FROM THE EDITOR'S DESK

CONCEPTUALISE
CHEMISTRY
C
hemistry is the most dependable subject among all the three. It may be the most favourite for some
and may be the scariest for others. Actually in my opinion some of the students have the aptitude of
this subject while others do not. So those who have the aptitude of this subject like it most, while
others develop a fear for this subject.

For me Chemistry is the mysterious subject. (Chemistry che + mistry or mystry). Imagine nobody has seen
electron till date but many of us has written books on it. Likewise nobody has seen interaction type between the
particles during the reaction but the explanation or mechanisms of almost all reactions are there with us. Actually
for that someone has to jump into the test tube while reaction is going on. So in a way it is a bit different and unique.
Before discussing more about the nature of this subject it is better to understand its importance for JEE. As
mentioned in the beginning it is the most dependable subject for JEE which simply indicates its importance. As far
as my experience and analysis says Physics and Maths are the two subjects on the basis of which the selection
of an aspirant in IIT is determined. Chemistry on the other hand is responsible for the merit position of an
aspirant. This analysis is based on the fact that whenever a comparison is made between the marks of a high ranker
and low ranker in IIT-JEE, the significant difference is visible only in the Chemistry marks, while the marks of
Physics and Maths remain more or less same. Naturewise I consider this subject as exactly opposite to that of
physics i.e. for me
Physics Chemistry
Now you will say HOW? Or Why I consider so?
My answer for this How and Why is very clear and based upon following assumptions :
You can yourself observe the same i.e. in the case of physics theory is developed first followed by practicals or
applications to verify it while in the case of chemistry practicals (reactions) occur first and later on the related theory
is developed on the basis of its end results.
 Physics Chemistry
A theory given first
which is then tested
Here, a reaction is
performed first which
MANTRAS TO CAPTURE THE
trough practicals or
application, i.e.
in followed by the
devlopment of theory or
MYSTERIOUS CHEMISTRY
Ist Theory
most possible theory. So Now, here the compulsion is that the theory must be
Ist Reaction developed in accordance with the result we got, instead the
Practicals

Then Practicals or Practical

Experiments Application
TESTED and results decide Theory developments through
whether the theory in correct or not and result of reaction
Thus, the placement of both theory and
practicals is opposite which in turn, make them
opposite naturewise. This is the only reason why
some students have a good command over :
1. Physics and Maths with the fear of chemistry
or
2. Chemistry and Maths with the fear of
physics.
However, the students with equal or almost equal
command over Physics and Chemistry are
comparatively less. Naturewise one more
interesting observation can be made about these
subjects, i.e. as Physics involves verification of
theory given through practicals or applications,
hence the end results in the case of this subject are
many and variable.
The more questions with marks like kyon or why,
how etc., you apply, the more variability you can
achieve. However, such a pattern is not applicable
in chemistry. Here, the end result is one and that is
certain, means it cannot be changed and we have to
develop the theory in accordance with the
end result.
Thats why in this particular subject such type of
questions are of lesser importance.
generalised perception about acids written above. In more
simple words, we can say that in chemistry, we have
limitations i.e. the limitations of end results of the reactions
and as these end results are certain (not changeable) hence,
we have to think or develop our concept logically in
accordance with the situation. Thats why the theory in
chemistry is not the certain theory rather, it is the most
probable theory. Further as the end result may change with
change in situations hence, one may found exceptions to
the theory developed more frequently as compared to any
other subject. So while going for chemistry remember!
1. There will be certain end result of any chemical reaction
which limits our working arena technically.
2. The end result may change in accordance with situations,
thus in turn give birth to so called exceptions in
chemistry.
3. Most of the theories or rules covered in chemistry are
results based and as nobody has seen interacting
particles in a test tube hence, these theories or rules are
considered under the most probable category.
4. In the purview of first three statements, we can conclude
that the aptitude of chemistry involves explorations into
the subject with very limited kyon or why or how like
punctuations.
5. Beside the above written aspects, language plays a very
important role in tackling chemistry. A small twist in
language changes the entire meaning of the question. So,
nature wise a substantial control over language is
required along with the aptitude to grip this subject
properly.
Keep only one thing in mind:

Its the constant and determined effort that breaks

down all resistance, sweeps away all obstacles
Claude M. Bristol
 ENTHALPY OF A REACTION AND CALORIMETRY
It is a branch of physical chemistry in which we study about the energy change associated with chemical reaction.
Enthalpy of a Reaction ( H)
Mostly chemical reactions in the laboratory are carried out
in open systems. The atmospheric pressure does not
change during the reaction, so the reaction occurs at
constant pressure. The heat released or absorbed during
the reaction at constant pressure is known as enthalpy of
reaction.
e.g. H2 (g) + Cl2 (g) 2HCl(g); H = 44 kcal
Enthalpy of a reaction (H) = Sum of enthalpies of products
(H P ) sum of enthalpies of reactants (H R ).
Standard Enthalpy of a
Reaction (H)
When enthalpy of a reaction is determined at 25C
temperature and 1 atm pressure, enthalpy of reaction is
referred as standard enthalpy of reaction.
Exothermic and Endothermic Reactions
l
The chemical reaction in which heat is evolved during
the course of reaction, is known as exothermic reaction.
e.g. C(s) + O2 (g) CO2 (g); H = 393.0 kJ
l
The chemical reaction in which heat is absorbed during
the course of reaction, is known as endothermic
reaction.
e.g. 2NH3 (g) N2 (g) + 3H2 (g); H = + 92.3 kJ
4
Flameless Heaters
These are used where cooking is difficult or impossible. Much of the
development work in this area was done for military uses. In combat,
lighting a fire is not advisable if you are trying to keep your location secret.
These are also useful where electricity is not available.
Flameless heaters rely on an exothermic reaction to provide hot food. In a
heatermeal products, the food is sealed inside a metal foil pouch and this is
placed inside a plastic bag containing a heating pad made up of a mixture of
magnesium and iron. To start the heating process, a little amount of water
(~30 mL) is poured into the plastic bag. An exothermic reaction starts and
the foil pouch containing the food gets hot. The heaters will heat 300 g of
food or water to 80C from room temperature in about 10 min.
Factors Affecting Enthalpy of a Reaction
1. Physical state of reactants and products Reactants having
different allotropic forms or physical states have different
enthalpies during course of their reactions. It is due to
different allotropic forms are held by forces of different
attraction strengths.
2. Reaction conditions At constant pressure, heat change
associated with chemical reaction is equal to enthalpy
change (H) while at constant volume it is equal to internal
energy change (U ).
H and U are related as, H = U + ng RT
where, ng = number of moles of gaseous products
number of moles of gaseous reactants.
 3. Temperature Values of H and U vary with temperature
according to following Kirchhoffs equations,
H2 H1 = C p (T2 T1 ) or H2 H1 = C p dT
U2 U1 = C V ( T2 T1 ) or U2 U1 = C V dT
(b) For reaction in solution Reaction involving solution are
carried out at constant pressure inside a coffee-cup
T2 calorimeter.
r H = Heat absorbed/released by calorimeter
T1 + heat absorbed/released by solution.
T2 = (mcT) calorimeter + (mcT) solution
Here, c = specific heat capacity.
T1

4. Amount of reactant H and U depend upon amount of Energetics of Food

reactant, e.g. 20 g of carbon produces more heat than n
A calorimeter is a piece of equipment designed to measure the
2.0 g of carbon on combustion. energy released or absorbed during a chemical reaction or phase
change.
Calculation of U and H values by a n
With the help of food calorimetry, we can determine the number of
calories per gram of food.
Calorimeter n
People who check nutrition labels to make decisions about which
(a) For gaseous reactions Reactions involving gases are foods to eat and which to avoid often base on the number of calories
carried out in a bomb calorimeter, as the reaction needs to per serving.
be carried out at constant volume. n
A calorie is a unit of energy as joule, however calorie is commonly
U value can be calculated as, used for a unit of food energy.
U = (Heat absorbed by bomb calorimeter)

1. For an endothermic reaction, if H is given in (a) 2KClO 3(g ) 2KCl(s ) + 3O 2(g )

kJ/mol. The minimum value for energy of activation (b) N 2( g ) + 3H 2( g ) 2NH 3( g )
(c) H 2( g ) + I 2( g ) 2HI( g )
will be
(d) 2SO 2( g )+ O 2( g ) 2SO 3( g )
(a) less than H (b) zero
(c) more than H (d) equal to H 6. Find the wrong statement among the following
Hint For an endothermic reaction products are at higher options, the heat of reaction depends on
energy level than reactants. (a) the temperature at which the reaction is carried out
(b) the manner by which the reaction is carried out
2. For the reaction,
(c) physical state of reactants and products
C2 H5 OH(l ) + 3O2 (g) 2CO2 (g) + 3H2 O(l ) (d) whether the reaction is carried out at constant pressure or at
The correct option is constant volume
(a) H = U RT (b) H = U + RT 7. For the reaction,
(c) H = U + 2 RT (d) H = U 2 RT C + O2 CO2; H = 393 kJ
3. C p for a reaction is given by 2.0 + 0.2 T cal/C, and 2Zn + O2 2ZnO; H = 412 kJ
its enthalpy of reaction at 10 K is 14.2 kcal. Which one is the correct statement?
Enthalpy of reaction at 100 K will be (in kcal) (a) Carbon can reduce ZnO to Zn
(a) 15.37 (b) 14.09 (b) Oxidation of carbon is not feasible
(c) 13.21 (d) 7.80 (c) Oxidation of carbon and zinc both takes place
T2 (d) Oxidation of zinc is not feasible
Hint H2 H1 = Cp dT
T1 Hint Since, H for Zn ZnO is more negative, indicates
that on coupling both the reactions, carbon can reduce ZnO to
4. Molar heat capacity of water in equilibrium with the Zn. Because on reversing the equation for zinc, the value of
ice at constant pressure is H becomes positive. This indicates, ZnO is less stable and
(a) zero (b) can be reduced to Zn by carbon.
(c) 40.45 kJ mol 1 (d) 57.6 kJ mol 1
8. (H U ) for the formation of CO from its elements
5. The reaction for which the difference (H U ) at 298K is (Given, R = 8.31JK 1 mol 1 )
would be minimum among the following reactions (a) 1238.78 J mol 1 (b) 1238.78 J mol 1
(at same temperature for all) is (c) 2477.57 J mol 1 (d) 2477.57 J mol 1

5
 DIFFERENT STANDARD ENTHALPY CHANGE
AND LAWS OF THERMOCHEMISTRY
Different Standard Enthalpy Change
The following table represents the name and definition of
different types of standard enthalpy change.
Definition of different types of
standard enthalpy change
Enthalpy of formation ( f H) The
enthalpy change for the formation
of one mole of a compound from
its elements in their most stable
state.
Enthalpy of combustion ( C H )
The amount of heat evolved or
absorbed when one mole of the
substance is completely burnt in
oxygen or air.
Enthalpy of fusion ( fus H ) The
enthalpy change when one mole
of solid substance changes into
its liquid form at constant
temperature.
Enthalpy of vaporisation ( vap H )
The enthalpy change when one
mole of liquid substance changes
into its vapour form.
Enthalpy of sublimation ( sub H )
The enthalpy change when one
mole of solid substance changes
into its vapour form.
Enthalpy of atomisation ( atomH )
Enthalpy change when one mole of
a substance is broken down into its
constituent isolated atoms in
gaseous state.
Enthalpy of neutralisation ( n H )
Enthalpy change when 1 mole of
water is formed by acid-base
neutralisation.
Bond dissociation enthalpy CH 4 ( g ) C( g ) + 4H( g );
( bond H )
Enthalpy change when all the bonds r H = bond H (reactants)
present in one mole of a compound
are broken in gaseous state.
Enthalpy of solution ( sol H )
Enthalpy change when one mole of
a solute is dissolved in excess of
solvent.
Lattice enthalpy ( lattice H )
Enthalpy change when one mole of
an ionic compound dissociates in
gaseous state.
6
CHEMISTRY CONCENTRATE
PROBLEMS RELATED TO ENTHALPY
n
First of all, write down all the balanced chemical reactions
including their enthalpy change value.
n
Mark these reactions in terms of equation number.
Example
n
Write down the chemical reaction for which we have to find out
1 enthalpy change value.
H 2( g ) + O 2 ( g ) H 2O( l );
2 n
Arrange the given equation in such a manner that we could get the
f H = 285.8 kJ mol 1
required equation.
f H value of an element in its most
n
For this purpose, we can apply operation such as addition or
stable state is taken as 0.
subtraction of equations and multiplying or dividing by an integer to
C 6H12O 6 ( g ) + 6O 2 ( g )
the equation.
6 CO 2 ( g ) + 6 H 2O( l );
n
Same operations should be applied for given enthalpy change
C H = [( 6 Hf ( CO 2 )) + ( 6 Hf(H 2O) )]
[ Hf(C 6H 12O 6 ) + ( 6 Hf( O 2 ) )] values as well.
C H = 2802 kJ mol 1
n
Finally, we get the required enthalpy change value.
The heat produced due to the
combustion of 1g of a fuel is called
calorific value. REMEMBER
H 2O( s) H 2O( l ); fus H = 6 kJ mol 1 Except bond dissociation, enthalpy change for any other process is
The temperature at which a solid is given as,
converted into liquid is called its Enthalpy change
melting point.
= Sum of enthalpies for all products sum of enthalpies for all reactants.
H 2O( l ) H 2O( g );
But for bond dissociation,
vap H = 40.8 kJ mol 1
Enthalpy change
= Sum of enthalpies of all reactants sum of enthalpies of all
products.
H 2O( s) H 2O( g );
sub H = 51.1kJ mol 1
sub H = fus H + vap H
Laws of Thermochemistry
H 2 ( g ) 2 H( g ); Lavoisier and Laplace's Law
atomH = 43.5 kJ mol 1 The enthalpy of decomposition of a compound is
numerically equal to the enthalpy of formation of that
compound with opposite sign,
H + ( aq ) + O H( aq ) H 2O( l ); e.g. A + B C; H = x
n H = 57.1kJ
C A+B; H = x
Hesss Law of Constant Heat
atomH = 1665 kJ mol 1
Summation
bond H (products) Enthalpy change for a reaction is same whether the reaction
is carried out in one step or in several steps.
NaCl( g ) Na +( aq ) + Cl ( aq );
e.g. C(g) + O2 (g) CO2 (g); r H
sol H = 4 kJ mol 1
1
sol H = lattice H + hyd H C(s) + O2 (g) CO(g); r H1
2
NaCl ( g ) Na + ( g ) + Cl ( g ); 1
CO(g) + O2 (g) CO2 (g); r H2
lattice H = 788 kJ mol 1 2
According the Hesss law,
r H = r H1 + r H2
9. When 1g of carbon-atom is converted to 1g molecule 13. The standard enthalpy of formation (Hf) at 298K for
of CO2 , the heat is same methane (CH4 ) is 74.8 kJ mol 1 .
(a) irrespective of whether the volume is kept constant or The additional information required to find the
pressure is kept constant average bond energy of C H bond formation would
(b) irrespective of the temperature at which the reaction is be
carried out
(a) first four ionisation energies of carbon and electron gain
(c) where carbon is in the form of graphite or diamond enthalpy of hydrogen
(d) None of the above (b) the dissociation energy of H 2( g )
10. For the reactions, H2 (g) + Cl2 (g) 2HCl(g) + x1 kJ (c) latent heat of vaporisation of methane
and 2HCl(g) H2 (g) + Cl2 (g) x2 kJ, the correct (d) the dissociation energy of H 2( g ) and enthalpy of sublimation
statement is of carbon
(a) x1 and x2 are numerically equal 14. The latent heat of vaporisation of water is
(b) x1 = 4 x2
10.5 kcal mol 1 at 25C and standard heat of
(c) x1 x2 > 0
(d) x1 x2 < 0 formation of liquid water is 68.3 kcal.
The enthalpy change of the reaction,
11. From the figure given below 1
2C (graphite (g)) + 4H2(g) H2 (g) + O2 (g) H2 O(g) is,
H1 H2 2
(a) 57.8 kcal (b) 78.8 kcal
2C (graphite (s)) + 8H (g) (c) + 57.8 kcal (d) + 78.8 kcal

15. A cylinder of gas supplied by a company is assumed

H3 H4
2CH4(g) to contain 14 kg of butane. If normal family requires
20,000 kJ of energy per day for cooking, how long
The values of will the cylinder last?
heat of formation of CH4 , heat of sublimation (Given, heat of combustion of butane = 2658 kJ)
of graphite and heat of dissociation of H2 , (in terms (a) 23 days (b) 32 days
of H1 , H2 , H3 and H4 ) respectively are (i.e. (c) 50 days (d) 42 days
correct order is) Hint Number of days cylinder works
H2 H1 H1 + H2 + H4 Energy provided by 14 10 3g gas
(a) , , =
4 2 2 Energy required per day
H1 + H2 + H4 H1 H2
(b) , ,
2 2 4 16. Bond dissociation energy of XX, XY and Y2 (all are
H3 H2 + H1 H4 diatomic) are in the ratio of 1 :1 : 0.5 respectively
(c) , ,
4 2 2 and Hf of XY is 200 kJmol 1 , then bond
H2 H3 + H1 H4
(d) , , dissociation energy for X 2 is
2 2 4
(a) 880 kJ mol 1 (b) 800 kJ mol 1
12. NH3 (g)+ 3Cl2 (g) e NCl3 (g)+ 3HCl(g); H1 (c) 200 kJ mol 1 (d) 400 kJ mol 1
1 1
Hint Required relation is X 2 + Y2 XY
N2 (g) + 3H2 (g) e 2NH 3 (g); H2 2 2
2HCl(g); H3 1 1
H2 (g) + Cl2 (g) e Hr = [BE ( X 2 ) + BE ( Y2 ) BE( XY )]
2 2
The heat of formation of NCl3 (g) in terms of Hr = 200 kJ mol 1
H1 , H2 , and H3 will be
(a) Hf = H1
H2 3 17. For enthalpy changes,
H3
2 2 Cl2 (g) 2Cl(g); 242.3kJ mol 1
H2 3
(b) Hf = H1 + H3 I2 (g) 2I(g); 151.0 kJ mol 1
2 2
H2 3 ICl(g) I(g) + Cl(g); 211.3 kJ mol 1
(c) Hf = H1 + . H3
2 2 I 2 (s) I2 (g); 62.76 kJ mol 1
(d) All of the above options give the same result

7
 If standard states for iodine and chlorine are Given, Hf for CO2 (g) = 94 kcal/mol
I2 (s) and Cl2 (g), the Hf for ICl(g) is Hf for H2 O(l) = 68 kcal/mol.
(a) 14.6 kJ mol 1 (b) 16.8 kJ mol 1 (The whole reaction occurs under standard
. kJ mol 1
(c) + 167 (d) + 14.6 kJ mol 1 conditions).
(a) 66 kcal/mol (b) 22 kcal/mol
18. When 1.4 g of iron combines with sulphur, 1.9 kJ of (c) 44 kcal/mol (d) 88 kcal/mol
heat comes out. Thus, standard enthalpy of formation
of FeS is 20. Sublimation energy for I2 (s) is 57.3 kJ/mol and
enthalpy of fusion is 15.5 kJ/mol. The enthalpy of
(a) 19 kJ (b) 76.0 kJ (c) 3.8 kJ (d) zero
vaporisation for I2 is
19. The enthalpy of formation of C2 H5 OH(l ) is 66 kcal/mol. (a) 41.8 kJ/mol (b) 418
. kJ/mol
The enthalpy of combustion of CH3 OCH3 (l ) is (c) 72.8 kJ/mol (d) 72.8 kJ/mol
348 kcal/mol. Find, H for isomerisation of ethanol Hint Hsub = Hfus + Hvap
to methoxymethane (CH3 OCH3 ).

ENTROPY (S ) AND GIBBS FREE ENERGY (G )

Entropy (S)
l
A thermodynamic quantity that provides a quantitative Formulae Related to Entropy and
measure of how much energy is spread out when something Gibbs Free Energy
happens during a chemical reaction.
or Entropy
l
A thermodynamic property that measures the extent of n
At constant pressure, when temperature changes,
molecular disorder or randomness. T
S = 2.303 nC p log 2
It is a state function, used to define the second law of T1
thermodynamics. n
At constant volume, when temperature changes,
T
S =2.303 nCV log 2
Gibbs Free Energy (G) n
T1
At constant temperature, when volume changes,
l
It is a state function. It is defined as hypothetical V
S =2.303 nR log 2
infinitesimal energy which is used up during a spontaneous T1
process. or n
At constant volume, when both temperature and pressure change,
It is defined as the maximum amount of energy available to a p
l

T
system during a process that can be converted into useful S =2.303 nCV log 2 + nR log 1
work. T1 p2
n
At constant pressure, when both temperature and volume change,
Spontaneity of a Chemical Reaction T V
S =2.303 nC p log 2 nR log 1
The spontaneity of a reaction depends on H, S and T, is given T1 V2
by the following table: H
n
When phase transition occur during the process, S =
H S G = H TS Reaction spontaneity T
For solid to liquid phase change, H = H fus
Exothermic () + Spontaneous at all temperatures.
For liquid to gas phase change, H = H vap
Spontaneous at low temperatures.
For solid to gas phase change, H = H sub
+ Non-spontaneous at high
temperatures.
Gibbs Free Energy
Endothermic (+) + + Non-spontaneous at low
temperatures. G =H TS
V2
+ Spontaneous at high temperatures. G = W = 2.303RT log
V1
+ Non-spontaneous at all
temperatures. G = G + 2.303 RT log Q
TS = H 0 Equilibrium At equilibrium, G = 2.303 RT log K

8
21. If, PbO2 PbO; G at 298 K < 0 and 26. The direct conversion of a substance is difficult from
SnO 2 SnO; G at 298 K > 0. Then, most A to B. Hence, the process is carried out as follows:
probable oxidation states for Pb and Sn are C D
(a) Pb 4+ ,Sn4+ (b) Pb 2+ , Sn4+
(c) Pb 2+ , Sn2+ (d) Pb 4+ , Sn2 +
Hint Given, A B
(i) G for the formation of Pb 2+ is negative means Pb 2 + is more
stable than Pb 4 + . Given, S ( A C ) = 50 units, S (C D) = 30 units
(ii) G for the formation of Sn2 + is positive means it is less stable. and S (B D) = 20 units
22. For a reaction, H2 O(s) H2 O(l ) at 0C
e Then, net entropy for the process from A to B is (in
temperature and normal pressure, the correct true of number of units)
choice is (a) 60 (b) +60
(a) H < TS (b) H = G (c) 100 (d) +100
(c) H = TS (d) S = 0 Hint Net entropy change (S) = S A C + SC D + S D B
Hint At equilibrium, = S A C + SC D S B D
G = 0 means
H = TS ; (Q G = H TS ) 27. For a cell reaction, (at 25C)
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s), the value
23. When an egg is boiled, its entropy of emf is 1 V.
(a) increases (b) decreases
If enthalpy of reaction is 197.5 kJ/mol, the change
(c) shows no change (d) becomes zero
in standard molar entropy will be (in JK 1 mol 1 )
24. Silane (SiH4 ) burns in air as, (a) 11.5 (b) 15.1
(c) 11.5 (d) 15.1
SiH4 (s) + 2O2 (g) SiO2 (s) + 2H2 O(l)
The standard Gibbs energies of formation of Hint G = nFE also G = H TS
SiH4 (g), SiO2 (s) and H2 O(l) are + 52.3, 805.0 and 28. T1 and T2 are freezing and melting points of a
228.6 kJ mol 1 respectively. Calculate Gibbs free substance, which of the following graphs represents
energy change in kJ for the reaction. correctly about the variation of S with temperature?
(a) 1314.5 (b) 1472.3 (c) 1582.3 (d) 1272.8
T2 T2
25. In a fuel cell, methanol is used as fuel and oxygen
gas is used as an oxidiser, the reaction is, (a) S (b) S
3 T1 T1
CH3 OH(l ) + O2 (g) CO2 (g) + 2H2 O(l )
2
At 298 K, G of formation for CH3 OH(l ), H2 O(l ) and T T

CO2 (g) are 166.2, 237.2 and 394.4 kJ mol 1

respectively. T1 T2
If standard enthalpy of combustion of methanol is T1 T2
(c) S (d) S
726 kJ mol 1 , efficiency of the fuel cell will be
(a) 70% (b) 80% (c) 90% (d) 97%
G T T
Hint Efficiency (%) = 100
H Hint T1 and T2 will be same for freezing and melting point.

