentioned, the temperature is also indicated.
Reversible cells
Cells obeying three conditions of thermodynamic reversibility are reversible
cells.
e.g. Daniel cell
Zn |ZnSO
4
||CuSO
4
| Cu
(1M) (1M)
(i) When an emf of 1.1 volt is applied from external source, no current flows in
the cell. Also no chemical reaction occurs at the electrodes.
(ii) When the external emf applied is slightly higher than 1.1 volt, small current
flows into the cell. Chemical reactions occur at the electrodes. Zn
2+
ions are
reduced. Cu atoms are oxidized.
(iii) When the external emf applied is slightly less than 1.1 volt, current flows in
the opposite direction. Electrode reactions are reversed.
Irreversible Cells :
Cells not obeying the conditions of thermodynamic reversibility are
irreversible cells.
(e.g.) Zinc-silver cell.
Zn | H
2
SO
4(aq)
| Ag
The cell reaction is
Zn + H
2
SO
4
ZnSO
4
+ H
2
|
When external emf slightly greater than the cell emf is applied, the cell
reaction is not reversed. This is because H
2
has escaped.
EMF OF A CELL
It is the potential difference that causes flow of electrons from the electrode of
higher potential to the electrode of lower potential.
EMF of a cell is related to electrode potentials as follows:
EMF of Cell = [Standard reduction potential of RHS electrode]
[Standard reduction potential of LHS electrode]
E cell = E right E left
Measurement of emf of a Cell :
Using Poggendorfs compensation principle, the emf of a cell can be measured
using a potentiometer.
AB is a uniform wire of high resistance. A battery W is connected to the ends
of the wire through a rheostat. The unknown cell X is connected in the circuit. Its
positive pole is connected to A and negative pole to a sliding contact D through a
galvanometer, G. The sliding contact is moved along the wire AB, till the
galvanometer shows null deflection. The distance AD is measured. The emf of
unknown cell is proportional to AD.
Ex o AD ----- (1)
Now the unknown cell is replaced by the standard cell S and the sliding
contact is moved along the wire, until galvanometer shows null deflection. The
distance AD' is measured.
Es o AD' ----- (2)
From equations (1) & (2)
Ex AD
=
Es AD'
AD
Ex = x Es
AD'
Knowing Es, the emf of unknown cell can be calculated.
W
Applications of emf measurement :
1. Potentiometric titrations are performed.
2. Solubility of sparingly soluble salt is determined.
3. Hydrolysis constants of salts are determined.
4. The valency of ions is determined.
5. The standard free energy change of a reaction is calculated using the equation
- G = nFE A
n = Number of electrons involved in the reaction
E = Standard emf of the cell
F = 96500 coulombs.
6. The equilibrium constant K of a reaction is calculated from E
o
.
log K =
nE
0.0591
7. pH of a solution is determined.
Electrode Potential :
When a metal M is dipped in its salt solution, one of the following reactions
occurs depending on the metal :
1. Positive metal ions pass into the solution :
M M
n+
+ ne
-
(oxidation)
(e.g.) When Zn rod is dipped in ZnSO
4
solution, Zn goes into solution as Zn
2+
.
The electrons attach to Zn rod, giving it a negative charge. The negative charge on the
rod attracts positive ions from solution. Thus a double layer of ions is formed close to
the rod.
2. Positive ions from the solution deposit over the metal.
M
n+
+ ne
-
M (reduction)
When Cu rod is dipped in CuSO
4
solution, Cu
+2
ions from the solution
deposit on metal rod. They attract negative ions from solution. Thus a double layer of
ions is formed close to the metal rod. This is called Helmholtz double layer.
As a result a potential difference is set up between the metal and the solution.
The equilibrium value of the potential difference is known as electrode potential.
Factors affecting electrode potential or emf of Cell :
(i) nature of the metal
(ii) temperature
(iii) concentration of metal ions in the solution
Single electrode potential (or) electrode potential :
It is a measure of the tendency of the metal electrode to lose or gain electrons,
when it is in contact with its own salt solution. It is developed due to the formation of
a double layer around the metal rod.
Standard electrode potential :
It is a measure of the tendency of the metal electrode to lose or gain electrons,
when it is in contact with its own salt solution of 1M strength at 25C.
Nernst equation for electrode potential :
Let us consider the reaction
M
n+
+ ne
-
M ----- (1)
The free energy change of this equilibrium AG is related to the equilibrium
constant K by the Vant Hoff isotherm.
[Product]
G=G +RTln -----(2)
[Reactant]
We know, AG = - nFE
AG = -nFE ------ (3)
Substituting equations (1) & (3) in equation (2)
n+
[M]
-nFE = -nFE RTln -----(4)
[M ]
+
Dividing by nF and using the fact that activity of solid metal [M]=1, we have
=
[ ]
( )
At 25C, R = 8.314J/K/mol
F = 96500 coulombs. So equation (5) becomes,
n+
n+
0.0591 1
E = E log ( )
n [M ]
0.0591
E = E log [M ]
n
or
+
This is Nernst equation for a single electrode potential.
Applications of Nernst Equation :
i) To calculate electrode potential of unknown metal.
ii) To predict corrosion of metals.
iii) To set up electrochemical series.
Nernst equation for a reversible cell :
Let us consider the reaction in a reversible cell :
A + B C + D ----- (1)
The free energy change AG of this equilibrium is related to the equilibrium
constant K by the Vant Hoff isotherm.
[Product]
G= G + RTln -----(2)
[Reactant]
We know, AG = - nFE
AG = -nFE ------ (3)
Substituting equations (1) & (3) in equation (2)
[C][D]
-nFE = -nFE RTln -----(4)
[A][B]
+
Dividing by nF
RT [C][D]
E = E- ln -----(5)
nF [A][B]
At 25C, R = 8.314J/K/mol,
F = 96500 coulombs. So equation (5) becomes,
0.0591 [C][D]
E = E log
n [A][B]
This is Nernst equation for a reversible cell.

Measurement of single electrode potential :
It is impossible to determine the value of a single electrode potential. But we
can always measure the potential difference between two electrodes using a
potentiometer, by combining the two electrodes to form a cell. For this purpose we
use reference electrode. Standard hydrogen electrode is called primary reference
electrode. Calomel electrode is called secondary reference electrode.
Standard hydrogen electrode (SHE) (Primary Reference Electrode)
It has a platinum foil connected to platinum wire and sealed in a glass tube.
The platinum foil is dipped in 1M HCl. Hydrogen gas 1 atm pressure is passed
through the side arm of glass tube as shown in the figure. The standard electrode
potential of SHE is taken as zero. The electrode is represented,
Pt | H
2
(g) (1 atm) | H
+
(1M)
The electrode reaction is
2H
+
+ 2e
-
H
2
Limitations (or) drawbacks of SHE:
1) H
2
gas reduces many ions like Ag
+
and affects compounds of Hg, Ag etc.
2) It is difficult to get pure H
2
.
3) The pressure of H
2
is to be kept 1 atm all the time.
4) It is difficult to set up and transport.
5) The electrode potential changes with barometric pressure.
6) A large volume of test solution is required.
7) It cannot be used in solutions of redox systems.
8) The solution may poison platinum surface.
So we use a secondary reference electrode.
Calomel Electrode (Secondary reference electrode):
It consists of a glass tube containing pure mercury at the bottom. A paste of
mercurous chloride covers the mercury. A solution of potassium chloride is present
over the paste. The bottom of the tube is sealed with a platinum wire. There is a side
tube for electrical contact. The electrode is represented as,
Hg | Hg
2
Cl
2(s)
| KCl
(aq)
The electrode reaction is,
Hg
2
Cl
2
+ 2e
-
2Hg + 2Cl
-
The electrode potential is,
- 2
-
RT
E = E ln [Cl ]
2F
RT
E = E ln [Cl ]
F
At 25
o
C,
E = E 0.0591 log (Cl
-
)
For saturated KCl, E = +0.242 volt.
Measurement of single electrode potential using a reference electrode (saturated
calomel electrode):
The given electrode, say zinc electrode, is coupled with saturated calomel
electrode as in the figure. Since the reduction potential of zinc electrode less than that
of calomel electrode, zinc acts as anode and calomel as cathode. The cell reaction will
be
Zn/ ZnSO
4
(1 M) // KCl (satd )/ Hg
2
Cl
2
/Hg
Zn + Hg
2
Cl
2
Zn
2+
+ 2Hg + 2Cl
-
The emf of the cell is measured using a potentiometer. The value of E
cell
=
1.002 volt.
Now, E
cell
= E
right
E
left
= E
cal
- E
Zn
1.002 = 0.242 - E
Zn
E
Zn
= 0.242-1.002
E
Zn
= - 0.76 volt.
Advantages of Reference Electrode (Calomel Electrode):
1. Easy to set up.
2. Easily transportable
3. Long shelf life
4. Reproducibility of emf
5. Low temperature coefficient
6. Electrode can be used in a variety of solutions.
7.
E
o
value is accurately known.
Ion sensitive electrode :
Ion sensitive electrodes have the ability to respond only to a specific ion and
develop a potential ignoring other ions in the solution.
Applications of Ion-sensitive electrode :
i) To determine ions like H
+
, K
+
, Li
+
, etc.
ii) To determine hardness of water (Ca
+2
and Mg
+2
ions)
iii) To determine concentration of F
-
, NO
3
-
, CN
-
etc.
iv) To determine concentration of a gas using gas-sensing electrodes.
v) To determine pH of a solution using H
+
ion sensitive electrode.
The types (classification) of ion-sensitive electrode :
1) Glass membrane electrodes
2) Solid state electrode
3) Pungor or precipitate electrodes
4) Liquid liquid electrode
Glass Electrode (or) Measurement of pH using glass electrode :
Glass electrode contains a thin-walled glass bulb. The glass has low melting
point and high electrical conductivity. 0.1M HCl is present in the bulb. A platinum
wire is inserted in the acid.
When the glass membrane separates two solutions differing in pH, exchange
of H
+
ions takes place between the solutions. As a result a potential is developed
across the membrane. The potential E
G
is given by,
E
G
= E
G
+ 0.0591 pH
Measurement of pH :
The glass electrode is dipped in the given solution. This system is connected to
saturated calomel electrode as in the figure. The emf of the resulting cell is measured
using a potentiometer.
From the emf, the pH of the solution is calculated as below:
E
cell
= E
right
E
left
E
cell
= E
cal
E
glass
E
cell
= 0.242 (E
G
+ 0.0591 pH)
E
cell
= 0.242 - E
G
- 0.0591 pH
pH =
G cell
0.242 - E - E
0.0591
Advantages of Glass Electrode :
i) It is easily constructed and used
ii) Results are accurate
iii) Electrode is not easily poisoned
iv) Equilibrium is quickly attained
v) It can be used in strong oxidizing solutions, coloured solutions and in
presence of metal ions
vi) Using special glass electrode, pH can be measured from 0 to 12.
vii) It is used in chemical, industrial, biological and agricultural laboratories.
Disadvantages or Limitations :
i) Glass has high resistance. So special electronic potentiometer must be
used.
ii) It cannot be used in highly alkaline solutions, in pure ethanol or in acetic
acid. If the solution pH is more than 12, glass membrane is affected by
cations.
Electrochemical Series :
Electrodes are arranged in the increasing order of their standard reduction
potential values. This order is called electrochemical series.
Use or Application or Significance of Electrochemical series or emf series:
1. Calculation of Standard emf of a Cell :
We can calculate the standard emf of a cell, by noting the standard reduction
potentials from the electrochemical series.
E E E
Cell RHS LHS

=
2. Predicting feasibility of a reaction :
The feasibility of a reaction can be predicted from the E value of the
corresponding cell reaction.
If E
Cell
is positive, the reaction occurs spontaneously. If E

Cell
is negative, the
reaction is not feasible.
3. Hydrogen displacement behavior:
We can find out which metals displace hydrogen gas from dilute acids.
Metals with negative electrode potential liberate hydrogen from dilute
sulphuric acid.
(e.g.) Zn with E = -0.76 V displaces H
2
from dil. H
2
SO
4
.
Zn + H
2
SO
4
ZnSO
4
+ H
2
Silver with a positive E value of 0.8, will not displace H
2
from dil.H
2
SO
4
.
Ag + H
2
SO
4
No reaction
4) Determination of Equilibrium constant of a reaction :
Standard electrode potentials are used to determine the equilibrium constants
as follows : We know,
- AG = nFE
- AG = 2.303 RT log K
Hence, 2.303 RT log K = nfE
log K =
nFE
2.303RT
Knowing E, n, F, R and T, K can be calculated.
5) Displacement of one element by another :
Metals with a lower value of reduction potential will displace metals with a
higher reduction potential from their solution.
(e.g.) Zn with E = -0.76V can displace copper (E=+0.34V) or silver
(E=+0.8V) from their solution.
Zn + CuSO
4
Cu+ + ZnSO
4
Potentiometric Titrations :
Principle :
We know the potential of an electrode depends on the concentration of the
solution in which it is dipped. As the concentration changes, the emf also changes.
In potentiometric titration, we measure the emf of the cell between a reference
electrode and indicator electrode. At the end point, there is a drastic change in the
potential.
There are three types of potentiometric titrations :
1) Redox titrations
2) Precipitation titrations
3) Acid-base titrations
1) Redox Titrations :
Let us consider the titration of FeSO
4
versus K
2
Cr
2
O
7
.
FeSO
4
solution is taken in a beaker and a platinum electrode (indicator
electrode) is dipped in it. It is then connected to a calomel reference electrode. The
emf of the resulting cell is measured using a potentiometer.
K
2
Cr
2
O
7
is added in small quantities from the burette. The Fe
2+
concentration
decreases because of the reaction.
Fe
+2
Fe
+3
+ e
-
So the emf changes as the titration proceeds. At the end point there is a drastic
change in the emf.
When the emf is plotted against volume of K
2
Cr
2
O
7
, we get a curve as in
figure. The end point is that point where the slope of the curve is maximum.
A better end point is obtained by plotting AE / AV against the volume of
K
2
Cr
2
O
7
. The resulting curve reaches a maximum at the end point.
2. Precipitation Titration :
Let us consider the titration of silver nitrate versus sodium chloride.
Silver nitrate is taken in the beaker and a silver electrode (indicator electrode)
is dipped in it. It is then connected to a calomel reference electrode through
ammonium nitrate salt bridge. The emf of the resulting cell is measured using a
potentiometer.
NaCl is added in small quantities from the burette. The Ag
+
concentration
decreases because of the reaction.
Ag
+
+ Cl
-
AgCl +
So the emf changes as the titration proceeds. At the end point there is a drastic
change in the emf.
When the emf is plotted against volume of NaCl, we get a curve as in figure.
The end point is that point, where the slope of the curve is maximum.
A better end point is obtained by plotting AE / AV against the volume of NaCl.
The resulting curve reaches a maximum at the end point.
Advantages of Potentiometric Titrations :
1) The apparatus is cheap and readily available.
2) Coloured solutions can be titrated.
3) Very dilute solutions can be accurately titrated.
4) Fixing of end point is easy.
5) Several components may be titrated in the same solution.
6) Indicator is not necessary.
Conductor :
A substance that permits electricity to flow through it is a conductor. (e.g.)
metal, fused salt aqueous solutions of salts, acid base etc.
Non-Conductor :
A substance that does not permit electricity to flow through it is a non-
conductor. (e.g.) plastic, wood, many non-metals.
Electrolyte and its conductivity :
Electrolyte like NaCl completely ionizes in solution.
NaCl Na
+
+ Cl
-
The ions formed move in an electric field to oppositely charged electrodes and
conduct electricity.
Strong electrolyte :
A strong electrolyte is completely ionized in solution at all concentrations.
E.g. NaCl.
NaCl Na
+
+ Cl
-
(100%)
Weak electrolyte :
A weak electrolyte is partially ionized in solution. (e.g.) CH
3
COOH.
CH
3
COOH CH
3
COO
-
+ H
+
(Partial)
Conductometric Titrations :
The conductance of a solution depends on the number of ions, nature and
charge of the ion and its mobility. During a titration, there is a change in the number
and nature of ions in solution. Hence there is a change in conductance. This can be
used to detect end point of a titration. This type of titration is called conductometric
titrations. The temperature should be maintained constant throughout. The titrant
should be 10 times stronger than the solution to be titrated so that volume change is
very small.
Titration of strong acid versus strong base :
Let us consider the titration of HCl versus NaOH.
A known volume of HCl is taken in a beaker. The conductivity cell is dipped
in the acid. The NaOH is added from the burette in small volumes and the
conductance is measured each time. When the alkali is added, the fast moving H
+
ions
is replaced by slow moving Na
+
ions. So the conductance decreases until all the acid
is neutralized.
H
+
+ Cl
-
+ (Na
+
+ OH
-
) Na
+
+ Cl
-
+ H
2
O
After neutralization, further addition of NaOH increases the conductance
sharply due to the presence of fast moving OH
-
ions in the solution.
A graph is plotted between conductance and volume of NaOH added. The
point of intersection of two straight lines gives the end point.
Titration of weak acid versus strong base:
Let us consider the titration of acetic acid versus NaOH.
A known volume of acetic acid is taken in a beaker. The conductivity cell is
dipped in the acid. The NaOH is added from the burette in small volumes and the
conductance is measured each time. When the alkali is added, the conductance of the
solution increases due to the formation of completely ionized sodium acetate.
CH
3
COOH + (Na
+
+ OH
-
) CH
3
COO
-
+ Na
+
+ H
2
O
After neutralization, further addition of NaOH increases conductance sharply
due to the presence of fast moving OH
-
ions in the solution.
A graph is plotted between conductance and volume of NaOH. The point of
intersection of two straight lines gives the end point.
Titration of a mixture of weak and strong acids versus strong base:
Let us consider the titration of a mixture of HCl and CH
3
COOH versus NaOH.
A known volume of HCl and CH
3
COOH is taken in a beaker. The
conductivity cell is dipped in the acid. The NaOH is added from the burette in small
volumes and the conductance is measured each time.
First the strong acid HCl is neutralized and the conductance decreases until all
the acid is neutralized. Then the neutralization of CH
3
COOH takes place. The
conductance slowly increases, until all CH
3
COOH is neutralized. Further addition of
alkali increases the conductance sharply due to the presence of fast moving OH
-
ions
in the solution.
A graph is plotted between conductance and volume of NaOH. The first end
point corresponds to neutralization of HCl. The second end point corresponds to
neutralization of CH
3
COOH.
Advantages (Merits) of Conductometric titrations :
1. Indicator is not necessary.
2. Dilute solutions can be titrated.
3. Accurate end point is obtained.
4. No special attention is necessary near the end point.
5. Coloured solutions can be titrated.
6. Weak acid can be titrated against weak base.
QUESTIONS :
PART A
1. Write about conductivity of electrolyte.
2. What are strong and weak electrolytes?
3. Define electrochemical cell.
4. Differentiate between Galvanic and Electrolytic cells.
5. Distinguish between reversible and irreversible cells.
6. Justify whether the reaction is irreversible or not.
Zn + H
2
SO
4
ZnSO
4
+ H
2
7. What is an electrode potential? How is it developed?
8. Define standard electrode potential.
9. What are the factors that affect electrode potentials?
10. What are the factors that affect the emf of a cell?
11. Define emf of a cell.
12. What is an electrochemical cell?
13. Why is it not possible to measure the potential of an isolated half cell or
electrode?
Answer : Let us connect the metal rod to one arm of voltmeter. When we connect
the other arm to the solution through a wire, the metal wire dipping in the solution
will produce another double layer.
14. Represent a galvanic cell according to IUPAC convention.
15. What is a salt bridge? What are its uses or functions?
Answer : Salt bridge is an inverted U tube containing a paste of KCl or NH
4
NO
3
and agar agar.
Functions or Uses : (i) It gives internal connection between the two electrode
solutions; (ii) It eliminates liquid junction potential; (iii) It maintains electrical
neutrality between electrodes; (iv) It helps accurate measurement of emf of the
cell.
16. Can we use a KCl salt bridge for a cell containing silver electrode?
Answer : No. Because the silver ions react with Cl
-
ions.
Ag
+
+ Cl
-
AgCl +
So, the concentration of Ag+ ion changes and emf also changes.
17. What are the factors that affect emf of a cell?
18. Can we use a nickel and zinc spatula to stir CuSO
4
solution?
Answer: No, Ni and Zn have more negative potentials than Cu. They displace Cu
from its solution.
Ni + Cu
2+
Ni
2+
+ Cu
Zn + Cu
+2
Zn
+2
+ Cu
19. How will you predict the spontaneity of a (redox) reaction using emf value?
20. Define reference electrode. Give example.
Answer : An electrode whose potential is accurately known or whose potential is
arbitrarily fixed is reference electrode. The potential is accurate, stable,
reproducible. The electrode has long shelf life. (E.g.) Calomel electrode.
21. Why cannot we use a voltmeter to measure the emf of a cell?
Answer : The cell current is drawn into the voltmeter. It may lower the cell emf.
We cannot get accurate value.
22. Zn reacts with H
2
SO
4
to liberate H
2
. But Ag does not. Explain.
23. Explain electrochemical series.
24. What are uses or significances of electrochemical series?
25. Write down the cell reaction and expression for the emf of the cell : Zn | ZnSO
4
|| CuSO
4
| Cu.
26. What are the applications of Nernst equation?
27. What are the applications of emf measurement?
28. Give two examples of reference electrodes.
29. What are the advantages of conductometric titrations?
30. What are the advantages of potentiometric titrations?
31. Give some advantages of glass electrode.
32. What are the disadvantages of glass electrode?
33. What are the differences between metallic conductance and electrolytic
conductance?
Metallic Conductance Electrolytic Conductance
1. It involves flow of electrons in a
conductor.
It involves movement of ions in
solution.
2. It does not involve transfer of matter. Transfer of ions occurs.
3. Conductance decreases with increase
in temperature. This is because the
flow of electrons is disturbed.
Conductance increases with increase
in temperature. This is because the
mobility of ions increases.
34. What is ion-sensitive electrode?
35. Write the Nernst equation for Daniel Cell.
Answer : Zn | Zn
2+
|| Cu
+2
| Cu
Zn + Cu
2+
Zn
2+
+ Cu
+2
+2
0.0591 [Zn ]
E = E - log
2 [Cu ]
36. Write the Nernst equation for any one electrode reaction.
Answer : M
n+
+ ne
-
M
n+
0.0591
E = E + log [M ]
n
37. What is Helmholtz double layer?