Answers
1. (c) 2. (a) 3. (c) 4. (b) 5. (b) 6. (b) 7. (a) 8. (b) 9. (a) 10. (a)
11. (b) 12. (a) 13. (d) 14. (a) 15. (b) 16. (b) 17. (c) 18. (b) 19. (b) 20. (a)
21. (b) 22. (c) 23. (a) 24. (a) 25. (d) 26. (b) 27. (b) 28. (b)

9
 MASTER
1. Heat of neutralisation for four acids A, B, C and D (ii) 10 g of ice at 0C 10 g of water at 0C
are 13.7, 9.4, 11.2 and 12.4 kcal respectively, (Transformation state)
when they are neutralised by a common base. The (iii) 10 g of water at 0C 10 g of water at10C.
order of their acidic strength is Thus, heat required mct + mL + mct
(a) A > B > C > D (b) D > C > B > A
(c) A > D > C > B (d) B > C > D > A 5. Which of the following reactions is said to be
Hint Lower be the heat of neutralisation more be the enthalpy driven?
dissociation energy. Thus, weaker be the acid. (a) Endothermic reaction with positive entropy change and high
temperature
2. A solution of 250 mL of 2M KOH is added to 250 mL (b) Endothermic reaction with negative entropy change and low
of 2 M HCl and shaken. The rise in temperature T1 is temperature
noted. The experiment again repeated, taking (c) Exothermic reaction with the entropy change and high
500 mL of each solution, the rise in temperature T2 is temperature
noted. Assume all the heat is taken up by the (d) Exothermic reaction with negative entropy change and low
temperature
solution in both the cases.
The relation between T1 and T2 is 6. The standard heat of combustion of Al is 837.8 kJ
(a) T1 = T2 (b) 2T1 = T2 mol 1 at 25C. If Al reacts with O2 at 25C, which of
(c) T1 = 2T2 (d) T1 = 4T2 the following releases 250 kJ (approx.) of heat?
Hint The heat evolved in first case is twice as compared with (a) The reaction of 0.625 mole of Al
second case but since, volume also becomes double, the (b) The reaction of 0.625 mole of Al 2O 3
temperature in both the cases remain same. (c) The reaction of 0.312 mole O of Al
(d) The reaction of 0.150 mole of Al 2O 3
3. The ionisation energy of solid NaCl is 180 kcal
per mol. The dissolution of the solid in water in form 7. Two moles of an ideal gas undergoes expansion
of ions is endothermic to the extent of 1 kcal per mol. under isothermal reversible condition from 5 to 50L
If the solvation energies of Na + and Cl ions are in at 27C. The entropy change associated with this
the ratio of 6 : 5. Then, enthalpy of hydration for process is [R = 8.3 J]
sodium ions per mol is (a) 10 JK 1 (b) 16.0 JK 1
(c) 38.2 JK 1 (d) 19.1 JK 1
(a) 82.6 kcal (b) 85.6 kcal
(c) 97.6 kcal (d) 100 kcal 3
8. Given, S(s) + O2 (g) SO3 (g) + 2x kcal
Hint H solution = Hi + Hh. 2
Given, H solution = 1 and Hi = 180. 1
and SO2 (g) + O2 (g) SO3 (g) + y kcal
1 = Hi + Hh 2
1 = 180 + Hh
Find the value of Hf for SO2
Hh = 179 = Hh(Na + ) + Hh(Cl )
(a) x 2 y (b) y 2 x
Q Na + and Cl has ratio of solvation energy = 5 : 6 2x
(c) x + 2 y (d)
6 5 y
H h = ( Na + ) + (Cl ) = 179
11 11
6 179 9. Determine the enthalpy of the reaction,
H h(Na + ) = = 97.6 kcal
11 C3 H8 (g) + H2 (g) C2 H6 (g) + CH4 (g)
4. The average molar heat capacities of ice and water at 25C, using the given heat of combustion values
are 37.6 and 75.2 J mol 1 K 1 respectively. Its under standard conditions.
enthalpy of fusion is 6.02 kJ mol 1 . The amount of Compound H2( g ) CH 4 ( g ) C 2H6 ( g ) C (graphite)
heat required to raise the temperature of 10 g of H (kJ/mol) 285.0 890.0 1560.0 393.0
water from 10C to 10C is equal to
(a) 2376 J (b) 4572 J
The standard heat of formation of C3 H8 (g) is
(c) 1129 J (d) 3971 J 103 kJ mol 1 .
Hint Required steps are: (a) 49 kJ (b) 60 kJ
(c) 50 kJ (d) 55 kJ
(i) 10 g of ice at 10C 10 g of ice at 0C

10
10. Compute the heat of formation of liquid methyl The standard Gibbs energies of formation of SiH4 (g),
alcohol in kJmol 1 , using the following data. Heat of SiO2 (s) and H2 O(l ) are + 52.3, 805 .0 and 228.6 kJ
vaporisation of liquid methyl alcohol = 38 kJ mol 1 . mol 1 respectively Calculate Gibbs energy change
Heat of formation of gaseous atoms from the for the reaction.
elements in their standard states, (a) 1314.5 kJ (b) 1314.5 kJ (c) 895.07 kJ (d) 905.4 kJ
H = 218 kJ mol 1, C = 715 kJ mol 1
12. Match the following columns.
O = 249 kJ mol 1
Column I Column II
Average bond energies,
A. Spontaneous process p. H = ve
C H = 415 kJ mol 1 B. Heat flow from high temperature of system q. G = + ve
C O = 356 kJ mol 1 to low temperature of surrounding
C. Exergonic process r. total S = + ve
O H = 463 kJ mol 1 D. Increase in randomness of system by s. G = ve
(a) 274 (b) 266 heating

(c) 220 (d) 277 Codes

A B C D A B C D
11. Silane (SiH4 ) burns in the air as (a) p q,r p,q s,p (b) p,r q,s p r,q
SiH4 (g) + 2O2 (g) SiO2 (s) + 2H2 O(l ) (c) r,s p,r,s q q,r (d) s,p r,s q p

Answers
1. (c) 2. (a) 3. (c) 4. (d) 5. (d) 6. (d) 7. (c) 8. (b) 9. (d) 10. (b)
11. (a) 12. (c)

11
 LAW OF CHEMICAL EQUILIBRIUM
AND EQUILIBRIUM CONSTANT
Chemical equilibrium is a state of reversible reactions in which the Case I When DH = 0, K1 = K 2, equilibrium constant (K) is
concentrations of reactants and products do not change with time. independent from temperature (T).
Case II When DH < 0, (endothermic),
Law of Chemical Equilibrium K 2 > K1, K increases with increase in temperature.
Case III When DH < 0, (exothermic),
(or Law of Mass Action) K 2 < K1, K decreases with increase in temperature.
According to this law, the rate at which a substance reacts is directly l
Dng = Moles of gaseous products - moles of
proportional to its active mass raised to the power of its stoichiometric gaseous reactants.
coefficient. For a chemical reaction, l
f = activity coefficient, for dilute solutions, f = 1
aA + bB - cC + dD l
For heterogeneous system, concentration of solid
Rf = K f [ A] [B]
a b reactants or solid product is taken to be unity.
Rb = K b [C]c [D]d
l
If Dng = 0, K p = K C
At equilibrium, Rf = Rb Dng > 0, K p > K C
Dng < 0, K p < K C
Formulae for equilibrium Constant in Terms of Different
Quantities and Different Conditions Units of Equilibrium Constant (K )
General reaction, aA + bB cC + dD K p = (atm)Dn ; K C = (mol/L)Dn
- K x = unitless ; K a = (mol/L)Dn
Quantity Equilibrium constant
1. Concentration [C ]c [ D]d
KC =
[ A] a [ B] b Characteristics of Equilibrium
2. Partial pressure ( pc ) ( pdD ) [C ] c [ D] d
K p = Ca =
( pA ) ( pBb ) [ A] a [ B] b
Dn
( RT ) g Constant (K p and KC )
Dn g
= KC ( RT ) l
K has a definite value for a given reaction at a
3. Active mass [ a ]C [ a ]d ( f )c ( f )d [C ]c [ D]d particular temperature and it does not influence by
Ka = C a D b = C a D b any other factors except temperature.
[ aA ] [ aB ] ( fA ) ( fB ) [ A] a [ B] b
l
It is independent of initial concentration of
= K f KC
reactants and products.
4. Mole fraction [ cC ]c [ c D ]d
Kx = l
The value of K remains same whether the
[c A ] a [c B ] b
equilibrium is achieved in forward or backward
direction.
General reaction, A - B equilibrium constant
Condition Equilibrium constant Based on the state of the reactants and products at
1. B e A 1 equilibrium, chemical reactions are divided into two
K -1 =
K types:
2. mA e mB K = ( K )m Homogeneous Equilibria
3. A B K = ( K )1/ m
m
e m All the reactants and products are in same phase
4. When temperature (T) is DH DS (either gas or liquid).
log K = - +
given 2.303RT R
5. When temperature KC 1 DH 1 1 Heterogeneous Equilibria
changes from T1 to T2 log = -
KC 2 2.303R T1 T2 The reactants and products are in different phases at
Kp1 DH 1 1 equilibrium.
log = -
K p2 2.303R T1 T2

12
 Procedure to find number of moles, mole fractions and K values at equilibrium
. Homogeneous equilibria Heterogeneous equilibria
H2 ( g ) + l 2(g ) - 2Hl( g ) NH 4CO 2NH 2 ( s) - 2NH 3 ( g ) + CO 2 ( g )
Initial moles a b 0 1 0 0
Equilibrium moles ( a - x) ( b - x) 2x 2x x
Total moles at equilibrium ( a + b) 3x
Active masses a b
V V
Mole fraction a - x b - x 2x 2 1

a + b a + b a + b 3 3

Partial pressure a - x b - x 2x 2p p
p p p
a + b a + b a + b 3 3

KC 4 x2 KC = 4 x3
( a - x)( b - x)
Kp 4 x2 4p 3
Kp =
( a - x)( b - x) 27

Note The active mass or concentration or partial pressure of pure solid, pure liquid and solvents are taken as unity(1), hence, they do not
appear in rate equation.

1. The equilibrium constant K p , for the reaction, Thus,

A - 2 B, is related to degree of dissociation (a ) of D[ A] = 0.2 M, D[B] = 0.4 M
A and total pressure p as Hence, n = 2
4a p2
4a p 2
(a) (b) Means A 2 B
1 - a2 1- a
(ii) At equilibrium, [ A] = 0.3 M
4 a 2 p2 4 a 2 p2
(c) (d) [B] = 0.6 M
1 - a2 1- a
[B]2 (0.6)2
2. Progress of the reaction, A nB, with respect to \ KC = = = 1.2
time is shown below.
- [ A ] (0.3)
Note Parallel lines with respect to x-axis at points x and y,
The stoichiometric coefficient of product B and value
show the equilibrium position of A and B respectively.
of equilibrium constant (K C) respectively.
3. For the reactions,
0.6
y
B A - B, K1 = 2
B - C, K2 = 4
0.5 z and C - D, K3 = 3
(M) 0.4
(Conc.)
0.3 x A
Then, for the reaction, A -
D, under similar
conditions, the value of equilibrium constant (K eq ) will
0.2
be
(a) 6 (b) 12 (c) 24 (d) 48

1 2 3 4 5
Hint On adding all the given reactions (three reactions) the
Time/Hour values of K will be multiplied.
4. For the reaction, N2 (g) + O2 (g) 2NO(g), K C at
-
(a) 2 and 1.2 (b) 2 and 2 800 C is 0.1, when equilibrium concentrations of both
(c) 4 and 1.2 (d) 2 and 4 the reactants are 0.5 molL- 1 , then value of K p at above
Hint (i) Concentration of A changes during 1h to 5h temperature is
= 0.5 to 0.3 = 0.2 M (a) 0.5 (b) 0.1 (c) 0.01 (d) 0.05
Concentration of B changes during 1h to 5h Hint At equilibrium,
= 0.2 to 0.6 = 0.4 M Q Dn = 0, \ KC = K p = 01
.

13
 K1

5. NO(g) + 1 O2 (g) - NO2 (g) SO3

2 K2

and 2NO2 (g) -

2NO(g) + O2 (g) (c) Conc. O2
Then, K1 and K2 are related with each other, as
1 K1 1 K12 SO2
(a) K 2 = (b) K 2 = (c) K 2 = (d) K 2 =
K1 2 K12 2 Time
1
Hint Multiply Eq. (i) by 2 and reverse it, K1 becomes
( K1 )2 SO3
1 (d) O2
Thus, K2 = Conc.
K12
SO2
6. Calculate the partial pressure of CO, if Time
D
CaCO3 (s) CaO(s) + CO2 (g); K p = 8 10 - 2
Hint Since, the value of Keq for forward reaction is high. The
CO2 (g) + C(s) 2CO(g); K p = 2 product SO 3 will be formed to large extent at equilibrium.
(a) 0.08 (b) 0.2 (c) 0.4 (d) 4 9. Sulphide ions in alkaline solution react with
Hint K p(CO 2 ) = p(CO 2 ) = 8 10 - 2 [From Eq. (i)] solid sulphide to form polysulphide ions having S22 - ,
S23 - etc., ions. If for, S + S2 --S22 - ; K1 = 12
( p(CO))2
Kp = [From Eq. (ii)]
p(CO 2 ) 2S + S2 - - S23 - ; K2 = 132
The value for K3 , for the following reaction
7. For the following reaction, A B, variation of - S + S22 - - S23 - , will be
concentration with time is shown below.
(a) 11 (b) 22 (c) 33 (d) 44
y
10. The rate of reaction for forward reaction is two times
B
that of reverse reaction at given temperature and
(M) x identical conditions, then K eq will be
Conc.
(a) 0.5 (b) 1 (c) 1.5 (d) 2
z A

O
Time
The concentrations A and B are minimum and
maximum respectively at points
(a) x and y (b) x and z (c) y and z JKCET will be on May 21 & 22, 2 016
(d) any two points between y and z
The Jammu & Kashmir Board of Professional
Hint Reversible feature of the reaction starts from point x, Examination has announced the dates for Jammu &
thereafter concentration of A starts to decrease and
Kashmir Common Entrance Test (JKCET) 2016,
concentration of B starts to increase. At point z concentration
conducted for admissions to undergraduate
of A becomes lowest and constant. At point y-concentration
of B becomes maximum and constant.
engineering courses across engineering colleges in
Jammu & Kashmir. JKCET 2016 is scheduled to be
8. A reaction is carried out in a closed vessel as follows: conducted on May 21 and May 22, 2016. Apart from the
2SO2 (g) + O2 (g) - 2SO3 (g) exam dates, the notification released by the exam
If the value of K eq for forward reaction is quite large; conducting authority also published the documents
which of the following graph is the correct required to be kept ready by a student before filling
representation for the above reaction? the Application Form of JKCET 2016. Candidates
aspiring for the exam have to be ready with the below
SO3 mentioned documents for filling the application
form:
(a) Conc. SO2 l
Permanent Resident Certificate (State Subject)
O2 l
Date of Birth Certificate
Time
l
Reserved Category Certificate (if applicable)
l
Marks Certificate/Marks Card of qualifying
Examination. (If qualifying exam is passed)
O2
SO2
l
Tuition Fee Waiver Certificates (where Annual
(b) Conc. income of the parents is less than Rs. 4.50/- Lacs)
SO3

Time

14
 LE-CHATELIER'S PRINCIPLE, IONIC EQUILIBRIUM
AND OSTWALD'S DILUTION LAW
Le-Chateliers Principle Here,
When a change is brought about on a system in equilibrium, Dng = 2 - (3 + 1) = - 2
the system tends to adjust itself to reduce the effect of change. Hence, to get more NH 3, pressure needs to be increased.
The Effect of Varying Conditions on the Equilibrium Step 4 Predicting the effect of temperature
For exothermic reaction, decrease in temperature favours
aA + bB - cC + dD; Dn = (c + d) - (a + b)
g
forward reaction and for endothermic reaction, increase in
Changes imposed Equilibrium position Equilibrium Any other temperature favours forward reactions.
on the system in
equilibrium moves constant points Since, the given reaction is exothermic, to get more NH 3,
Concentration of A To right No change temperature needs to be decreased.
and/ or B increased Conclusion Hence, the production of NH 3 can be increased
Concentration of C To left No change by increasing pressure, decreasing temperature and
and/or D increased
Pressure increased To right if No change Very little
increasing the concentration of H 2 and N 2.
(c + d ) < ( a + b ) , i.e. effect, if any,
Dng = -ve on reactions
in liquid
Ionic Equilibrium
solution. Equilibrium attained between undissociated electrolyte and
To left if No change ions furnished by it in solution is known as ionic equilibrium.
(c + d ) > ( a + b ) , i.e.
Dng = +ve
No change if Degree of Dissociation (a)
No change
(c + d ) = ( a + b ), i.e For a dissociation reaction, degree of dissociation,
Dng = 0 Total number of moles undergo dissociation
To left if DH = -ve Value Equilibrium a=
decreased achieved
Total number of moles taken initially
Temperature (exothermic)
faster. HA H +A
- + -
increased
To right if DH = +ve Value Equilibrium At t = 0, n 0 0
(endothermic) increased achieved At t, (n - na) na na
faster.
Addition of a No change No change Equilibrium na
\ Degree of dissociation = =a
catalyst achieved n
faster.
(1 - a 1 as weak electrolyte)

CHEMISTRY CONCENTRATE
TIPS TO SOLVE PROBLEMS REMEMBER
RELATED TO LE-CHATELIER'S PRINCIPLE The value of a depends on
(i) nature of solute.
The following steps can be followed to solve problems related to (ii) nature of solvent (higher the value of dielectric constant of solvent,
Le-Chateliers principle and to decide the favourable conditions for higher is the value of a ).
a chemical reaction. (iii) Dilution (the value of a of a weak electrolyte increases on dilution).
Step 1 Write down the balanced thermochemical equation (iv) Temperature (a increases with increase in temperature).
indicating the phase of each of the reactants and products
and the K value for the reaction.
Ostwalds Dilution Law
N 2( g ) + 3H 2( g ) e 2NH 3( g ); DH = - 92 KJ
2
For dissociation of a weak electrolyte,
( pNH )
Kp = 3
AB - A+ + B-
( pN 2 ) ( pH3 2 ) At C 0 0
t = 0,
Step 2 To increase the concentration of product NH 3, more At equilibrium, C(1 - a) Ca Ca
reactants need to be added or the product need to be
K 1
removed as soon as it is formed. 2
\ K = Ca or a = or a V [Qa << 1; 1 - a 1]
Step 3 Predicting the effect of pressure Find out Dng for the C C
reaction and then apply the fact that when pressure is According to this law, degree of dissociation is proportional
increased, the reaction shifts in a direction where number of to the square root of dilution for weak electrolytes.
moles decreases.

15
 2
11. 56 g of N2 and 8 g of H2 are heated in a closed vessel. 2x

At equilibrium, 34 g of NH3 is present in the vessel. 1 + x 4 x2
=
p1
Thus, K p1 =
The number of moles of N2 , H2 and NH3 at equilibrium 1 - x (1 - x ) (1 + x )
are respectively. p
(a) 1, 2, 2 (b) 1, 1, 2 (c) 2, 2, 2 (d) 2, 1, 2 1 + x
2
Hint (i) Convert given masses into number of moles. x p2
Similarly, K p 2 =
(ii) At equilibrium, equate number of moles of ammonia (1 - x ) (1 + x )
equal to 2 and find value of x (dissociated moles of N2 K p1 4 p1
at equilibrium). Therefore, =
K p2 p2
(iii) With the help of x, find the value of number of moles of
N2 , H2 and NH3 at equilibrium respectively.
16. Vapour density of equilibrium mixture of NO2 and
12. When alcohol (C2H5OH) and acetic acid (CH3COOH) N2O4 is found to be 40 for the equilibrium,
are mixed together in equimolar proportion, 66.5% of N2O4 (g) - 2NO2 (g)
these are converted to ester.
The degree of dissociation and percentage of NO2 in
How much ester (in moles) will be formed, if 1 mole of
the mixture is respectively.
acetic acid and 0.5 mole of alcohol react under same
(a) 0.15 and 26% (approx.) (b) 0.15 and 74% (approx.)
conditions?
(c) 0.85 and 26% (approx.) (d) 0.85 and 74% (approx.)
(a) 0.423 (b) 1.57 (c) 1.15 (d) 0.545
Hint (i) To find molecular weights calculated and observed.
Hint (i) Calculate the value of KC with the help of provided
percentage of ester. Let, vapour density (VD) (calculated) = D and
VD (observed) = d
(ii) Now, calculate number of moles of ester formed from
1 mole of acetic acid. (a) Calculated molecular weight = 2 D
(b) Observed (exp.) molecular weight = 2 d
13. If water and ice are in equilibrium, on applying (ii) To find degree of dissociation
pressure on the above system.
D-d
(a) More ice will form a=
(b) More ice will melt d
(c) Has no effect (iii) To find % of NO 2
(d) Ice becomes gas at same temperature. N 2O 4 2NO 2 -
Hint Water (ice) - Water (liquid)
n
Initially
At equilibrium
1
1- a
0
2a Q a = 0.15
Q For gases, at equilibrium, value of remains constant,
V At equilibrium [NO 2 ] = 2 0.15 = 0.30
applying pressure, volume of gas decreases. Total number of moles = 1 - a + 2 a = 1 + a = 1.15
Since, volume of W(Liquid) < W(Ice) 2a 0.30
\ % of NO 2 = = 100 = 26.08%
Thus, more ice will melt. 1 + a 1.15
14. Ionisation constant of CH3COOH is 1.7 10 -5 and H+ 17. Consider the following reaction,
concentration is 3.4 10 - 4 . Then initial concentration
of the acid is I2 + I - - I3-
(a) 3.4 10 - 4 (b) 6.8 10 - 3 This reaction is set up in aqueous medium. We
(c) 1.7 10 - 3 (d) 3.4 10 - 3 start with 1 mole of I2 and 0.5 mol of I- in 1L flask. After
15. Equilibrium constants K p and K p for the reactions equilibrium is reached, excess of AgNO3 gave
2 Y and Z
1
P + Q, respectively are in the
2 0.25 mole of yellow precipitate. Calculate the
X - -
ratio of 1 : 9, if degree of dissociation of X and Z are equilibrium constant.
equal, then the ratio of total pressure at these (a) 1.33 (b) 2.66
(c) 2.00 (d) 3.00
equilibria is
(a) 1 : 36 (b) 1 : 9 Hint Excess AgNO 3 gave 0.25 mol of yellow precipitate
(c) 1 : 1 (d) 1 : 3 (AgNO 3 + I - AgI)
Hint For X -2Y Yellow ppt

Initial 1 0 \ Mole of I -3 at equilibrium = 0.25

At equilibrium 1 - x 2x At equilibrium I 2 + I I3
1-x 0. 5 - x x
Total number of moles = 1 - x + 2 x = 1 + x Given, 0.5 - x = 0.25
x = 0.25

16
 18. The following reaction occurs in our body. (c) has no effect of temperature (d) All (a), (b) and (c) are wrong
+ - Hint In the given plot,
CO2 + H2O H2CO3 - H + HCO 3
1
If CO2 escapes from our body, increasing
T
(a) hydrogen ions concentration will diminish
Means T decreasing
(b) pH will decreases
and T decreasing, value of ln Keq increasing.
(c) H2CO 3 concentration will be altered
(d) forward reaction will be accelerated Which shows that, the reaction is exothermic by nature.
Hint When CO 2 escapes, equilibrium shift to the backward (QIn exothermic reactions, as T decreases value of K increases).
direction, thus, H + ions will diminish. 20. For the reaction,
19. Plot of K eq and inverse of temperature 1 is given; SO2Cl2 (g) - SO2 (g) + Cl2 (g)
T
this indicates that reaction must be The equilibrium is attained at 25C in a closed vessel
and an inert gas (He) is introduced.
Which of the following statement is correct?
(a) Concentration of SO 2 , Cl 2 and SO 2Cl 2 changes
Keq

(b) More Cl 2 is formed

(c) Concentration of SO 2Cl 2 increased
(d) All above statements are wrong
Hint At constant volume inert gas show no effect at
1/T
equilibrium.
(a) exothermic (b) endothermic
(QReactions occur in closed vessel).

pH SCALE, SALT HYDROLYSIS, BUFFER

SOLUTIONS AND SOLUBILITY PRODUCT
Ionic Product of Water Similarly, pOH = - log[OH- ]
Pure water acts as a very weak electrolyte with a equals to l
pH and pOH are related as
1.8 10 -9 at 25C. pH + pOH = 14 [Q[H+ ][OH- ] =10 -14 ]
For ionisation of water,
l
For neutral solution, [H+ ] = [OH- ] or pH = pOH = 7
H2O -H + OH-
+ For acidic solution, [H+ ] > [OH- ], pH < 7
[H ][OH- ]
+ For basic solution, [H+ ] < [OH- ], pH > 7
Ki = or K w = K i [H2O] = [H+ ][OH- ]
[H2O]
CHEMISTRY CONCENTRATE
where, K w = ionic product of water depends only on
temperature. CALCULATION OF pH IN CASE OF
+
For pure water, [H ] = [OH ] =10 - -7
M MIXTURE OF ACID AND BASE
\ K w = [H+ ][OH- ] = 10 -14 at 25C The following steps can be followed to find the pH:
Step 1 Calculate the moles of the strong acid and strong base present in
pH Scale the solution, e.g. when 100 mL of 1M HCl is mixed with 50 mL of 0.5 M
NaOH, Moles of HCl = M V = 100 1 = 100 m mol
To express the concentration of H+ ions from 1 M to10 -14 M in Moles of NaOH = M V = 50 0. 5 = 25 m mol
a simple way, pH scale was introduced in which pH is Step 2 Write down the balanced neutralisation reaction occurring in the
calculated as solution. HCl + NaOH NaCl + H2O
pH = - log[H+ ] Step 3 Find out the limiting reagent,
+
The [H ] is always expressed in mol/L. HCl + NaOH NaCl + H2O
t = 0, 100 m mol 25 m mol 0 0
After neutralisation 75 m mol 0 25 m mol 25 m mol
THE CONCEPT OF NEGATIVE pH Here, NaOH is the limiting reagent.
In case of highly concentrated solutions having [H+ ] > 1 M, the value of Step 4 If acid is the limiting reagent, then it will used up completely and
log[H+ ] becomes greater than 0, making pH negative. e.g. for 3 M HCl the solution will be basic. If base is the limiting reagent, then it will be
solution, pH = - log3 = - 0.4771 which is negative. used up completely and the solution will be acidic. Since, here NaOH is the
Hence, a negative pH simply means, the [H+ ] of the solution is greater limiting reagent, the solution will be acidic and pH can be calculated as
Moles of H+ 75 m mol
than 1M. pH = - log[H+ ], [H+ ] = = = 0.5 M
A solution having negative pH also occurs naturally in some mine areas, Total volume 150 mL
+
where the minerals form highly concentrated acidic solution. pH = - log [H ] = - log(0.5) = 0.3

17
 Importance of pH
Salt Hydrolysis
For soils and plant
It is a reverse process of acid-base neutralisation reaction in For humans For animals growth
which the salt reacts with water to form acid and base. Hence, n
For good digestion pH in n
The aquatic n
Most of the plants
the pH of the resulting solution can be acidic (acidic salt), stomach and small animals (like fish) grow best when the
basic (basic salt) or neutral. intestine should be can survive in pH of the soil is close
approximately 1.5 and 8.4 river water within to 7.
Formulae for pH respectively. a narrow pH n
If the soil is too acidic
n
The blood that goes to the range. or too basic, the
Type of acid/base pH heart and lungs, should n
When the pH of plants grow badly or
Strong acid (completely pH = - log[H + ] have pH ~ 6.5 means it rain water in do not grow at all.
dissociated) should be slightly acidic. about 5.6, it is n
The soil pH is also
Strong base (completely pOH = -log[OH - ] and pH = 14 - pOH n
Our mouth pH should not called acid rain. affected by the use of
dissociated) be lower than 5.5 Too much acid chemical fertilisers in
1 otherwise tooth decay can rain can lower the the field.
Weak acid (partially [H + ] = Ca = K aC ); pH = ( pK a - log C ) start. pH of river water n
If soil is too acidic, it
dissociated) 2 to such an extent
1
n
Bacteria present in our is treated with
Weak base (partially [OH - ] = Ca = K bC ; pOH = (pK b - log C ) that the survival of
mouth produce acids by materials like,
dissociated) 2 degradation of sugar and aquatic animals quick lime or slaked
pH = 14 - pOH food particles. become difficult lime or chalk.
Mixture of weak acids [H + ] = K a 1 C1 + K a 2 C 2 ...; pH = - log [H + ] n
The best way to prevent
n
The high acidity of n
If soil is alkaline, it is
from this is to clean the river water even treated with organic
-
Mixture of weak bases [OH ] = K b 1 C1 + K b 2 C 2 K; mouth after eating. kill the aquatic matter which is acidic.
pOH = - log [OH - ] animals.
Mixture of strong acid and C s + C 2s + 4K aC w
weak acid [H + ] =
2
where, C s and C w Solubility and Solubility Product
are concentrations of strong and weak acid Salts can be either completely soluble (NaCl, Na2SO4 etc),
respectively. sparingly soluble (Mg(OH)2 , AgCl etc) or insoluble (LiF) in a
Mixture of strong acid and When strong acid and strong base are mixed, given amount of solvent.
strong base neutralisation reaction occur and the final l
In case of sparingly soluble salt, the salt dissolves till a
solution may be acidic, basic or neutral based saturated solution is obtained. After saturation, if we
on the equivalents of acid or base left. further add the salt, then precipitation occurs.
In Case of Hydration of Salts l
For a sparingly soluble salt, if S is the molar solubility,
K h (Hydrolysis h (Degree of Ax By (s) + H2O -xA y+
+ yBx - (aq)
Salt pH of solution
constant) hydrolysis) At saturation, K [ Ax By (s)] =[ A ] [Bx - ]y = [xS]x [yS ]y
y+ x

Strong acid + Hydration do - - 1/x + y

strong base not occur K
or K sp = x x y y S x + y
or S = x spy
Weak acid + Kw Kw 1 1 1 x y
pK w + pK a - pK b
Weak base Ka Kb Ka Kb 2 2 2
Conditions for Precipitation
Strong acid + Kw 1 1 1
Kw pK w - pK b - log C (i) When ionic product, [ Ay + ]x [Bx - ]y < K sp , the solution is
Weak base Kb K b C 2 2 2
unsaturated and no precipitation occurs.
Weak acid + Kw Kw 1 1 1 (ii) When ionic product = K sp , the solution becomes just
pK w + pK a + log C
strong base Ka Ka C 2 2 2 saturated.
(iii) When ionic product > K sp , the solution becomes
Buffer Solution saturated enough and precipitation occurs to make
ionisation product equals to K sp .
A solution, which maintains its pH constant even upon
addition of small amount of acid or base.
l
Mixed buffers are the solutions of more than one compound.
Common Ion Effect
These are classified into following types: The phenomenon in which the degree of dissociation of a
weak electrolyte is suppressed by adding a substance
(i) Acidic buffer (ii) Basic buffer
having an ion common to the weak electrolyte, e.g. the
(iii) A mixture of polyprotic acid and its acidic salt. dissociation of CH3COOH can be suppressed by adding
(iv) Buffer containing amphoteric electrolyte such as CH3COONa .
amino acids.
Applications of Common Ion Effect and Solubility Product
Acidic buffer Basic buffer l
Pure NaCl is recovered from sea water by passing dry HCl
1. It is a mixture of weak acid and its It is a mixture of weak base and its gas over crude salt (contains impurities like CaCl2 , KBr
salt with strong base, e.g. salt with a strong acid, e.g. NH 4OH etc). The ionic product of NaCl exceeds its solubility
CH 3COOH + CH 3COONa and NH 4Cl. product due to the addition of HCl and it is precipitated as
pure NaCl. It is further purified by crystallisation.
2. Its pH can be calculated as pH Its pOH can be calculated as
[Salt] [Salt] l
Precipitation of salts during qualitative inorganic analysis
= pK a + log pOH = pK b + log
[Acid] [Base] is also based on the principle of solubility product and
common ion effect.

18
21. The pH of 0.1 M CH3COOH which is 2% ionised in Hint
aqueous solution is (i) For similar type (i.e. AB type e.g. CaSO 4 and BaSO 4 ) of
(a) 2.0 (b) 1.0 (c) 2.7 (d) 11.3 salts more be the value of Ksp , more be the solubility of
that salt.
22. For the reaction,
(ii) Between AB and A 2 B type.
NH4 COONH2 (s) - 2NH3 (g) + CO2 (g)
(e.g. CaSO 4 and Ag 2SO 4 )
If equilibrium pressure is 3 atm, then value of K sp is S for AB type = Ksp ; (Q Ksp = S 2 )
(a) 4 (b) 27 (c) 1/4 (d) 1/27 1/ 3
K
23. pH of a reaction between 0.1 N NH4 OH and 0.1 N HCl and S for A 2 B type = sp ; (Q Ksp = 4S 3 )
4
will be
Obviously, the value of S in case of AB is larger as
(a) equal to 7 (b) more than 7
compared to A 2 B type, unless the value of Ksp for
(c) less than 7 (d) equal to 14
A 2 B type is very large, (e.g. as in case of BaSO 4 and
24. Fear or excitement, causes one to breathe rapidly Ag 2SO 4 )
which results a decrease in CO2 concentration in
blood. In what way will it change the pH of blood? 29. A solution has pH = 5 is diluted to 100 times. The new
(a) pH will increase (b) pH will decrease solution becomes
(c) No effect on pH (d) pH becomes zero (a) acidic (b) basic
(c) no change (d) neutral
Hint Blood is buffer solution of H 2CO 3 / HCO -3 thus, pH
10 - 5
remains same. Hint After dilution [H + ] = = 10 - 7
100
25. Which of the following salts undergoes for anionic
hydrolysis? 30. Which has highest pH in solution?
(a) NH4Cl (b) FeCl 3 (c) Na 2CO 3 (d) CuSO 4 (a) CH3COOH (b) Na 2CO 3
(c) NH4Cl (d) NaNO 3
Hint Anionic hydrolysis means anionic part of the salt will
react with water, while cationic part comes from strong base Hint Q Na 2CO 3 solution is basic by nature, solution of
remain as such in the solution. CH 3COOH and NH 4Cl is acidic by nature, while NaNO 3
solution is neutral.
Na 2CO 3 + 2H 2O 2Na + + 2OH - + H 2CO 3
Thus, pH of Na 2CO 3 is highest.
Note (i) Ions of strong acid or base are weak ions, they do not
react with water. 31. pK a of HCN is 9.30, the pH of solution, prepared by
(ii) Ions of weak acid or base are strong ions and will react mixing 2.5 mol of KCN and 2.5 mol of HCN in water,
with water. so that total volume becomes 500 mL is
(i.e. combine with counter part, i.e. acidic radicals with H + ions (a) 9.3 (b) 0.93 (c) 3.9 (d) 0.39
and basic radicals with OH - ions).
32. pH of a weak acid (HA) is 3 if concentration of weak
The process is called hydrolysis. acid is 0.1 M, then its degree of dissociation is
-3 -
26. What is the pH of 10 M, OH ion solution at 333 K, if (a) 1% (b) 10% (c) 50% (d) 99%
K w at 333 K is 10 - 12.6? 33. A certain buffer solution contains equal concentration
(a) 4 (b) 9 (c) 9.02 (d) 9.6 of X - ions and HX. The K a for HX is 10 - 8 , the pH of this
Hint At 333 K, pK w = 12 .6 buffer solution is
(a) 3 (b) 8 (c) 11 (d) 6
27. Solubility products (K sp ) of salts of type MX,MX2 and
M2 X3 at temperature T are 4.0 10 , 3.2 10 -8 -14
and 34. Precipitate of CaF2 (K sp = 1.7 10 -10 ) will be obtained,
2.7 10 - 15 respectively. when equal volume of the followings is mixed.
- 1
(a) 10 - 4 M, Ca 2 + ions and 10 - 4 M, F ions
Solubilities (in mol L ) of these salts at temperature (b) 10 - 2 M, Ca 2 + ions and 10 - 8 M, F ions
( T) are in order. (c) 10 - 2 M, Ca 2 + ions and 10 - 3 M, F ions
(a) MX > M 2 X 3 > MX 3 (b) M 2 X 3 > MX 2 > MX (d) 10 - 3 M, Ca 2 + ions and 10 - 5 M, F ions
(c) MX > M 2 X 3 > MX 2 (d) MX 2 > M 2 X 3 > MX
Hint For precipitation, ionic product should be greater than
28. On adding 0.1 M solution of each Ag+ , Ba2 + and Ca2 + solubility product.
ions in Na2 SO4 solution. Species first precipitate is
35. The compound whose 0.1 M solution is basic is
(Given, K sp for CaSO4 = 10 -6 , BaSO4 = 10 -11 and
(a) ammonium acetate
Ag2SO4 = 10 -5 ) (b) ammonium chloride
(a) Ag 2SO 4 (b) CaSO 4 (c) BaSO 4 (c) ammonium sulphate
(d) All precipitate at the same time (d) sodium acetate

19
 Answers
1. (a) 2. (a) 3. (c) 4. (b) 5. (c) 6. (c) 7. (c) 8. (a) 9. (a) 10. (d)
11. (b) 12. (a) 13. (b) 14. (b) 15. (a) 16. (a) 17. (a) 18. (a) 19. (a) 20. (d)
21. (c) 22. (a) 23. (c) 24. (c) 25. (c) 26. (d) 27. (c) 28. (c) 29. (d) 30. (b)
31. (a) 32. (a) 33. (b) 34. (c) 35. (d)

MASTER
1. Which causes largest change in pH on adding 20 mL, 6. A solution which is 10 -3 M of each in Mn2 + , Fe2 + , Zn2 +
0.1 M acetic acid solution to and Hg 2 + is treated with 10 - 16 M sulphide ions. If K sp of
(a) distilled water MnS, FeS, ZnS and HgS are 10 - 15 , 10 - 23 , 10 - 20 and
(b) 20 mL of 0.01 M CH3COOH 10 - 54 respectively, Which one will precipitate first?
(c) 20 mL of 0.01 M NaOH (a) FeS (b) HgS
(d) 20 mL of 0.01 M HCl (c) ZnS (d) MnS
Hint pH changes when solution becomes neutral or basic from
acidic.
7. What is the pH of 10 - 3 M ammonium cyanide solution,
if K HCN = 7.2 10 -11 and K NH3 = 1.8 10 -5 mol L-1 ?
2. At equilibrium, a 500 mL vessel contains 1.5 M of each (a) 7.5 (b) 9.7
A+ B - C + D, if 0.5 M of C and D expelled out, at
equilibrium, what would be the value of K C.
(c) 12 (d) 14

1 8. For a given reaction,

(a) 1 (b) 2 X (g) + Y(g) - Z(g) + 75 kcal; which combination
9
1 4 of pressure and temperature give highest yield of Z at
(c) (d)
4 9 equilibrium?
Hint A+ B - C+ D (a) 1000 atm and 100C
(b) 1000 atm and 500C
At equilibrium = 15
. 1.5 1.5 1.5 (Given)
(c) 100 atm and 500C
Concentration of products
KC = (d) 10 atm and 500C
Concentration of reactants
Hint (i) For the given reaction Dng = - ve.
Value of KC does not depend on concentration.
Thus, high pressure favours formation of product.
Initial concentration at equilibrium is 1, (Q all are at same
(ii) For the given reaction, value of DH = - ve.
concentration and have same number of moles at equilibrium).
Thus, low temperature is favourable.
Thus, value of KC remains as before the reaction after removal of
0.5 mole of C and D, reaction readjust itself to attain the same 9. Which H+ is removed in step I?
value of KC . COOH COOH

3. When two reactants A and B are mixed to give

+
products C and D, at equilibrium the value of reaction (a) + H2O + H2O
quotient (Q)
(a) decreases with time
OH O_
(b) increases with time
(c) becomes zero at equilibrium
COOH COO
(d) is independent with time
Hint Q is zero at t = 0 and increases with time.
+
At equilibrium Q = Keq (b) + H2O + H3O

4. The pK a of HCN is 9.30, the pH of a solution prepared

by mixing 2.5 moles of KCN and 2.5 moles of HCN in OH OH
water and making up the total volume to 500 mL is
(a) 7.30 (b) 8.30 COOH COOH
(c) 9.30 (d) 10.30
+
5. 0.365 g of HCl gas was passed through 100 cm3 of (c) + 2H2O + H3O + O H
0.2 M NaOH solution. The pH of the resulting
solution would be
OH OH
(a) 1 (b) 5
(c) 9 (d) 13 (d) 50% H+ ions comes from (a) and 50% H ions comes from (b)
Hint (i) Calculate the number of moles of HCl and NaOH. Hint Q K a for COOH group > K a for OH group, also
(ii) At neutralisation point find out which species (acid or base) COOH is more reactive and acidic as compared to OH
remains in the solution and calculate pH of the solution. group.

20
10. For a reaction at equilibrium,
CaCO3 (s) CaO(s) + CO2 (g), the value of DH R can be
-
represented, by which of the following curve?

(1+x)

(1+x)
(c) (d)
log10 (pCO2 )

log10 (pCO2 )
(a) (b)
D/d D/d
Hint (1 + x ) is total number of moles which remains
1/T 1/T constant throughout the reaction.
14. For the reaction, passes through the following
log10 (pCO2 )

log10 (pCO2 )
three stages I, II and III,
(c) (d) A I
B II
C III
D quantity of product
formed (x), varies with temperature (T) will be
B D
T I II III
T (x) C
DHR A
Hint Qlog10 K p = log10 A - on comparing with equation
2.303 RT (T)
of straight line equation.
y = mx + c, y = log K p = log10 p(CO 2 ) (a) Stages I and III are exothermic and II is endothermic
1 (b) Stages I and III are endothermic and II is exothermic
x= , m = - DHR /2 .303 R
T (c) Stages II and III are exothermic and I is endothermic
Thus, slope as shown in curve (a) is the right choice. (d) Stages I and II are endothermic and III is exothermic
Hint For Stage I- x increases as T increases.
11. For a reversible equilibrium reaction, A + B - AB, Thus, is endothermic.
The true statement is For Stage II-x decreases as T increases
(a) Both reactions are endothermic
Thus, is exothermic.
(b) Both reactions are exothermic
(c) Association reaction is endothermic and dissociation reaction is For Stage III-x increases as T increases.
exothermic Thus, is endothermic.
(d) Association reaction is exothermic and dissociation reaction is Hence, I and III are endothermic and II is exothermic.
endothermic
15. For dissociation of PCl5 into PCl3 and Cl2 in
Hint In association, bond is formed between A and B, thus release
energy, hence is an exothermic process while, during gaseous phase reaction. If d is the observed vapour
dissociation, energy is required to break the bonds ( A B). Thus,
pressure (exp.) and D is the theoretical
(calculated) vapour density with x as degree of
is an endothermic process. D
dissociation, variation of with x is given by
12. pH of 10 - 8 M, NaOH solution will be d
(Given, log 11 = 1.04)
(a) 6.96 (b) 7.04 (c) 8 (d) 12
(1+x)

(1+x)

Hint Total [OH - ] = 10 - 8 M from NaOH + 10 - 7 M from H 2O (a) (b)

= 11 10 - 8 M
13. In dissociation of N2O4 into NO2 , (1 + x) varies with the D/d D/d
D
vapour densities ratio as
d
(c) (d)
(1+x)

(1+x)
(1+x)

(1+x)

(a) (b)
D/d D/d

D/d D/d

Answers
1. (c) 2. (a) 3. (b) 4. (c) 5. (d) 6. (b) 7. (b) 8. (a) 9. (b) 10. (a)
11. (d) 12. (b) 13. (d) 14. (b) 15. (d)

21
 Redox Reactions
INTRODUCTION, OXIDATION NUMBER,
TYPES OF REDOX REACTIONS
In a redox reaction, both oxidation and reduction occur Rules for Finding Oxidation Number
simultaneously. 1. Oxidation number of an atom in free state is always 0.
Redox reaction e.g. oxidation number of H in H2 , O in O2 , Cl in Cl2 , Na,
Oxidation Reduction K, Fe etc., is zero.
Addition of oxygen/ Removal of oxygen/ 2. Oxidation number of hydrogen in a
electronegative element electronegative element compound is always +1 except in case of metal hydrides
(or) removal of (or) addition of
(NaH, CaH2 , etc) where the oxidation number of H is 1.
hydrogen/electropositive element hydrogen/electropositive 3. Oxidation number of oxygen in a compound is always
(or) loss of electron(s). element 2 except in peroxides (H2 O2 , Na2 O2 , etc) where it
(or) gain of electron(s). is 1, in superoxides ( KO2 , etc) it is 1 / 2 and in OF2 , it
is+ 2.
An oxidising agent (oxidant) helps in oxidation of other
species by accepting electrons lost during oxidation and itself 4. Oxidation number of fluorine in a compound is
gets reduced. A reducing agent (reductant) helps in always 1.
reduction by donating electrons to the species undergoing 5. Oxidation number of alkali metals and alkaline earth
reduction and itself gets oxidised. metals in a compound are always + 1 and + 2
respectively.
6. Oxidation number of metals are always positive, except
REMEMBER in some metallic hydrides like CuH ( 1) and metal
Elements in their highest oxidation state in a compound always act carbonyls such as [Rh(CO)4 ] .
as oxidising agent as they always get reduced. 7. The algebraic sum of oxidation number of all atoms in a
e.g. KMnO4 , K 2Cr2O7, H2SO4 ,HClO4 , HNO3, SO3, CrO3, CO2 , etc. neutral compound is always zero and in an ion, it is
Elements in their lowest oxidation state in a compound always act equal to the total charge on the ion.
as reducing agent as they always get oxidised. e.g. H2S, most of the
metals, etc. Types of redox reactions
Elements having intermediate oxidation state can act as oxidising Intermolecular redox Intramolecular Disproportiona-
reaction redox reaction tion reaction
as well as reducing agents, e.g. SO2, Fe 2 + , MnO2, IO , etc.
Two different Different elements of (Auto-redox)
molecules/compounds same compound is A single atom in a
Oxidation Number (ON) are oxidised and oxidised as well as molecule compound
l
Oxidation number of an element in a particular compound reduced. reduced. is oxidised as well as
is equal to the number of electrons lost, gained or shared by e.g. Fe 2 + + MnO 4 e.g. (NH 4 )2 Cr2O 7 reduced.
that compound. It is positive when electrons are lost and Fe 3 + + Mn2 + N 2 + Cr2O 3 + 4 H 2O e.g. I 2 I + IO 3
negative when electrons are gained.

1. Arrange the followings in the increasing oxidation 3. Find out the oxidation number of elements underlined
number of Mn, N and X respectively. in each case.
(a) MnCl2 , MnO2 , KMnO4 (a) FeSO4 (NH4 )2 SO4 6H2 O.
(b) N2 O, NH3 , N3 H, NO, N2 O5 (b) Na2 S4 O6
(c) HXO, HXO3 , HXO2 , HXO4 (c) Na2 [Fe(CN)5 NO]
Hint (a) MnCl 2 < MnO 2 < KMnO 4 Hint (a) x 2 + 0 + 0 = 0, x = 2
(b) NH3 < N3H < N2O < NO < N2O 5 (b) 2 (1) + 4 x + 6 ( 2 ) = 0, x = 5 / 2
(c) HXO < HXO 2 < HXO 3 < HXO 4 (c) 2 + x + 5( 1) + 1 = 0, x = 2
2. Find out the oxidation number of Cr in CrO2 Cl2 ,
Na2 Cr3 O10 and Cr2 (SO4 )3 respectively. 4. Write down the name of the following redox reactions.
Hint +6, +6 and +3 (a) H2 O2 (aq) 2H2 O(l) + O2 (g)

22
 (b) Fe + N2 H4 NH3 + Fe(OH)2 8. Which of the reactant act as oxidant and reductant in
(c) 2KClO3 2KCl + 3O2 the following reaction?
Hint (a) Disproportionation reaction (a) KIO3 + 5KI + 6HCl 3I2 + 6KCl + 3H2 O
(b) Intermolecular redox reaction (b) C2 H4 + Br2 C2 H4 Br2
(c) Intramolecular redox reaction Hint (a) Oxidant KIO 3 , Reductant KI
5. Find out the oxidation number of sulphur in the (b) Oxidant Br2 , Reductant C 2H4
following compounds: HSO3 , S2 O28 , S2 O24 , H2 S and 9. Sulphur dioxide (SO2 ) under atmospheric condition
H2 SO4 .
changes into SO2x . If the oxidation number of
Hint The oxidation number of sulphur in HSO 3 , S 2O 2 2
8 , S 2O 4 , S in SO2x is + 6. What is the value of x in SO2x ?
and H2SO 4 are +4, +7, +3, 2 and +6 respectively.
Hint The value of x = 4
6. What is the highest oxidation number of P, S and I? +6 2 x = 2 + 6 + 2 = 2 x; 8 = 2 x; x=4
Hint Highest oxidation number of P = +5 , S = +6, I = +7
10. Name one compound each in which oxidation
7. Write the following equations in ionic form, number of
(a) NaHCO3 + H2 SO4 Na2 SO4 + H2 O + CO2 (a) oxygen is +2 (b) nitrogen is +1 (c) chlorine is +4
(b) K2 Cr2 O7 +14HI 2CrI3 + 2KI + 3I2 + 7H2 O Hint (a) F2O (b) N2O (c) ClO 2
+ +
Hint (a) Na + HCO 3 + 2H + SO 24 11. Why HgCl2 and SnCl2 cannot exist as such if present
2Na + + SO 24 + H2O + CO 2 together in an aqueous solution?
or Na + + HCO 3 + 2H+ 2Na + + H2O + CO 2
Hint When both HgCl 2 and SnCl 2 present together, undergoes
(b) 2K + + Cr2O 27 + 14H+ + 14I redox reaction (double displacement occur) and a white
2Cr 3+ + 6I + 2K + + 2I + 3I 2 + 7H2O precipitate will formed.
or 14H+ + Cr2O 2 3+ 2HgCl 2 + SnCl 2 SnCl 4 + Hg 2Cl 2
7 + 6I 2Cr + 3I 2 + 7H2O
(white ppt)

BALANCING OF REDOX REACTIONS

Balancing of Redox Reaction Step 4 Equalise the number of electrons on opposite side of
While balancing a redox reaction, both mass and charge the oxidation and reduction half-cell by multiplying
must be balanced on both sides of the chemical reaction. The with suitable coefficients so that these would cancel out
while adding.
following are different methods followed while balancing a
redox reaction. Since, there are same number of electrons on both sides,
hence there is no need to multiply by coefficients.
(a) Half-cell Reaction Method Step 5 Add both the oxidation and reduction half-cell equations to
get the final balanced equation.
This method is usually followed while balancing redox
I2 + 2 e 2I
reaction occurs inside a cell.
2S 2O32 S 4O 26 + 2 e
Steps followed while balancing a redox reaction
I2 + 2S 2O32 2I + S 4O 26
using half-cell reaction method
Step 1 Assign oxidation state to the elements undergoing (Final balanced redox reaction)
oxidation and reduction,
0 +2 1 2.5 (b) Oxidation Number Change Method
e.g. I2 + S 2O32 I + S 4 O 26 This method is also similar to half-cell reaction method but
Here, I2 is reduced and S 2O32 is oxidised. here the two half-cell reactions are not separated.
Step 2 Write down the oxidation half-cell and reduction half-cell
separately.
I2 I (Reduction half-cell)
REMEMBER
S 2O3 S 4O 26
2
(Oxidation half-cell) We can balance redox reactions occurring in acidic and basic medium by
Step 3 Balance charge and mass of each half-cell separately. following both of the above methods. Here, we follow one more step to
balance H and O-atoms in both acidic and basic medium as discussed on
I2 + 2 e 2I ; 2S 2O32 S 4O 26 + 2 e the next page.