PART B
1. Describe the construction and working of any galvanic cell.
2. Derive Nernst equation for the emf of a cell.
3. Derive the Nernst equation for the emf of an electrode.
4. What are the conventions followed in the representation of a cell?
5. What are the differences between electrolytic cell and electrochemical cell?
6. How is the emf of a cell measured?
7. Describe standard hydrogen electrode.
8. Explain the construction of calomel electrode. How is it used to measure the emf
of an electrode?
9. What is ion sensitive electrode? What are its applications?
10. Write a note on glass electrode and its use in pH measurement.
11. What is electrochemical series? What are its applications?
12. What is the principle of potentiometric titration? Explain any one potentiometric
titration.
13. What is the principle of conductometric titrations? Describe the conductometric
titration of a strong acid with a strong base.
14. What are the advantages of conductometric titrations? Explain the conductometric
titration of a mixture of strong and weak acids with a strong base.
UNIT - II
CORROSION AND CORROSION CONTROL
Corrosion
It is the gradual deterioration of metals by chemical, electrochemical or
biochemical interaction with the environment.
Causes of Corrosion
Metals occur in nature as their oxides, sulphides carbonates etc. The
chemically combined state is thermodynamically more stable. When we extract a
metal from its ore, the metal is in a higher energy state, which is thermodynamically
unstable. So it tries to go back to the stable state by chemical or electrochemical
interaction with the environment.
Consequences or effects of Corrosion
1. Efficiency of the machine decreases.
2. Plant has to be shut down due to failure.
3. Product is contaminated.
4. The toxic products of corrosion cause health hazards.
5. There is a necessity to over design to allow for corrosion.
Classification or Theories of Corrosion
I. Dry or Chemical Corrosion
II. Wet or Electrochemical Corrosion
I. Dry or Chemical Corrosion
It is due to the attack on metal surface by atmospheric gases like O
2
, SO
2
, H
2
S
etc. (e.g.) Tarnishing of silver by H
2
S.
There are three types of dry or chemical corrosion.
1) Oxidation Corrosion
2) Corrosion by Hydrogen
3) Liquid Metal Corrosion
(1) Oxidation Corrosion
It is due to the direct attack of oxygen on metal surface in the absence of
moisture. Alkali and Alkaline earth metals are corroded at low temperatures. At high
temperatures, most metals except Au, Pt and Ag are oxidized.
Mechanism
i) Oxidation occurs at the surface of the metal to form M
2+
ions.
M M
2+
+ 2e
-
ii) Oxygen takes up the electrons. O
2
is reduced to O
2-
O
2
+ 2e
-
O
2-
iii) O
2-
ion reacts with M
2+
to form metal oxide.
M
2+
+ O
2-
MO
The metal surface is converted to a monolayer of metal oxide. Further
corrosion occurs by diffusion of M
2+
ion through the metal oxide barrier. The growth
of oxide film is perpendicular to the metal surface.
Different types of oxide films are formed.
(i) Porous and Non-Porous Oxide Film (or) Pilling-Bedworth Rule
(a) If the volume of the oxide layer formed is less than the volume of the metal
consumed, the oxide layer is porous.
(e.g.) The volumes of oxides of alkali and alkaline earth metals are less than
the volume of the metal consumed. So the oxide layer is porous and non-protective.
Mechanism
2+
ions.
M M
2+
+ 2e
-
2
is reduced to O
2-
O
2
+ 2e
-
O
2-
iii) O
2-
ion reacts with M
2+
M
2+
+ O
2-
MO
2+
Mechanism
2+
ions.
M M
2+
+ 2e
-
2
is reduced to O
2-
O
2
+ 2e
-
O
2-
iii) O
2-
ion reacts with M
2+
M
2+
+ O
2-
MO
2+
(b) If the volume of the oxide layer formed is greater than the volume of the metal
consumed, the oxide layer is non-porous.
(e.g.) The volumes of oxides of heavy metals such as Pb, Sn are greater than
the volumes of the metal consumed. So the oxide layer is non-porous and protective.
(ii) Stable Oxide Layer
A stable oxide layer is firmly adsorbed on the metal surface. The layer is
impervious and prevents further corrosion. So the layer itself acts as a protective
coating. (E.g.) Oxides of Al, Cu etc.
(iii) Unstable oxide Layer
This is mainly produced on the surface of noble metals such Ag, Au etc. The
unstable oxide decomposes to stable metal and oxygen.
Metal Oxide Metal + Oxygen
(iv) Volatile Oxide
The oxide film volatilizes as soon as it is formed. It leaves fresh metal surface
for further continuous attack. (e.g.) Molybdenum oxide MoO
3
.
(2) Corrosion by Hydrogen
(a) Hydrogen embrittlement
Definition
It is formation of cracks and blisters on the metal by hydrogen gas when the
metal comes into contact with H
2
S.
Iron liberates atomic hydrogen by reacting with H
2
S.
Fe + H
2
S FeS + 2H
Hydrogen atoms diffuse into the voids of metal matrix. When the pressure of
the gas increases, cracks and blisters develop on the metal.
(b) Decarburisation
It is the process of decrease in the carbon content of steel. At high
temperature, molecular hydrogen decomposes to atomic hydrogen.
2
High Temperature
H 2H
When steel is exposed to this environment, carbon in the steel reacts with
atomic hydrogen.
C + 4H CH
4
Hence the carbon content in steel decreases. Collection of methane gas in the
voids of steel develops high pressure and causes cracking.
(3) Liquid Metal Corrosion
It is due to the chemical action of flowing liquid metal at high temperature. It
involves :
(i) dissolution of a solid metal by the liquid metal.
(ii) Penetration of liquid metal into the solid metal.
II. Wet (or) Electrochemical Corrosion :
It occurs under the following conditions.
(i) When two dissimilar metals or alloys are in contact with each other in
presence of an aqueous solution or moisture.
(ii) When the metal is exposed to an electrolyte with varying amounts of
oxygen.
Mechanism of Wet Corrosion
(1) Metal dissolution occurs at the anode.
M M
n+
+ ne
-
(2) Reduction reaction occurs at the cathode in different environments.
(a) Acidic environment : Here hydrogen gas is evolved at the cathode.
2 H
+
+ 2e
-
H
2
|
(b) Neutral environment : In neutral or slightly alkaline medium, hydroxide
ions are formed at the cathode.
O
2
+ 2e
-
+ H
2
O 2OH
-
(a) Hydrogen Evolution type corrosion (In Acidic Medium)
All metals above hydrogen in the electrochemical series tend to get dissolved
in acidic solution with simultaneous evolution of H
2
gas.
(e.g.) When iron comes into contact with non-oxidising acid like HCl,
hydrogen evolution occurs.
At anode : Iron is oxidized to Fe
2+
Fe Fe
+2
+ 2e
-
At cathode : H
+
ion is reduced to H
2
.
2 H
+
+ 2e
-
H
2
|
(b) Absorption of Oxygen (or) Formation of hydroxide ion type corrosion (In
neutral or weakly alkaline medium)
The surface of iron is normally coated with a thin film of iron oxide. But if
some cracks develop on the film, anodic areas are created on the surface. The rest of
the metal part acts as cathode.
(e.g.) When iron is in contact with an electrolyte solution in presence of
oxygen, OH
-
ions are formed.
+2
2
gas.
2+
Fe Fe
+2
+ 2e
-
At cathode : H
+
ion is reduced to H
2
.
2 H
+
+ 2e
-
H
2
|
oxygen, OH
-
ions are formed.
+2
2
gas.
2+
Fe Fe
+2
+ 2e
-
At cathode : H
+
ion is reduced to H
2
.
2 H
+
+ 2e
-
H
2
|
oxygen, OH
-
ions are formed.
+2
Fe Fe
2+
+ 2e
-
At cathode : O
2
is reduced to OH
-
.
O
2
+ 2e
-
+ H
2
O 2OH
-
Overall Reaction
Fe
+2
+ 2OH
-
Fe(OH)
2
If enough oxygen is present, Fe(OH)
2
is oxidized to Fe(OH)
3
.
4Fe(OH)
2
+ O
2
+ H
2
O 4Fe(OH)
3
Differences between chemical corrosion and electrochemical corrosion:
Chemical Corrosion Electrochemical Corrosion
1. It occurs in dry condition It occurs in presence of moisture or
electrolyte.
2. It occurs by the direct chemical attack
on the metal by the environment.
It occurs by the formation of a large
number of anodic and cathodic areas.
3. Even a homogenous metal surface is
corroded.
Only heterogeneous or bimetallic
surface is corroded.
4. Corrosion products gather at the place
of corrosion.
Corrosion occurs at the anode, while
the products form elsewhere.
5. It is a self controlled process It is a continuous process
6. It takes place by adsorption
mechanism.
It follows electrochemical reaction.
(e.g.) Mild scale formation on iron
surface
(e.g.) Rusting of iron under moist
atmosphere
Types of electrochemical corrosion
There are two types:
(i) Galvanic corrosion
(ii) Differential aeration or Concentration cell corrosion
(i) Galvanic corrosion
When two different metals are in contact with each other in presence of
aqueous solution or moisture, galvanic corrosion takes place.
The metal with more negative electrode potential acts as anode. Metal with
less negative electrode potential acts as cathode.
In the Zn-Fe couple as shown in the figure, zinc with more negative electrode
potential, dissolves in preference to iron. Zn acts as anode and Fe as cathode.
Example :
Steel screw in a brass marine hardware easily undergoes corrosion. Iron has
E
0
= -0.44V. For Cu E
0
= +0.34 V. Iron corrodes in preference to Cu.
Prevention
Galvanic corrosion is minimized by providing an insulation between the two
metals.
(ii) Differential aeration (or) concentration cell corrosion
Let a metal be partially immersed in a conducting solution. The part of the
metal above the solution is more aerated and acts like cathode. The less aerated metal
part inside the solution acts as anode and corrodes.
At anode : Corrosion occurs (less aeration)
M M
2+
+ 2e
-
Example :
E
0
= -0.44V. For Cu E
0
Prevention
metals.
M M
2+
+ 2e
-
Example :
E
0
= -0.44V. For Cu E
0
Prevention
metals.
M M
2+
+ 2e
-
At cathode : Production of OH
-
ions (more aeration)
O
2
+ 2e
-
+ H
2
O 2OH
-
Water line corrosion
Let us consider metal tank partially filled up with water. The metal area above
water line is exposed to higher concentration of oxygen (cathode) than the metal
below water level. The metal less exposed to O
2
acts as anode and corrodes. This is
called water line corrosion.
Examples of differential aeration corrosion
i) Pitting or localized corrosion
ii) Crevice corrosion
iii) Pipeline corrosion
iv) Corrosion on wire fence
(i) Pitting Corrosion
It is the localized attack resulting in the formation of a hole due to corrosion.
Example : Metal area covered by a drop of water, sand, dirt etc.
The area covered by the drop or dirt acts as anode and corrodes. The
uncovered area exposed to air or O
2
acts as cathode.
The rate of corrosion is more if the cathodic area is larger and anodic area is
smaller. Thus more material is removed from the same area and a pit is formed.
+2
Fe Fe
2+
+ 2e
-
At cathode : O
2
is reduced to OH
-
.
O
2
+ H
2
O + 2e
-
2OH
-
Overall reaction :
Fe
2+
+ OH
-
Fe(OH)
2
-
O
2
+ 2e
-
+ H
2
O 2OH
-
2
2
acts as cathode.
+2
Fe Fe
2+
+ 2e
-
At cathode : O
2
is reduced to OH
-
.
O
2
+ H
2
O + 2e
-
2OH
-
Overall reaction :
Fe
2+
+ OH
-
Fe(OH)
2
-
O
2
+ 2e
-
+ H
2
O 2OH
-
2
2
acts as cathode.
+2
Fe Fe
2+
+ 2e
-
At cathode : O
2
is reduced to OH
-
.
O
2
+ H
2
O + 2e
-
2OH
-
Overall reaction :
Fe
2+
+ OH
-
Fe(OH)
2
(ii) Crevice Corrosion
Let a crevice or crack between two different metallic objects be in contact
with a liquid. The crevice acts like anode due to less oxygen availability and corrodes.
The exposed area acts as cathode.
(e.g.) rivets, joints.
(iii) Pipeline Corrosion
Buried pipelines or cables passing from one type of soil (clay, less aerated) to
another type (sand, more aerated) get corroded due to differential aeration.
(iv) Corrosion on wire fence
In a wire fence, the wires at the crossings are less aerated than the rest of the
fence. So corrosion takes place at the wire crossings, which become anodic.
Factors influencing corrosion
1. Nature of the metal
(i) Position in emf series
Metals above hydrogen in the electrochemical series corrode easily because
they have negative reduction potential. When two metals are in contact, the more
active metal with a higher negative potential corrodes.
(ii) Areas of anode and cathode
Corrosion will be severe if the anodic area is smaller and cathodic area is
larger. The larger cathodic area demands more electrons. So the anodic area corrodes
faster.
(iii) Purity
100% pure metal will not corrode. (e.g.) Pure Zn does not corrode. If the metal
has trace amount of impurity, it corrodes. (e.g.) Zinc metal with iron or copper
impurity forms an electrochemical cell. The base metal Zn acts as anode and corrodes.
(iv) Over Voltage
Corrosion rate is inversely proportional to the over voltage of the metal in a
corrosive surroundings. (e.g.) The hydrogen over voltage of Zn in 1M H
2
SO
4
is 0.7V.
So the rate of corrosion is low. But when some Cu impurity is present, the over
voltage is reduced and corrosion rate increases.
(v) Nature of the Film
Nature of film formed on the metal surface determines extent of corrosion.
(e.g.) In the case of alkali and alkaline earth metals, the oxide film formed is porous.
The corrosion continues. In the case of heavy metals, the oxide film is non-porous.
The film acts as a protective layer.
(vi) Nature of corrosion product
If the corrosion product is soluble in the corroding medium, corrosion rate is
faster. Similarly if the corrosion product is volatile (e.g. MoO
3
), corrosion will be
more.
2. Nature of Environment
(i) Temperature
Increase of temperature increases corrosion rate because the rate of diffusion
of ions increases.
(ii) Humidity
Rate of corrosion is more, if humidity of environment is high. Moisture acts as
solvent for O
2
, CO
2
etc, to produce electrolyte necessary for formation of corrosion
cell.
(iii) Corrosive gases
Acidic gases like CO
2
, SO
2
, H
2
S etc, produce electrolytes and increase
corrosion.
(iv) Presence of suspended particles
Particles like NaCl, (NH
4
)
2
SO
4
along with moisture are powerful electrolytes
and increase rate of corrosion.
(v) Effect of pH
Generally in alkaline medium, the rate of corrosion is less compared to acidic
medium.
The effect of pH on the corrosion of iron in water is shown in the Pourbaix
diagram as indicated in the figure.
The figure shows zones of corrosion, immunity and passivity. Z is the point at
which pH=7 and corresponding electrode potential is E= -0.2V. This is in the
corrosion zone. So iron rusts under these conditions.
The rate of corrosion can be altered by shifting the point Z to different regions.
1) If the potential is changed to -0.8V by applying external current, iron becomes
immune to corrosion.
2) If the potential applied is positive, iron becomes passive.
3) If the pH is increased to more than 7, corrosion rate decreases.
4) If the pH is reduced to less than 7, rate of corrosion increases.
solvent for O
2
, CO
2
cell.
2
, SO
2
, H
2
corrosion.
4
)
2
SO
4
(v) Effect of pH
medium.
solvent for O
2
, CO
2
cell.
2
, SO
2
, H
2
corrosion.
4
)
2
SO
4
(v) Effect of pH
medium.
CORROSION CONTROL
The rate of corrosion can be controlled by modifying the metal or
environment. Some control methods are
1) proper selection of metals
2) Use of pure metals
3) Use of metal alloys
4) Cathodic protection
a. Sacrificial anode protection
b. Impressed current cathodic protection
5) Changing the environment
6) Use of inhibitors
a. Anodic inhibitors
b. Cathodic inhibitors
7) Applying protective coatings
1) Proper selection of metals
Noble metals are used in ornaments and in surgical instruments, because they
do not corrode. Contact of dissimilar metals far away from each other in
electrochemical series should be avoided.
2) By using pure metals
Pure metals have high corrosion resistance. Even a trace of impurity will lead
to corrosion, the base metal becoming anode.
3) Use of alloys
Use of metal alloys is a good method of protection against corrosion. (e.g.)
Stainless steel containing chromium forms a coherent oxide film which protects steel
against further attack.
4) Proper designing
i. Complicated designs with more angles, sharp edges and corners should be
avoided.
ii. Direct contact of dissimilar metals lead to galvanic corrosion. So insulating
material between the two metals should be inserted.
iii. Smaller area for cathode and larger area for anode must be provided.
iv. Tanks and containers should be designed such that the liquid should be
drained off completely.
v. Crevices should be avoided or they should be filled using fillers.
vi. Bendings should be smooth.
vii. Annealing minimizes corrosion.
5) Cathodic Protection
The metal to be protected is made to act like a cathode. This is achieved in two
ways.
a) Sacrificial anodic protection
Here the metal to be protected is made cathode by connecting it to a more
active metal (anodic metal) called sacrificial anode. Only the more active metal will
ways.
ways.
be corroded, protecting the parent metal. Since the anodic metal is sacrificed, the
method is called sacrificial anodic protection. Mg, Zn are used as sacrificial anodes.
Metal to be protected
Applications
i) Protection of buried pipelines, cables
ii) Protection of ships and boats
iii) Calcium metal is used to minimize engine corrosion
iv) Magnesium sheets are inserted into domestic water boilers to prevent rust
formation.
b) Impressed current cathodic protection method
Here an impressed current is applied in an opposite direction to annul the
corrosion current. Thus the corroding metal is converted to cathode from anode.
The negative terminal of battery is connected to the metal to be protected. The
positive terminal is connected to an inert electrode like graphite. The anode is buried
in a back-fill (containing a mixture of gypsum, coke breeze and sodium sulphate) to
increase electrical contact.
Mg Metal to be protected
Applications
Applications
formation.
Applications
Applications
formation.
Applications
i) Protection of tanks, transmission line towers, underground water pipes, oil
pipe line, ships etc.
Limitations
i) It is costly
ii) It fails when current is switched off.
Corrosion inhibitors
A corrosion inhibitor is a substance that reduces corrosion, when added to the
corrosive environment. There are three types of inhibitors.
i) Anodic inhibitors - chromate, nitrate
ii) Cathodic inhibitors - amines