23
Steps followed to balance redox reactions in acidic Steps followed to balance redox reaction in basic
medium by oxidation number change method medium by oxidation number change method
Step 1 Assign oxidation number of elements undergoing oxidation The first five steps followed while balancing a redox reaction
and reduction. in acidic medium is also followed here. However, while
0 +5 +5 +4
balancing H and O, we follow a different method as described
I2 + N O3 I O3 + N O 2
below
Step 2 Balance only those elements that undergo a change in Step 6 In basic medium, for each excess O-atom, add one H 2O on
oxidation state. Here, I and N-atom undergo a change in same side and 2OH (basic) on opposite side.
oxidation state. If H-atoms are not yet balanced, for one excess H add one
I2 + NO3 2IO3 + NO 2 OH on same side and one H 2O on the opposite side, e.g.
Step 3 Connect the elements undergoing oxidation and reduction
2Fe3O4 + MnO 4 3Fe2O3 + MnO2 (basic medium)
by a closed bracket. Here, I2 undergoes oxidation and
N-atom of NO3 undergoes reduction. [3(8/3)32=2]3
0 +5 +5 +4 32
I2 + NO3 2IO3 + NO2
Oxidation 6Fe3O 4 + 2MnO 4 9Fe2O3 + 2MnO 2 (Basic medium)

Reduction (1 excess O-atom) H 2O 2OH
Step 4 Indicate the increase in oxidation number for oxidation
reaction and decrease in oxidation number for reduction 6Fe3O 4 + 2MnO 4 + H 2O 9Fe 2O3 + 2MnO 2 + 2OH
reaction. Multiply them with suitable coefficients to make (Final balanced equation)
the increase in oxidation number in oxidation process equal
to the decrease in oxidation number in reduction process. Applications of Redox Reactions
Here, we need to multiply the reduction reaction by 10. Redox reactions are used in a wide range of industrial applications,
0 +5 +5 +4
I2 + NO3 2IO3 + NO2 e.g. in metallurgical processes for extracting metals from their ores,
[O] 2x(5 0) =10 combustion of fuels and energy generating using electrochemical
[R] (5 4) = 110 cells.
In photosynthesis process, green plants convert carbon dioxide and
Step 5 Write down the new equation after multiplying by water into carbohydrates in presence of sunlight. During this
coefficients and balance all elements except H and O. reaction, CO2 is reduced to carbohydrates while water is oxidised to
I2 + 10NO3 2IO3 + 10NO 2 oxygen. The energy need for the reaction is provided by sunlight and
Here, all elements except O-atom are balanced. sensitised by chlorophyll.
Step 6 In acidic medium, for each excess O-atom, add one H 2O Many chemicals of our daily needs such as chlorine, caustic soda,
molecule on opposite side and 2H + on same side. There are etc., are produced by electrolysis which is based on redox reactions.
4 extra O-atom on reactants side. Hence, In quantitative analysis, redox titrations involve the reactions
I2 + 10NO3 + 8H + 2IO3 + 10NO 2 + 4H 2O between oxidising and reducing agents and help in estimating the
Now, the reaction is balanced. amount of unknown substances in solutions.

12. Balance the following equations, 13. Balance the following equations in acidic medium.
(a) BaCrO4 + KI + HCl (a) HCl + KMnO4 Cl2 + KCl + MnCl2
BaCl2 + I2 + KCl + CrCl3 + H2 O (b) HNO3 +HBr NO +Br2 +H2 O
(b) Mn2 O7 MnO2 + O2 (c) Cu2+ + SO2 Cu+ +SO24
(c) As2 S3 + HNO3 H3 AsO4 + H2 SO4 + NO Hint (a) 16HCl + 2KMnO 4 5Cl 2 + 2KCl + 2MnCl 2 + 8H2O
(b) 2HNO 3 + 6HBr 2NO + 3Br2 + 4H2O
Hint (a) 2BaCrO 4 + 6KI + 16HCl
(c) 2Cu 2+ + SO 2 + 2H2O 2Cu+ + 4H+ + SO 24
2CrCl 3 + 3I 2 + 6KCl + 2BaCl 2 + 8H2O
(b) 2Mn 2O 7 4MnO 2 + 3O 2 14. Balance the following equations in basic medium.

(c) 3As 2 S 3 + 28HNO 3 + 4H2O 6H3 As 3O 4 (a) MnO 4 + Fe 2+

OH
Mn2+ + Fe 3+

+ 9H2SO 4 + 28NO (b) S 2O 24 + Ag 2O
OH
Ag + SO 23

(c) H 2 + ReO 4
OH
ReO 2 + H 2O

(d) ClO 2 + SbO 2
OH
ClO 2 + Sb(OH)6

24
 Hint (a) MnO 4 + 5Fe 2+ + 4H2O Mn 2+ + 5Fe 3+ + 8O H
(b) MnO4 + SO23 SO24 + MnO2
(c) Fe3+ + Sn2+ Sn4+ + Fe2+
(b) S 2O 24 + Ag 2O + 2 O H 2Ag + 2SO 23 + H2O

(d) Zn + NO3 Zn2+ + NH+ 4
(c) 3H2 + 2ReO 4 2ReO 2 + 2H2O + 2 O H
Hint (a) Cl 2 + IO 3 + 2 O H 2 Cl + IO 4 + H2O

(d) 2ClO 2 + SbO 2 + 2 O H+ 2H2O 2ClO 2 + Sb(OH)6
(b) 2H+ +2MnO 4 + 3SO 23 2MnO 2 + 3SO 24 + H2O
15. Balance the following equations by ion electron (c) 2Fe 3+
+ Sn 2+ Sn 4+ + 2Fe 2+
(half-reaction) method for each of the following (d) 4Zn + NO 3 + 10H+ 4Zn 2+ + NH+4 + 3H2O
equations.
(a) Cr2 O27 + Fe2+ Cr3+ + Fe3+ + H2 O 17. Use the arbitrary coefficient method to balance the
following equations.
(b) H2 O2 + I + H+ H2 O + I2
(a) Pb(N3 )2 + Co(MnO4 )3 CoO
(c) Cr2 O27 + C2 H4 O + H+ Cr3+ + C2 H4 O2 + H2 O
+ MnO2 + Pb3 O4 + NO
(d) Cu2 O + H+ + NO3 Cu2++ NO + H2 O
(b) K4 [Fe(CN)6 ] + KOH + Ce(NO3 )4
Hint (a) Cr2O 27 + 6Fe 2+ + 14H + 2Cr 3+ + 6Fe 3+ + 7H2O
Fe(OH)3 + Ce(OH)3 + K2 CO3 + KNO3 + H2 O
(b) H2O 2 + 2H+ + 2I 2H2O + I 2
Hint (a) 30Pb(N3 )2 + 44Co(MnO 4 )3
(c) Cr2O 27 + 8H+ + 3C 2H4 O 2Cr 3+ + 4H2O + 3C 2H4 O 2
(d) 3Cu 2O + 14H + +
2NO 3 6Cu 2+
+ 7H2O + 2NO 44CoO + 132MnO 2 + 10Pb 3O 4 + 180NO
(b) K 4 [Fe(CN)6 ] + 258KOH+ 61Ce(NO 3 )4 Fe(OH)3
16. Balance the following equations by oxidation number
method : + 61Ce(OH)3 + 250KNO 3 + 6K 2CO 3 + 36H2O
(a) Cl2 + IO3 Cl + IO4 (in basic medium)

25
 MASTER
1. Why H2 O2 acts as a reductant as well as an oxidant? 6. Write one equation each for decomposition reactions
Hint Oxidation number of O in H2O 2 is 1. Maximum oxidation where energy is supplied in the form of heat, light or
state of O is +2 and minimum is 2. electricity.
Explanation Hydrogen peroxide has the ability to gain or lose Hint Heat
CaCO 3( s ) CaO( s ) + CO 2( g )
electrons, as its oxygen atoms are in the +1 oxidation state. By
hv
gaining electrons they can go to 2 oxidation state and by losing Light 2AgCl( s ) 2Ag( s ) + Cl 2( g )
electrons they can go to the zero oxidation state. Electric current
Electricity 2H2O( l ) 2H2( g ) + O 2( g )
2. Which of the followings is/are oxidant and which is/are Acidulated
reductant?
7. Consider the following redox reaction and identify
Br2 , Fe3+ , I ? which element is oxidised and reduced both?
Hint Fe 3+ + e Fe 2+ [oxidant]
4P + 3KOH +3H2 O 3KH2 PO2 + PH3
Br2 + 2 e 2Br [oxidant]
Hint P
2I I 2 + 2 e [reductant]
8. For the redox reaction,
3. Find out the oxidation numbers of Cl in Cl2 , HOCl, MnO4 + C2 O24 + H+ Mn2+ + CO2 +H2 O
Cl2 O, ClO2 , KClO3 and Cl2 O7 .
Determine the correct stoichiometric coefficients of
Hint The oxidation number of Cl in Cl 2 , HOCl, Cl 2O , ClO 2 , KClO 3
MnO4 , C2 O24 and H+
and Cl 2O 7 are 0, +1, +1, +4, +5 and +7 respectively.
Hint 2, 5 and 16 respectively.
4. Find out the oxidation number of underlined atom. 9. Identify whether the following reaction is redox or not.
[Co(NH3 )6 ]3 + , KCrO3 Cl, P2 O47 , ClO2 2K[Ag(CN)2 ] + Zn 2Ag + K2 [Zn(CN)4 ]
Hint Co (NH3 )3+ 4
6 = +3, KCrO 3Cl = +6; P 2O 7 = +5; ClO 2 = +3 Hint No

5. Identify the species undergoing oxidation and 10. What products are expected from the
reduction. disproportionation reaction of hypochlorous acid?
(a) H2 S(g) + Cl2 (g) 2HCl(g) + S(s) Hint HClO 3 and Cl 2O

(b) 2Fe3 O4 (s) + 8Al(s) 9Fe(s) + 4Al2 O3 (s) 11. What are the oxidation states of iodine in HIO4 , H3 IO5
Hint and H5 IO6 respectively?
Reduced Hint +7, +7, +7

2 0 1 0
12. Identify whether the following redox reaction is
(a) H2S(g) + Cl2(g) 2HCl(g) + S(s) correctly balanced or not.
Cu + 2HNO3 Cu(NO3 )2 + 2NO + H2 O
Oxidised
Hint No, correct balanced reaction is
Reduced
3Cu + 8HNO 3 3Cu(NO 3 )2 + 2NO + 4H2O
0 0 +3 13. Balance the following redox reaction,
(b) 3Fe3O4(s) + 8Al(s) 9Fe(s) + 4Al2O3(s)
MnCl2 + PbO2 + HNO3 HMnO4
Oxidised + PbCl2 + Pb(NO3 )2
In Fe 3O 4 , Fe exists in both +2 and +3 oxidation states. Hint 2MnCl 2 + 5PbO 2 + 6HNO 3
2HMnO 4 + 2PbCl 2 + 3Pb(NO 3 )2 + 2H2O

26
1. Match the Column I (Reaction) with Column II 3. Two moles of a perfect gas undergo the following
(Reaction type). process.
Column I Column II I. A reversible isobaric expansion from
(1 atm 20 L) to (1 atm 40 L).
p. Addition II. A reversible isochoric change of state from
A. elimination (ArSN) (1 atm 40 L) to (0.5 atm 40 L).
+||
III. A reversible isothermal compression from
(0.5 atm 40 L) to (1 atm 20 L).
OMe q. Nucleophilic
B. O2N F
addition (NA) Calculate the total heat change involved in the
above process.
NH2 r. Pericyclic reaction
C. Me Cl (a) - 622.06 J
(b) 121.8 J
COONa Electrolysis
D. s. Elimination (c) 249.8 J
COONa addition (ArSN) (d) 368.4 J
+ HBr
E. t. Rearrangement
H
4. Fill in the blanks, using the correct option.
+ ROH u. Electrophilic
F.
addition (EA) I. Passing H2 S into the mixture of Mn2+, Ni2 + ,
Cu2 + and Hg2 + ions in an acidified aqueous
Codes
solution precipitates A .
A B C D E F
(a) p s u q r t II. NaX + MgCl2 White ppt. X is B .
(Boiling)
(b) r p s t u q
K Cr O / H+
(c) s u t p q r III. X + H2 SO4 Y 2 2 7

(d) t q r s p u Colourless gas
irritating smell
Green solution
2. Which of the following pair(s) is/are correctly
X and Y are C .
matched?
I. Coloured but does not have unpaired IV. The reagents NH4 Cl and NH3 (aq) will
electrons MnSO4 precipitate D .
II. Electronic configuration of actinoids is not A B C D
certain energy difference is small in 5f and
6d energy levels. (a) CuS and HgS HCO 3 SO 2-
3 and SO 2 Al 3+
III. d-block elements Interstitial hydride. (b) MnS and CuS NO 3 -
Cl and HCl Ca 2+
IV. Alloys of transition elements same atomic (c) MnS and NiS CO 2-
3 S 2-
and H 2S Mg 2+
sizes. NiS and HgS SO 2- CO 2- Zn2+
(d) 4 3 and CO 2
(a) I and II (b) Only I (c) II, III and IV (d) III and IV

27
 5. Fill in the blanks, using the correct option. 9. Fill in the blanks, using the correct option.
I. Coefficient of volume expansion of a gas is I. The IUPAC name of following spiro compound
A . is A .
Me
II. B will have identical rate of effusion under
similar conditions.
III. At the same temperature, the ratio of average II. The volume of ozone formed, when two litre of
velocity of SO2 to CH4 is C . air, i.e. 1915 mL of ozonised air is passed
through Brodios apparatus is B .
IV. At high pressure, van der Waals equation
becomes D . III. Tautomerism is not exhibited by C .
IV. D gives the most stable carbocation upon
A B C D dehydration.
1 Dideuterium and helium 1:2 pV = RT + pb
(a) A B C D
273
(a) 2-methyl spiro 225 mL OH
2 Diprotium and dideuterium 2 : 3 a
(b) pV = RT - [3.4] octane
273 V
3 Carbon dioxide and ethane 3 : 4 pV = RT (b) 3-methyl spiro 85 mL OH
(c)
273 [3.4] octane
4 Ethene and ethane 1:6 a
(d) pV = RT +
273 V
(c) 6-methyl spiro 170 mL OH
[3.4] octane
6. Match the catalysts to the correct process.
OH
Catalyst Process (d) 7-methyl spiro 42.5 mL
[3.4] octane
A. TiCl 3 p. Wacker process
B. PdCl 3 q. Ziegler-Natta polymerisation
C. CuCl 2 r. Contact process 10. Which of the following statements are correct?
D. V2O 5 s. Deacons process Choose the correct option.
I. EAN of Fe in K3 [Fe(CN)6 ] is 36.
Codes
II. Complex with bidentate ligands are called
A B C D
chelates.
(a) r q s p
(b) q p s r III. IUPAC name of the following complex,
(c) q r s p OH
(d) r p q s
CH3C==N
7. Consider to following statements. CoCl2 is
I. Ni(CN)4 is diamagnetic in nature. CH3C==N
II. [Cr(NH3 )6 ]3 + is expected to absorb visible light OH
and shown colour. bis (dimethylglyoxime)dichlorocobalt (II).
III. [Co(ox)2 (OH)2 ]- is exhibits highest IV. M(ABCD) shows cis-trans isomerism.
paramagnetic behaviour.
V. The existence of two different coloured
IV. [Co(NH3 )6 ]3 + is an inner orbital complex and complexes with the composition of
diamagnetic. [Co(NH3 )4 Cl2 ]+ is due to coordination
Choose the correct statements. isomerism.
(a) I and II (b) Only III (a) II and IV (b) I and III (c) II, IV and V (d) I, III and V
(c) II and IV (d) All are correct
11. Fill in the blanks, using the correct option.
8. Calculate the percentage of HI dissociated when I. The isotopes of chlorine with mass number
0.96 g of it was heated to 450C till equilibrium was 35 and 37 exist in the ratio of A . Its
reached. It was then quickly cooled and the amount average atomic mass is 35.5.
N
of iodine liberated required 15.7 cm3 of Na 2 S2 O3 . II. A compound of Na, C and O contain
10 0.0887 mole of Na, 0.132 mole of O and
(a) 0.75 (b) 20.9 2.65 1022 atoms of carbon. The empirical
(c) 7.85 (d) 0.78 formula of the compound is B .

28
 III. The vapour density of 5.6 L gas weighing 60 g 14. Fill in the blanks, using the correct option.
at STP is C . I. Atomic radius of lithium (bcc structure), if
IV. If repeated measurements give values close to edge length is 351 pm, is A .
one another, the number is D . II. The edge length of unit cell of NaCl crystal
A B C D with density 2.165 g/cm3 is B .
(a) 1:1 Na 3C 5O 2 60 Surely accurate III. The edge length of cube containing one mole
(b) 2:1 NaCO 30 Surely precise and accurate of NaCl (d = 2165
. g/cm3 ) is C .
(c) 3:2 Na 2CO 2 240 May be precise or accurate IV. Packing fraction of the element that crystallises
(d) 3:1 Na 2CO 3 120 Surely precise in simple cubic arrangement is D .
V. Number of unit cells present in 39 g of
12. Which of the following statements are correct? potassium (bcc structure) is E .
Choose the correct option.
A B C D E
I. The half-life period of 1g sample with activity of
(a) 409 pm 6.02 10 -8cm 2.78 cm p/4 NA
0.4 curie (atomic mass = 226) is 1.2 1010 s.
[Given, 1 curie = 3.7 1010 dps] (b) 151.98 pm 5.64 10 -8cm 3 cm p/6 0.5 NA
-8
II. Bleeding is stopped by application of ferric (c) 154.15 pm 5.85 10 cm 2.89 cm p/3 NA /4
chloride because ferric chloride seals the blood (d) 182 pm 5.98 10 -8cm 3.12 cm p /2 0.75 NA
vessel.
15. Match the Column I (Reaction) with Column II
III. Gelatin is added in manufacture of ice-cream in
(Stereochemistry involved).
order to stabilise the colloid and prevent
crystallisation. Column I Column II
IV. In the Haber process for synthesis of NH3 , A. Ph Me p. Syn-hydration with
molybdenum acts as catalyst and Fe as a anti-Markownikoffs
H (I) H
promoter. regio specificity.
Hg(OAc) 2 + H 2O
(a) Only III (b) II, III and IV (c) I, III and V (d) II and IV
NaBH4, OH
13. Two aliphatic aldehydes, (P) and (Q) react in the
(i) Hg (OCOCF ) + PhOH
presence of aq.K2 CO3 to give compound (R), which B. (I) 3 2
q. Anti-hydration with
(ii) NaBH 4
upon treatment with HCN gives compound(S). On Markownikoffs regio
acidification and heating, (S) gives selectivity.
(i) B H / THF
C. (I) 26 - r. Cyclic intermediate
Me OH (ii) H 2O 2 /O H
transition state.
Me B 2H 6 / THF
D. Ph Me s. Overall
O CH3 COOH
non-stereospecific.
O t. Overall stereospecific.
Identify the compounds P, Q, R and S.
Codes
P Q R S A B C D
(a) q,s q,s p,r,t p,r,t
(b) q,r p,r,t q,s p,r,t
(c) p,r,t p,r,t q,s q,s
(d) p,r q q, r,t
16. The degree of dissociation of Ca(NO3 )2 in a dilute
solution containing 14 g of the salt per 200 g of
water at 100C is 70%. If the vapour pressure of
water is 760 mm. The vapour pressure of solution is
(a) 785 mm (b) 769 mm (c) 746 mm (d) 753 mm
17. Choose the correct option after reading following
information given below.
[ O]
I. ( A)C8 H14 (B)+ (C )+ (D),
Alk. KMnO4
2 moles of H2 is required for saturation of (A).
II. (B) reduces ammonical AgNO3 and gives
yellow colour with NaOH + I2 .

29
 III. (C) does not reduce Tollens reagent but gives IV. Out of the reagents,
iodoform test. NH3 + CuO,
IV. (D) on dehydration with conc. H2 SO4 gives NH4 NO3 ,
mixture of colourless gases.
(NH4 )2 Cr2 O3 and
A B C D
Ba(N3 )2 extra pure N2 can be obtained by
OH
(a) NH4 NO3 .
(a) Only I (b) II, III and IV
OH (c) I and II (d) All of these

(b) OH 22. Which of the following statements are incorrect?

Choose the correct option.
OH I. Solubility of AgCl is 1.31 10-5 M, when
specific conductance of saturated solution of
COOH AgCl is 186. 10-6 ohm-1 cm-1 and that of
(c) water is 6 10-8 ohm-1 cm-1 , ( LAgCl = 137.2
COOH ohm-1 cm2 eq -1 ).
II. Equivalent conductance will be 4.6 ohm-1 cm-1
OH eq -1 , when resistance of 1N solution of
(d) CH3 COOH is 250 ohm.
(Cell constant = 1.15 cm-1 ).
18. Two first order reactions proceed at 25C at the III. Ag(s)/AgNO3 (0.01M)|| AgNO3 (0.05M)/Ag(s).
same rate. Find the ratio of rates of these reactions The emf of cell is - 0.0414 V.
at 75C, when temperature coefficient of the rate of IV. 2Fe3+(aq)+ 2I- (aq) 2Fe2 + (aq) + I2 (s). The
-
the first reaction is 2 and that of second reaction is 3. value of E Fe3+ / Fe2+ is 0.77V.
(a) 1 : 7.6 (b) 7.6 : 1 (c) 2 : 1 (d) 1 : 2
(Given, E I - = + 0.54 V, Keq = 108 at 298 K).
2/I
19. Which of the following statements is/are correct?
(a) I and II (b) III and IV
Choose from the option.
(c) I and III (d) II and IV
I. Ozone is an allotrope of oxygen.
II. Hydrolysis of one mole of peroxodisulphuric 23. Complete the reaction. Choose the correct option.
acid produces two moles of peroxomono Me
Br
sulphuric acid. Reagent Reagent Reagent 5-oxo-hexanoic
III. Bond dissociation energy increases in the A B C acid
order: I2 < F2 < Br2 < Cl2 . I II III IV

IV. The ease of liquifaction of noble gases A B C

decrease in the order: Xe < Kr < Ar < Ne < He. (a) HBr high temperature O 3 /H 2O 2
(a) I and II (b) III and IV (c) I and III (d) II and IV (b) HBr + ROOR CH 3O - + high O 3 /Ph3P
+ hn temperature
20. Calculate the amount of current required to
produce 85 g of H2 O2 per hour during hydrolysis of (c) HI EtO + high temperature O 3 / NaBH 4

ammonium persulphate. Which is produced during (d) HCl + R OOR CsOH + C 2H 5OH KMnO 4 /OH
anodic oxidation of ammonium hydrogen sulphate,
if the current efficiency is 60% and hydrolysis yield
24. Which of the following statements are true? Choose
the correct option.
is 100%?
(a) 446.8 (b) 223.38 (c) 379.6 A (d) 146.2 A
I. Lattice energy decreases in the order as
LiF > LiCl > LiBr > LiI.
21. Which of the following statements is/are incorrect? II. Acidified solution of chromic acid on treatment
Choose the correct option. with H2 O2 yield blue solution of CrO3 .
I. Basic nature of oxides increases as III. Ionic radii increase in magnitude as atomic
Al2 O3 < MgO < Na 2 O < K2 O. number of alkali metals increases.
II. In silicon dioxide, each silicon and oxygen are IV. The activity of alkaline earth metals as
bonded by double bonds and each silicon atom reducing agents decreases from Be to Ca and
is surrounded by two oxygen atoms. increases from Ca to Ba.
III. The number of P O P bonds in cyclic (a) I and III (b) II and IV
metaphosphoric acid is four. (c) I and IV (d) II and III

30
25. Match the Column I (Reactants) with Column II CH2OH
(Products). H O O H
Column I Column II H H HOH2C
OH H OCH2CH2O H OH
OH CH2OH

H OH HO H
Zn,Hg
A. ; ? p. (i) (ii)
H
r HCl
is A .
OH II. The weakest intermolecular forces of
attraction are found in B (polymer).
Electrolysis Al2O3
B. ; q. O
Cr2O3
COOK 600C
COOK OCCH3 is used as C .
III.
C. Di-(3-pentyl) lithium cuperate r.
C 2H 5Br COOH

IV. Smog is essentially caused by presence of D .
D. Di-(2-pentyl) lithium cuperate s.
A B C D
C 2H 5Br
(a) Ring (i) is pyranose Natural Analgesic Oxides of
with a-glycosidic link rubber N and S
E. Se (b) Ring (i) is furanose Nylon Anti O 3 and N 2
600C with a-glycosidic link inflammetory
(c) Ring (ii) is furanose Cellulose Hypnotic O 2 and N 2
Codes with a-glycosidic link
A B C D E (d) Ring (ii) is pyranose PVC Antiseptic O 2 and O 3
(a) r s q p r with b-glycosidic link
(b) q s p s r
(c) s r p q r 28. At 700K, 0.45 mole of CO2 and 0.45 mole of H2
(d) p q r r s reacts to form CO and H2 O at equilibrium
(KC = 0.11). After equilibrium is reached, another
26. Fill in the blanks, using the correct option. 0.34 mole of CO2 and 0.34 mole of H2 are added to
I. pH changes from A to B upon ten-fold the reaction mixture. The composition of the
dilution of 0.1 M NH4 Cl. (Kb = 1.8 10-5 ) mixture (CO2 , CO) at the new equilibrium state is
II. pH of 0.02M NH4 Cl (aq) equal to C (a) 0.594, 0.196 (b) 0.34, 0.11 (c) 0.196, 0.594 (d) 0.11, 0.34
(pKb =4.73) 29. In which of the following hybridisation of central
III. Degree of hydrolysis of D (salt) is atom(s) is not affected?
(a) PCl 5 solid dissociates into PCl +4 and PCl -6
independent of concentration of salt solution.
(b) NH 3 is protonated to give NH +4
IV. pH of 1M PO34 - (aq) solution will be E (c) NH 4NO 3 is heated to give N 2O
(pKb [PO34 - ] = 1.62). (d) LiH reacts with AlH 3 and forms LiAlH 4
30. Which of the following statements is/are true?
A B C D E Choose the correct option.
(a) 5.128 5.627 5.48 CH 3COONH 4 13.19 I. Energy of radiation emitted for electronic
(b) 2.87 3.37 3.78 CH 3COONa 12.38 transition from infinite to stationary state of
(c) 1.00 2.00 4.73 NH 4Cl 1.62 H-atom is 2.17 10-18 J.
(d) 5.48 6.48 7.00 NaCl 7 II. Velocity of an electron placed in the third orbit
of H-atom is 0.729 108 cm/s.
27. Fill in the blanks, using the correct option.
III. The electron of the first Bohr s orbit of H-atom
I. The disaccharide goes around 6.59 1015 times in one second.
(a) Only I (b) II and III
(c) All of these (d) None of these

Answers
1. (b) 2. (c) 3. (a) 4. (a) 5. (a) 6. (b) 7. (d) 8. (b) 9. (c) 10. (a)
11. (d) 12. (a) 13. (a) 14. (b) 15. (a) 16. (c) 17. (a) 18. (b) 19. (c) 20. (b)
21. (b) 22. (b) 23. (a) 24. (a) 25. (c) 26. (a) 27. (a) 28. (a) 29. (b) 30. (c)

31
 Comprehensive Simulator Test Series for JEE Main & Advanced
2

Questions to Measure Your Problem Solving Skills

1. Which of the following statements are correct? P
III. Novolac is prepared when < 1 and bakelite is
Choose the correct option. F
P
I. Dissolution of a non-volatile solute into a prepared when > 1.
liquid leads to a decrease in tendency of the F
liquid to freeze. IV. Novolac is used in manufacture of adhesives
II. The vapour pressure of the solution remains and bakelite is used for making switches and
constant, when increasing amounts of a solid plugs.
HgI2 is added to aqueous solution of NaI. (a) II and III (b) I and III (c) I and II (d) III and I
III. A liquid possessing low freezing point and 4. Which of the following statements is/are incorrect?
high enthalpy of freezing will be most suitable Choose the correct option.
for determining the molecular mass of a I. t-butyl ethanoate can be prepared by the
compound by cryoscopic measurement. reaction of CH3 COOH and Me3 C Br in basic
IV. A mixture of two immiscible liquids at a medium.
constant pressure of 1 atm boils at temperature II. HCl cannot be used for conversion of RCOOH
smaller than the normal boiling point of either to RCOCl.
liquids. III. Esters can be prepared more efficiently by the
(a) I and IV (b) II and III sequence,
(c) I and II (d) III and IV R COOH RCOCl RCOOR rather
than RCOOH RCOOR.
2. A mixture contains CO23 - , SO23 - and SO24 - . Scheme is IV. Acyl azides are more reactive than RCOCl but
provided but in disordered form. Arrange the less reactive than anhydrides.
scheme and choose the correct option. (a) II and III (b) I and IV (c) I, II and III (d) Only IV
I. Add dil. HCl. 5. Match the Column I with Column II.
II. Pass the evolved gas into the lime water.
Column I Column II
III. Add dil. HCl and BaCl2 .
A. Fe 3+ (Fe 2+ Fe 3+ ) O 4 p. Rutile structure
IV. Add K2 Cr2 O7 .
B. Mg 2+ Al 23+ O 4 q. Inverse 2 : 3 spinel structure
(a) I, IV, II then III (b) I, II, III then IV 2+ 3+
(c) II, I, III then IV (d) IV, III, I then II and CO (CO )2O 4
C. MnO 2 and SnO 2 r. Normal 2 : 3 spinel structure
3. Which of the following statements are correct?
D. BaTiO 3 s. Perovskite structure
Choose the correct option.
E. CaF2 and SrCl 2 t. Fluorite type structure
I. Nylon fibres have lower tensile strength than
terylene fibres. Codes
A B C D E A B C D E
II. In terylene, there is weak dipole-dipole
(a) s t q p r (b) q r p s t
interaction while in nylon, there is strong
(c) q r p s t (d) r q s p t
intermolecular H-bonding.

32
6. Two second order reactions A and B have identical Codes
frequency factors. Activation energy of A exceeds A B C D A B C D
that of B by 10.46 kJ/mol. At 100C, the reaction A is (a) s p q r (b) q r s p
30% completed after 60 min, when (c) p q r s (d) r s p q
initial concentration is 0.1 mol /dm3 . How long will 10. Which of the following statements are correct?
it take reaction B to reach 70%, completion at Choose the correct option.
the same temperature of an initial concentration I. On adding Cl2 water to solution of starch and
of 0.05 mol/dm3 ? KI, it turns blue.
(a) 13.4 min (b) 22.4 min (c) 16.7 min (d) 28.2 min
II. Bleaching action of SO2 is unstable while that
7. Which of the following statements are correct? of Cl2 is stable.
Choose the correct option. III. Nitrous oxide is more helpful in combustion
I. Pb can be obtained by reduction of roasted ore than air.
with coke. IV. Ge and Sn are reducing agents, while Pb is an
II. SnO2 can be used to concentrate tin stone. oxidising agent.
III. Tin stone is amphoteric. (a) I and II
(b) III and IV
IV. Scrap tin plate can be recycled by dissolving (c) All of the above
tin in NaOH solution followed by electrolysis. (d) None of the above
(a) I and II (b) III and IV
(c) I and III (d) All of these 11. Identify B and E. Choose the correct option.
SOCl 2 H2 O
8. MeCH2 COOH
B C CH3 CHO B
HCHO + O H
C
HCHO + O H
CH2 N2
Ag2 O/ Pt
D
HCHO + O H
E + HCOO
HCHO + O H

Which of the following statements are incorrect

about the given reaction? Choose the correct option. I. (HOCH2 )3 C CHO
I. The products B and C respectively are II. C(CH2 OH)4
MeCH == C ==O and MeCH2 COOMe. III. CH2 == CH CHO
II. The reaction proceeds via the formation of IV. C H2 CH2 CHO
acyl carbene MeCOCH as the intermediate

OH
species.
(a) I and III (b) II and IV (c) I and IV (d) II and III
III. The compound B on reaction with MeNH 2
forms the product MeCH2 CH2 CONHMe. 12. A hydrogen electrode and a calomel half-cell are
IV. The compound B on reaction with MeOH used to determine the pH of a solution on a
forms the product MeCH2 CH2 COOMe. mountain top where the pressure is 500 mm of Hg.
(a) I and II (b) III and IV (c) II and III (d) I and IV The pressure was wrongly assumed to be 760 mm
of Hg and pH was found to be 4. What is the correct
9. The standard reduction potential data at 25C is pH?
given below.
Cell: H2 (g)/solution || KCl, Hg2 Cl2 / Hg
E( Fe3 + / Fe2 + )
= + 0.77V; E( Fe2 + / Fe ) = - 0.44V (a) 4.09 (b) 3.92 (c) 3.75 (d) 4.25
E( Cu2 + / Cu ) = + 0.34V; E( Cu+ / Cu ) = + 0.52V 13. Fill in the blanks with appropriate options. Choose
E , O2 (g) + 4H + + 4e - 2H2 O = + 1.23V the correct option.
-
E , O2 (g) + 2H2 O + 4e 4OH = + 0.40V I. The IUPAC name of the complex
E( Cr 3 + = - 0.74; E( Cr 2 + = + 0.91V OH
/ Cr ) / Cr )

Match the Column I (Redox pair) with Column II CH3 C ==N :
(E values). CoCl2 is A
Column I Column II CH3 C ==N :

A. E(Fe 3 + /Fe ) p. - 018
. V OH
-
B. E ( 4H 2O - 4 H + + 4O H) q. - 0.40 V II. B cannot show linkage isomerism.
2+ III. C exhibits optical isomerism.
C. E (Cu + Cu 2Cu ) +
r. - 0.04 V
D. E s. - 0.83 V
IV. D forms a p-complex.
(Cr 3+ , Cr 2+ )

33
 A B C D III. [Fe(CN)6 ]3 - is weakly paramagnetic, while
(a) Dichlorodimethylgly- NH 3 cis- Ferrocene [Fe(CN)6 ]4 - is diamagnetic.
oximatocobalt (II) [Co(en)2Cl 2 ]
IV. NH2 NH2 although possesses two electron
(b) Bis-(dimethylglyoxime) NO
2 trans- Trimethyl
dichlorocobalt (II) aluminium
pair for donation but does not act as chelating
[Co(en)2Cl 2 ]
agent.
(c) Dimethylglyoximecoba SCN trans- Diethyl
(a) I and II (b) III and IV
-lt (II) chloride [Pt(NH 3 )2Cl 2 ] zinc
(c) I, II and III (d) All of these
(d) Dichlorodimethylglyoxi CN cis- Nickel
me-N, N-cobalt (II) [Pt(NH 3 )2Cl 2 ] carbonyl F
D D
14. Match the Column I (Reaction) with Column II 17. NaNH2
Products
Liq.NH3
(Mechanism). Choose the correct option.
Column I Column II Which of the following statements are correct for
NH2 p. Ring expansion the above reaction? Choose the correct option.
A. HNO2
I. The product is a mixture of

NH2
OH q. Ring contraction
D D NH2
B. H+/
and
OH PCl5 r. Carbocation A B
C. N
II. The product B is a cine-substitution product.
s. Rearrangement III. The reaction proceeds via benzyne
intermediate.
D. Me Me t. Radical anion
+
IV. The reaction is ArSN (addition-elimination).
Mg/ether/H
(a) I, II and III (b) II and III (c) Only III (d) Only IV
H2SO4
18. A 6.25g sample of NH4 Cl is placed in an evaluated
Codes
4.0 L container at 27C. After equilibrium the total
A B C D
pressure inside the container is 0.820 bar and some
(a) p, r, s r, s, t q, r, s s
(b) q, r, s p, r, s s r, s, t
solid remain in the container.
(c) r, s, t q, r, s p, r, s p, s, t NH4 Cl(s) - NH3 (g) + HCl(g)
(d) p, s, t q, s, t q, r, s s
Which of the following statements are correct?
15. The following solutions are mixed, 500 mL of Choose the correct option.
0.01 M AgNO3 and 500 mL solution that was both I. The value of Kp for the reaction is 0.168.
0.01 M in NaCl and 0.01 M in NaBr. Given, II. The amount of solid NH4 Cl left behind in the
Ksp (AgCl) = 10- 10 ; Ksp (AgBr) = 5 10-13 . Consider container at equilibrium is 2.856 g.
the following statements and mark them as True (T) III. If the volume of container was doubled at
or False (F). Choose the correct option. constant temperature, amount of solid in the
I. AgCl does not precipitate. container decreases.
II. [Cl - ]equil. = 5 10-3 M IV. The extent of decomposition can be increased
III. [Ag + ]equil. = 2.5 10-8 M by increasing the temperature.
IV. [Br - ]equil. = 2.0 10-5 M (a) I and II (b) III and IV
(c) I, II, III and IV (d) None of these
I II III IV I II III IV
(a) T F T T (b) F T F F 19. Fill in the blanks. Choose the correct option.
(c) T T F F (d) T F T F Uranium ( 238 206
92 U) decayed to 82 Pb. The decay process
(xa, yb)
16. Which of the following statements are correct? is 92 U238
82 Pb206 ; t1 / 2 = 4.5 109 yrs.
Choose the correct option.
I. x and y in the above decay series are ...A... .
I. Magnetic moment of [Fe(H2 O)6 ]2 + is 4.9 BM,
II. The age of the rock containing equal amounts
while that of [Fe(CN)6 ]4 - is zero. of 238 U and 206 Pb is B .
II. [Co(NH3 )6 ]3 + is an inner orbital complex, while III. Packing fraction of 238 U with atomic mass
[Ni(NH3 )6 ]2+ is an outer orbital complex. 238.125 amu is C

34
 IV. The analysis of rock shows the relative number 22. Match the Column I with Column II.
of U 238 and Pb206 atoms (Pb/U = 0.25). The age
Column I Column II
of rock will be ...D... .
Propane p. Zn Hg | conc. HCl
A B C D A. MgBr
(a) 6 and 8 9 10 9 yrs 2.303 6.25
4.5 10 9 log 0.25 q. B 2 H 6 + Ether
0.693 B. Propane
+ CH 3COOH
(b) 9 and 6 13.5 10 9 yrs 0.125 2.303 4.5 10 9 log 4
0.693 C. Propane r. Propanoic acid
(c) 8 and 8 2.25 10 9 yrs 12.5 2.303
0.693 log 4 D. Me Cl
4.5 10 9
(d) 8 and 6 4.5 10 9 yrs 5.25 2.303 4.5 10 9 log 1.25 s. NH 2 NH 2 + C 2H 5O -
0.693 t. P + HI
Me Me u. Cu + D
2 Cs+EtOH Br
20. Me C C Me A D
(i) BH3 + THF Br2
Codes
B E A B C D
( ii ) CH3 COOH
(a) p, q r, s t u
Si 2 BH Br2 (b) p q, r s t, u
C F (c) r p, s, t q u
CH3 COOH
(d) s, t q, u p r
Products A, B, C, D, E and F repectively are
23. Two flasks A and B have equal volumes. A is
Me Me
maintained at 300 K and B at 600 K, while A
Me Me Me H Br H Br contains H2 gas, B has an equal mass of CH4 gas.
H Br Br H
Assuming ideal behaviour for both the gases,
Me Me Me
(Meso) (Racemic mixture)
identify the correct statements.
I II III IV
I. Greater number of molecules are present in
flask B.
Codes
II. High pressure is attained in flask A.
A B C D E F
(a) I II I IV III IV III. Compressibility factor of both the flasks is same.
(b) I I II IV IV III IV. Total kinetic energy is same in both the flasks.
(c) II I I IV III III V. Molar kinetic energy is greater for flask B.
(d) II I I III IV IV VI. Molecules are travelling with the same speed
in both flasks.
21. Find out the correct value of x in the statements Mark the statements as True (T) or False (F).
given below. Choose the correct option. I II III IV V VI
I. Bond dissociation energy of XY , X 2 , Y2 (all (a) F F F F F F
diatomic molecules) are in the ratio 1 : 1 : 0.5 (b) T T T T T T
and DHf of XY is - 100 kJ/mol. The bond (c) T F F T F T
dissociation energy of X 2 is 100x. (d) F T T F T F
II. D f H of hypothetical MgCl is - 125 kJ/mol and 24. Under ambient conditions, the total number of
for MgCl2 is - 642 kJ/mol. The enthalpy of gases released as products in the final step of the
disproportionation of MgCl is - 49x. reaction scheme shown below is
-
III. The lattice energy of solid KCl is 181 kcal/mol XeF6 Complete
P + Other products O
H
Q
and enthalpy of solution of KCl in H2 O is hydrolysis H2 O
Slow disproportionation in HO - / H2 O
1.0 kcal/mol. If the hydration enthalpies of K + Products
and Cl - ions are in ratio 2 :1, then enthalpy of (a) 0 (b) 1 (c) 2 (d) 3
hydration of K + is - 20x kcal/mol.
IV. A heated iron block at 127C loses 300 J of heat 25. Which of the following statements are incorrect?
to the surroundings which are at a temperature Choose the correct option.
of 27C. This process is 0.05x J/K. Me
Codes
I. does not undergo ring
I II III IV
(a) 8 4 5 6 Me
(b) 4 8 6 5 expansion but does.
(c) 6 5 4 8
(d) 5 6 8 4

35
 II. Order of decreasing basic character is 28. Which of the following statements are correct about
O the given below compound? Choose the correct
> > > option.
N N N N CH3 CH3
H H H
H C CH == CH C H
III. Decreasing order of acidic character is
c < a < d < b, Br Br
c
COOH Me I. The total number of stereoisomers possible for
Me
the compound is 6.
O2 N a
COOH II. The total number of diastereomers possible for
b the compound is 3.
COOH III. If the stereochemistry about the double bond
Me
in the compound is trans the number of
enantiomers possible for the compound is 4.
d IV. If the stereochemistry about the double bond
COOH in the compound is cis, the number of
IV. Alkyl group acts as electron donor, when enantiomers possible for the compound is 2.
attached to a p-system. (a) I and IV (b) II and III
(a) II and IV (b) I and III (c) I and II (d) III and IV (c) I and III (d) II and IV
26. 40 mL 0.05 M solution of sodium sesquicarbonate 29. Which of the following statement is incorrect?
dehydrate (Na 2 CO3 NaHCO3 2H2 O) is titrated Choose the correct option.
against 0.05 M HCl solution, x mL of acid is required I. Presence of orbitals within a subshell is
to reach the phenolphthalein end-point, while y mL proved by Zeeman effect.
of same acid was required when methyl orange II. Bohr s atomic model is against
indicator was used in a separate titration. Which of Heisenbergs uncertainty principle.
the following statements are correct? Choose correct
III. Bond length decreases when N2+ is formed from
option. N2 but increases when O2+ is formed from O2 .
I. y - x = 80 mL II. y + x = 160 mL
IV. BF3 and graphite, both are sp2 hybridised. BF3
III. If the titration is started with phenolphthalein
is bad conductor and graphite is good
indicator and methyl orange is added at the
conductor of electricity.
end-point, 2x mL of HCl would be required
(a) Only IV (b) Only III
further to reach end-point.
(c) Only II (d) Only I
IV. If the same volume of same solution is titrated
against 0.10 M NaOH, x/2 mL of base would be 30. Which of the following statements are correct?
required. Choose the right option.
(a) I and II (b) III and IV (c) I, II and III (d) All of these I. Acid rain water have a pH normally about 7.6.
27. Which series of reactions correctly represents II. The process of adsorption is always
chemical relations related to iron and its compound? exothermic.
Dil. H SO H 2SO 4 ,O 2
(a) Fe 2
4
FeSO 4
Fe 2(SO 4 )3 III. Mutarotation of b-D-glucopyranose faster in
D the presence of 2-pyridinol.
Fe
O 2, Heat Dil. H SO 4 D IV. 5 moles of SO23 - reacts with 2 moles of KMnO4
(b) Fe FeO 2 FeSO 4 Fe in acidic medium.
Cl , Heat Heat, air Zn
(c) Fe 2 FeCl 3 FeCl 2 Fe (a) I and II (b) III and IV
O 2 , Heat CO, 600C CO, 700 C (c) I, II and III (d) I, III and IV
(d) Fe Fe 3O 4 FeO
Fe

Answers
1. (a) 2. (a) 3. (a) 4. (b) 5. (c) 6. (b) 7. (d) 8. (a) 9. (d) 10. (c)
11. (b) 12. (a) 13. (a) 14. (b) 15. (b) 16. (d) 17. (a) 18. (c) 19. (d) 20. (d)
21. (b) 22. (c) 23. (d) 24. (c) 25. (b) 26. (d) 27. (d) 28. (a) 29. (b) 30. (d)

36
 Paper 1
One or More than One Options Correct Type OH OMe
NaOH
1. Choose the correct options from the following. (b)
(MeO)2SO2
(a) Cyclopentadiene is much more acidic than
1, 3-cyclohexadiene MeOH
(c)
(b) Cyclopropenyl cation is the smallest aromatic substance
Cl OMe
(c) H of the CH 2 group in cycloheptatriene is much more acidic O
than a typical allylic H Br COOMe
(d) Cyclopentadienyl cation is a diradical MeOH
(d)
2. Consider the geometrical isomer(s) of PBr2Cl3 (excess)

molecule and choose the correct options from the
following.
5. Consider the following complex compounds
[Ir(CO)Cl(PPh3 )2 ] and [Mn(CN)6 ]4 and choose the
(a) There are three geometrical isomers and all have zero dipole
I II
moment
correct option(s) from the following.
(b) There are three geometrical isomers and two of them have
(a) CO and CN act as -accepting ligands
same dipole moment
(b) Magnetic moment of metal ion in II is 1.73 BM
(c) Bigger atoms are far apart in the structure so that dipole
(c) Both I and II follow 18 electron rule
moment becomes zero
(d) Both I and II show characteristic colour
(d) There is involvement of bent rule
6. At 50C the vapour pressure of pure CS 2 is 854 torr.
3. G f for the formation of HI(g) from its gaseous A solution of 2.0 g of sulphur in 100 g of CS2 has a
elements is 10.10 kJ/mol at 500 K. When the partial vapour pressure of 848.9 torr.
pressure of HI is 10.0 atm and that of I2 is 0.001 atm, Choose the correct choices from the following.
the partial pressure of dihydrogen at this (a) Formula of the sulphur molecule is S 8
temperature would be to reduce the magnitude of (b) Formula of the molecule is C 2 S 2
G for the reaction to zero (c) Molality of sulphur molecule is 0.079 m
(a) 700 atm (b) 70 atm (d) Mole fraction of CS 2 is found out by Raoults law
(c) 775 atm (d) 77 atm
4. Which of the following reactions show(s) 7. O
MgBr2
P
NaBH4
Q
SN 1 mechanism?
(a) MgBr2 activates the epoxide
OMe OMe HO OMe (b) P is an ester while Q is an acid
H2O
(a) (c) P and Q are strained aldehyde and alcohol respectively
R R R R (d) P undergoes nucleophilic addition reaction readily, while Q
readily undergoes dehydration upon heating

37
 8. Choose the correct option from the following. 14. An electron in a hydrogen atom in its ground state
(a) The fluoro derivative of diazene are more stable than absorbs 1.50 times as much energy as the
diazene minimum required for it to escape from the atom.
(b) Oxidation of hydrazine is an endothermic reaction The value of the emitted electron can be calculated
(c) Hydrazine is an oxidising agent in basic medium in the form of x 1010 m, where x is approximate
(d) Phosphine has stronger intermolecular attraction than value.
ammonia in solid state 15. SeOCl2 has pyramidal structure with Cl Se Cl
NH2 angle is 97. How many double bonds causing the
HNO2 B2H6/H2O2
9. P Q R distortion in the structure?
A CH3 16. Ph Ph
(a) P, Q and R are cyclic alcohols
(b) P and R are cyclic alcohols, while Q is unsubstituted alkene + HBr P+Q
(c) P and R are cyclic ester, while Q is open chain alkene
(d) Step A to P : Diazotisation OEt
P to Q : Dehydration How many active hydrogens are present in the
Q to R : Hydroboration-oxidation product P?
10. Select the correct reaction(s) from the following. 17. Calculate the per cent error in the hydronium ion
(a) [CH 3 Hg(H 2O)] + + BH + - [CH 3 HgB] + + H 3 O + concentration made by neglecting the ionisation of
(b) [CH 3 Hg(H 2O)] + + SH - [CH 3 HgSH] + H 3 O + water in a 1.0 106 M NaOH solution.
(c) [CH 3 Hg(H 2O)] + + HSCN - CH 3 HgSCN + H 3 O + CuCl H2 + Ni 2 B
18. 2H H A B
Br Li NH4 Cl
Br2
B C (major)
(d) + n-BuLi n-BuBr + How many allylic hydrogen present in the major
product of this reaction?
Single Integer Type 19. 20% surface sites have absorbed N2 . On heating
11. The same quantity of electricity that liberated N2 gas is evolved from sites and were collected at
2.158 g silver was passed through a solution of a 0.001 atm and 298 K in a container of volume 2.46
gold salt and 1.314 g gold was deposited. The cm3 . Density of surface sites is 6.023 1014 /cm3 and
equivalent weight of silver is 107.9. What is the surface area is 1000 cm2 . Find out the number of
oxidation state of gold in this gold salt? surface sites occupied per molecule of N2 .
12. How many P O P bond(s) present in OH Cl
cyclotrimetaphosphoric acid?
NaOH
CH2CH3 20. Ph C C CH3 P
HCl /AgNO3

COOH Ph CH3
13. NBS A
M
How many hydrogen atom(s) in product P can
Calculate the number of conjugated double bonds participate in tautomerism?
in the product M.