iii) Vapour phase inhibitors - benzonitrile.
i) Anodic inhibitors
(e.g.) chromate, nitrate, phosphates, tungstate.
The inhibitors form insoluble compound with the newly produced metal ions
and prevent corrosion. This compound is adsorbed on the metal surface to form a
passive film. Anodic inhibitors are used to repair
i) the crack of oxide film on metal surface
ii) pitting corrosion
iii) porous oxide film on metal surface
ii) Cathodic inhibitors
There are two types depending on the nature of cathodic reaction in an
electrochemical reaction.
a) In acidic solution
Example : amines, thiourea, mercaptans act as inhibitors.
Here evolution of H
2
is the cathodic reaction.
2 H
+
+ 2e
-
H
2
|
The corrosion is controlled by slowing down the diffusion of H
+
ions to
cathode by addition of the inhibitor which is adsorbed on the metal surface.
b) In neutral solution
Example : hydrazine, sodium sulphite act as inhibitors.
Here OH
-
ions are formed at cathode.
H
2
O + O
2
+ 2e
-
2 OH
-
Corrosion is controlled by eliminating O
2
from the corroding medium by
adding Na
2
SO
3
. The OH
-
ions can be eliminated by salts of Mg, Zn etc.
iii) Vapour phase inhibitors
(e.g.) benzotriazole, dicyclohexyl ammonium chromate act as inhibitors.
These organic inhibitors readily vapourise and form a protective layer on the
metal surface.
Applications
To prevent corrosion in closed space, storage containers, sophisticated
equipment etc.
PROTECTIVE COATINGS
Metal surface is covered by a protective coating to prevent corrosion. The
coating acts as a physical barrier between the metal surface and the environment. The
coating gives a decorative appeal and also imparts hardness, oxidation resistance and
thermal insulation to the surface. The main types of coating are:
1) Metallic coating
2) Chemical conversion coating
3) Organic coating
4) Non-metallic coating
PAINTS
Paint is a mechanical dispersion of one or more fine pigments in a medium
(thinner + vehicle). When a paint is applied to metal surface, the thinner evaporates.
The vehicle undergoes slow oxidation to form a pigmented film.
Requirements or requisites of a good paint
A good paint should,
i) have good covering power
ii) spread easily on the surface
iii) not crack on drying
iv) adhere well to the surface
v) give a glossy film
vi) be corrosion and water resistant
vii) have stable colour
Constituents of Paint
Pigment
Vehicle
Thinner
Drier
Filler
Plasticizer
Antiskinning agent
1. Pigment
It is a solid that gives colour to the paint.
Functions:
To give colour and opacity to the film.
To provide strength to the film.
To protect film by reflecting U.V. rays.
To provide resistance to abrasion and weather.
Example:
White pigment - White lead, TiO
2
Blue pigment - Prussion blue
Green pigment - Chromium oxide
Red pigment - Red lead, Fe
3
O
4
2. Vehicle (or) Drying Oil
It is the film-forming liquid. It holds the ingredients of the paint. It is a non-
volatile high molecular weight fatty acid of vegetable or animal.
Function
To hold the pigment on the surface.
To form a protective layer by oxidation and polymerization.
To impart water repellency, toughness and durability of film.
To improve adhesion of film.
Example
Lin seed oil, Castor oil.
3. Thinner
It is the volatile portion of paint. It is added to reduce the viscosity of the paint
for easy application on the surface. It easily evaporates after paint is applied.
Functions
To reduce viscosity of paint.
To dissolve vehicle and other additives.
To suspend the pigments.
To increase elasticity of film.
To increase penetration of vehicle.
To improve drying of film.
Example
Turpentine, Dipentine, Xylol.
4. Drier
It is a substance used to speed up drying of the paint.
Functions
To act as oxygen carrier or catalyst.
To provide oxygen essential for oxidation and polymerization of drying oil.
Example
Metallic soap, linoleate and resinate of Co, Mn etc.
5. Extender or Filler
These are white pigments that form bulk of the paint.
Functions
To reduce cost of paint
To prevent shrinkage and cracking of film
To modify shades of pigment
To retard settling of pigments in paint.
Example
Talc gypsum, china-day.
6. Plasticizer
It is added to the paint to provide elasticity to the film and prevent its cracking.
Example
Triphenyl phosphate, Tricresyl phosphate
7. Antiskinning agent
It is a chemical added to the paint to prevent gelling and peeling of the paint.
Example
Polyhydroxy phenols.
Pigment Volume Concentration (P.V.C.)
The P.V.C. of a paint is calculated using the equation.
P.V.C. =
Volume of pigment in the paint
Volume of pigment in the paint + Volume of non-volatile vehicle in the paint
If P.V.C. is high, durability, adhesion and consistency of the paint will be low.
Failure of Paints
A paint may fail due to any one of the following reasons:
i) Chalking : It is the gradual powdering of the paint film on the painted
surface. This happens due to improper dispersion of pigment in vehicle.
ii) Cracking : A paint film cracks due to unequal expansion or contraction of
paint coats.
iii) Evasion : This is very quick chalking.
iv) Blistering : It is due to improper surface exposure of paint to strong
sunshine.
Metallic Coating
Electroplating or Electro-deposition
It is the deposition of coat metal on the base metal by passing direct current
through an electrolytic solution of a soluble salt of the coat metal.
The base metal to be electroplated acts as cathode. The coat metal or an inert
electrode forms anode. The electrolyte is a soluble salt of coat metal.
Objectives or uses or applications of Electroplating:
i) To enhance resistance to corrosion of base metals.
ii) To give a decorative appearance.
iii) To enhance resistance to chemical attack.
iv) To improve hardness and wearing resistance.
v) To obtain polished surface.
Theory
If the coating metal itself forms the anode, the concentration of electrolyte
bath does not change during electrolysis. The metal ions deposited on the cathode are
replenished continuously by dissolution of the anode.
Example
Electroplating of Gold
sunshine.
Metallic Coating
Theory
Example
sunshine.
Metallic Coating
Theory
Example
The object to be gold plated is treated with organic solvent like acetone, CCl
4
to remove grease, oil etc. It is then washed with dil H
2
SO
4
to remove scales, oxides
etc.
The cleaned object is made cathode of electrolytic cell. Anode is a gold plate.
AuCl
3
solution is the electrolyte. When current is passed into the solution, gold ions
migrate to the cathode, get reduced and deposit on the object.
Ionisation : AuCl
3
Au
+3
+ 3Cl
-
At Cathode :
Au
+3
+ 3e
-
Au
At anode :
Au Au
+3
+ 3e
-
Au
+3
+ 3Cl
-
AuCl
3
To achieve a strong adherent and smooth deposit, glue or gelatin is added to
the electrolyte bath.
To enhance the brightness of the deposit, brightening agents are added to the
bath.
Conditions
i) Temperature : 60
0
C
ii) Current density : 1 to 10 mA/cm
2
iii) Low metal ion concentration
iv) Buffer solution to maintain pH.
Applications or Uses or Objectives
i) To give a decorative appearance.
ii) Electrical and electronic applications
iii) To get a thin coating of gold on cheap jewellery
iv) To achieve oxidation resistance, corrosion resistance etc.
Electroless Plating
It is the deposition of a noble metal (from its salt solution) on a catalytically
active metal surface using a reducing agent without use of electric current.
The reducing agent reduces the metal ions. The metal atoms get deposited
over the surface to give a thin uniform coating.
Metal ions + reducing agent metal (deposited) + oxidation product
Example
Electroless nickel plating
The various steps are:
Step I : Pretreatment and activation of the surface:
The surface to be plated is degreased by using organic solvents or alkali and
then accompanied by acid treatment.
i) The surface of stainless steel is activated by dipping in hot solution of 50%
H
2
SO
4
.
ii) Mg alloy surface is activated by giving a thin coating of zinc and copper over
it.
iii) Al, Cu, Fe, brass etc, do not require activation.
iv) Plastic, glass etc, are activated by dipping in a solution of SnCl
2
/HCl and then
in PdCl
2
solution. On drying a thin layer of palladium is formed on the
surface.
Step II : Preparation of plating bath:
The plating bath consists of:
i) Coating Metal : A solution of NiCl
2
20g/lit.
ii) Reducing agent : Sodium hypophosphite 20g/lit.
iii) Exaltant to accelerate coating rate and complexing agent : Sodium succinate
15g/lit.
iv) Buffer to maintain pH at 4.5 : Sodium acetate 10g/lit.
v) Temperature 93
o
C
The pretreated object is immersed in the plating bath for required time. The
following reactions occur and nickel is coated on the object.
Cathode : Ni
2+
+ 2e
-
Ni
Anode : H
2
PO
2
-
+ H
2
O H
2
PO
3
-
+ 2H
+
+ 2e
-
Overall Reaction : Ni
2+
+ H
2
PO
2
-
+ H
2
O Ni + H
2
PO
3
-
+ 2H
+
Uses of Nickel Plating
i) For decorative coating of jewellery, decorative items and automobile spares
ii) For coating of polymers for decorative purpose.
iii) For electronic appliances.
Advantages of electroless plating over electro plating
i) Electricity is not necessary
ii) Complicated parts are uniformly coated
iii) Plastics, glass etc, are easily coated
iv) Good mechanical, chemical and magnetic properties are obtained.
Differences between Electroplating and Electroless plating:
Electroplating Electroless Plating
1. It is done by passing current. It is done by auto catalytic redox
reaction.
2. Separate anode is required. Catalytic surface of the object acts as
anode.
3. Anode reaction: M M
n+
+ ne
-
Anode reaction : R O + ne
-
4. Cathode reaction: M
n+
+ ne
-
M Cathode reaction: M
n+
+ ne
-
M
5. Irregular objects are not satisfactorily
plated
All objects are satisfactorily plated.
6. Object to be coated forms the cathode Object to be coated forms catalytically
active surface.
7. It is carried out on conducting
materials
It is carried out even on insulators.
Control of corrosion by modifying the environment:
There are five methods
1. Deaeration :
Presence of oxygen increases corrosion rate. Deaeration involves removal of
dissolved oxygen by increasing the temperature together with the mechanical
agitation. This also removes dissolved oxygen.
2. Deactivation:
It is the removal of dissolved oxygen by adding chemicals in aqueous solution.
(E.g.) 2Na
2
SO
3
+ O
2
2Na
2
SO
4
3. Dehumidification:
It is the removal of moisture from the air by reducing the relative humidity of
the surrounding air. It can be achieved by adding silica gel or alumina which absorbs
moisture.
4. Alkaline neutralization:
The acidic nature of the corrosive environment is due to the presence of HCl,
SO
2
, CO
2
etc. They are neutralized with alkali spray. E.g. NaOH, lime etc.
5. Using corrosion inhibitors :
A corrosion inhibitor is a substance that reduces the corrosion of a metal when
added to corrosive environment.
PART - A QUESTIONS
1) What is meant by corrosion?
2) Explain the cause of corrosion.
3) Write the consequences of corrosion.
4) Define dry corrosion. Give an example.
5) State Pilling Bedworth rule.
6) What is the importance of Pilling Bedworth rule?
Ans : The protective and non-protective nature of oxide films can be predicted.
7) Explain hydrogen embrittlement.
8) Define decarburization.
9) What is wet corrosion?
10) State the conditions for wet corrosion.
11) Explain liquid metal corrosion.
12) Define Galvanic corrosion.
13) What are the differences between dry and wet corrosions?
14) Explain the terms with examples.
Ans: a) Pipeline corrosion, b) Pitting corrosion, c) Crevice corrosion
15) What is concentration cell corrosion?
Ans : It is the corrosion occurring when a metal is exposed to an electrolyte with
varying amount of oxygen. (E.g.) pitting corrosion.
16) Name some factors that affect corrosion.
17) A steel screw in a brass marine hardware corrodes. Explain.
18) Wire mesh corrodes faster at the joints. Why?
Ans : The joints are welded and stressed. The joints become anodic with respect to
wires. At the anodic part oxidation takes place and the metal is corroded.
19) Iron corrodes faster than aluminium. Explain.
Ans : During corrosion, aluminium forms a non-porous tightly adhering protective
oxide film (Al
2
O
3
) on the surface. So further corrosion is prevented by the film.
20) How does the nature of the metal affect corrosion?
21) Impure metal corrodes faster than pure metal explain.
Ans : The impurity in the metal causes heterogeneity. Tiny electrochemical cells
are formed at the exposed parts, with impurity acting as cathode. The anodic part
corrodes.
22) Bolt and nut made of the same metal is preferred. Explain.
Ans : Such a combination does not permit local galvanic cell formation. So
corrosion cannot take place.
23) How does the nature of environment affect corrosion?
24) Using chemical equations explain the corrosion of iron in weakly alkaline
solutions.
25) Corrosion of metal is the highest at the metal junction in a galvanic couple. Why?
Ans : At the metal junction, air cannot diffuse easily. So the junction is less
aerated and acts as anode. The more aerated remaining part acts as cathode. Thus
a galvanic cell is formed at the junction and the anodic part corrodes.
26) State the basic design rules in controlling corrosion.
27) What is cathodic protection?
Ans : The metal to be protected from corrosion is connected to more active metal
like Mg, Al. The Mg or Al metal forms anode and undergoes corrosion, protecting
the parent metal, which acts as cathode.
28) Why does a drop of oil, water, dust or salt solution resting on iron surface lead to
corrosion?
Ans : The area covered by water or solution is less exposed to air. So the covered
area acts as anode and corrodes. The uncovered area is exposed to air and acts as
cathode.
29) Which of the following metals provide cathodic protection of iron? Al,Zn,Cu,Ni.
Ans : Al and Zn.
30) What is a sacrificial anode? How does it protect a submerged pipeline?
31) How is impressed current cathodic protection carried out?
32) What are (corrosion) inhibitors? Give example.
33) How do inhibitors resist corrosion?
Ans : Anodic inhibitors form a sparingly soluble salt with newly formed metal
ions and get adsorbed on the metal surface. Thus further corrosion is prevented.
Cathodic inhibitors decrease the rate of corrosion, by blocking active metal
sites due to adsorption.
34) What are vapour phase inhibitors? How do they function?
35) State some requirements of a good paint.
36) Describe the role of pigment in a paint. Give an example.
37) Explain the function of drier in a paint.
38) What is the role of extender in paints?
39) Explain the following terms : (a) Plasticizer; (b) Thinner; (c) Vehicle or drying oil.
40) Define electroplating (or) electrodeposition.
41) Mention some factors that affect the quality of electroplating.
42) What is meant by electroless plating?
43) Mention some uses or applications or advantage of (i) Ni plating; (ii) Au plating.
44) What is galvanization?
Ans : The process of giving a zinc coating on a base metal is galvanization.
45) What are the reasons for failure of a paint?
PART - B : QUESTIONS
1) What are the differences between chemical and electrochemical corrosion?
Explain any four factors that affect electrochemical corrosion.
2) Discuss the mechanism of electrochemical corrosion.
3) Explain the various types of dry or chemical corrosion.
4) Discuss the different types of oxide films formed in chemical corrosion.
5) Write notes on a) Hydrogen embrittlement corrosion; (b) Decarburisation;
(c)Liquid metal corrosion.
6) Explain hydrogen evolution type corrosion.
7) Discuss the following types of electrochemical corrosion.
a. Galvanic corrosion
b. Differential aeration or concentration cell corrosion
8) Write briefly about a) Pitting corrosion; b) Pipeline corrosion; c) Crevice
corrosion.
9) What are the factors affecting corrosion?
10) Explain water line corrosion.
11) Proper designing controls corrosion - Elucidate.
12) What is sacrificial anode? Discuss its role in the prevention of corrosion.
13) Write notes on
a. Impressed current cathodic protection
b. Corrosion inhibitors
14) Discuss the effect of pH on corrosion.
15) Explain Galvanic corrosion.
16) What are the important constituents of a paint? Explain the function of various
constituents.
17) What are the main objectives of electroplating? Explain the electroplating of gold.
18) Write a note on nickel electroplating.
19) Give a brief account of electroless plating.
UNIT-III
FUELS & COMBUSTION
Introduction
Most of the industries depend largely upon the power generated by the
combustion of fuels. Any source of heat energy is called as fuel. Fuel is a substance
that combines with oxygen and produce large amount of heat.
Definition
Fuel may be defined as any substance which undergoes combustion with
oxygen to supply heat energy without producing any objectionable gases.
Classification of Fuels
On the basis of physical state fuels are broadly classified into three types.
FUEL
Solid Liquid Gaseous
Characteristics of a good fuel
A good fuel should have the following characteristics
1. It should have high calorific value.
2. It should have moderate ignition temperature.
3. It should contain low moisture content.
4. It should not give any harmful gases during combustion.
5. It should have low% of non-combustible matter.
6. It should be cheap and readily available.
7. It should not undergo spontaneous combustion.
8. Transportation should be easy.
Calorific value
It may be defined as the amount of heat liberated when unit mass of fuel
undergoes complete combustion.
Solid Fuels
Coal
Coal is formed by the decay of vegetable and woody materials under high
pressure and heat.
The process of conversion of woody material to coal is known as coalification
or metamorphism.
Classification of coal by rank
Various types of coal can be recognized on the basis of rank from the parent
material. Various types of coals are;
The progressive transformation of coal by rank results in
i. Decrease in the moisture content
ii. Decrease in H
2
,O
2
,N