Paper 2
Single Option Correct Type 2. Consider the following compounds and choose the
correct option from the following.
1. Bio-chemists often define Q10 for a reaction as the
ratio of the rate constant at 37C to the rate constant
at 27C. The energy of activation for a reaction that N N
has a Q10 of 2.5 must be H
(a) 7.1 kJ/mol I II
(a) I is antiaromatic whereas II is aromatic
(b) 71 kJ/mol
(b) I is less basic than II
(c) 7100 kJ/mol (c) Both undergo electrophilic reaction at C-2 position
(d) 51.7 kJ/mol (d) I is easily protonated than II

38
3. Sulphur reacts with chlorine in1 : 2 ratio and forms 9. Which one of the following intermediate undergoes
X. Hydrolysis of X gives a sulphur compound Y. the fastest SN1 reaction?
The hybridisation of S-atom in Y is CH3
(a) sp (b) sp3d H2C H
H C H
(c) sp3 (d) sp2 (a) (b) C C
H H
4. A certain solution of benzoic acid in benzene has H H
a freezing point of 3.1C and a normal boiling
point of 82.6C. The structure of solute particles (H3C)2C H2C
(c) C CH2 (d) C CH2
at the two temperatures would be
H H3C
O
(a) C C H H H
O 10. H3C C CH3 H3C C CH3
O C C C C
H
(b) C C O O O O
O H H
(c) Both (a) and (b) I II
(d) None of the above Which one of the above molecule is likely to form more
stable H-bonds?
O (a) Only I (b) Both I and II
(i) MeMgBr (c) Only II (d) None of these
5. P
Me 1% CuCl
(ii) H2O Paragraph-I (For Q.Nos. 11 and 12)
(i) MeMgBr
(ii) H2O In the following reaction sequence, M to R are formed.
Q (i) CH3ONa
Ethyne + Methanol (2 moles) + M
Choose the correct choice from the following. (ii) H3O
H2+Ni
(a) Q is formed through conjugate addition
BrCCl3 Conc.H2SO4
(b) P is formed through conjugate addition Q + P + ROOR O N
(c) Catalyst provide the path of direct addition Br2 in hexane
(d) None of the above
R
6. Hydrogen peroxide when reacts with KIO4 and 11. Product O is
NH2OH separately. What type of behaviour it
(a) (b)
shows with respect to these reagents? H H
Me
(a) Reducing agent and oxidising agent
(b) Reducing agent and reducing agent (c) Me Me (d)
(c) Oxidising agent and oxidising agent
(d) Oxidising agent and reducing agent 12. How many halogen group(s) are present in the product
7. 1, 3, 5-trihydroxy benzene reacts with H2NOH to R?
(a) Zero (b) One (c) Two (d) Three
give an oximino derivative, whereas phenol does
not react because
(a) phenol does not give tautomer
Paragraph-II (For Q. Nos. 13 and14)
(b) tautomer of 1, 3, 5-trihydroxy benzene is stable Pseudohalides are anions having resemblance with halide
(c) tautomer of 1, 3, 5,-trihydroxy benzene has sufficient ions. Group I metals can form salts with pseudohalides.
concentration in the phenol-keto equilibrium Pseudohalogens can act as ligands and form coordinate
(d) None of the above complexes. Their hydrides are weakly acidic and can be
prepared in analogous way as halogen hydrides are prepared.
8. The correct statement for orthoboric acid is
(a) it behaves as strong electrolyte in water
13. Sodium cyanide reacts with H2SO4 , the product
formed is
(b) acidity of its aqueous solution increases upon addition of
(a) HCN and NaHSO4
ethylene glycol
(b) (CN)2Na 2 SO 4 and H 2O
(c) it has a 3-D structure due to H-bonding (c) HCN and Na 2SO4
(d) it behaves as a weak acid in water due to self ionisation (d) N3H and H 2 O

39
14. When sodium azide reacts with conc. H2SO4 , the Codes
product formed is A B C D A B C D
(a) ascorbic acid (b) hydrazoic acid (a) r p s q (b) p r q s
(c) hydrochloric acid (d) None of these (c) r p q s (d) s p r q
18. Match the following.
Paragraph-III (For Q. Nos. 15 and 16)
Column I Column II
Fuel cells are galvanic cells in which chemical energy of (Metal) (Extraction process)
fuel is directly converted into electrical energy. A type of A. Silver p. Fused salt electrolysis
fuel cell is a hydrogen-oxygen fuel cell. It consists of two B. Calcium q. Carbon reduction
electrodes made up of two porous graphite impregnated C. Zinc r. Carbon monoxide reduction
with a catalyst like Pt, Ag or metal oxide. The electrodes D. Iron s. Amalgamation
are placed in aqueous-solution of NaOH. Oxygen and E. Copper t. Self reduction
hydrogen are continuously fed into the cell. Hydrogen Codes

gets oxidised to H+ which is neutralised by OH. A B C D E A B C D E
At anode H2 - 2H + 2e
+ (a) p q r t,s s (b) s p q q,r t
(c) s p,q q r t (d) s t,s r q,r p

2H+ + 2OH - 2H2O 19. Match the following.

H2 + 2OH - 2H2O + 2e Column I Column II
A. Diffusion of a gas p. High when molecular

At cathode O2 gets reduced to O H mass is low
B. Compressibility of a gas, Z < 1 q. Vreal < Videal
C. v rms r. Increases with increase
O2 + 2H2O + 4e - 4 OH
in temperature
Overall reaction D. Liquification of a gas s. Attractive force
2H2 + O 2 - 2H2O dominates

The overall reaction has Codes

A B C D A B C D
H = 285.6 kJ mol 1
and G = 237.4 kJ mol 1
at 25C (a) p r q s (b) r p q s
15. What is the value of S for the fuel cell at 25C? (c) p s r q (d) p q r s
(a) 1600 JK 1 (b) 1600 JK 1 (c) 160 JK 1 (d) 160 JK 1 20. Match the following.
16. If the concentration of hydroxide ion in the cell is Column I Column II
doubled, then the cell-voltage will be A. D-glucose 2+
p. [Cu(NH3 )4 ] (OH)2 + Tartarate ion
(a) unchanged (b) increased by a factor of 2
(c) increased by a factor of 4 (d) reduced by half B. Sucrose q. Mutarotation
C. Lactose r. [Cu(NH3 )4 ]2 +(OH)2 + citrate ion
Matching Type
D. Maltose s. Maltase
17. Match the following.
Codes
Column I Column II A B C D
A. [CO(en)3 ]3 + p. Hexadentate (a) p s r p, r, s
B. EDTA q. Bidentate (b) q s p p, r, s
C. en r. Optically active (c) p, s q, r r r, s
D. [Ni(DMG)2 ]2 + s. Insoluble complex (d) q, r r q, s q, s

Answers
Paper 1
1. (a, b, d) 2. (b, c, d) 3. (c) 4. (a, c) 5. (a,b,d) 6. (a,c,d) 7. (a,d) 8. (a) 9. (b,d) 10. (a,c,d)
11. (3) 12. (3) 13. (4) 14. (5) 15. (1) 16. (0) 17. (1) 18. (4) 19. (2) 20. (3)
Paper 2
1. (b) 2. (b) 3. (c) 4. (b) 5. (b) 6. (a) 7. (c) 8. (b) 9. (c) 10. (a)
11. (d) 12. (c) 13. (c) 14. (b) 15. (d) 16. (a) 17. (c) 18. (b) 19. (d) 20. (b)

40
1. Four successive members of the first row of transition 6. Cu+(aq) is unstable in solution and undergoes
elements are listed below with their atomic numbers: simultaneous oxidation and reduction according to the
23 V, 24 Cr, 26 Fe, and 25 Mn
reaction,
Which one of them is expected to have the highest third 2Cu+(aq) 2 Cu 2+
(aq) + Cu(s)
ionisation enthalpy? Choose the correct E for above reaction, if
(a) Vanadium (b) Chromium
E 2+ = 0.34 V; E 2+ + = 0.15 V
(c) Iron (d) Manganese Cu / Cu Cu / Cu

2. Number of isomeric forms for [Rh(en)2 (NO2 )(SCN)]+ are (a) 0.38 V (b) +0.49 V (c) +0.38 V (d) 0.19 V
(a) 3 (b) 6 (c) 9 (d) 12 7. For the second order reaction, concentration (x) of the
3. Which one of the following is wrongly matched? product at time (t) starting with initial concentration
(a) [Cu(NH 3 )4 ]2+ - has square planar geometry [ A] 0 is
kt + [ A ]20 k + [ A ]20 1 + kt [ A ]20
(b) [Ni(CO)4 ] - contains neutral ligand (a) (b) (c) (d) None of these
(c) [Fe(CN)6 ]3+ - sp3d 2 hybridised 1 + kt [ A ]20 1 + kt k + [ A ]20
3+
(d) [Co(en)3 ] - follows EAN rule 8. Which of the following statements is wrong for
4. The increasing order of hydrolysis for the following physisorption?
compounds is (a) It is a reversible reaction (b) Requires activation energy
Br Br Br (c) Adsorption enthalpy value is low
(d) Generally occurs at low temperature

(CH3)3CBr 9. The temperature of the slag zone in the metallurgy of

the iron using blast furnace is
I II III IV (a) 1500-1600C (b) 400-700C
(a) I < III < II < IV (b) I < II < III < II (c) 800-1000C (d) 1200-1000C
(c) IV < II < III < I (d) I < III < IV < II 10. Select correct statements regarding behavior of HF as
5. What is the freezing point of a solution containing non-aqueous solvent.
8.1 g HBr in 100 g of water, assuming the acid to be (a) HCl behaves as an acid and HF as a base
90% ionised? (K f (H2 O) =1.86 K mol 1 kg) (b) HClO4 behaves as a base and HF as an acid
(a) 0.85C (b) 3.53C (c) HNO3 and H 2 SO 4 behave as base and HF as an acid
(c) 0C (d) 0.35C (d) All of the above are correct statements

41
11. Among the following molecules, 18. Match the Column I (Elements) with Column II
I. XeO3 II. XeOF4 III. XeF6 (Unique properties).
those having same number of lone pairs on Xe are Column I Column II
(a) I and III A. F p. Maximum ionisation energy
(b) I and II
B. Cl q. Maximum electronegativity
(c) II and III
C. Fe r. Maximum electron affinity
(d) I, II and III
D. He s. Recently named by IUPAC
12. By the electrolysis of aqueous sodium succinate, E. Ds t. Variable valency
ethene is formed at along with .
(a) anode, H 2 (b) cathode, H 2 Codes
A B C D E
(c) anode, CO 2 (d) cathode, CO 2
(a) t q r s p
13. Identify the alkyne in the following sequence of (b) p s t r q
reaction. (c) q r t p s
2 H Ozonolysis Wacker (d) s p r q t
Alkyne
A B CH2 == CH2
Lindlar s only process
catalyst 19. Match the species in Column I with their structures in
Column II.
(a) CH 3 C C CH 3
(b) CH 3 CH 2 C CH Column I Column II
(c) CH 2 == CH C CH A. CIF3 p. Square planar
(d) HC C CH 2 C CH
B. PCl 5 q. Tetrahedral

CH2CH2CHCH==CH2 C. IF5 r. Trigonal bipyramidal

+ D. CCl 4 s. Square pyramidal
H
14. CH3 A
E. XeF4 t. T-shape
Codes
A is A B C D E A B C D E
CH3 (a) p r t s q (b) t r s q p
(c) q s r t p (d) r s t p q
(a) (b)
CH2CH3 20. Consider the following pairs of gases (A and B).
CH3 I. CO2 , N2 O II. CO, N2
III. O2 , O3 IV. H2 O, D2 O
Relative rates of effusion of gases A and B is in the
(c) CH2CH3 (d)
order:
(a) I < II < III < IV (b) I = II < III < IV
CH3 CH3 (c) I = II < IV < III (d) I = II < IV < III

15. The number of -particles emitted during the 21. Concentrations of benzoic acid, which is distributed in
two layers of water and benzene are (in three different
transformation of xy A to m
n B is samples)
nm xm
(a) (b) n + + y Water (C 1 ) Benzene (C 2 )
4 4
xm Sample I 0.3 0.09
(c) x + + y (d) 2 y n + x m
4 Sample II 0.4 0.16
16. 50 mL solution of BaCl2 (20.8% w/V) and 100 mL Sample III 0.5 0.25
solution of H2 SO4 (9.8% w/V) are mixed, BaSO4 formed Hence, benzoic acid is
is (a) monomer in both layers
BaCl2 +H2 SO4 BaSO4 ()+2HCl (b) dimer in both layers
(c) monomer in water and dimer in benzene
(a) 23.30 g (b) 46.60 g
(d) monomer in benzene and dimer in water
(c) 29.80 g (d) 11.65 g
22. A monoatomic ideal gas undergoes a process in which
17. Wave number of a spectral line for a given transition is ratio of p to V at any instant is constant and equals to 1.
x cm1 for He+ , then its value for Be3 + (isoelectronic of What is the molar heat capacity of the gas?
He+ ) for same transition is 4R 3R
(a) (b)
(a) x cm1 (b) 4 x cm1 2 2
x 5R
(c) cm1 (d) 2 x cm1 (c) (d) 0
4 2

42
 +
23. 44 g of CH3 COOC2 H5 is formed at equilibrium, when Cl 2 / Cl
33. C6 H4 Cl2 C6 H3 Cl3
60 g of CH3 COOH and 46 g of CH3 CH2 OH react in A B
5 L flask. Calculate amount of CH3 COOC2 H5 formed, Which of the following statement is/are correct?
when 120 g of CH3 COOH and 46 g of CH3 CH2 OH is (a) o-isomer of A will give two types of B
taken. (b) m-isomer will give three types of B
(a) 58.66 g (b) 20.33 g (c) 22 g (d) 44 g (c) p-isomer will give one type of B
24. There is maximum pH change in case, (d) All of the above are correct statements
(a) 1 mL of a solution, pH equals to 2, is diluted to 100 mL 34. Match the Column I (Reactions) with Column II (Types
(b) 0.01 mole of NaOH, is added to 100 mL of 0.01M NaOH of reaction).
solution
(c) 100 mL of H 2O is added to 900 mL of 10 6M HCl Column I Column II
(d) 100 mL of a solution, pH equals to 2, is mixed with 100 mL of
O
a solution of pH equals to 12 A. p. Nucleophilic
addition
25. Sodium crystallises in bcc arrangement with the Br
interfacial separation between the atoms at the edge of
53 pm. The density of the solid is ZnCl2/HCl
(a) 1.23 g/cc (b) 485 g/cc (c) 4.85 g/cc (d) 123 g/cc B. OH q. E2
Cl
26. Which one of the following reactions involves
oxidation and reduction both? EtOH/EtO
(a) H 2 + Br2 2HBr C. OEt
r. SN 2
O
(b) NaBr + HCl NaCl + HBr OH
(c) HBr + AgNO 3 AgBr + HNO 3
(d) 2NaOH + H 2SO 4 Na 2 SO 4 + 2H 2O CHO HOCHCN
D. s. SN 2
27. Electrolysis of aqueous solution of the compounds Ba(CN) 2
liberates H2 gas at both cathode and anode except in + HCN
(a) LiH (b) NaH (c) HCOONa (d) NaCl
28. Which of the following is the incorrect statement? t. E1
(a) Alkali metals form two types of sulphides : M 2S and M 2Sn
( n = 2, 3, 4) Codes
(b) Alkali metals form covalent hydrides and are non-reactive A B C D A B C D
with water (a) q r s p (b) q s p q
(c) Alkali carbides are decomposed by H 2O forming acetylene (c) s r q p (d) s p q r
(d) Solubility of alkali carbonates in the order 35. By which species in Wurtz reaction, only one type of
Li 2 CO 3 < Na 2CO 3 < K 2CO 3 < Rb 2CO 3 hydrocarbon is obtained?
29. Amphoteric nature is shown by (a) CH 3CH 2Cl (b) PhCH 2Cl
(a) Be, Mg and La (b) Be, Ca and Al (c) CH 3 C H CH 3 (d) All of these
|
(c) Be, Zn and Al (d) Ca, Mg and Sr
Cl
30. Select the correct statement(s). 36. Consider the following reactions for the formation of
(a) Aluminium dissolves in dilute mineral acids but is made picric acid.
passive by concentrated nitric acid
Cl OH
(b) Aluminium vessel can be used as storage for NaOH
(c) Both of the above NO2 O2N NO2
+
(i) NaOH/H 3O
(d) None of the above I.
(ii) HNO 3/H2SO4
31. The strongest Lewis acid among the boron halides is
(a) BF3 (b) BCl 3 (c) BBr3 (d) BI 3 NO2 NO2
32. The correct IUPAC name of the compound, Cl Cl
NO2 O2 N NO2
(i) HNO3/H2SO4
is II. +
(ii) NaOH/H3O

NO2 NO2
(a) 3-(1- ethyl propyl) hex-1-ene
(b) 4-ethyl -3-propylhex-1-ene Which of the above paths is/are possible?
(c) 3-ethyl - 4 - ethenylheptane (a) Path I (b) Path II
(d) 3 - ethyl - 4 - propylhex-5-ene (c) Both I and II (d) None of these

43
37. Indicate the reagent in the following conversion: Indicate the compounds in which decarboxylation
takes place on heating.
CH==CH2 CHCH3 (a) III and IV (b) I and III
(c) II and IV (d) I and II
OCH3
+ 41. Which of the following statements is correct?
(a) H 3O /CH 3OH
(a) Aniline is a stronger base than ethyl amine
(b) B 2 H 6 / H 2O 2, OH/ CH 3OH (b) Aniline is a stronger base than p-methane aniline

(c) Hg(OAc) 2, CH 3OH/NaBH 4 , OH (c) Aniline must be acetylated before nitration with an acid
(d) All of the above derivative
(d) Aniline is soluble in an ammonium hydroxide solution.
38. Which of the two routes shown below, actually lead to
the product? 42. Commonly used catalyst in the preparation of a
O acrylonitrile from propylene, ammonia and order is
(i) HCl (i) EtMgBr
(a) silver (b) bismuth molybdate
(ii) HCl
Route Y (ii) EtMgBr Route X (c) cerium chloride (d) nickel
43. The one which has least iodine value is
HO (a) ginger oil (b) ghee
Cl (c) groundnut oil (d) sunflower oil
Product
(a) Route X (b) Route Y
44. A polymer is made of 30% molecules of molar mass
(c) Both (a) and (b) (d) None of these
20000; 40% molecules of molar mass 30000 and rest
have 60000. Calculate the number average and weight
39. Which of the following statements is incorrect? average of molecular masses.
(a) CrO 2
4 solution turns yellow to orange upon addition of acid (a) 36000;43333
(b) Fe 3 + ( aq ) reacts with KSCN ( aq ) to give deep real solution (b) 48000;5666
(c) Copper metal reacts with nitric acid to give NO gas and a (c) 43333;36000
blue solution (d) 56666;48000
(d) A deep green solution of Cr(OH)3 in excess base turns 45. Parkinsons disease is linked to abnormalities in the
orange on addition of hydrogen peroxide
levels of dopamine in the body. The structure of
40. Consider the following carboxylic acids. dopamine is
O CH2NH2 CH2CH2CH2NH2

I. CH2 ==CHCH2 C OH
O O (a) (b)
OH OH
II. CH3 C CH2 C OH
OH OH
O
III. COH CH2CH2NH2 CH2CHCOOH

NH2
O (c) (d)
VI. CH2COH OH OH
OH OH

Answers
1. (d) 2. (d) 3. (c) 4. (d) 5. (b) 6. (c) 7. (a) 8. (b) 9. (c) 10. (c)
11. (d) 12. (c) 13. (a) 14. (a) 15. (c) 16. (d) 17. (b) 18. (c) 19. (b) 20. (c)
21. (c) 22. (a) 23. (a) 24. (d) 25. (a) 26. (a) 27. (d) 28. (b) 29. (c) 30. (a)
31. (d) 32. (b) 33. (d) 34. (a) 35. (b) 36. (a) 37. (c) 38. (b) 39. (d) 40. (d)
41. (c) 42. (b) 43. (b) 44. (a) 45. (c)

44
 ELECTROLYSIS, CONDUCTANCE AND
CONDUCTIVITY OF ELECTROLYTIC SOLUTION
Electrochemistry is the branch of science which deals with
the interaction of electrical energy with chemical species. CHEMISTRY CONCENTRATE
FORMULAE FOR FARADAYS LAW
Electrolysis n
w = ZIt ; Z = Electrochemical equivalent (ECE) of the ion deposited at
The process of decomposition of an electrolyte (conduct
electrode.
electricity through ions in solutions) on passing electric w 1 E1
current through its aqueous solution or in the fused state is
n
=
w 2 E2
called electrolysis. In electrolysis, electric current is used to
bring a non-spontaneous chemical reaction (the reaction for n
E = FZ ; F = Faraday constant, 96500 C,
which G = +ve and E = ve), e.g. electrolysis of molten w=
EIt
NaCl. 96500
NaCl (molten) Na+ + Cl n
w = VQ = VIt ; w = electrical energy, V = voltage, Q = charge.
At anode 2Cl 2 e Cl2 n
For gaseous products,
At cathode 2 Na+ + 2 e 2Na(l) V It
Vg = E
96500
Faradays Laws of Electrolysis where, V g = volume of gas evolved at electrode
The laws which are governed during the decomposition of VE = equivalent volume of gas
substances at electrodes with passage of electric current are For O 2 , VE = 5. 6 L at STP
called Faradays laws of electrolysis.
For H2 , VE = 11.2 L at STP
Faradays first law Faradays second law
The weight (w) of an ion When same quantity of electricity is passed
For Cl 2 , VE = 11.2 L at STP
discharged during through different solution of electrolytes, the
electrolysis is directly masses of different ions (say w1 and w2 ) Applications of Electrolysis
proportional to the quantity liberated at electrodes are directly proportional
of electricity (I) passed. to their equivalent masses (E1 and E2 ).
l
Non-metals like H2 ,O2 ,Cl2 etc., are obtained by electrolysis
in pure form. Alkanes are obtained by Kolbes electrolytic
Preferential Discharge During Electrolysis method.
During electrolysis, if more than two electrolytes are present l
Metals like Na, Al, Ca, Mg, K are obtained by the
in the solution, only the ions requiring least energy are electrolysis of fused electrolytes.
discharged in preference to other. The increasing power of l
Metals like Au, Ag, Al, Sn etc., are refined by electrolysis.
deposition of some ions are given below: Inferior metals are coated with a superior metal like Ag, Au,
For cations Pt by electrolysis.
K+ <Na+ <Ca2+ <Mg2+ < Al3+ <Zn2+ < H+ <Cu2+ <Hg2+ < Ag+ l
Thickness of the coated layer can be calculated as
s EIt
For anions SO24 <NO3 <OH <Cl <Br <I (length breadth height) =
96500

50
 The limiting value of molar conductivity for either
Conductance and Conductivity of
l

strong or weak electrolytes can be obtained by

Electrolytic Solution extrapolating the respective curves to C=0. This
limiting value of molar conductivity is known as molar
Conductance (C) is the power of an electrolytic solution to conduct
1 A conductivity at infinite dilution ( ).
electricity and is related to resistance (R) as C = =
R l = (when, C 0)

where, is the specific resistance and is defined as the resistance

of a conductor of 1 cm length and 1cm2 area of cross-section. Kohlrauschs Law of Independent
l
is called cell constant and has unit cm 1 . Migration of Ions
A
According to this law, the molar conductivity at infinite
Units of conductance ohm 1 or mho ( 1 ) or Siemen (in SI) dilution m of the electrolyte must be equal to the sum of
the molar conductivities of the ions produced by the
Types of Conductivity electrolyte at infinite dilution.
There are three types of conductivity as shown in the table below:
m ( AB ) = A+ + B
Conductivity
type Definition Formula Units where, and B are the ionic /molar conductivities

A+
+
of cation, A and anion, B respectively.
Specific It is the reciprocal of =
1 1 l
= 1 cm1 ,
conductivity specific resistance R A S cm1
() 1 l Applications of Kohlrauschs Law
= =C
A (i) With the help of this law, we can determine the
Molar It is the conducting 1000 1 cm2 molar conductivity of weak electrolytes at infinite
= = VmL
conductivity power of a solution M mol 1 , dilution.
( m or ) containing 1 g-mol of (VmL = volume of solution S m2 mol 1 (ii) For calculating degree of dissociation () of weak
an electrolyte. containing 1 g-mol of an C
electrolyte) electrolyte the formula used is =

Equivalent It is the conducting 1000 1 cm2 eq 1 ,
= = VmL
conductivity power of a solution N S m2 eq 1 where, C = molar conductance at any concentration
( eq or ) containing (VmL = volume of solution = molar conductance at infinite dilution.
1 g-equivalent of an containing 1 g-eq of an
electrolyte (iii) To determine the ionisation constant of a weak
electrolyte)
electrolyte.
(iv) For calculating the solubility of a sparingly
Variation of Conductivity with Dilution soluble salt with the help of the following formula.
l
At infinite dilution, the conductivity of both weak and strong 1000
electrolytes become almost same and a weak electrolyte eq =
S
behaves as a strong electrolyte.
l
The equivalent and molar conductivity of a solution increases Transport Number
with dilution, whereas the specific conductivity decreases with
dilution, as the number of ions per unit volume decreases.
n
It is defined as the fraction of the current carried by an ion.
Current carried by an ion
l
The equivalent and molar conductances increase with dilution, n
Transport number =
because these are the product of specific conductance and Total current carried
volume of solution containing 1 equivalent and 1 mole of n
Transport number of cation + transport number of anion = 1.
electrolyte respectively.
The variation of molar conductance ( ) for strong electrolyte with
concentration (C) is given by Debye-Huckel-Onsager equation
Effect of Temperature on Conductivity
which is, = b C The conductance of an electrolytic solution increases
with increase in temperature, because the kinetic energy
where, b = constant, = molar conductance at infinite dilution
of ions increases resulting to increase in the movement
l
The value of b for a given solvent and temperature depends of ions.
upon the nature of electrolyte Strong electrolyte For a small increase in temperature, the temperature
(charge on cation and anion dependence of molar conductivity is given by
produced after dissociation). All t = 25 [1 + (t 2 b)]
electrolytes of a particular type have
where, = constant,
same value of b.
l
It is clear from the graph that for a Weak electrolyte t = molar conductivity at t C
strong electrolyte, extrapolation of 25 = molar conductivity at 25C.
curve at C =0 gives for strong Molar conductivity of a dilute solution increases by
Concentration
electrolytes. However, such an around 2% per degree increase in temperature.
extrapolation cannot be made for weak electrolytes.

51
1. Which of the following solutions has highest (c) The flow of current does not generate heat
equivalent conductance? (d) The resistance is independent of the length of the
conductor
(a) 0.01 M KCl (b) 0.05 M KCl
(c) 0.02 M KCl (d) 0.005 M KCl Hint On increasing temperature the ions in the solution move
faster and hence, the resistance decreases.
2. If conductivity of 0.00241 M acetic acid solution is
7. How many molecules of chlorine should be deposited
7.896 10 5 Scm1 , calculate its molar conductivity in
from molten sodium chloride in one minute by a
this solution. If m for acetic acid be 390.5 Scm2 mol 1 ,
current of 300 m A?
then dissociation constant is
(a) 2.616 1019 molecules (b) 1.216 1012 molecules
(a) 12.2 S cm2 mol 1 , 1.11 10 4
(c) 5.616 1019 molecules (d) 6.616 1012 molecules
(b) 10.7 S cm2 mol 1 , 2.85 10 4
(c) 22.7 S cm2 mol 1 , 1.85 10 5 Hint 2Cl Cl 2 + 2e
(d) 32.76 S cm2 mol 1 , 1.85 10 5 2 F or 2 96500 C deposit Cl 2 = 1 mol
1000 C C 2 8. Which of the following expressions correctly
Hint Cm = , = m , =
M m 1 represents the equivalent conductance of Al2 (SO4 )3 at
infinite dilution. Given that Al 3 + and SO24 are the
3. A current of 2.0 A passed for 5 h through a molten metal equivalent conductances at infinite dilution of
salt deposits 22.2 g of metal (atomic weight = 177). The respective ions?
oxidation state of the metal in the metal salt is
(a) 2 Al 3 + + 3SO 2 (b) Al 3 + + SO 2
(a) +1 (b) +2 (c) +3 (d) +4 4 4

1 1
Atomic weight (c) ( Al 3 + + SO 2 ) 6 (d) 3 + + SO 2
Hint Q = It , Oxidation state = 4
3 Al 2 4
Equivalent weight
9. The molar conductances of NaOH, NaCl and BaCl2 at
4. Ionic mobility of Ag + is (Ag = 5 10 4 ohm1 cm2 eq1 )
+
infinite dilution are 2.481 10 2 , 1.265 10 2 and
(a) 5.2 10 9 (b) 2.4 10 9 (c) 152
. 10 9 (d) 8.25 10 9 2.800 10 2 Sm2 mol 1 respectively. Calculate the
Ionic conductance m for Ba(OH)2 .
Hint Ionic mobility = (a) 4.232 10 2 Sm2mol 1
96500
(b) 1.121 10 2 Sm2mol 1
5. What current is to be passed for 0.25s for (c) 5.232 10 2 Sm2mol 1
decomposition of a certain weight of metal which is (d) 4.132 10 2 Sm2mol 1
equal to its electrochemical equivalent?
(a) 4 A (b) 100 A (c) 200 A (d) 2 A 10. The sequence of ionic mobility in the aqueous solution
is
Hint Electrochemical equivalent is the weight deposited by
(a) K + > Na + > Rb + > Cs + (b) Cs + > Rb + > K + > Na +
1C of charge.
(c) Rb + > K + > Cs + > Na + (d) Na + > K + > Rb + > Cs +
6. Electrolytic conduction differs from metallic Hint Smaller the size of cation, more strongly it is hydrated
conduction. In the case of electrolyte conduction and less is the ionic mobility. The sizes of the unhydrated ions
(a) The resistance increases with increasing temperature increase in the order: Na + < K + < Rb + < Cs +
(b) The resistance decreases with increasing temperature So, ionic mobility is Cs + > Rb + > K + > Na +

52
 ELECTROCHEMICAL CELLS, ELECTRODE
POTENTIAL AND EMF OF A GAL VANIC CELL
Electrochemical Cells Reduction Potential
These are the devices in which interconversion of electrical The tendency of an electrode to gain electrons, i.e. to get
energy and chemical energy takes place. reduced is known as reduction potential.
e.g. Mn + (aq) + ne M(s) s
Types of electrochemical cells
Such an electrode is positively charged with respect to its
Electrolytic cell Galvanic cell (Voltaic cell) salt solution.
Electrical energy is converted Chemical energy is converted into
into chemical energy. electrical energy.
Thus, Eoxidation = E reduction
Non-spontaneous redox Spontaneous redox reaction takes place. The electrode potential depends upon:
reaction occurs. (i) nature of metal and its ions
Anode is positive electrode and Anode is negative electrode and cathode (ii) concentration of ions in the solution
cathode is negative electrode. is positive electrode. (iii) temperature
Ions are discharged at both the Ions are discharged only on the cathode.
electrodes. Standard Electrode Potential (E)
If the electrodes are inert, Concentration of the anodic half-cell The potential difference developed between metal electrodes
concentration of the electrolyte increases while that of cathodic half-cell
and the solution of its ions of unit molarity at 1 atm pressure
decreases when the electriic decreases when the two electrodes are
current is circulated. joined by a wire. and 25C temperature is called standard electrode potential.
Both electrodes are dipped into Electrode reactions occur in separate If a reaction is reversed,then the magnitude of standard
same electrolytic solution. half-cells. electrode potential remains same but the sign changes,
No salt bridge needed. Salt bridge is an essential requirement. e.g. Eoxidation = Ereduction
Working of an electrolytic cell Working of a galvanic cell can be shown
can be shown as as
Electron flow
Bipotential Electrode Sensors
Battery Cathode Anode
Cathode Anode Electrocardiography (ECG), electromyography (EMG) and
Salt bridge ()
() (+) (+)
electroencephalography (EEG) systems measure heart, muscle and
brain activity respectively over time by measuring electric potentials
on the surface of living tissue.
Nervous stimuli and muscle contractions can be detected by
Cl
measuring the ionic current flow in the body. This is accomplished
Na+ using a biopotential electrode.
+
Molten NaCI NO3 Ag Cu2+ The current flow in the human body is due to ion flow, not electrons.
NO 3

Electrolysis of molten NaCI

A biopotential electrode is a transducer that senses ion distribution on
+
the surface of tissue and converts the ion current to electron current.
Na + Cl Na ( s ) Reduction half-cell Oxidation half-cell
1
+ Cl 2 ( g ) 2Ag + ( aq ) + Cu( s)
2 Cu 2 + ( aq ) + 2Ag( s) Different Types of Reference Electrodes
Some important reference electrodes are as follows:
Representation of an Electrochemical Cell
Electron flow in external circuit Normal Hydrogen Electrode (NHE)
Hydrogen electrode is the primary reference electrode and it
Reactive metal Solution of Solution of Reactive metal
electrode metal ions metal ions electrode is used normally to know the electrode potential of a half-cell
Phase boundary Salt bridge Phase boundary of galvanic cell. The reason for such a usage is that it can act
(oxidation half -cell) (reduction half -cell) as a cathode as well as an anode with respect to other
electrode, due to the following reactions.
Electrode Potential (E)
H2 (g) 2H + + 2 e ;
When a metal is placed in a solution of its ions, a definite
potential difference is developed between the metal and the 2H+ + 2e H2 (g)
solution. This potential is called electrode potential. The electrode potential of NHE is taken as zero. It is
Oxidation Potential represented as Pt| H2 (atm) |H+ (1M).
The tendency of an electrode to lose electrons or to get Standard Hydrogen Electrode (SHE)
oxidised is called its oxidation potential.
A hydrogen electrode in which the pressure of H2 gas is
e.g. M(s) Mn + (aq) + ne
s maintained at 1 atm and concentration of H+ ions in the
Such an electrode is negatively charged with respect to its solution is 1M, is called standard hydrogen electrode (SHE).
salt solution.

53
The electrode potential for SHE is taken as 0.00 V at all (v) In the extracton of metal Less electropositive metals are
temperatures. displaced from their ores by adding salt of more
electropositive metal.
Electrochemical Series
It is a series of chemical elements arranged in the order of EMF of a Galvanic Cell
their standard electrode potentials.
The galvanic cell is made up of two half-cells (anode and
The standard reduction potentials of different ions with cathode). The potential of these half-cells are always
reference to SHE are given below: different. On account of this difference in electrode
Standard Electrode Potentials at 25C potentials, the electric current moves from the electrode at
higher potential to the electrode at lower potential, i.e. from
The Electrochemical Series
cathode to anode. The direction of the flow of electrons is from
Element Electrode reaction Standard electrode red- anode to cathode.
(reduction) uction potential E (volt) Flow of
electrons
Li Li + + e Li 3.05
K K + + e K 2.93
Anode sFlow of
current
Cathode
Na Na + + e Na 2.71
The difference in electrode potentials of the two half-cells is
Mg 2 + + 2e Mg
Increasing strength as reducing agent

Mg 2.37
Increasing tendency to lose electrons

known as the electromotive force (emf) of the cell or cell

Increasing strength as oxidising agent

Al Al 3+
+ 3 e Al 1.66
Increasing tendency for reduction

Increasing tendency for oxidation

potential.
Increasing tendency to accept e

Zn Zn 2 + + 2e Zn 0.762
Fe Fe 2 + + 2e Fe 0.44 Measurement of EMF
Ni Ni 2 + + 2e Ni 0.25 The emf of the cell or cell potential can be measured from the
Sn Sn 2 + + 2e Sn 0.14 values of electrode potentials of the two half-cells
constituting the cell.
H2 2H + + 2e H 2 0.00
The following three methods are in use:
Cu Cu 2 + + 2e Cu +0.337 (i) Ecell = oxidation potential of anode
Ag Ag + + e Ag +0.799 + reduction potential of cathode
Hg Hg 2 + + 2e Hg +0.885 = E oxi + E red
Br2 Br2+ + 2e 2Br +1.08 (ii) Ecelll = standard reduction potential of cathode
Cl 2 Cl +2 + 2e 2Cl +1.36 standard reduction potential of anode
Au Au 3 + + 3e Au +1.50 = Ecathode Eanode = Eright Eleft
(iii) E cell = oxidation potential of anode
F2 F2+ + 2e 2F +2.87
oxidation potential of cathode
= Eoxi (anode) Eoxi (cathode)
Characteristics of Electrochemical Series
(i) Electrodes with negative standard reduction potential CHEMISTRY CONCENTRATE
(SRP), when joined to SHE, behave as anode. Electrodes TIPS TO CALCULATE CORRECT CELL POTENTIAL VALUE
with positive SRP behave as cathode when joined to SHE. In entrance exams, most of the students do common mistakes while
(ii) Elements which are better reducing agents than solving problems related to calculation of cell potential value. These
hydrogen are placed above hydrogen (they have mistakes can be removed if you follow following conditions :
negative value of SRP). Elements which are better n
You can cross check your final answer whether it is correct or not just
oxidising agents than hydrogen are placed below by seeing the value of cell potential.
hydrogen (they have positive value of SRP) in For a forward spontaneous reaction, cell potential value should be
electrochemical series. positive.
(iii) Elements which get oxidised easily are good reducing For a backward spontaneous reaction, cell potential value should
agents and elements which get reduced easily are good be negative.
oxidising agents. n
Mostly we use reduction potential value for both cells for calculating
the cell potential value as follow :
Applications of Electrochemical Series E cell = E cathode E anode = E R E L
(i) Metal with lower SRP value displace metal with higher But if oxidation potential of anodic half cell and reduction potential
SRP from their solutions. Hence, reactivity of metals of cathodic half cell is given then E cell is calculated as,
decreases from top to bottom in electrochemical series. E cell = E cathode + E anode = E R + E L
(ii) Elements above hydrogen displace hydrogen from any n
If simply potential value is provided along with cell or half cell
protic solution, whereas elements below hydrogen are reaction, this value is considered same as the corresponding
unable to displace. phenomena
(iii) Thermal stability of metallic oxides decreases down the e.g. Zn + Cu2 + Zn2 + + Cu ; E = E cell
series due to decrease in electropositive character. Zn Zn2 + + 2e ; E = E oxidation
(iv) To prevent corrosion Less reactive metals are coated
Zn2 + + 2e Zn; E = E reduction = E Zn 2 + / Zn
over more reactive metal to prevent corrosion.

54
11. In the electrolytic cell, flow of electron is from (c) 2Ag + + H 2 2Ag + 2H +
(a) cathode to anode in the solution (d) 2Ag + 2H + 2Ag + + H 2
(b) cathode to anode through external supply 17. The standard reduction potentials at 298 K for the
(c) cathode to anode through internal supply following half cells are given
(d) anode to cathode through internal supply
Zn2 + (aq) + 2 e Zn(s); E = 0.726 V
2
12. Ecell is Cr3 + (aq) + 3 e Cr(s); E = 0.740 V
2
(a) intensive (b) extensive 2H+ (aq) + 2 e H2 (g); E = 0.000V
2
(c) Both (a) and (b) (d) None of these Fe3 + (aq) + e Fe2 + (aq); E = 0.770 V
2
Hint E is an intensive quantity because it depends on the Which is the strongest reducing agent?
nature of the cell reaction. (a) Cr(s) (b) Zn(s) (c) H 2 ( g ) (d) Fe 2+ ( aq )

13. A gas X, at 1 atm is bubbled through a solution 18. On the basis of the following E values, the strongest
containing a mixture of 1 M Y and 1 M Z at 25 C. If oxidising agent is
the reduction potential is in the order, Z > Y > X, then [Fe(CN)6 ]4 [Fe(CN)6 ]3 + e; E = 0.35 V
(a) Y will oxidise X but not Z (b) Y will oxidise Z but not X Fe2+ Fe3+ + e1 ; E = 0.77 V
(c) Y will oxidise both X and Z (d) Y will reduce both X and Z (a) [Fe(CN)6 ]4 (b) Fe 2+
Hint Reduction potential of Y is greater than that of X but less (c) Fe 3+ (d) [Fe(CN)6 ]3
than that of Z. Hence, Y will oxidise X but not Z.
19. What change occurs when a zinc rod is dipped into a
14. Standard electrode potentials are: blue coloured copper sulphate solution?
Fe2+ /Fe; E = 0.44 V, Fe3 + /Fe2 + ; E = + 0.77 V (Given, E Cu 2+ / Cu = + 0.34 V, E Zn / Zn 2+ = + 0.76 V)
Fe2 + , Fe3 + and Fe blocks are kept together, then Select the correct, option.
(a) Fe 3+ increases (b) Fe 3+ decreases (a) Reaction takes place changing blue CuSO 4 to colourless
2+ 3+
(c) Fe / Fe remains unchanged ZnSO 4
(d) Fe 2+ decreases (b) Reaction takes places changing blue CuSO 4 to red
coloured ZnSO 4
15. Cr2O27 + I I2 + Cr3 + (c) Both are correct
Ecell = 0.79 V, E Cr 2 = 1.33 V, E I 2 = ? (d) None of the above
2 O7

(a) 0.54 V (b) 0.054 V (c) + 018

. V (d) 018
. V 20. Which of the following reaction is possible at anode?
16. The reaction taking place in the cell, (a) 2Cr 3+ + 7H 2O Cr2O 27 + 14H +
(b) F2 2F + 2e
Pt|H2 (g)|HCl (1.0) M|AgCl|Ag| is 1 atm 1
1 (c) O 2 + 2H + H 2O
(a) AgCl + H 2 Ag + H + + Cl 2
2 (d) None of the above
1
(b) Ag + + H + + Cl AgCl + H 2
2

NERNST EQUATION, BATTERY AND CORROSION

Nernst Equation Applications of the Nernst Equation

It relates the cell potential of an electrochemical cell to the (i) To calculate the value of potential of a concentration
concentrations of the reactants and products of a chemical cell A concentration cell is an electrochemical cell in
reaction at any point of time. For the following reaction at which potential is generated due to difference in
equilibrium, concentration of electrolyte in different half cells. As the
cell operates, the concentration increases in the dilute
pA + qB + K - rX + sY + K
half-cell and decreases in concentrated half-cell. We can
Nernst equation is calculate the generated potential with the help of Nernst
0.0591 [Products] equation. e.g. Zn|Zn2+ (C1 )||Zn2+ (C2 )|Zn
Ecell = E cell log
n [Reactants] 0.0591 C
Ecell = log 2 , [C2 > C1 ; E cell = 0]
2 C1

55
CHEMISTRY CONCENTRATE presence of other ions and a lack of information about
activity coefficients. In such cases, it is often possible to
TRICKS TO SOLVE PROBLEMS determine the ion indirectly by titration with some other
RELATED TO CONCENTRATION CELL ion by the help of Nernst equation.
Different kinds of problems have been asked in JEE Main and advanced. (iv) Measurement of pH A hydrogen electrode allows a
Generally, it is observed that students get very confuse while solving direct measurement of [H + ] and thus pH is given as
problems related to concentration cell. But these problems are very easy E Ereference
pH = cell
to solve if we approach the questions stepwise written as below: 0.0591
Step 1 Write down the concentration cell, M | M n + ( conc. )|| M n + ( dil. )| M
Relationship between Standard Potentials of Half-cells
Step 2 If half-reactions are mentioned at cathode and anode, then write Containing a Metal in Different Oxidation State
the half-cell in which reaction occurs at cathode on RHS in the cell l
If two half-reactions having potentials E1o and E2o are
representation. M | M n + ( anode )|| M n + ( cathode )| M combined to form a third half-reaction having a potential
Step 3 Write down the Nernst equation, for concentration cell, E3o , then we can write
2.303 RT [M n + ]
E cell = E cell log n + anode (LHS) G3 = G1 + G2 or n3 FE3 = n1 FE1 n2 FE2
nF [M ] cathode ( RHS ) n E + n2 E2
or n3 E3 = n1 E1 + n2 E2 or E3 = 1 1
2.303 RT [M n + ] conc.
E cell = E cell log n3
nF [M n + ] dil.
Note A reaction will be feasible if, G < 0, Ecell > 0.
Step 4 For concentration cell, E cell = 0, put this value in Nernst
2.303 RT [M n + ] CHEMISTRYCONCENTRATE
equation, E cell = log n + LHS FORMULAEOFTHERMOD YNAMICQUANTITIES
nF [M ] RHS
INELECTROCHEMISTR Y
Step 5 Find out the required quantity with the help of Nernst equation.
n
Maximum work done by a cell, W max = nFE cell
Step 6 If solubility product (K sp ) is asked to find out, then determine the
n
Gibbs free energy change of a cell, G = nFE cell
concentrations of M n + and X m . n
Temperature coefficient of emf of a cell reaction,
Step 7 Determine solubility product as K sp = ( mS ) m ( nS ) n .
dE cell H E cell
= +
(ii) Determination of solubility products The dT P nFT T
concentrations of ions in equilibrium with a sparingly dE cell
Enthalpy change, H = nF E cell T
dT P
n

soluble salt are sufficiently low and the Nernst equation

can be used to determine the value of K sp . dE
(iii) Potentiometric titrations In many situations, accurate
n
Entropy change, S = nF cell
dT P
determination of an ion concentration by direct
measurement of a cell potential is impossible due to the
n
Relation between G and K C G = G + 2.303RT log Q
At equilibrium, G = 0 and K C = Q G = 2.303RT log K C
Various reference half-cell reactions showing Nernst equation

Type Example Half-cell reaction Q Reversible Electrode potential

to (E) (oxidation),
1. Gas-ion half-cell Pt(H 2 )|H + ( aq ) 1
H 2 ( g ) H + ( aq ) + e [H + ] H + ion E 0.0591log[H + ]
2
Pt(Cl 2 )|Cl ( aq ) 1
Cl ( aq ) Cl 2 ( g ) + e
1 Cl ion E + 0.0591log[Cl ]
2 [Cl ]
2. Metal-metal ion half-cell Ag| Ag + ( aq ) Ag ( s) Ag + ( aq ) + e [ Ag + ] Ag + ion E 0.0591log[ Ag + ]
3. Metal-insoluble salt Ag, AgCl|Cl ( aq ) Ag( s) + Cl ( aq ) AgCl( s) + e 1 Cl ion E + 0.0591log[Cl ]
anion half-cell [Cl ]
4. Calomel electrode Hg, Hg 2Cl 2|Cl ( aq ) 2Hg( l ) + 2Cl ( aq ) 1 Cl ion E + 0.0591log[Cl ]
Hg 2Cl 2 ( s) + 2e [Cl ]2

5. Metal-metal oxide Hg, HgO|O H ( aq ) Hg( l ) + 2 OH ( aq ) 1 OH ion E + 0.0591log[OH ]
hydroxide half-cell HgO( s) + H 2O( l ) + 2e [OH ]2
6. Oxidation-reduction Pt |Fe 2 + ( aq ), Fe 3 + ( aq ) Fe 2 + ( aq ) Fe 3 + ( aq ) + e [Fe 3 + ] Fe 2 + , Fe 3 + ion [Fe 3 + ]
E 0.0591log
half-cell [Fe 2 + ] [Fe 2 + ]
7. Mercury-mercury Hg, HgSO 4|SO 24 ( aq ) SO 24 ( aq ) + Hg( l ) 1 SO 24 E +
0.0591
log[SO 24 ]
sulphate half-cell HgSO 4 ( s) + 2e [SO 24 ] 2

OH

8. Quinhydrone half-cell Pt|Quinhydrone| [H + ]2 H+ E 0.0591log[H + ]

H +( aq ) +2H+ + 2e

OH

56
Cell or Battery
A cell or a battery (arrangement of one or more cells
connected in series) is basically a galvanic cell where the
chemical energy of redox reaction is converted into electrical
energy.
Following are the various voltaic cells:
Primary Voltaic Cell (The Dry Cell)
The primary voltaic cells are those in which the cell
reaction occurs only once and the cell becomes dead after
use over a period of time and cannot be reused again, e.g.
dry cells like Leclanche cell, mercury cell etc.
(i) Leclanche cell The electrode reaction for Leclanche
cell is
At anode Zn (s) Zn2 + + 2 e
At cathode
MnO2 + NH +4 + e MnO(OH) + NH3
Ammonia (NH3 ) formed in reaction at cathode
combines with Zn2 + to form the complex like
[Zn(NH3 )4 ]2 + . The cell has a potential of nearly 1.5 V.
(ii) Mercury cell It shows the following electrode
reactions:
At anode Zn(Hg) + 2OH ZnO(s) + H2O + 2 e
At cathode HgO(s)+ H2O + 2 e Hg(l) + 2OH
The overall reaction is
Zn(Hg) + HgO(s) ZnO(s) + Hg(l)
The potential of this cell is approximately 1.35 V and it
remains constant during its life because overall
reaction does not involve any ion whose concentration
can change during the process.
Secondary Voltaic Cell
The cell in which original reactants are regenerated by
passing direct current from external source (recharged), is
called secondary cell.
(i) Lead accumulator (lead storage battery) The most
important secondary voltaic cell is lead storage
battery, commonly used in automobiles and invertors.
A 38% solution of H2SO4 is used as electrolyte.
The reaction taking place during discharging [when
cell is in use] is
Pb(s) + PbO2 (s) + 2H2SO4 (aq)
2PbSO4 (s) + 2H2O(l)
Reverse reaction occurs when cell is charged Ecell is
2.041 V.
(ii) Nickel cadmium battery Another important
secondary battery is Ni-Cd battery with longer life but
more expensive. The overall reaction during
discharge is
Cd(s) + 2Ni(OH)3 (s) CdO(s)
+ 2Ni(OH)2 (s) + H2O(l)
The reverse reaction occurs when cell is charged.
Batteries Used in Digital Watches
n
Several watch batteries (button cells) used mercury technology until a
few years ago but mercury is highly toxic and there is no reasonable way
to safely extract and recycle the mercury in watch batteries. Hence, this
technology is not used now because of environmental reasons.
n
Now a days, silver oxide technology is used for high quality batteries of
watches because these are most efficient when squeezing the last bit of
electricity into a confined space for storage.
n
Over time, watch industry has added new features such as background
lighting, audible alarms or even feature calculators. This has lead to the
development of additional high drain versions of watch batteries to feed
the extra requirement of power.
n
A few brands are considered as the best by fine watchmakers and are
popular choices as replacement batteries. They include Renata, Maxwell,
Varta, Sony and Energizer batteries.
Fuel Cells
Galvanic cells which use energy of combustion of fuels like
H2 , CH4 , CH3OH etc., as the source to produce electrical energy
are called fuel cells. One of the most successful fuel cell uses the
energy of reaction of H2 and O2 in gaseous state to form water.
The electrode reactions for the cell are :
At anode 2H2 (g) + 4OH (aq) 4H2O(l) + 4 e
At cathode O2 (g) + 2H2O(l ) + 4 e 4OH (aq)
The overall reaction is
2H2 (g) + O2 (g) 2H2O(l)
This type of cell runs continuously as long as the fuels are
supplied and produce electricity up to 70% efficiency. The
advantage of fuel cells over batteries is that these are pollution
free and highly efficient.
Some Other Fuel Cells
1. Phosphoric acid fuel cell Liquid H3PO4 is used as an
electrolyte. This is the first fuel cell to be commercialised.
Anode reaction 2 H2 4H + + 4 e
Cathode reaction O2 (g) + 4H + + 4 e 2H2O
2. Alkaline fuel cell It is one of the most efficient fuel cell,
used by NASA since mid 1960s to propagate launching
verticles.
Anode reaction 2 H2 + 4 OH 4 H2O + 4 e
Cathode reaction O2 + 2H2O + 4 e 4 OH
3. Molten carbonate fuel cell This can operate at extreme
high temperature of 600C and above. It is generally used
for industrial purpose.
Anode reaction H2 + CO23 H2O + CO2 + 2 e
`
1
Cathode reaction CO2 + O2 + 2 e CO23 `
2
4. Direct methanol fuel cell Methanol is used as fuel.
+
Anode reaction CH3OH + H2O `6H + 6e + CO 2
3
Cathode reaction O2 + 6H +
+ 6 e ` 3H O 2
2
57

Corrosion
It is the oxidative deterioration of metal surface with the
action of its environment to form unwanted corrosion
products like oxides, sulphides, carbonates, sulphates.
It usually affects metallic substances and typically produce
oxide(s) or salt(s) of metal, e.g. conversion of iron to rust
[Fe2O3 xH2O] , the tarnishing of silver (due to the formation of
Ag2O), development of a green coating on copper and bronze.
Corrosion of iron or rusting involves the following reactions:
2+
Oxidation half-cell 2Fe(s) 2Fe2 + + 4 e ; E(Fe = 0.44V
/ Fe)
Prevention of Rusting
The followings are the most effective way of preventing rusting:
(a) Galvanisation In galvanisation, a thin film of Zn is coated over iron,
where Zn forms a protective oxide layer. Even if the zinc coating
breaks down and iron is exposed to air, Zn reduces Fe 2 + back to Fe(s ),
as reduction potential of Fe is more than that of Zn.
(b) Cathodic protection Here, the equipment made of Fe is attached to
a more easily oxidisable metal like Mg. Here, Mg acts as a sacrificial
anode, as it reacts in preference to iron. The Mg rod should be
replaced periodically.