2
and S content
iii. Decrease in volatile matter content
iv. Increase in 'C' content
v. Increase in calorific value
vi. Increase in hardness
Analysis of coal
In order to confirm the quality or rank of the coal the following two methods are
carried out. They are,
1) Proximate analysis.
2) Ultimate analysis.
1. Proximate analysis
This method is used for the determination of
i) Moisture content
ii) Volatile matter
iii) Ash content
iv) Fixed carbon
i) Determination of moisture
A known weight of coal sample is taken in silica crucible and it is heated in an
electric hot air oven at 100-110
o
C for 1 hour. After 1 hour, the crucible is cooled and
weighed. The process of heating, cooling and weighing is repeated until the weight of
the crucible becomes constant.
Loss in weight of coal due to moisture content is calculated as follows.
% of moisture = Loss in weight x 100
Weight of coal taken
ii) Determination of volatile matter
The dried sample of coal from the first experiment is covered with a lid and
heated is a muffle furnace at 950
o
c for 7 minutes. Then, the crucible is cooled and
the crucible becomes constant.
Loss in weight of coal due to volatile matter is calculated as follows.
% of volatile matter = Loss in weight x 100
Weight of dried coal
iii) Determination of ash
After the removal of volatile matter, the coal left in the crucible is heated in
the muffle furnace without lid at 700-750
o
C for 30 minutes. Then, the crucible is
cooled and
the crucible becomes constant. The residual weight of coal due to formation of ash
can be
calculated as follows
% of ash = Weight of ash formed x
100
Weight of dried coal after removed of volatile matter
iv) Fixed carbon
It is determined by deducing the moisture, volatile and ash contents from 100.
% of fixed carbon = [100-( % of moisture + % of volatile matter + % of
ash)]
Significance (or) Importance of proximate analysis
S.No.
Coal
Composition Merits
Demerits
1.
Moisture
content
i) It reduces the dry ash
ii) It makes the coal bed in
uniform
i) It increases the transport
charges.
ii) It reduces the calorific
value.
2.
Volatile
matter
Low volatile matter
containing coal is suitable for
the manufacture of coal gas
and metallurgical coke.
i) It reduces the calorific
value
ii) The coal with large
amount of volatile matter
burns with a smoky and
long flame.
3.
Ash
Content
The ash consists of silica,
alumina, magnesia, lime etc.,
which are used in various
small
scale industries.
i) It reduces calorific
value
ii) It increases the
transport charges.
iii) It is a useless matter
and its disposal is a big
problem
4.
Fixed
Carbon
i) It has high calorific value
ii) It helps to design the
furnace and the shape of the
fire box
--------
2) Ultimate analysis
This method is used for the determination of
i) Carbon and hydrogen
ii) Nitrogen
iii)Sulphur
iv) Oxygen
i) Determination of carbon and hydrogen
A known weight of coal sample is heated in the presence of cupric oxide in
combustion apparatus. The carbon and hydrogen in the coal sample are oxidised to
CO
2
and H
2
O respectively.
C + O
2
CO
2
(12) (44)
H
2
+ O
2
H
2
O
(2) (18)
The liberated CO
2
and H
2
O vapour are passed through the tubes containing
known weight of KOH solution and anhydrous CaCl
2
respectively. When the reaction
is over, the tubes are disconnected and weighed. The increase in weight of KOH tube
represent the weight of CO
2
while increase in weight of CaCl
2
tube represents the
weight of H
2
O respectively.
Knowing the weights of CO
2
and H
2
O, the % of C and H can be calculated as
follows:
% of carbon =(12/44) x (Weight of CO
2
formed / Weight of coal sample) x
100
% of Hydrogen = (2/18) x (Weight of H
2
O formed / Weight of coal sample) x
100
ii) Determination of nitrogen
Nitrogen can be determined by Kjeldal's method. In this method, a known
weight of coal sample is heated with con. H
2
SO
4
is the presence of K
2
SO
4
and CuSO
4
.Nitrogen present in the coal sample is converted into ammonium sulphate and a clear
solution is obtained.
The % of N2 present is the coal sample can be determined by volumetric
analysis.
2N +3H
2
+ H
2
SO
4
(NH
4
)
2
SO
4
The solution is then treated with excess NaOH, the ammonia gas is liberated.
(NH
4
)
2
SO
4
+2NaOH 2NH
3
+ Na
2
SO
4
+2H
2
O
The liberated ammonia is distilled over and absorbed by known volume of 0.1N
H
2
SO
4
.
The volume of unused 0.1N H
2
SO
4
is determined by titrating it against 0.1N
NaOH . Thus, the amount of acid neutralized by liberated ammonia is determined.
From this the % of nitrogen can be calculated as follows.
% of N = (V1-V2 ) m1 x Normality x 14 x 100
Weight of coal sample x 1000
% of N = Volume of acid (ml) x Normality x 1.4
Weight of coal sample
Where,
V1 = Initial volume of 0.1 N H
2
SO
4
V2 = Final Volume of 0.1 N H
2
SO
4
(V1-V2) = Acid neutralized by ammonia.
iii) Determination of sulphur
A known amount coal sample is burnt completely in bomb calorimeter. During
burning, sulphur present in the coal is converted as sulphates (SO
4
2-
). It is extracted
by dilute hydrochloric acid. Then it is treated with barium chloride solution. BaSO
4
precipitate is obtained. It is filtered, dried and weighed. From the weight of BaSO
4
,
the % of sulphur can be calculated.
Calculation
S + 20
2
SO
4
2-
+ BaSO
4
32 233
233g of BaSO
4
contains 32g of sulphur
X g of BaSO
4
contains = (32 /233) x X g of sulphur
W g of coal sample contains = (32 /233) x (X/W) g of sulphur
% of sulphur = (32/233) x (X/W) x 100
(or) % of sulphur = (32/233) x (weight of BaSO
4
formed / weight of coal) x 100
Where,
X = weight of BaSO
4
formed
W = Weight of coal sample taken
iv) Determination of oxygen
It is determined by deducting the C & H, N and S from 100
% of oxygen = [ 100- (% of C&H + % of N + % of S) ]
Significance of ultimate analysis
S.No
Elements
in
coal
sample
Merits
Demerits
1.
C & H
i)It increases calorific value
ii)The quality of coal will be
better
Hydrogen produces water
vapour during combination.
Hence, a major portion of
heat energy is wasted.
2.
N
Good quality of coal should
have very little amount of N
Nitrogen is incombustible
one. Therefore, it does not
have any calorific value.
3.
S It increases the calorific It emits harmful gases like
value. SO
2
, SO
3
etc. which make
air pollution.
4.
Oxygen
Lower the % of O 2 higher is
its calorific value.
If the coal has high % of O
2
,
it absorbs moisture and will
reduce the calorificvalue.
Carbonisation
The process of conversion of coal in to coke by strong heating in the absence
of air is known as carbonization. This is also called as destructive distillation.
Caking and coking coals
The product obtained from the carbonisation is soft, plastic and coherent mass
is called coking coal. On the other hand if the product is hard and strong then the coke
is called coking coal.
Metallurgical coke
A coke which is used in metallurgical purposes is called as metallurgical coke.
They are hard, strong, porous and coherent.
Requisites or Characteristics of metallurgical coke
1. It should have minimum percentage of moisture, ash, sulphur and
phosphorous.
2. It should have pores in nature, so that the oxygen can easily contact the carbon
which ensures the complete combustion
3. It should have high mechanical strength to with stand high pressure.
4. It should have low rate of combustion
5. It must be uniform and medium in size.
6. It should have high calorific value
7. It must be cheap and readily available
8. It should burn easily
9. It should have very low reactivity
Manufacture of metallurgical coke - Otto Hoffmann by product oven
Otto Hoffmann oven consists of a number of series of narrow silica chambers.
Each chamber is provided with a charging hole at the top. The oven is provided with
iron door at each end for discharging the coke.
Coal is charged into chambers and the doors are closed. The chambers are
heated by a mixture of preheated air and producer gas at 1200
o
C. The coal undergoes
combustion and liberate waste gases. The heat of the waste gases are used for heat the
regeneration of oven at about 1000
o
C before leaving the chamber.
Therefore, heating of the oven is continued till the liberation of volatile gases
is completely. After 24 hours, the coke is removed from the oven and quenched with
water.
The yield of coke is about 75%.
The valuable by products like coal gas, tar, ammonia, H
2
S benzol etc., are
recovered.
Advantages
1.The carbonization time is less
2.Heating can be done externally by producer gas.
3.Variable by products can be recovered.
Liquid Fuels
Types of Petrol
Depending upon the type and nature of hydrocarbons (paraffin) present in the
crude oil, petrol can be classified into the following three types.
1. Straight run petrol
2. Cracked Petrol
3. Polymer petrol
1. Straight run petrol
The crude oil on fractional distillation yields only about 15 - 20% gasoline.
This is known as straight run gasoline. The quality of straight run gasoline is not so
good. It contains
mainly straight chain paraffin, which ignite readily and more rapidly than any other
hydrocarbons and hence it produces knocking (unwanted sound) in IC engines.
2. Cracked petrol.
Cracking is defined as the decomposition of high boiling hydrocarbons of
high molecular weight into simpler, low boiling hydrocarbons of low molecular
weight.
C
10
H
22
C
5
H
12
+ C
5
H
10
Decane n-Pentane Pentene
B.Pt : 174
o
C B.Pt : 36
o
C
Thus the petrol obtained by cracking is known as cracked petrol.
Types of Cracking
There are two kinds of cracking
1. Thermal cracking
2. Catalytic cracking
1. Thermal Cracking
If cracking is carried out at higher temperature and pressure without any
catalyst, it is called Thermal Cracking. The petrol so obtained is called cracked petrol.
There are two types of thermal cracking.
(i) Liquid Phase Thermal Cracking
In this method, the heavy oil is cracked at a temperature of 475 - 530
o
C under
high pressure of 100 kg/cm
2
to keep the reaction product in liquid state. The cracked
products are then separated into various fractions in a fractionating column. The yield
of gasoline is about 50-60% and the octane number is 65-70.
(ii) Vapour phase thermal cracking
In this method, the heavy oil is first vapourised and then cracked at a
temperature of 600 - 650
o
C under a lower pressure of 10 - 20 kg/cm
2
. The yield of
gasoline is about, 70%. This process is suitable only for those oils which are readily
vapourised.
2. Catatytic Cracking
When cracking is carried out at lower temperature and pressure in the presence
of suitable catalyst, it is called Catalytic Cracking. The catalyst used is aluminium
silicate or alumina.
3. Polymer petrol
The gaseous by-products, obtained during cracking, contain olefins (like
ethylene, propene and butene) and alkanes (like methane, ethane, propane). These
gases undergo polymerization at high temperature and pressure with or without
catalyst to give petrol rich in branched alkanes. Thus the gasoline obtained by
polymerisation is called polymer petrol.
Types of polymerisation
There are two types of polymerisation.
(a) Thermal polymerisation
It is carried out at 500 - 600
o
C and 70 - 350 kg / cm
2
pressure. The products
are gasoline and gas oil mixture, from which gasoline is separated by fractional
distillation.
(b) Catalytic polymerisation.
It is carried out at lower temperature of 150 - 200
o
C in presence of catalyst
like
H
3
PO
4 .
Synthetic petrol
The synthetic petrol can be obtained by hydrogenation of coal. It is nothing
but heating of coal with hydrogen at high temperature and pressure, gasoline or petrol
is obtained. The following two methods are available for the hydrogenation of coal.
1.Bergius process (or) direct hydrogenation.
2.Fischer- Tropsch process (or) indirect hydrogenation.
1.Bergius process (or) Direct hydrogenation of coal
In this process, the finely powdered coal is made in to a paste with heavy oil
and nickel oleate catalyst. The coal paste and hydrogen gas mixture is pumped into
the converter. The mixture is heated to 400-500
0
C under 200-250 atmosphere. During
this process, the unsaturated coal becomes saturated hydrocarbons.
Coal dust + H
2
Catalyst
Saturated hydrocarbon 2
200 - 250 atm
400-450
0
C
The saturated hydrocarbon further undergoes decomposition to yield a mixture
of lower hydrocarbons.
Decomposition
Saturated hydrocarbon Crude oil (or) lower
hydrocarbons
2
The mixture is passed through a condenser, where the crude oil is obtained.
The crude oil is then fractioned to get
i) Gasoline
ii) Middle oil and
iii) Heavy oil.
The middle oil is further hydrogenated in the presence of catalyst to give more
gasoline. The heavy oil is again used for making a paste with fresh coal dust.
2. Fisher Tropsch Process or Indirect hydrogenation of coal
In this process, coal is first converted to coke. Then, coke is heated and steam
is passed over it. Water gas is produced.
C + H
2
O
1200 C
CO + H
2
The water gas is mixed with hydrogen and the mixture is passed through
chamber containing Fe
2
O
3
to remove H
2
S. Then it is passed through a chamber
containing mixture of Fe
2
O
3
+ Na
2
O
3
to remove organic sulphur compounds.
The purified gas is compressed to 5 to 25 atmospheres over a cobalt, thorium
and MgO catalyst on kieselghur at 200
o
C. A mixture of straight chain paraffins and
olefins are
produced.
nCO + 2
n
H
2
C
n
H
2n
+ nH2O
olefin
nCO + (2n+1)H
2
C
n
H
2n+2
+ nH
2
O
parafin
The mixture of olefins and straight chains are passed through a condenser,
where the crude oil is obtained.
The crude oil is then sent through fractionating column to yields,
i) Gasoline and
ii) Heavy oil.
The heavy oil is used for cracking to get more gasoline.
Knocking
Definition
Knocking is defined as a sharp metallic sound produced in the internal
combustion engine by immature ignition of air and gasoline mixture.
Causes of knocking
In an internal combustion engine (Petrol engine), a mixture of gasoline vapour
and air is used as fuel. The mixture is ignited by an electric spark. But in some cases,
the rate of combustion will not be uniform due to unwanted impurities present in
gasoline. Therefore, the rate of ignition increases gradually and the final portion of the
air fuel mixture gets ignited instantaneously, producing an explosive sound called as
knocking. Knocking reduces the efficiency of the engine.
Chemical structure and knocking
The tendency of knocking of a fuel depends upon the molecular structure,
design of engine, fuel-air ratio etc., The knocking tendency decreases as follows.
Straight chain alkanes > Monosubstituted alkanes > Cyclo alkanes > alkanes >
aromatics.
Octane number or octane rating
The knocking tendency of gasoline is usually expressed in terms of octane
number. Isooctane has better resistance to knocking and its antiknock value has been
given as 100. On the other hand n-heptane has very poor resistance to knocking and
its antiknock value has been given as zero.
Definition
Octane number is defined as the percentage by volume of isooctane present in
a mixture of isooctane and n-heptane.
Isooctane (octane No = 100)
CH
3
-CH
2
CH
2
-CH
2
-CH
2
-CH
2
-CH
3
n- heptanes (Octane Number = 0)
Anti-knocking agents/leaded petrol
Knocking can be minimized or prevented by addition of suitable additives
such as tetraethyl lead (CH
2
)
4
Pb to petrol. This petrol is called leaded petrol and the
process is called as sweetening of petrol.
Mechanism of prevention of knocking
Proper combustion causes knocking due to formation of free radical
mechanism. When addition of TEL to petrol, it under goes thermal decomposition to
form ethyl free radical. It combines with the free radicals in knocking process and
thus the chain growth is stopped.
Disadvantages of TEL
During thermal decomposition of TEL, certain amount of lead oxide and
metallic lead may deposit on the plug and cylinder wall. In order to avoid this,
ethylene dibromide is added to dilute the lead pollution.
CH Br
2
Pb+ CH
2
= CH
2
+ PbBr
2
CH Br
2
Diesel oil
It is obtained from fractional distillation of petroleum between 250 - 320
o
C.It
is a mixture of C
15
H
32
to C
18
H
38
hydrocarbons. Its calorific value is about 11000
kcal/kg. It is used as a very good diesel engine fuel.
Ignition lag or Ignition delay
The combustion of a fuel in a diesel engine is not instantaneous and the time
between injection of the fuel and its ignition is called as ignition lag or ignition delay.
Diesel index
The quality of a diesel oil is indicated by diesel index number using the
following formula.
Diesel index number
Specific gravity (API) x Aniline point in F
o
100
Aniline point and specific gravity are noted from API. (American Petroleum Institute)
scale.
Cetane number (or) Cetane rating
The knocking tendency of diesel is usually expressed in terms of cetane
number. Cetane has better resistance to knocking and its antiknock value has been
given as 100. On the other hand 2-methyl naphthalene has poor resistance to knocking
and its antiknock value has been given as zero.
CH
3
- (CH
2
)
14
- CH
3
Cetane (or) hexa decans
(Cetene number = 100)
2 Methyl naphthalene (Cetane number = 0)
The cetane number is defined as the percentage by volume of hexa decane
present in a mixture of hexa decane and o - methyl naphthalene, which has the same
ignition lag as the fuel under test
The cetane number decreases in the following order
Straight chain alkanes > naphthalene > alkenes > branched alkanes > aromatic.
The cetane number of diesel can be improved by addition of additives such as
ethyl nitrate or isoamyl nitrate to diesel. This process is called as doping.
Gaseous fuels
Producer gas
The average composition of the producer gas is as follows.
CO 30%
N 52-55%2
H 8-12%2
CO 3%2
It's calorific value is 1300 Kcal/kg
Manufacture
The furnace consists of a tall steel vessel lined with silica bricks inside. It is
provided with cup and cone arrangement to feed coal into furnace. It is also provided
with inlet and outlet for passing air and steam and removes the ash respectively.
The low grade coal is fed in to the furnace as shown in the figure. Then a
mixture of air and steam is passed over a red hot coke at 1100
0
C; the producer gas is
produced. The following reactions take place in different zones.
Manufacture of producer gas
i) Ash zone
}
The lowest zone consists mainly of ash. It is used to preheat the incoming air
and steam.
ii) Oxidation zone
In this zone, the coal undergoes oxidation to form CO and CO
2
. It is an
exothermic reaction. The temperature of this zone is 1100
0
C.
C + O
2
CO + N
2
(Air) + N2
Exothermic
C + O
2
CO
2
iii) Distillation zone
This is the upper part of the fuel bed. The incoming coal is heated by outgoing
gases to remove volatile matter. The temperature of this zone is 400-500
0
C.
Uses
1. It is used for heating open hearth furnace, glass furnace, muffle furnace etc.,
2. It can be used as reducing agent in metallurgical operation.
Water gas
The average composition of water gas is as follows.
CO = 40 - 42 %
H = 48 - 51%2
CO = 3 - 5 %2
N = 3-6 %2
It's calorific value is about 2800 Kcal/kg.
Manufacture
The furnace consists of a tall steel vessel lined with silica bricks inside. It is
provided with cup and cone arrangement to feed the coke into furnace .At the bottom,
it is provided with two inlets for passing air and steam.
The coke is fed into the furnace as shown in the figure. When steam and air
are passed alternatively over a red hot coke at 900 - 1000
0
C, water gas is produced.
Reaction
The reaction of water gas production involves the following steps.
i. Air is passed through the coke bed, carbon burns to CO
2
and the temperature of the
fuel bed increase to over 1000
0
C.
C + O
2
CO
2
(Exothermic)
ii. Steam is passed through the red hot coke; CO and H2 are produced. The reaction is
being endothermic, the temperature of the fuel and falls below 10000c.
C + H
2
O CO + H
2
( Exothermic)
In order to maintain the temperature of the fuel bed above 1000
0
C, the air and
steam are passed alternatively.
Uses
1. It is used as a source of hydrogen.
2. A mixture of water gas and producer gas is used for the manufacture of
ammonia.
3. It is mixed with hydrogen to produce methanol.
4. It is used for the preparation of carbureted water gas (Water gas + gaseous
hydrocarbon) which can be used for lighting and heating purposes.
Liquefied Petroleum Gas (LPG)
It is obtained as a by - Product during fractional distillation of crude petroleum
oil or by cracking of heavy oil. It consists of propane and butane. It can be readily
liquefied under pressure, so it can be economically stored and transported in
cylinders. The average composition of LPG is as follows.
Constituents
n - Butane = 38.5 %
Iso butane = 37 %
Propane = 24.5 %
Its calorific value is about 25,000 kcal /kg
Uses
1. It is used as a domestic and industrial fuel.
2. It is also used as a motor fuel.
Anna University Questions
1. What is water gas? How is it manufactured? Write the chemical reaction taking
place in
different zones. [June 05, Dec 06]
2. How will you obtain coke by Otto Hottmann method.[June 05, Dec 05, Dec06]
3. Explain the proximate analysis of coal. [June 05, Dec 05, Dec06]
4. How is ultimate analysis carried out? [Dec 06].
5. Describe the different methods by which synthetic petrol can be obtained [Dec 05].
6. How will you obtain synthetic petrol by Bergius process [June 05].
7. Describe the manufacture of gasoline by Fischer Troprch method [ June 06 May
07].
8 .Explain the mechanism of petrol knocks [Dec 06].
9. What are the characteristics of good metallurgical coke [ May 07].
10. How is producer gas manufactured? State its composition and uses [ June 06].
11. What are the significances of proximate and ultimate analysis of coal?
12. Write note on leaded petrol?
13. Explain octane and cetane number?
14. Explain the causes, mechanism and prevention of knocking of petrol in IC
engines.
15. How hydrogenation of coal carried out?
COMBUSTION OF FUELS
Combustion is an exothermic reaction, in which a fuel burns in the presence of
oxygen with evolution of heat and light.
The chief elements present in most of the fuels are C and H. In addition, a
trace amount of S, N etc are also present. During combustion, they undergo oxidation
to produce CO
2
, H
2
O, SO
2
etc.,
C + O
2
CO
2
H
2
+ O
2
H
2
O
S + O
2
SO
2
Factors in influencing the rate of combustion
The factors influencing the rate of combustion are as follows.
- It increases with the increase in surface area of the fuel
- It depends upon the temperature
- It increases with the increases in concentration of the fuel
- It increase with increase in pressure of air
- It depends upon the nature of fuel
- It increases with preheating of fuel and air.
Calorific value:
Calorific value is the most important one which decides the efficiency of the
fuel. It may be defined as the total amount of heat liberated when a unit mass of fuel
undergoes complete combustion.
Units of heat: The quantity of heat can be measured by the following units.
1.Calories: The amount of heat required to raise the temperature of one gram of water
through 1
0
C.
2.Kilocalories: The amount of heat required to raise the temperature of 1 kg of water
through 1
0
C.
3.British thermal unit (BTU): The amount of heat required to raise the temperature
of one pound of water through 1
0
F.
4.Centigrade heat unit (CHU): The amount of heat required to raise the temperature
of one
pound of water through 1
0
C.
Higher and Lower calorific values
a) Higher (or) Gross calorific values (or) GCV (or) HCV
In general, all fuels contain hydrogen whose calorific value can be determined
by experimentally. During combustion, H is converted to H O, the latent heat 2of
steam also gets included in the measured heat. It is called as higher (or) gross calorific
value.
Definition
It may be defined as the total amount of heat liberated when a unit mass fuel
undergoes complete combustion and the products of combustion are cooled to room
temperature.
b) Lower or Net calorific value (or) NCV (or) LCV
In most of the combustion process, the steam and moisture are not condensed,
but they escape along with combustion gases. Hence, a lesser amount of heat is
available. This is known as lower or net calorific value.
Definition
It may be defined as the total amount of heat liberated when a unit mass of
fuel undergoes complete combustion and the products of combustion are allowed to
escape.
[NCV = GCV - Latent heat of steam]
H
2
+ O
2
H
2
O
2gms 16gms 18gms
1 8 9
'1' part of H
2
produces '9' parts of steam. The latent heat of steam is 587 cal/gm
NCV = {GCV - Mass of hydrogen x 9 x Latent heat of steam}
NCV =[ GCV (9H/100) x 587]
Where 'H' is % of hydrogen in fuel
Theoretical calculation of calorific value by Dulong formula
The formula based on the following assumptions
i. Most of the fuels have C, H, S and O
ii. Calorific value is the sum of the calorific value of each element.
iii. The calorific values of C, H and S are found to be 8080, 34500 and 2240 k cal
/ kg respectively.
Therefore, the Dulong's formula can be written as follows.
HCV = 1/100 { 8080 C + 34500 (H- O/8) + 2240S }kcal/kg
LCV = HCV- { (9/100) H x 587} kcal/kg
Problems based on calorific values
Problem 1.
Calculate the gross and net calorific value of coal having the following
combustions, C = 85% H = 8%; S = 1 %, N = 2% ash = 4%, latent heat of steam = 587
cal/g [June : 07].
Problem 2. A coal has the following composition by weight: C = 90%; 0=3%; S =
0.5%: N = 0.5% and ash = 2.5%. Net calorific value of the coal was found to be
8,490.5 kcal/kg. Calculate the percentage of hydrogen and higher calorific value
of coal.
Calculation of minimum air requirements
1. Theoretical oxygen demand Substances always combine in definite proportions
which are determined by their molecular weights ie, stoichiometric equation.
Ex:
Combustion of carbon
C + O
2
CO
2
12 32 44 (by weight)
1 1 1 (by volume)
12 parts by weight of C requires 32 parts by weight of O
2
of produce 44 parts
by weight of CO
2
2. Nitrogen, ash, carbondioxide etc are present in the fuel are incombustible.
3. Air contains 21% oxygen (79% being nitrogen) by volume and 23% oxygen (77%
being nitrogen) by weight. Therefore,
Minimum weight of air required = (100/23) x Minimum O
2
Minimum volume of air required = (100/21) x Minimum O
2
4. At STP (273 K and 760mm. Pressure ) 22.4 liters of any gas weights equal to its
one gram molecule.
Example: 22.4 litres of CO
2
at STP will weight 44 gm.
5. At NTP, all perfect gases obey the following gas equation
PV = n RT
Where
P - Pressure
V - Volume
n - Number of moles of gas
R - gas constant
T - absolute temperature.
6. Net amount of O
2
required can be calculated as follows.
Net amount of O
2
required = Total amount of O
2
required - O
2
present in the
fuel.
7. The amount of air required if any excess air is supplied
Theoretical amount of air
= ------------------------------- x {100 + % Excess air}
100
Problems based on combustion reaction
Problem 1.
On analysis, an oil was found to have the following percentage composition C
= 50%, H = 10% 0 = 5% and S = 1.8% calculate the weight of oxygen and required
for the complete burning of 1 kg of this oil. (Air contains 23% oxygen by weight).
Also calculate GCV & NCV.
Solution
1. 1 kg of the fuel contains
50/100 = 0.5 kg of carbon
10/100 = 0.1 kg of Hydrogen
5/100 = 0.5 kg of Oxygen
1.8/100 = 0.18 kg of Sulphur
2. The combustion equations of the various elements present in the fuel are as
follows:
a. C + O
2
CO
2
12kg 32kg 44kg
b. H
2
+ O
2
H
2
O
2kg 16kg 18kg
c. S + O
2
SO
2
32kg 32kg 64kg
a) 12 kgs of carbon requires 32 kgs of oxygen
0.5 kg of carbon requires = (32 x 0.5) / 12
= 1.33 kg of oxygen
b) 2 kgs of hydrogen requires 16 kgs of oxygen
0.1 kg of hydrogen requires = (16 x 0.1)/2
= 0.8 kg of oxygen
c) 32 kgs of sulphur requires 32 kgs of oxygen
0.018 kg of sulphur requires = (32 x 0.018) / 32
= 0.018 kg of oxygen
Total amount of O
2
required = 1.33 + 0.8 + 0.018
= 2.148 kgs
But, the amount of O
2
already present in the fuel = 0.05 kg of O
2
Net amount of O
2
required = Total amount of O
2
- O
2
already present in the
fuel
= 2.148 -0.05
= 2.098 kgs
We know that, 23 kgs of O
2
is supplied by 100 kgs of air
2.098 kg of O
2
is supplied by = (100x 2.098) / 23= 9.12 kgs of air
The minimum amount of air required for complete combustion of 1 kg of a fuel =
9.12 kgs
GCV = (1/100) {8080 C + 34500 (H- O/8) + 2240 S } kcal/kg
= (1/100) {8080 x 50 + 34500 (10 - 5/ 8 ) + 2240 x 1.8 }
kcal/kg
= (1/100) {404000 + 323437.5 + 4032} kcal/kg
= 4040 + 3234.375 + 40.32 kcal/kg
GCV = 7314.695 kcal/kg
NCV = GCV - { (9/100) H x 587} kcal/kg
= 7314.695- { (9/100) x 10 x 587} kcal/kg
= 7314.695 528.3 kcal/kg
NCV = 6786.39 kcal/kg
Problem 2.
Calculate the volume of air required for the complete combustion of 100 m
3
of
the gaseous fuel having following composition by volume
H
2
= 50% CH
4
= 36% N
2
= 1.5% CO = 6% C
2
H
4
= 4% CO
2
= 4%.
Air contains 21% oxygen by volume.
1.1 m
3
of fuel contains
50/100 = 0.5 m
3
of H
2
36/100 = 0.63 m
3
of CH
4
1.5/100 = 0.015 m
3
of N
2
6/100 = 0.06 m
3
of CO
4/100 = 0.04 m
3
of C
2
H
4
4/100 = 0.04 m
3
CO
2
2. N
2
and CO
2
are non combustible constituents they do not undergo combustion.
3. The combustion equation of the remaining constituents is written as follows.
a) H
2
+ O
2
H
2
O
1 vol 0.5 vol
1 m
3
of H
2
requires 0.5 m
3
of O
2
0.5m
3
of H
2
requires = 0.5 x 0.5
1
= 0.25 m
3
of O
2
b) CH
4
+ 2O
2
CO
2
+ 2H
2
O
1 vol 2 vol
1 m
3
of CH
4
requires 2 m
3
of O
2
0.36 m3 of CH requires = 0.36 x 2
1
= 0.72 m
3
of O
2
c) CO + O
2
CO
2
1 vol 0.5 vol
1 m3 of CO requires 0.5 m
3
of O
2
0.6 m
3
of CO requires = 0.06 x 0.5
1
= 0.03 m
3
of O
2
d) C
2
H
4
+ 3O
2
2 CO
2
+ 2H
2
O
1 vol 3 vol
1 m
3
of C
2
H
4
requires 3 m
3
of O
2
0.04 m
3
of C
2
H
4
requires = 0.04 x 3
1
= 0.12 m
3
of O
2
Total volume of O
2
required = 0.25 + 0.72 + 0.03 + 0.12
= 1.12 m
3
of O
2
We know that
21 m
3
of O
2
is supplied by 100 m
3
of air 2
1.12 m
3
of O2 is supplied by = 100 x 1.12
21
= 5.33 m
3
of air
Amount of oxygen required my 100 m
3
of fuel =533.33 m
3
of air
Flue gas analysis (Orsat method)
The mixture of gases like CO
2
,CO, O
2
etc, coming out from the combustion
chamber is called as flue gas.
Aim
To estimate the amount of flue gases like CO
2
,CO, O
2
etc by using Orsat's
apparatus
Principle
This method is based on the absorption principle.The gases like CO
2
,CO and
O
2
are absorbed by KOH,alkaline pyrogallol and ammoniacal cuprous chloride
solutions respectively.
Significance
Analysis of these gases give an idea about the complete combustion of fuel or
not.
i. If CO is high in the flue gas shows incomplete combustion of the fuel and
short supply of oxygen.
ii. If CO
2
and O
2
are high in the flue gas shows complete combustions of the fuel
and excess supply of oxygen.
Description of Orsat's apparatus
It consists of a horizontal tube having three way stop cock at one end. The end
of three way stop cock is connected to a U tube containing fused CaCl
2
to remove
moisture in the gas. The another end of the tube is connected with a graduated burette.
The burette is surrounded by a water jacket in order to keep the temperature of gas
constantly. The lower end of the burette is connected by a water reservoir by means of
rubber tube. The level of the water in burette can be raised or loweredby raising or
lowering the reservoir.
The middle of the horizontal tube is connected with 3 bulbs(A, B and C) for
absorbing flue gases as follows:
i. Bulb 'A' containing KOH solution and it absorbs only CO
2
ii. Bulb 'B' containing alkaline pyrogallol solution and it absorbs only O
2
iii. Bulb 'C' containing ammoniacal cuprous chloride solution and it absorbs
CO.
Working of Orsat apparatus
The bulbs A, B and C are cleaned and filled by respective solutions. Now, the
three way stop cock is opened and the burette is filled with water, by raising the water
reservoir to remove air from the burette. Then, the flue gas is taken in the burette up
to 100 cc by raising and lowering the reservoir. The 3 way stop cock is now closed.
Absorption of gases in bulbs
i) Absorption of CO
2
The stopper of the bulb 'A' is opened and the flue gas is allowed to pass by
raising the water reservoir. CO
2
present in flue gas is absorbed by KOH. This process
is repeated several times by raising and lowering the water reservoir until the volume
of burette becomes constant. The decrease in volume of burette indicates the volume
of CO
2
in 100 cc of the flue gas. Now the stopper of the bulb A is closed.
ii) Absorption of O2
The stopper of the bulb 'B' is opened and the flue gas is allowed to pass. O
2
present in the flue gas is absorbed by alkaline pyrogallol. This process is repeated
several times until the volume of burette becomes constant. The decrease in volume of
flue gas in burette indicates the volume of O
2
. Now the stopper is closed.
c) Absorption of CO
The stopper of the bulb 'C' is opened and the flue gas is allowed to pass. 'CO'
present in the flue gas is absorbed by ammoniacal cuprous chloride solution. This
process is repeated several times until the volume of burette becomes constant. The
decrease in volume of flue
gas in burette indicates the volume of CO. The remaining gas in the burette after the
absorption of CO
2
, O
2
and CO is taken as nitrogen.
The % of N
2
= [100 (% of CO
2
+ % of O
2
+ % of CO)]
Anna university Questions
1. How is flue gas analysed by orsat method? Explain with neat diagram (Apr.
Dec-06)
2. Define gross and net calorific values of a fuel. How are they related? (June-06)
3. Calculate the gross and net calorific value of coal having the following
compositions
C = 85%, H = 8%, S = 1%, N = 2% ash = 4% (May-07).
Exercise
1. A sample of coal was found to contain the following. C = 81%, H = 4%,
O=2% N = 1% the remaining being ash. Estimate the quantity of minimum air
required for the complete combustion of 1 kg of the sample, if 40% of the
excess air is supplied (Ans: 14.95kg).
2. Calculate the minimum amount of air required for complete combustion of
50kg of fuel containing 80% carbon, 6% hydrogen 2% sulphur and the rest
nitrogen by weight. (Ans: 572 kg).
3. A coal sample on analysis gives C = 75%, H
2
= 52%, O
2
= 12.8%, S = 2% and
the rest ash.Calculate the amount of air needed for the complete combustion, if
1kg of the coal is bunt with 30% excess air (Ans: 13kg).
4. A fuel contains C = 75%, H = 4%, O = 5%, S = 7% remaining ash. Calculate
the minimum quantity of air required for the complete combustion of 1kg of
fuel. (Ans: 10.18 kg).
5. What is the volume of air required for complete combustion of 1m3 of mixture
containing 80% CH
4
and 20% C
2
H
6
(Ans: 10.95m
3
)
UNIT - IV
PHASE RULE AND ALLOYS
PHASE RULE
Let the equilibrium between a number of phases be not influenced by gravity,
electrical or magnetic forces, but only by pressure, temperature and concentration.
Then the number of degrees of freedom (F) of the system is related to the number of
components (C) and the number of phases (P) as follows:
F = C - P + 2
Phase :
Phase is a homogeneous, physically distinct and mechanically separable
portion of a system which is separated from other parts of the system by well-defined
boundaries.
Examples :
Air a mixture of N
2
, O
2
, CO
2
etc. But it forms a single gaseous phase.
Two immiscible liquids form two liquid phases and a vapour phase e.g.
Benzene-water.
Two completely miscible liquids form one liquid phase and one vapour phase.
e.g. alcohol-water.
Every solid forms a separate single phase.
Example : Let us consider the decomposition of CaCO
3
.
CaCO
3(s)
CaO
(s)
+ CO
2(g)
There are three phases, two solids and a gas.
Let us consider the equilibrium:
ice
(s)
water
(l)
vapour
(g)
There are three phases, because each phase is physically distinct.
A solution contains a single phase. (e.g.) sugar solution.
Component
Component is the minimum number of independently variable constituents by
means of which the composition of each phase can be expressed in the form of a
chemical equation.
Let us consider the equilibrium :
ice
(s)
i
water
(l)
vapour
(g)
There are three phases. All have the same chemical composition namely H
2
O.
The component of the system is one.
Thermal decomposition of CaCO
3
: It is a two component system.
CaCO
3(s)
CaO
(s)
+ CO
2(g)
The composition of each phase can be expressed in the form of a chemical
equation using two constituents. When CaCO
3
and CO
2
are components,
Phase Component
CaCO
3
CaCO
3
+0 CO
2
CaO CaCO
3
- CO
2
CO
2
0 CaCO
3
+ CO
2
PCl
5(s)
PCl
3(l)
+ Cl
2(g)
is a two component system.
While NH
4
Cl dissociates, the following equilibrium exists.
NH
4
Cl
(s)
NH
3(g)
+ HCl
(g)
The system has two phases namely solid and gas. Each can be expressed using
one chemical constituent namely NH
4
Cl, as long as NH
3
and HCl exists in equal
amounts. It is a one component system.
Degree of Freedom
It is the minimum number of independent variables such as pressure,
temperature and concentration that must be fixed to define the system completely.
Let us consider the equilibrium :
ice
(s)
iq
(s)
water
(l)
vapour
(g)
All the three phases will be in equilibrium only at a particular temperature and
pressure. So we need not specify any variable. The degree of freedom of the system is
zero. The system is non-variant.
For a gas or mixture of gases, we have to specify both temperature and
pressure. So the degree of freedom is two.
Let us consider the equilibrium
water
(l)
vapour
(g)
To define the system we have to mention either pressure or temperature. The
degree of freedom is one. The system is univariant.
Phase Diagram
Phase diagram is the graph obtained by plotting one degree of freedom against
another.
When a phase diagram is plotted between temperature and pressure, it is called
P-T diagram. It is used for one component system.
When a phase diagram is plotted between temperature and composition, it is
called T-C diagram. It is used for two component system.
Uses of Phase Diagram
i) We can predict from phase diagram whether a eutectic mixture or solid
solution or compound is formed on cooling a liquid mixture of two metals.
ii) We can understand the properties of materials in a heterogeneous equilibrium
system.
iii) A study of low melting eutectic alloys used in soldering can be made using
phase diagram.
Application of Phase rule to Water system
Water system is a one component system. There are three equilibria:
ice
(s)
water
(l)
water
(l)
vapour
(g)
ice
(s)
vapour
(g)
The phase diagram contains curves, areas and a triple point.
Curves
Along the vapourisation curve OA, water and vapour are in equilibrium.
water
(l)
vapour
(g)
Along the sublimation curve OB, ice and vapour are in equilibrium.
ice
(s)
vapour
(g)
Along the melting point curve OC, ice and water are in equilibrium.
ice
(s)
water
(l)
OC is slightly inclined towards pressure axis. This shows that melting point of
ice decreases with increase of pressure.
Along all the curves, two phases are in equilibrium. Applying phase rule,
F = C - P + 2 = 1 - 2 + 2 = 1
The degree of freedom is one or univariant. To define any point along the
curve, it is enough to mention either pressure or temperature.
Areas
Areas AOC, BOC, AOB represent water, ice and vapour respectively. In any
area, only one phase is present. Applying phase rule,
F = C - P + 2 = 1 - 1 + 2 = 2
To define any point in an area, we have to mention both pressure and
temperature.
P
r
e
s
s
u
r
e
Temperature
Triple Point
The three curves OA, OB and OC meet at the tripe point O. At O ice, water
and vapour are in equilibrium,
ice
(s)
water
(l)
vapour
(g)
Applying phase rule, F = C P+2 = 1 3 + 2 = 0
The degree of freedom is zero. The triple point is self-defined. Temperature
and pressure at O are 0.0075C and 4.58mm respectively.
Metastable curve OA
Sometimes water can be cooled carefully below 0C without ice formation.
Thus we realize the super cooled water - vapour pressure curve OA'. The metastable
equilibrium is,
Super-cooled water vapour
The equilibrium is unstable. Water can be converted into ice by slight
disturbance.
Reduced or Condensed phase rule
A solid-liquid equilibrium of an alloy has practically no vapour phase and the
effect of pressure is negligible. The experiment is regarded as being conducted at
constant atmospheric pressure. Since the vapour phase is neglected, the system is
called a condensed system. As pressure is kept constant, the phase rule becomes F' =
C - P + 1. This is called reduced phase rule or condensed phase rule.
Classification of a two component system
Two component system is classified into three types based on solubility and
reactivity.
i) Simple eutectic formation
ii) a) Compound formation with congruent melting point
b) Compound formation with incongruent melting point
iii) Solid solution
i) Simple eutectic formation
It is a two component system of two solids which are completely miscible in
the molten state. But the two solids are completely immiscible in the solid state. They
do not form any solid solution or react chemically. Of the different mixtures of the
two solids, the mixture with the lowest melting point is called eutectic mixture.
ii) a) Compound formation with congruent melting point
Here the two component system of two solids form one or more compounds
with definite composition. If the compound melts at a constant temperature, with the
same composition in the solid and molten state, the compound has a congruent
melting point.
b) Compound formation with incongruent melting point
If the compound formed in a two component solid system, decomposes at a
temperature below its melting point, the compound has incongruent melting point.
Also there is formation of a new solid phase with a different composition from that of
the original.
iii) Formation of solid solution
It is a two component system of two solids, which are completely miscible
both in the solid and molten state. They form solid solution with atomic level mixing.
The condition for formation of solid solution is that the two solids must not differ in
atomic radius by more than 15%.
Thermal analysis or Cooling curve
It is the study of the cooling curves of various compositions of a system during
solidification.
Example 1 :
A pure substance in the molten state is cooled slowly. The temperature is
noted at different intervals. Temperature is plotted against time.
The cooling from A to B is continuous. At the freezing point B, solid begins to
separate. The temperature remains constant, until all the liquid is solidified from B to
C . Then temperature of the solid begins to decrease gradually.
Example 2 :
A molten mixture of A and B is cooled slowly. The cooling from E to F is
continuous. At F one solid begins to separate. There is a break in the rate of cooling
from F to G. At G the second solid also begins to separate. Now the temperature
remains constant until all the molten liquid is completely solidified at H. From H
cooling of the solid mass starts. The temperature along the horizontal line GH is the
eutectic temperature.
For different compositions of A and B, the experiment is repeated and cooling
curves are drawn. From these curves, a phase diagram is drawn with temperature in Y
axis and composition in X axis.
Use of Cooling curves
1) From cooling curves, melting points and eutectic points are obtained.
2) Behaviour of compounds is understood.
3) Percentage purity of compounds is determined.
4) The composition corresponding to the freezing point gives the composition of
an alloy.
Simple eutectic system or lead-silver system
The lead-silver system is a two component system with the formation of a
simple eutectic. The phase diagram has areas, curves and a eutectic point.
i) Curve AO:
A is the freezing point of pure silver. As lead is gradually added to silver,
melting point of silver decreases along AO. Solid Ag and liquid melt are in
equilibrium along AO.
Solid Ag melt
Applying reduced phase rule,
F' = C - P + 1 = 2 - 2 + 1; F' = 1
Along AO the system is univariant.
ii) Curve BO:
B is the freezing point of pure lead. As silver is gradually added to lead, the
melting point of lead decreases along BO. Solid lead and liquid melt are in
equilibrium along BO.
Solid Pb melt
F' = C - P + 1 = 2 - 2 + 1; F' = 1
Along BO, the system is univariant.
iii) Eutectic point O:
The curves AO and BO meet at the point O. The temperature at O is 303C. At
O, solid Pb Solid Ag and their liquid are at equilibrium.
F' = C - P + 1 = 2 - 3 + 1 = 0
At O, the system is non-variant.
The eutectic point O is the lowest temperature at which any mixture of silver
and lead will melt. Below this temperature, liquid phase cannot exist. The eutectic
composition is 2.6% Ag and 97.4% Pb.
iv) Areas :
In the area below curve AO, solid Ag and liquid melt are present. In the area
below BO solid Pb and liquid melt are present.
F' = C - P + 1 = 2 - 2 + 1 = 1
At any point in these areas, the system is univariant.
In the area above curve AOB only a molten liquid of Pb and Ag exists.
F' = C - P + 1 = 2 - 1 + 1 = 2
At any point above AOB, the system is bivariant.
v) Applying Pattinsons process in the desilverisation of argentiferrous lead
Argentiferrous lead contains about 0.1% silver. It is melted to liquid state. Let
us consider the melt at the point p as in the figure. If the melt is allowed to cool, Pb
begins to crystallize at q. The solution becomes richer and richer in silver. If cooled
further, more lead separates along BO. The melt becomes richer in Ag. When the
eutectic point is reached the percentage of Ag rises to 2.6%. The process of raising the
percentage of lead in the alloy is Pattinsons process.
Uses of eutectic systems
i) Study of eutectic system helps to predict suitable alloy composition.
ii) Eutectic system is useful to prepare solders, used to join two metal pieces.
Differences between melting point, eutectic point and triple point
Melting point : It is the temperature at which a solid and its liquid phase, having the
same composition are at equilibrium.
Solid A liquid A
Eutectic point : It is the temperature at which two solids A and B and a liquid phase
are at equilibrium.
Solid A + Solid B Liquid
Triple point : It is the temperature at which three phases namely, solid, liquid and
vapour are in equilibrium.
Solid A liquid A vapour A
Eutectic point is a melting point. But melting point need not be eutectic point.
Merits of phase rule
1) The rule is applied to physical as well as chemical equilibrium.
2) It shows that different systems with the same degree of freedom have similar
behavior.
3) We can decide whether the given number of substances can remain in
equilibrium or not.
4) We can classify equilibrium states in terms of phases, components and degrees
of freedom.
Limitations of phase rule
i) The rule is applied to only systems in equilibrium.
ii) All the phases must be at the same temperature and pressure.
iii) Solid and liquid states must not be in finely divided state. Otherwise there may
be deviations.
iv) External forces like electrical, magnetic and gravitational forces should be
absent. Only P, T, C variables are to be considered.
ALLOYS
Alloy
Alloy is a homogeneous solid solution of two or more elements, one of which
is a metal. Alloy with mercury as a constituent is called amalgam.
Properties of alloys
1) Alloys are harder and less malleable. They have lower melting point than the
component metals.
2) Alloys have low electrical conductivity.
3) They resist corrosion and action of acids.
Importance or need or purpose or use or advantages of making alloy
i) Increasing the hardness of metals
In general pure metals are soft, but their alloys are hard. Gold and silver are
usually soft. When alloyed with copper they become hard. On addition of 0.5%
Arsenic, lead becomes so hard that we can make bullets.
ii) Lowering the melting point
The melting point of a metal decreases on alloying. (e.g.) Woods metal (alloy
of lead bismuth, tin and cadmium) melts at 60.5C. This is below the melting point of
any constituent metal.
iii) Increasing corrosion resistance
Alloying a metal makes it less reactive and helps resist corrosion. (e.g.) Pure
iron rusts. When alloyed with chromium, it opposes corrosion.
iv) Change in chemical activity
The chemical reactivity of a metal can be increased or decreased by alloying.
v) Change in colour
Alloying improves the colour of metal. (e.g.) Brass with 90% Cu and 10% Zn
is golden yellow in colour.
vi) Casting property
Alloying makes a soft, brittle metal into hard, fusible and easily castable.
Alloy of lead with 5% tin and 2% antimony is used for casting printing type.
Function (or) Effect of alloying elements
If we add small amounts of Ni, Cr, Mn, V, Mo, W etc., to steel, there is a
drastic change in properties like tensile strength, resistance to corrosion, coefficient of
expansion etc. The resulting products are called alloy steels or special steels.
Element Effect on properties Use
1. Nickel Fine grain formation, low
coefficient of expansion, high
corrosion resistance.
Making balance wheels.
2. Chromium High tensible strength,
hardening, high corrosion
resistance.
Making surgical
instruments, cutlery
3. Manganese High abrasion resistance Making grinding wheel
steering, spindles, rails
4. Vanadium Production of reversible stress,
increase in tensile strength and
abrasion resistance
Making axles, crank pin,
piston and locomotive
forgings
5. Molybdenum Cutting hardness at high
temperature
Making high speed stools
6. Tungsten Increase in magnetic retention
and cutting hardness
Making cutting tools,
permanent magnets
Heat treatment of alloys (steel)
Definition : It is the process of heating and cooling steel under carefully controlled
conditions.
Purpose or objectives of heat treatment
1. To improve corrosion resistance
2. To remove internal stress and strain
3. To improve electrical and magnetic properties
4. To remove trapped gases
5. To refine grain structure
6. To reduce brittleness and increase toughness and ductility.
Various types (methods) of Heat treatment of alloys (steel).
There are several types, 1. Annealing, 2. Hardening, 3. Tempering,
4.Normalizing, 5.Carburizing, 6. Nitriding, 7.Cyaniding.
1. Annealing
The alloy or steel is heated to a high temperature and then slowly cooled in a
furnace.
Purpose
To increase machinability
To remove trapped gases
Types of annealing
Low temperature annealing
High temperature annealing.
Low temperature annealing
The steel is heated to a temperature below the lower critical temperature and
then cooled slowly.
Purpose
To increase machinability
To reduce hardness
To increase ductility and shock-resistance
To remove internal stress and strain.
High temperature annealing
The steel is heated to 30 to 50C above the higher critical temperature. It is
held at that temperature for sufficient time to allow for internal changes. Then it is
cooled to room temperature.
Purpose
To make steel soft with increase in toughness.
To increase ductility and machinability
2. Hardening (Quenching)
The steel is heated beyond the critical temperature and then cooled suddenly in
oil or brine-water. This process increases the hardness of steel.
Purpose
To increase abrasion resistance for making cutting tools.
To increase resistance to wear.
3. Tempering
Already hardened steel is heated to a temperature below its hardening
temperature and cooled slowly. To retain strength and hardness, reheating temperature
should not exceed 400C. To increase ductility and toughness, reheating temperature
must be in the range 400 to 600C.
Purpose
To increase ductility and toughness and to reduce brittleness.
To make cutting tools, blades etc.
To remove internal stress and strain.
4. Normalising
Steel is heated to a temperature above its higher critical temperature and
cooled gradually in air.
Purpose
To make steel suitable for engineering works.
To have homogeneity in structure with refined grains.
To remove internal strain and stress
To increase toughness.
5. Carburising
Mild steel article is placed in a cast iron box containing pieces of charcoal. It
is heated to 900-950C and kept at the temperature for sufficient time. Carbon is
absorbed to required depth. The article is cooled slowly within the iron box. The outer
part of the of the article becomes a high-carbon steel with 0.8 to 1.2% carbon.
6. Nitriding
Steel or alloy is heated to about 550C in pressure of ammonia. Ammonia
decomposes to give N
2
which combines with the surface of alloy to form hard nitride.
Purpose
To form super hard surface.
7. Cyaniding:
Steel is immersed in molten salt bath containing KCN at 1120K and then
quenched in oil or water. Purpose to get hard surface.
Classification (or) types of alloys
Based on the type of base metal, alloys are classified into ferrous and non-
ferrous alloys.
Properties of Ferrous alloys
They have high strength and yield point.
The possess ductility and weldability.
They are corrosion and abrasion resistant.
They have less cracks and distortion.
Important ferrous alloys
Nichrome
It is an alloy with 60%nickel, 12% chromium, 25% iron and 2% manganese.
Properties
It has high resistance to oxidation and heat.
It has high melting point.
It possesses high electrical resistance.
It withstands heat upto 1100C.
Use
To make heating elements and resistance coils.
To make machineries exposed to high temperature.
Used in electric irons other household electrical equipments.
To manufacture boiler parts, steam lines stills, retort, aero-engine valves, gas-
turbines.
Stainless steel
It is an alloy steel containing chromium with other elements like Nickel,
Molybdenum. It is corrosion resistant due to the formation of a tough film of
chromium oxide at the surface.
There are two types of stainless steels.
a. Heat treatable stainless steel
b. Non-heat treatable stainless steel
a. Heat treatable stainless steel
This steel contains upto 1.2% carbon, less than 12-16% of chromium.
Properties
It is magnetic, tough and resistant to weather and water. It can be heated upto
800C.
Use
Making surgical instruments, scissors, blades etc.
b. Non-heat treatable stainless steel
It has less strength at high temperature. Corrosion resistance is more. There
are two types.
i) Magnetic type
Composition
12-20% chromium and 0.35% carbon.
Properties
It has very high corrosion resistance.
It can be forged and rolled.
Use
To make chemical equipments and automobile parts.
ii) Non-magnetic type
Composition
0.15% carbon, 18-25% chromium, 8 to 20% of nickel. Total percentage of
nickel and chromium is above 23%.
18/8 stainless steel
It has 18% chromium and 8% nickel and 0.15% carbon.
Properties
It has extreme resistance to corrosion. The resistance is increased by the
addition of a small amount of molybdenum.
Use
To make household utensils, sinks and surgical instruments.
Non-ferrous alloys
These do not have iron as a constituent. The main constituents of non-ferrous
alloys are copper, zinc, lead, tin etc. They have low melting points compared to
ferrous alloys.
Properties
Non-ferrous alloys are characterized by
i) Softness and ductility
ii) Attractive colours
iii) Low density and coefficient of friction
iv) Corrosion resistance
Important Non-ferrous alloys
Copper alloys
Brass and Bronze are alloys of copper.
Brass
Brass is copper alloy with copper and zinc as main constituents.
Some important brasses, their properties and uses are tabulated below.
Type of Brass Composition Property Use
Commercial
brass
Cu = 90%
Zn = 10%
i. Golden colour
ii. Stronger and harder
than Cu
Forging, rivet
hardwares jewellery
Dutch metal Cu = 80%
Zn = 20%
i. Golden colour
ii. Suitable for
drawing and
forming operation
Tube, flexible hoses
jewellery
Cartridge brass Cu = 70%
Zn = 30%
Soft and ductile cold,
-deformed
Condenser tubes,
sheets household
articles
German Silver Cu = 25 to 50%
Zn = 10 to 35%
Sn = 5 to 30%
Silver colour,
malleable, corrosion
resistance
Ornament, bolt nut,
utensil, coins
Jobin brass Cu = 59 to 62%
Zn = 35 to 38%
Sn = 0.5 to 1.5%
High corrosion and
abrasion resistance
Propeller and marine
works
Bronze
Bronze is a copper alloy with copper and tin as main constituents. Bronze has
lower melting point than steel. It has better heat and electricity conducting property
than steel. It has good corrosion resistance.
Some important bronzes, their properties and uses are tabulated below:
Type of Bronze Composition Property Use
Coinage Bronze Cu = 89-92%
Sn = 8-11%
Soft, ductile Pump, valve, coin,
statue wire, utensils
Gun metal Cu = 85% Hard and tough, Foundry work, heavy
Zn = 4%
Sn = 8%
Pb = 3%
resistant to explosive
forces.
load bearing, steam
plant
Aluminium
bronze
Cu = 90-93%
Al = 7-10%
Yellow colour,
fusible, resistant to
corrosion and
abrasion.
Jewellery, utensil,
coin bushes
Phosphorus
Bronze
Cu = 87-90%
Sn = 10-13%
P = 0.4 - 1%
Hard, brittle, low
coefficient of friction
Bearing, gear, tap,
spring turbine, blade.
Nickel bronze Cu = 90%
Ni = 9%
Fe = 1%
Hard, good tensile
strength, corrosion
resistant
Valves, semi-hard
bearings.
QUESTIONS
PART - A
1. Define phase rule.
2. Define the terms : phase, component, degrees of freedom.
3. Comment on degrees of freedom.
Ans : It is the minimum number of independent variables such as pressure,
temperature, concentration that must be fixed to define the system completely.
(e.g.) In water system, at the triple point, three phases are in equilibrium.
Applying phase rule,
F = C - P + 2 = 1 - 3 + 2 = 0
The degree of freedom is zero; the triple point is self-defined and non-variant.
If F=1, the system is called univariant. We have to mention one variable to
define the system.
4. Calculate the number of components in the following:
KCl
(s)
+ Water
(l)
KCl hydrate
(s)
MgCO
3(s)
A
MgO
(s)
+ CO
2(g)
PCl
5(s)
PCl
3(l)
+ Cl
2(g)
5. Calculate the number of phases in the following:
A gaseous mixture of N
2
, H
2
, NH
3
.
H
2(g)
+ Cl
2(g)
2HCl
(g)
NH
4
Cl
(s)
NH
3(g)
+ HCl
(g)
Rhombic sulphur
(s)
Monoclinic sulphur
(s)
6. Calculate the number of phases, degree of freedom and components for the
equilibrium:
NH
4
Cl
(s)
NH
3(g)
+ HCl
(g)
7. What is a phase diagram?
8. What is triple point?
9. Explain metastable equilibrium.
10. Explain invariant point.
11. How does the melting point of ice change with pressure?
12. What is meant by reduced phase rule?
13. Define eutectic point.
14. Eutectic mixture is a mixture and not a compound. Explain.
Ans : In the solid eutectic, the two components are completely immiscible, though
they are miscible in the liquid state. Also the solid eutectic shows the properties of
both the components. So it is a mixture and not a compound.
15. What are the uses of eutectic mixture?
16. What are the applications of phase rule?
17. State the merits of phase rule.
18. Explain the limitations of phase rule.
19. Define an alloy.
20. Name some properties of alloys.
21. What are the advantages of alloys?
22. State some ferrous and non-ferrous alloys.
23. What is the composition of nichrome? What are its uses?
24. Write the composition and uses of the following alloys :
German silver, Dutch metal, Gun metal, brass (commercial), solder, phosphor
bronze, wood metal.
25. Explain the following terms. What are their purposes?
Hardening, tempering, annealing, normalizing, carburising, cyaniding, nitriding.
26. What is quenching?
27. What is 18/8 steel? What are its uses?
PART - B
1. Apply phase rule to a one component system.
2. Discuss in detail lead-silver system with the help of the phase diagram.
3. What is thermal analysis? Draw the cooling curves of a pure substance and its
mixture with another solid and discuss.
4. Why is condensed phase rule applied to a two component alloy system?
5. Apply phase rule to a two component system forming eutectic mixture.
6. Define alloy. What is the effect of alloying a metal? Explain with examples.
7. What are the properties of alloys?
8. Mention the purposes of making alloys.
9. Name some ferrous and non-ferrous alloys. Give their composition, properties and
uses.
10. Write a note on stainless steels.
11. Discuss the various methods of heat treatment of alloys and steel.
12. What is Bronze? Name some important bronzes, their composition, properties and
uses.
13. Define Brass. Write briefly about different types of brass.
14. Explain with examples how the property of steel changes with the addition of
small amounts of nickel, chromium, manganese vanadium, molybdenum and
tungsten.
UNIT - V
Analytical techniques
Spectroscopy
The study of interaction of electromagnetic radiation with atoms or molecules
is spectroscopy. During this interaction, radiation is absorbed or emitted by the
molecules or atoms. The measurement of the intensity of the emitted or absorbed
radiation forms the basis of spectroscopy.
Absorption spectrumor absorption spectroscopy
When electromagnetic radiation is passed through a solution or vapour, certain
wavelengths are absorbed by the solution or the vapour. The atoms or molecules
undergo transition to a higher energy level. The measurement of the decrease in the
intensity of the radiation is absorption spectroscopy. The spectrum obtained is
absorption spectrum.
Emission spectrum (emission spectroscopy)
Atoms or molecules are excited to higher energy levels by heat or electric
discharge. The excited atoms or molecules come to the ground state by emitting
radiation. The study of the emitted radiation is emission spectroscopy. The spectrum
obtained is emission spectrum.
Atomic spectra
It is the study of interaction of electromagnetic radiation with atoms. Atoms
are excited to higher electronic energy levels. The spectrum contains discrete lines.
Molecular spectra
It is the study of interaction of electromagnetic radiation with molecules.
Molecules are excited to higher rotational, vibrational and electronic energy levels.
The spectrum contains bands.
Differences between atomic and molecular spectra
Atomic spectra Molecular spectra
1. It arises due to the interaction of
electromagnetic radiation with atoms
It arise due to the interaction of
electromagnetic radiation with
molecules
2. The spectrum has discrete lines The spectrum has complicated bands.
3. It is due to electronic transitions It is due to rotational vibrational and
electronic transitions
Absorption laws
Lamberts law:
Let a beam of monochromatic radiation pass through a homogeneous
absorbing medium. Now the rate of decrease in intensity of the radiation dI with the
thickness of the absorbing medium dx, is proportional to intensity I of the incident
radiation.
dI dI
kI (or) kdx
dx I
= =
k= absorption coefficient - (1)
Let I
o
and I be the intensities before entering the medium (x=0) and after
passing through any thickness x respectively.
Integrating equation (1)between these limits.
o
I x
I o
dI
kdx
I
=
} }
o
I
ln kx
I
= - (2)
This is Lamberts Law.
Beers law or Beer-Lamberts law
Let a beam of monochromatic radiation pass through a homogeneous
absorbing medium. Now the rate of decrease in intensity of the radiation dI with the
thickness of the absorbing medium dx is proportional to the intensity of the incident
radiation I as well as the concentration C of the solution.
dI
kI C
dx
=
k = molar absorption coefficient (or)
dI
I
= kCdx -(1)
Let I
o
and I be the intensities before entering the medium (x=0) and after
passing through thickness x respectively. Integrating equation (1) between these
limits,
o
I x
I o
dI
kC dx
I
=
} }
o
I
ln kCx
I
= (or)
o
I
ln kCx
I
=
2.303 =
o
I k
log Cx
I 2.303
= (2)
A = eCx
o
I
A log
I
= = absorbance or optical density
k
2.303
c = = molar extinction coefficient.
Equation (2) is Beers law (or) Beer - Lamberts law.
Application of Beer Lamberts law
Absorbance A
s
of solution of known concentration C
s
is measured. Now,
A
s
= eC
s
x
ex = A
s
/C
s
-(1)
Then the absorbance A
u
of unknown solution is measured.
A
u
= eC
u
x
u
u
A
x
C
= c - (2)
From equations (1) and (2)
s u
s u
A A
C C
= (or)
u
u s
s
A
C C
A
=
knowing A
u
, A
s
and C
s
, unknown concentration C
u
can be calculated.
Limitation of Beer - Lamberts law
1. Applicable only for dilute solutions.
2. Monochromatic radiation must be used.
3. The solute should not dissociate or associate in solution.
4. Not applicable to suspensions.
5. Solution should not contain impurities.
6. Temperature should not change to a large extent.
Colorimetry (or) Colorimetric analysis
Colorimetry is an analytical technique to measure the concentration of
coloured solutions. The absorbance A of the solution is measured using a
photoelectric colorimeter. Then the concentration is determined using Beer-Lamberts
law. If the substance is colourless, a suitable complexing agent is added to convert it
into a coloured compound.
Photoelectric colorimeter - Instrumentation
I. Components
1. Radiation Source: Tungsten filament lamp is used to get visible light between
400-750nm.
2. Monochromator: It allows the radiation of required wavelength to pass through
the solution. It absorbs other wavelengths.
3. Slit i) Entrance slit: It selects a narrow source of light.
ii) Exit slit : It provides narrow band of dispersed spectrum for observation by
the detector.
4. Cell: It holds the test solution. It is transparent. It is made of colour-corrected fused
glass or quartz.
5. Detector : It measures the intensity of the transmitted radiation from the test
solution. Photosensitive devices are used. They produce a current which is
proportional to the transmitted radiation.
6. Recorder (or) Meter: It measures the fraction of radiation abosorbed.
II. Working
A narrow beam of light enters through the monochromator and passes through
the test solution in the cell. The light then passes into the detector. The instrument is
provided with filters and slits to select desired wavelength. The detector generates a
current proportional to the intensity of light transmitted from the test solution. The
current or intensity of transmitted light is more if the solution absorbs less light, i.e.,
the concentration is low.
Current o transmitted light o 1 / Concentration
Now a days, the transmitted light passes into a meter which shows the fraction
of light absorbed, which is proportional to the concentration.
Estimation of Iron by colorimeter
Principle
Iron (III) forms an intense blood-red coloured complex with thiocyanate in
solution.
Fe
3+
+ 6NH
4
CNS [Fe(CNS)
6
]
3-
+ 6
+
4
NH
Blood-red
coloured complex
Reagents
i) Standard iron solution : 0.865 g of FAS is dissolved in minimum amount
of distilled water. 10 ml of conc.HNO
3
is added and the solution is diluted
to one litre. 1ml of this solution conatins 0.1 mg of Fe.
ii) Ammonium thiocyanate solution : A 10% solution in distilled water is
prepared.
iii) 1:1 HCl acid: 50ml conc.HCl is added to 50ml distilled water.
Procedure
A series of standard solutions of Fe
3+
are prepared by adding NH
4
CNS
solution and a little 1:1 HCl.
A blank is prepared by adding same amount of reagents.
The colorimeter is set at zero absorbance using the blank solution with a
suitable filter. The absorbance of each standard solution is measured using the same
filter. Absorbance is plotted against concentration in a graph. A straight line passing
through the origin is obtained. This is calibration curve.
According to Beer-Lamberts law,
A = eCx
Since the thickness x is a constant for the given cell,
A C.
The absorbance of the test solution is measured under the same conditions.
The concentration of the test solution is read from the calibration curve.
Applications of Colorimetry
1. Very small concentrations of many metal ions can be determined.
2. Stability constants of complexes can be evaluated.
3. Geometry of inorganic complexes, cis-trans isomers can be examined.
4. Dissociation constants of acid-base indicators can be determined.
5. Molar extinction coefficients of complexes can be evaluated.
Flame photometry
Atomised metal is introduced into a flame. The metal atoms are excited and
then come to the ground state. The intensity of the emitted light is measured. The
wavelength of the light emitted identifies the metal. Its intensity measures the
concentration of the metal.
Theory or Principle
A metal salt solution is introduced into the flame.
i) The solvent evaporates leaving behind the solid salt.
ii) The solid salt vaporises and dissociates into atoms.
iii) Some of the metal atoms are excited to higher energy levels by absorbing
heat energy.
iv) The excited atoms return to the ground state by emitting radiation.
v) The emitted radiation passes through the filter and falls on a detector. The
detector generates a current which is amplified and recorded.
Evaporation vapourization dissociaton
M
+
X
-
=========== MX============MX==========M + X
(solution) (solid) (gas) (gas) (gas)
(gas) M*------------- M
excited state ground
state
Instrumentation
Components
1. Burner
Propane-air or acetylene-air flame is used. The flame should,
i) vapourise the solvent from the test solution.
ii) dissociate the solid into atoms.
iii) excite atoms and make them emit radiation.
2. Mirror
Radiation from the flame is emitted in all directions. To increase the radiation
reaching the detector, a concave mirror is kept behind the burner.
3. Slit
i) Entrance slit : It is kept between flame and monochromator. It allows only radiation
from the flame and mirror.
ii) Exit slit : It is placed between detector and monochromator. It prevents entry of
interfering radiations.
4. Monochromator
It permits only radiation of required wavelength to pass through. It absorbs
other radiations.
5. Detector
Radiation from the monochromator falls on a detector. It generates a current
which is proportional to the intensity of radiation.
6. Amplifier and Recorder
The current from the detector is amplified and recorded.
Working
At a constant pressure, air is sent into an atomiser. This suction draws some
test solution into the atomiser. The mixture of air and sample solution is mixed with
fuel and burnt in the burner. The radiation emitted from the burner flame is sent
successively through lense, filter, detector, amplifier and recorder. A graph, called
calibration curve, is drawn between recorder reading (intensity of emitted radiation)
and concentration of sample solution. A similar experiment is performed for the test
solution. Its concentration is read from the graph.
Applications of flame photometry
1. Estimation of sodium
The flame photometer is switched on. Air and gas supplies are regulated.
Initially double distilled water is sent in and ignition is started. After the instrument is
warmed up for nearly 10 minutes, it is adjusted for zero reading in the display.
Sodium gives a characteristic yellow emission at 589nm. The instrument is set
at this wavelength.
Series of standard solutions of sodium chloride (1,2,3,4,....10ppm) are
prepared. They are introduced one by one into the flame and readings (intensity of
emitted light) are noted. A calibration graph is drawn between intensity of emitted
light and concentration. A straight line passing through origin is obtained.
Now the test solution is introduced into the flame and the reading is noted.
The concentration of sodium in the (water) sample is read from the graph.
2. Quantitative analysis
Alkali and alkaline earth metals, transition metals like Fe, Mn, Cu can be
estimated.
3. Qualitative analysis
Alkali and alkaline earth metals can be detected from the colour of the flame.
Element i
max
(nm) Colour of the flame
Ca 422 nm Brick red
Li 670 nm Scarlet red
K 766 nm Red
4. Measurement of alkali and alkaline earth metals, Fe, Cu, Mn etc are useful in
medicine, agriculture and botany.
5. It is highly useful in the analysis of biological fluids and tissues.
6. Industrial and natural waters, petroleum products, glass, cement are analysed
by this technique.
Interferences in flame photometry
i) Spectral interference : When two elements show different spectra but both emit at
the same wavelength, this interference occurs.
ii) Ionic interference : It occurs due to ionisation of metal atoms at high temperature.
Ionisation reduces atomic emission.
iii) Cation-anion interference : Anions like oxalate, phosphate form stable complexes
with cations and so interfere.
Cation-Cation Interference: This reduces intensity of the signal.
Limitations of flame photometry
i) Inert gases and all metal ions cannot be determined.
ii) Molecular nature of the metal present in the original sample cannot be ascertained.
iii) Liquid samples alone are to be used.
Atomic absorption spectroscopy (AAS)
Principle
It is based on the atomisation of sample accompanied by absorption of
characteristic radiation by the ground state gaseous atoms. When a radiation of
suitable wavelength is passed through the flame containing metal atoms, part of the
radiation is absorbed. The extent of absorption is proportional to the concentration of
metal atoms in the flame. The amount of radiation absorbed is determined in AAS.
Components
i. Radiation source
It is a hollow cathode lamp.It has a glass tube containing a noble gas like
argon (anode) and a hollow cathode made of the analyte metal. The lamp emits stable
intense characteristic radiation of the metal to be estimated.
ii. Chopper
It is a rotating wheel placed between the hollow cathode lamp and the flame. It
breaks the steady light from the lamp into a pulsating light. This is because the
recorder recognises only a pulsating current.
iii. Burner
Total combustion burners or premixed burners are used to convert liquid
sample into gas and the molecules into atomic state.
iv. Nebuliser
Before the liquid sample enters the burner, it is converted into small droplets
by the nebuliser.
v. Monochromator
It selects a particular wavelength from the radiation emitted by the hollow
cathode lamp. Prisoms and gratings are used as monochromators.
vi. Detector
Photomultiplier tubes are used as detectors. They convert the light falling on
them into electric current.
vii. Recorder
The signal from the amplifier is recorded in a chart paper or digital read out
device.
Working
The characteristic radiation from the radiation source passes through the flame
to which the sample solution is aspirated. The metallic compounds are decomposed
and reduced to the elemental state forming a cloud of atoms. The atoms absorb a
fraction of radiation in the flame. The unabsorbed radiation from the flame passes
through the monochromator, and then to the detector, amplifier and recorder.
Quantitative estimation of nickel
Requirements
i) Wavelength : 232 nm
ii) Light source : Hollow cathode lamp (nickel)
iii) Flame : Nitrous oxide - acetylene flame-reducing (rich, red)
Step I : Preparation of standard stock solution
1.0g of nickel nitrate is dissolved in minimum amount of dil. 1:1 HNO
3
and
made up to one lit. with 1% HNO
3
. This standard nickel solution has a strength of
1000ppm.
Step II : Construction of calibration curve
The instrument is switched on and allowed to warm up for ten minutes. 232nm
wavelength is selected. A blank solution is aspirated into the flame and the assembly
is adjusted for zero absorbance.
From the standard nickel stock solution, a series of standard solutions are
prepared. They are aspirated into the flame one by one and the absorbance is
measured. A calibration graph is plotted between absorbance and concentration of
nickel (ppm).
Step III : Estimation of unknown concentration
The test solution is aspirated into the flame under the same conditions and its
absorbance is measured. The corresponding concentration is read from the graph.
Applications of AAS
i) Nearly seventy to eighty metals present in any sample can be accurately and
rapidly determined.
ii) Trace amount of lead in alloy can be estimated.
iii) Vanadium in lubricating oil can be determined.
iv) AAS is used to analyse clinical samples like blood, urine, hair, teeth and tissues
etc.
v) AAS is applied in food industry, soil analysis and pharmaceutical industry.
Limitations of AAS
i) Sample preparation is tedious and time consuming.
ii) Chemical form of metal cannot be ascertained.
iii) Only metals can be determined.
UV - Visible Spectroscopy
UV-Visible spectroscopy involves transition of valence electrons of molecules
or ions from the ground electronic state E
0
to a higher electronic state E
1
. The ultra
violet region is 100 to 400 nm. The visible region is 400 to 800 nm. The amount of
energy required for the transition is,
AE = h = E
1
- E
0
Type of transitions involved in organic molecules
There are three types of electrons in organic molecules - o bonded electrons, t
bonded electrons and non-bonded electrons (n). All the three types of electrons are
present in formaldehyde :
H
H
C
o
H
: n
The types of transitions and their order of energeis are:
n H* < H H* < n o* << o o*
1. n * transitions
These are shown by unsaturated molecules with heteroatoms like N, O, S and
halogen. They are due to the excitation of an electron from non-bonding lone pair (n)
to an empty anti-bonding H* orbital.
Example :
Acetaldehyde and acetone
n H* transition occurs at 270 to 300 nm. An electron from the non-bonding
orbital of oxygen atom is excited to a H* orbital.
2. * transitions
These are shown by molecules with H electrons. (e.g.) olefins, aromatic
compounds. They are due to the excitation of an electron from H bonding orbital to
anti-bonding H* orbital.
Example :
Ethylene CH
2
= CH
2
A H H* transition occurs at 200 nm.
3. n * transitions
These are shown by saturated compounds containing a lone pair of electrons.
They are due to the excitation of an electron from non-bonding orbital (n) to a o*
anti-bonding orbital.
Example :
Trimethyl amine (CH
3
)
3
N:
n o* transition occurs at 227 nm. An electron from the non-bonding orbital
of N atom is excited to a o* orbital.
3. * transitions
These are shown by all saturated compounds. They are due to the excitation of
an electron from o bonding orbital to a o* anti-bonding orbital.
Example : CH
4
o o* transition occurs at 122 nm. o o* are high energy transitions.
They are weak, and usually not observed.
Chromophores
These are groups with multiple bonds and are responsible for the colour of a
compound.
N O
nitroso
azo nitro carbonyl
N N
N
O
O
O C
Auxochromes
These are groups that are not themselves responsible for the colour of the
compound. But they enhance the colour of chromophore by conjugation.
(e.g.) - OH - NH
2
Chromophore Auxochrome
1. This group is responsible for
colour
This group is not responsible for colour,
but enhances the colour of chromophore
2. Contains multiple bond. Contains lone pair of electrons
3. (e.g.) - N = O - N = N - - NH
2
- OH
Instrumentation of UV- Visible SpectrophotometerComponents
i) Radiation source
Hydrogen discharge and deuterium lamps as well as mercury lamps are the
common sources. They must supply a steady radiation of sufficient intensity.
ii) Monochromator
It disperses the radiation according to the desired wavelength. It comprises an
entrance slit, a dispersing prism or grating and an exit slit.
iii) Cells
They hold the sample and reference solutions. The cell must be uniform in
construction, inert to solvents and transparent.
iv) Detector
Barrier layer cell, photomultiplier tube, photocell are used as detectors. The
detector converts the radiation falling on it into electric current.
v) Recorder
The signal from the detector is recorded on a chart paper by the recorder.
Working
The radiation from the source passes through the monochromator, which
selects a narrow range of wavelength to pass through an exit slit. The radiation from
the monochromator is split into two equal beams. One half (reference beam) passes
through cell containing the blank solution. The other half (sample beam) passes
through the cell containing test solution. The detector compares the intensities of the
two beams. If sample absorbs, the intensity of the sample beamI will be less than
that of reference beam (I
0
). The recorder plots absorbance versus wavelength.
Applications
i) Determination of structure of compound
Hartley established that compounds of similar constitution have similar
absorption spectra. This is Hartley rule. Using this, we can characterise organic
compounds by comparing the UV-visible of spectrum unknown compound with that
of known compounds available in the reference books.
ii) Study of coordinate complexes
Visible spectroscopy is used to study the structure of coordination complexes.
We can identify the cis-trans isomers, octahedral, tetrahedral and square planar
structures.
iii) Determination of formation constants
Visible spectroscopy is used to determine the composition and the formation
constants of coordination complexes.
iv) Kinetic studies
UV-visible spectroscopy is used to study the kinetics of reactions involving
coloured complexes. The absorbance is directly proportional to the concentration. If
the concentration changes, the absorbance also changes. The change in absorption
(concentration) with time is used as a tool in studying the kinetics of ligand
displacement reactions and hydrolysis of coordination complexes.
v) Determination of concentration of solutions
Beer Lamberts law is,
0
I
log cx
I
= c
This law is used to determine molar extinction coefficient e of a compound.
Also we can determine concentration of solutions, since absorbance
0
I
log
I
is directly
proportional to concentration. Absorbances of solutions of known concentrations are
measured. A graph is plotted between absorbance and concentration. The absorbance
of unknown solution is measured. Its concentration is read from the graph.
vi) Study of Tautomerism
The percentage of keto and enol forms in a tautomeric equilibrium is estimated
from the relative intensities of absorbance bands of the UV spectrum.
(e.g.) Acetoacetic ester.
CH
3
C CH
2
COOC
2
H
5
O
Keto form
i
max
= 275nm
CH
3
C COOC
2
H
5
OH
Enol form
i
max
= 244nm
vii) Determination of calcium in blood
The amount of calcium in blood is estimated. The Ca present in 1 ml of serum
is converted into its oxalate. It is dissolved in dil.H
2
SO
4
and treated with ceric
sulphate solution. The absorbance is measured at 315nm. The amount of calcium in
the blood is determined.
viii) Molecular weight determination
The molecular weight of a compound can be determined by converting it into
a derivative which gives an absorption band. (e.g.) The molecular weight of an amine
is determined by converting it into a picrate derivative.
Infrared (IR) Spectroscopy
If infra red radiation (400-4000 cm
-1
) is passed through molecules, vibrational-
rotational transitions occur in them.
There are two types of fundamental vibrations in a molecule.
1) Stretching vibration
In this vibration, the bonds are elongated and compressed. But the bond angle
remains unchanged. There are two kinds of stretching vibrations:
i) Symmetric stretching
ii) Asymmetric stretching
2) Bending or deformation vibrations
In this vibration, the bond angle increases and decreases but the bond length
does not change. Bending vibrations are of two kinds.
i) In plane bending vibrations: Here all the atoms are in the same plane during
vibration.
ii) Out of plane bending vibration : Here the atoms go out of plane during vibration.
In plane bending Out of plane bending
Number of modes of vibrations
i) A linear molecule has (3n-5) fundamental vibrational modes. n= number of atoms
in a molecule.
(e.g.) CO
2
is a linear molecule.
It can exhibit 3 x 3 - 5 = 4 vibrations. They are shown above.
ii) A non-linear molecule has (3n-6) fundamental vibrational modes. n= number of
atoms in the molecule.
(e.g.) Water (H
2
O) is a non-linear molecule. It has (3n-6) = 3 x 3 - 6 = 3 vibrational
modes. They are shown below.
O
H H
O
H
H
O
H H
symmetric
stretching
Asymmetric
stretching
Bending
Instrumentation of IR Spectrometer
Components
i) Radiation Source
Nichrome wire and Nernst glower are the main sources of IR radiation. Nernst
glower is filament made of oxides of Zr, Th and Ce held together using a binder.
ii) Monochromator
It permits only radiation of desired wavelength to pass through and absorbs
other wavelengths.
iii) Cell
The cell holding the sample solution should be transparent to IR radiation.
NaCl cells are used.
iv) Detector
The IR radiation falling on the detector is converted into an electric signal.
Some detectors are:
i) Thermocouple
ii) Pyroelectric detectors
v) Recorder
The electrical signal from the detector is recorded as percentage transmittance
against wavelength.
Working
The radiation from the source is split into two beams of equal intensity. One
beam passes through the sample and the other through the reference.
When the sample absorbs, the two emerging beams will have different
intensities. This produces an oscillating signal to be measured by the detector. The
signal from detector gets amplified and goes to the recorder which gives a print out or
display.
Applications of IR spectroscopy
1. Identification of Compounds
Each molecule gives its own unique IR spectrum. If two samples give the
same IR spectra, they contain identical molecules. Thus the identity of a compound
can be established by comparing the IR spectrum of a compound with the standard IR
spectra available in the literature.
2. Detection of functional groups
Different functional groups absorb at different IR regions. So from the
absorption frequency, the nature of functional group present in the molecule can be
identified.
Examples
v) Recorder
against wavelength.
Working
display.
identified.
Examples
v) Recorder
against wavelength.
Working
display.
identified.
Examples
Functional group IR Frequency (cm
-1
)
C O
aldehyde & ketones 1680 - 1720
N H amines 3300 - 3400
O H alcohols, phenols 3500 - 3650
C N cyanides 2200 - 2250
NO
2
nitro compound 1350 - 1380
Ar C H aromatic ring 3000 - 3100
R O R ether 1100 - 1200
3. The progress of a reaction can be studied by observing the decrease or
increase in the intensity of a particular peak at different time intervals.
4. Structure determination
We can easily find out whether a molecule is linear or not.
Example :
Let us consider NO
2
. If it is linear, it will show (3n-5) = 3 x 3 - 5 = 4 bands. If
it is non-linear, it will show (3n-6) = 3 x 3 - 6 = 3 bands. The actual IR spectrum of
NO
2
showed 3 bands. So we conclude that NO
2
is non-linear.
N
O O
5. Cis-trans isomers can be identified.
6. Purity of samples
Pure sample gives a sharp and well-resolved IR bands. Impure sample gives
not only broad and poorly resolved bands but also additional bands. So from the IR
spectrum of the sample we can ascertain the purity.
7. Molecular weight of a compound can be determined by measuring end group
concentrations in the IR spectrum.
8. The crystallinity of a solid can be ascertained by changes in the IR spectrum.
PART - A QUESTIONS
1. What is the relation between wavelength (i) frequency (v) and wave number ( o)?
Ans :
1
C
o
= o =
i
2. What is absorption spectrum (spectroscopy)?
3. What is emission spectrum (spectroscopy)?
4. Explain atomic spectrum.
5. Define molecular spectrum.
6. Name the differences between atomic and molecular spectra.
7. State Lamberts law.
8. State Beer-Lamberts law.
9. Name some factors that affect absorption.
Ans : Path length, wavelength of light, concentration of solution and nature of the
absorbing molecule.
10. What are the common features of absorption instruments?
Ans : Source, analyser, detector, recorder.
11. What are the applications of colorimetry?
12. What is flame photometry? Name a few metals that can be estimated by this
method.
13. What are the limitations of Beer-Lamberts law?
14. What is colorimeter?
15. Write the complexes formed in spectroscopic determination of Fe and Ni.
Ans : Fe
3+
+ 6 CNS
-
[Fe(CNS)
6
]
-3
Ni
+2
+ 2 DMG
-
[Ni(DMG)
2
]
16. What are the important processes that occur in the flame photometry?
17. Write the various types of electronic transitions.
18. What is bathochromic shift?
Ans: Shifting of absorption to a longer wavelength is bathochromic or red shift.
19. Explain the terms : Auxochrome, Chromophore.
20. Write a few differences between auxochrome and chromophore.
21. Name some transitions responsible for molecular spectra.
Ans : Rotational, vibrational and electronic transitions.
22. What is finger-print region in IR? What is its importance?
Ans : The region 700-1400 cm
-1
is finger-print region. It has rich and complicated
intense IR bands. The region is used to identify a molecule just as we use finger
prints of people to identify them.
23. Calculate the number of vibrational modes (or) bands for H
2
, H
2
O
2
, CH
4
, C
6
H
6
,
CO
2
, H
2
O, C
2
H
2
, C
2
H
6
.
24. Name some applications of IR spectroscopy.
25. What is the principle of atomic absorption spectroscopy?
26. Explain the principle of flame photometry?
27. What is the frequency of a radiation of wavelength 5000.
Ans :
10
14 1
8
C 3 x10
6 x10 s
5000 x10
o= = =
i
PART B QUESTIONS
1. Derive Beer-Lamberts law. What are its limitations?
2. What is the principle of colorimetry? Explain the various parts and working of a
colorimeter. Write about its applications.
3. What is flame photometry? Discuss its principle.
4. Write briefly about the instrumentation, working and applications of flame
photometry.
5. Explain the interferences in flame photometry. What are the limitations of flame
photometry?
6. State the principle of atomic absorption spectroscopy. Write a note on the
instrumentation and working and applications of the spectrometer.
7. How is nickel quantitatively estimated using AAS?
8. Narrate the applications and limitations of AAS.
9. What is UV-visible spectroscopy?
10. Discuss the various types of transitions in UV-visible spectroscopy.
11. Explain the instrumentation, working and applications of UV-visible
spectroscopy.
12. Write about the various types of fundamental vibrations in IR spectroscopy.
13. Sketch the possible vibrational modes of Water and CO
2
.
14. Explain the instrumentation, working and applications of IR spectroscopy.

Chemisty - II - NOL

Transféré par

Informations du document

Description originale:

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Chemisty - II - NOL

Transféré par

Droits d'auteur :

Formats disponibles

V.S.

This is Nernst equation for a reversible cell.

is positive, the reaction occurs spontaneously. If E

37. What is Helmholtz double layer?

Vous aimerez peut-être aussi