Reduction half-cell O2 (g) + 4H + (aq) + 4 e 2H2O(l);

E(H + / O / H O) = 1.23V Soil
2 2
Overall reaction Mg e
2Fe(s) + O2 (g) + 4H+ (aq) 2Fe2 + (aq) + 2H2O(l) ;
= 1.67 V
Ecell
2+ Iron storage tank
Ferrous ions, Fe undergo oxidation with O2 to form rust
[Fe2O3 xH2O] .
Mg(s ) Mg 2 + (aq ) + 2e Oxidation
1 H2 O
2Fe + 2H2O + O2 Fe2O3 + 4H + Fe2O3 x H2O
2+
O 2(g ) + 2H2O(l ) + 4e 4OH (aq ) Reduction
2 (Rust)
Hydrated ferric oxide

21. The following cell is found to have emf equal to zero 25. Zn gives H2 gas with H2SO4 and HCl but not with
Pt, H2 (x atm) | 0.01 MH +|| 0.1 MH +|H2 (y atm), Pt HNO3 because
The ratio x / y is (a) Zn acts as oxidising agent when reacts with HNO 3
(a) 0.01 (b) 0.1 (b) HNO 3 is weaker acid than H 2SO 4 and HCl
(c) 10 (d) 100 (c) In electrochemical series, Zn is above hydrogen
22. If Zn2+ / Zn electrode is diluted 100 times, then the (d) NO 3 is reduced in preference to hydronium ion
change in emf is 26. The emf (E) of a cell is related to its variation in
E
(a) increase by 59 mV
temperature and H as
(b) decrease by 59 mV dT p
(c) increase by 29.5 mV H E H E
(d) decrease by 29.5 mV (a) E = + T (b) E = T
nF T p nF T p
0.0591 log 1
Hint Ecell = Ecell H E H E
2 [Zn2 + ] (c) E = + T (d) E = T
nF T p nF T p
= E cell + 0.0295 log [Zn2 + ]
2+ 27. For the cell reaction,
After dilution Ecell + 0.0295 log [Zn ]
= Ecell
100 Cu2+ (C1 , aq) + Zn(s) Zn2+ (C2 , aq) + Cu(s)
Ecell will decrease by 0.02955 2 V = 0.059 V = 59 mV of an electrochemical cell, the change in free energy,
23. Which one of the following statement is always true G, at a given temperature is a function of
about the spontaneous cell reaction in a galvanic cell? (a) ln C1 (b) ln C 2 /C1 (c) ln C 2 (d) ln(C1 + C 2 )
(a) Ecell > 0, G > 0, Q > KC 28. The temperature coefficient of a galvanic cell is
(b) Ecell < 0, G < 0, Q < KC + 5.0 10 5 mV/K. During the discharge of the cell, the
(c) Ecell > 0, G < 0, Q < KC cell temperature?
(d) Ecell > 0, G < 0, Q > KC (a) increases (b) decreases (c) does not change
24. When a lead storage battery is discharged (d) first increases and then decreases
(a) SO 2 is evolved 29. The potential of hydrogen electrode at pH = 10 is
(b) lead is formed
(c) lead sulphate is consumed (a) 0.59 V (b) 0.00 V (c) 0.59 V (d) 0.059 V
(d) sulphuric acid is consumed Hint E = 0.0591 pH

58
30. At what pH of HCl solution will hydrogen gas 34. For the calomel electrode, Hg, Hg2Cl2|Cl (aq),
electrode potential of 0.118 V? H2 gas is bubbled at electrode potential measured at different Cl ion
298 K and 1 atm pressure concentration are plotted against log[Cl ]. The
(a) 2 (b) 3 variation is correctly represented by plot.
(c) 4 (d) 5

31. In an experiment 0.04 F was passed through 400 mL of (a) E (b) E

1M solution of NaCl. What would be the pH of the
solution after the electrolysis?
(a) 8 (b) 10
(c) 13 (d) 6 log [Cl] log [Cl]

Hint Find molar concentration of NaOH

Find [OH ] concentration pH = 14 pOH (c) E (d) E

32. The potential of the cell for the reaction,

M(s) + 2H+ (1 M) H2 (g) + M2 +
( 1 atm ) ( 0.1 M ) log [Cl] log [Cl]
is 1.50 V. The standard reduction potential for Hint From equation,
M2+ / M(s) couple is 2Hg( l ) + 2Cl ( aq ) Hg 2Cl 2 ( s ) + 2e
(a) 0.147 V (b) 1.47 V 0.0591 1
E = E log 2
(c) 1.47 V (d) None of these 2 [Cl ]
33. The half-cell reactions for rusting of iron are or compare this equation with y = mx + c
1 E = E + 0.0591log[Cl ].
2H + O2 + 2 e H2O; E = + 1.23 V
+

2 35. Value of EH at 298 K would be

2 O/ H2 ( 1 atm ) pt
= 0.44 V
Fe2+ + 2 e Fe (s); Ecell
(a) 0.207 V (b) + 0.207 V (c) 0.414 V (d) + 0.414 V
G (in kJ) for the reaction is RT pH1 /22
(a) 76 (b) 322 (c) 122 (d) 176 Hint E = ln
F [H + ]

Answers
1. (d) 2. (d) 3. (c) 4. (a) 5. (a) 6. (b) 7. (c) 8. (a) 9. (c) 10. (b)
11. (b) 12. (a) 13. (a) 14. (b) 15. (a) 16. (a) 17. (b) 18. (c) 19. (a) 20. (a)
21. (a) 22. (b) 23. (c) 24. (d) 25. (d) 26. (c) 27. (b) 28. (b) 29. (c) 30. (a)
31. (c) 32. (c) 33. (b) 34. (c) 35. (c)

MASTER
1. The equivalent conductance at infinite dilution of HCl 2. What is the potential of a zinc-zinc ion electrode in
and NaCl are 426.15 and 126.15 mho cm2 g-eq1 which the zinc ion activity is 0.001 M?
respectively. It can be said that the mobility of (E Zn 2+ / Zn = 0.76 V, R = 8.314 J/K mol, F = 96500 C mol)
(a) H + ions is much more than that of Cl ions (a) 0.648 V (b) 0.849 V (c) + 0.648 V (d) + 0.849 V
(b) Cl ions is much more than that of H + ions
2.303 RT 1
(c) H + ions is much more than that of Na + ions Hint E = E log
nF aZn 2 +
(d) Na + ions is much more than that of H + ions

Hint eq (HCl) >> eq (NaCl) . 3. Half-cell reaction, 2H2O + 2 e H2 + 2OH
As, Cl ions are common, this implies that ionic conductance E = 0.8277 V at 298 K
of H + >> ionic conductance of Na + ions. Auto-protolysis constant of water calculated from this
As ionic conductance ionic mobility. (cation cation , value will be
(anion anion ), therefore, H + ions have much greater mobility (a) 1 10 10 (b)1 10 12
than Na + ions. (c) 1 10 13 (d) 1 10 14

59
4. What will be the emf of the given cell? 10. Which of the following reaction takes place in fuel cell?
+
Pt|H2 (p1 )|H (aq)|H2 (p2 )|Pt (a) 2H 2 ( g ) + O 2 ( g ) 2H 2O( l )
RT p1 RT p1 (b) 2H 2O( l ) 2H 2 ( g ) + O 2 ( g )
(a) ln (b) ln
F p2 2 F p2 (c) 2H 2O( l ) + H 2 ( g ) OH( aq )
RT p2 (d) None of the above
(c) ln (d) None of these
F p1 11. The amount of an ion liberated on an electrode during
electrolysis does not depend upon
5. eq for BaCl2 , H2SO4 and HCl are x1 , x2 and x3 Scm2
(a) the conductance of the solution
eq1 respectively. If conductivity of saturated BaSO4 (b) current strength
solution is y Scm1 , then K sp for BaSO4 is (c) time
10 6 y 2 (d) electrochemical equivalent of the element
(a)
2( x1 + x2 2 x3 )
12. E1 , E2 and E3 are the emf values of the three galvanic
10 9 y 3 cells respectively are
(b)
8( x1 + x3 2 x3 )3 (i) Zn|Zn2+ (1 M)||Cu2+ (0.1 M)|Cu
10 3 y (ii) Zn|Zn2+ (1 M)||Cu2+ (1 M)|Cu
(c)
2( x1 + x2 2 x3 )
(iii) Zn|Zn2+ (0.1 M)||Cu2+ (0.1 M)|Cu
10 6 y 2
(d) Which one of the following is true?
4( x1 + x2 2 x3 )2
(a) E 2 > E 3 > E1 (b) E 3 > E 2 > E1
Hint eq (BaSO 4 ) = eq (BaCl 2 ) + eq (H 2SO 4 ) 2 eq (HCl) (c) E1 > E 2 > E 3 (d) E1 > E 3 > E 2
= x1 + x2 2 x3 Hint Use Nernst equation.
1000
eq (BaSO 4 ) = 13. The standard emf of a cell, involving one electron
Normality change is found to be 0.591 V at 25C.
1000 y The equilibrium constant of the reaction is
Solubility = ; Ksp = [Ba 2+ ][SO 24 ] = S 2
x1 + x2 2 x3 (F = 96500 C mol 1 ; R = 8.314 JK 1 mol 1 )
6. Which has maximum potential for the half-cell reaction? . 101
(a) 10 . 10 30
(b) 10
. 1010
(c) 10 . 10 5
(d) 10
2H+ + 2 e H2
14. A dilute aqueous solution of Na2 SO4 is electrolysed
(a) 1.0 M HCl (b) 1.0 M NaOH
using platinum electrodes. The products at the anode
(c) Pure water (d) A solution with pH = 4
and cathode are
7. How many moles of Pt may be deposited on cathode (a) O 2 , H 2 (b) SO 2 , Na
when 0.80 F of electricity is passed through 1.0 M (c) O 2 , Na (d) S 2O 2
8 , H2
solution of Pt4 + ?
Hint H 2O is more readily reduced than Na + . It is also more
(a) 1 mol (b) 0.20 mol (c) 0.40 mol (d) 0.80 mol readily oxidised than SO 2
4 .
8. Given the standard reduction potential (E) value of 15. Resistance of 0.2 M solution of an electrolyte is 50 .
Fe3+ + e Fe2+ ; E = 0.77 V The specific conductance of the solution of 0.5 M
Fe3+ + 3 e Fe; E = 0.04 V solution of same electrolyte is 1.4 S m1 and resistance
What is the value of E for Fe2+ + 2 e Fe? of same solution of the same electrolyte is 280 . The
(a) 0.730 V (b) 0195
. V (c) 0.445 V (d) 0.89 V molar conductivity of 0.5 M solution of the electrolyte
in Sm2 mol 1 is
9. Which of the following statement is correct? (a) 5 10 4 (b) 5 10 3
(a) More reactive metals are readily corroded (c) 5 10 3 (d) 5 10 2
(b) Corrosion takes place rapidly at bends, scratches, nicks
and cuts in the metal Hint Calculate the value of cell constant of the first solution.
(c) Presence of impurities in metals enhances the chances of l Use this value of cell constant to calculate of second
corrosion solution.
(d) All of the above l Finally calculate molar conductivity using value of and M.

Answers
1. (c) 2. (b) 3. (d) 4. (b) 5. (d) 6. (a) 7. (b) 8. (c) 9. (d) 10. (a)
11. (a) 12. (b) 13. (c) 14. (a) 15. (a)

60
 Chemical Kinetics
RATE OF A CHEMICAL REACTION, DIFFERENTIAL RATE
LAW AND FACTORS AFFECTING RATE OF A REACTION
Chemical kinetics is the branch of chemistry in
which we study about the speeds of reactions or
rearrangements by which atoms and molecules are
transformed from reactants to products.
Rate of a Chemical Reaction
It is defined as the change in concentration of a
reactant or product per unit time.
Types of Rates of a Reaction
(a) Average rate It is defined as change in molar
concentration of either reactants or products
in unit time.
(b) Instantaneous rate It is the slope of a line
tangent drawn on the concentration-time
curve at the point corresponding to the
specific concentration and time.
Factors Affecting Rate of a Reaction
l
Concentration of reactants It is directly
proportional to the rate of reaction.
l
Nature of the reactants
Physical state of reactants
Gaseous state > Liquid state > Solid state
equations.
Decreasing rate of reaction
Physical size of the reactants In solids, rate
increases with decrease in particle size because in
powdered state, particles possess larger surface
area.
l
Temperatures Generally for most of the reactions
rate becomes double for every 10 C rise in
temperature.
l
Presence of catalyst Positive catalyst increases
however negative catalyst decreases the rate of a
reaction.
Rate Expression and
Rate Constant (k)
An expression which relates the rate of a reaction to
the concentrations of the reactants is called the rate
expression. For a general reaction,
aA +bB cC +dD
Rate [ A]a [B]b or Rate = k [ A]a [B]b
The constant of proportionality, k is known as the
rate constant.
Note k depends on the temperature and is independent
of the initial concentrations of the reactants.
Molecularity of a Reaction
It is defined as the numbers of particles (atoms, ions, groups or
molecules) of reactants actually taking part in a single rate
determining step of a chemical reaction. On the basis of molecularity
reactions are of three types:
(i) Unimolecular involves participation of only one molecule.
e.g. O2 F2 -O2 + F2
(ii) Bimolecular involves participation of two molecules.
e.g. 2HI H2 +I2
(iii) Trimolecular involves participation of three molecules .
e.g. 2NO +Cl2 2NOCl
REMEMBER
Molecularity of a reaction is always a whole number (except zero) and never a
fraction.
The value of molecularity of a simple or one step reaction does not exceed
more than three because probability of colloiding more than three molecules is
almost negligible.
Order of a Reaction
It is defined as the sum of the exponents (powers) of the molar
concentrations of the reactants in the experimentally determined rate
l
For a zero or
l
der reaction, rate does not depend upon the concentration of reactant.
l
For a nth order reaction, rate depends upon the nth power of
concentration. e.g. nA Products
For n = 0; rate = k; Zero order reaction.
For n = 1; rate = k[ A]; First order reaction.
For n = 2; rate = k [ A]2 ; Second order reaction.
For n = n; rate = k [ A]n ; nth order reaction.
Relevance of Chemical Kinetics in Medicine
Nitric oxide (NO), is central to many physiological processes including
regulation of blood pressure and nerve signal transmission. Enzymes in
endothelial cells and in the brain of mammals continuously synthesise it
(generally in low and carefully regulated concentrations). NO reacts with
oxygen and produce toxic nitrogen dioxide (NO2 ).
The order of this reaction is two with respect to NO. High concentrations of
NO are found often in industrial plants and cigarettes. NO reacts rapidly with
oxygen to produce toxic NO2 .
The half-life of NO in blood vessels, brain and lungs is sufficiently long for
biochemical process. Kinetics determines the harmful and helpful aspects of
nitric oxide. At concentrations below 80 ppm. NO is used in hospitals for lung
vasodilation of preterm new borns and patients with Acute Respiratory
Distress Syndrome (ARDS).
61
Methods for Determination of Graphical method In this method, the order of reaction
can be obtained by plotting a graph between log
dx
Order of Reaction dt
Initial rate method In this method, the order of a reaction is versus log [ A]t or log (a x).
determined by varying the concentration of one of the reactants,
while keeping others constant, e.g. Note There are some reactions which show fractional and
negative orders.
aA + bB Product
e.g. CO + Cl 2 COCl 2; rate = k[CO]2[Cl 2 ]1/ 2;
r = k [ A]a [B]b
order = 2.5
If [B] remains constant, r = k1 [ A]a , where, k1 = k [B]b
2O 3 3O 2; rate = k[O 3 ]2[O 2 ]1; order with respect to
The value of a can be determined by inspecting the rate at O 2 is 1.
different concentrations of A.
Integration method Also called hit and trial method. In this Formulae Related to the Rate
method, different values of [ A]0 , [ A]t and t are determined and Order of a Reaction
experimentally and substituted in rate equation of various order. For a general reaction,
Half-life method It is also called fractional change method. For aA + bB cC + dD
n 1
[A ] 1 [A ] 1 [ B ] 1 [C ] 1 [D ]
(t1 / 2 )1 Rate (r ) = = = =
a reaction of nth order, t1 / 2 (1/[ A]0 )n 1 or = 0 2 a t b t c t d dt
(t1 / 2 )2 [ A 0 ]1
[R ] [P ]
Average rate r av = =
Taking logarithm on both sides, n = 1 +
log[(t1 / 2 )1 / (t1 / 2 )2 ] t t
log{[ A0 ]2 /[ A0 ]1 } [C ] d [C ]
Instantaneous rate r ins = lim = ; [C ] = conc.
Zero order Third order
t 0 t dt
of reactant
t1/2 t1/2
First order d [C ] = Change in the concentration of reactant in infinitesimally
small interval of time dt.
Second order
Differential rate equation rate = k [A]x [B ]y
[A]0 1 where, x and y are calculated experimentally.
[A]02 Order of a chemical reaction x + y (experimentally)
1
t av = and for first order reaction, t av = 1.44 t1 / 2 Order of an elementary chemical reaction a + b
k

T1 )/100
1. The correct relation in between dC , dn and dp where, Hint Increase in rate = 2 (T2 times.
dt dt dt 4. For the reaction, O3 - O2 + O (fast)
C, n and p represent concentration, number of moles
O + O3 2O2 (slow).
and pressure of gaseous reactant, A(g) Product, is
The rate law is
dC 1 dn 1 dp dC RT dn dp
(a) = = (b) = = (a) r = k [O 3 ]2[O 2 ]1 (b) r = k [O 3 ]
dt V dt RT dt dt V dt dt
dC dn dp (c) r = k [O 3 ][O]2 (d) r = [O 3 ]2[O]
(c) = = (d) All of these
dt dt dt 5. For a gaseous reaction, the rate law is r = k[ A]2 [B]. If
1 dn
= QC =
dC n
Hint (i) Rate = volume of reaction decreases to 1/3rd of initial volume,
dt V dt V the new concentration and order of reaction
dC 1 dp p
(ii) Rate = = ; QC = respectively becomes,
dt RT dt RT (a) rate will increase by 27 times and order remains same
k1 k2 k3 (b) rate will decrease by 27 times and order remains same
2. For the sequence of reactions, A B C D 1
(c) rate will increase by 27 times and order becomes rd of its
If k3 > k2 > k1 , then rate determining step is 3
initial order
(a) A B (b) B C (c) C D (d) A D
(d) show no change in rate or order
3. Temperature coefficient of a reaction is 2. What will be Hint When volume decreases to V/3 rate becomes
the rate of reaction when temperature increases from 2
A B
30C to 100C? r = k
V / 3 V / 3
(a) 120 times (b) 150 times (c) 128 times (d) 100 times

62
 6. Hydrogenation of vegetable ghee at 25C reduces (a) 64 times (b) 256 times (c) 512 times (d) 1024 times
pressure of H2 (g) from 2 atm to 1.2 atm in 50 min. The Hint Rate becomes 2 10 times
rate of reaction in terms of change in molarity per 9. Which one of the following statements is not correct for
second is order of reaction?
. 10 6 (b) 119
(a) 119 . 10 5 (c) 119
. 10 7 . 10 8
(d) 119 (a) Order is determined experimentally
n n p
Hint Change in molarity is, , = (b) Order of reaction is equal to sum of the powers of
V V RT concentration terms in experimentally determined
differential rate law
7. Half-lives of two samples are 0.1 and 0.8 s. Their
(c) It is not affected with stoichiometric coefficient of the reactant
respective concentrations are 400 and 50 mol L1 . The
(d) Order cannot be fractional
order of reaction is
(a) 0 (b) 2 (c) 1 (d) 4 10. In a reversible reaction, the rate of backward reaction is
8. The rate of reaction is doubled when temperature (a) positive (b) negative
increases by 10 C, if temperature is increased by 100C (c) zero (d) can not be predicted
then rate of reaction will become Hint Rate of reaction can never be negative.

INTEGRATED RATE LAWS AND

VARIOUS FIRST ORDER REACTIONS
It is an approach to determine rate law and rate constant for a reaction by using calculus to derive what is called the integrated
rate law.
Different integrated laws for different orders of reaction
Order of Half-life ( t 1/ 2) Unit of rate
Graphs Rate expression Examples
reaction constant
1 1
Zero order
[A]0 [ A ]t = [ A ]0 kt [ A ]0 mol L s Photochemical
r[A]0t 2k reaction,
enzyme
Rate

[A]t catalysed
reactions etc.
Time [A]t
First order
[ A ]t = [ A ]0e kt , k =
2.303
log
[ A ]0 0.693 s 1 Radioactive
reaction log [A]0 t [ A ]t k disintegration,
[A] log [A]t
log 0 regeneration of
[A]t 2.303 p0
k= log (for gaseous bacteria etc.
t p0 px
Time Time reaction) time required to
complete 1/nth of a reaction,
[A]0 2.303 n
t = log
[A]t k n 1

Time

Second order 1 1 1 mol 1 Ls 1 Saponification

(i) kt = , when both
reaction [ A ]t [ A ]0 k[ A ]0 reaction.
1
[A]t reactants have same initial
1 concentrations
[A]0
2.303 b( a x )
(ii) k = log ,( a > b )
Time t (a b ) a( b x )
when both reactants have different
concentrations.
nth order 1 1 1 2n 1 1 (mol L1 )1 ns 1
reaction kt = n1 n1
n1
1 n 1 [ A ]t [ A ]0 k( n 1)[ A ]0
[A]n1
n1
(n = 1,0) n 1 (First order), where n is
order of the reaction
Time

Note Here, [ A ]0 and [ A ]t are the concentrations of reactant at initially and after time, t respectively.

63
Pseudo First Order Reaction Formulae Related to Parallel,
If the concentration of one of the reactant in a second order Consecutive and Reversible
reaction remains constant because it was supplied in a large First Order Reactions
excess, its concentration can be neglected from the rate law
equation. Hence, the obtaining reaction is known as pseudo d [B ] d [C ]
Parallel first order = k 1 [ A ], = k 2 [ A ],
first order reaction. dt dt
d (A )
e.g. r = k[ A][B] = k [A ]
dt
If [B] in large excess, r = k [ A] [B ] k 1
At any instant: =
Parallel First Order Reaction [C ] k 2
Rate constant (k) = k1 + k2 d [B ]
k1
Consecutive first order = k 1 [A ] k 2 [B ]
B dt
k1 k2
A
B
C A k2 k [A ]
[ B ] = 1 0 [e k 1t e k 2t ]
C
k2 k1
Consecutive First Order Reaction 2.303 k
t max = log 2
k2 k1 k1
k1>k2 k1>k2 [C] k2
[B]max k k 1 k 2
[ B ] max = [A ] 0 2
[C] k1
Conc.

Conc.

[A]
[B]max where, [ A ] 0 = Initial concentration of A
[A] [ B ] max = Maximum concentration of B
[B] [B] t max = Time in which [ B ] max converts into C
Time Time dx k [A ]
Reversible reactions = kf [[ A ] 0 x ] k b x = f 0 [ x eq x ]
dt x eq
Reversible reactions (First order opposed by first order)
kf kf [ A ] 0
A -B x eq =
kb [ kf + k b ]
At t = 0, [ A]0 0 x
( kf + k b )t = ln eq
At time t, [ A]0 x x x eq x
At equilibrium, [ A]0 x eq x eq [ B eq ] K f
Equilibrium constant K c = =
Rate of reaction = Rate of forward reaction Rate of backward [ Aeq ] K b
reaction

11. For a reaction, graph between 13. Consider the following data for the decomposition of
logarithm of concentration of ammonium nitrite in aqueous solution.
reactant versus time (t ) is given
log [R]

Volume of N 2 in cc Time (min)

below.
6.25 10
The order and slope for this 9.00 15
reaction are respectively 11.40 20
Time (t)
13.65 25
k 2.303 35.05 infinity
(a) 1st and (b) 1st and
2.303 k The order of the reaction is
k 2.303
(c) 1st and + (d) 1st and + (a) zero (b) one (c) two (d) three
2.303 k
14. Diazonium salt decomposes as
12. The rate constant for first order reaction is
5.78 10 5 s 1 . Percentage of initial concentration of 2 Cl C6 H5 Cl + N2
C6 H6 N+
reactant which reacts in 10 h is At 0C, the evolution of N2 becomes two times faster
[Given, antilog of 0.9031 = 8] when the initial concentration of the salt is doubled.
(a) 75% (b) 66.66% (c) 87.5% (d) 50% Therefore, it is

64
 (a) a first order reaction 19. Hydrolysis of amyl acetate was carried out separately
(b) a second order reaction in the presence of 0.02 M HCl and 0.02 M H2 SO4 . The
(c) independent of the initial concentration rate constant was found to be k1 and k2 respectively.
(d) a zero order reaction Then,
15. Which of the following reactions is a first order reaction? (a) k1 > k 2 (b) k 2 > k1 (c) k1 = k 2 (d) k1 = 2 k 2
(a) NH 2NO 2 N 2 + 2H 2O (b) 2HI H 2 + I 2 Hint Acidic hydrolysis of an ester is a first order reaction,
(c) 2NO 2 2NO + O 2 (d) 2NO + O 2 2NO 2 r = k [ester].
Thus, rate constant does not depends on [H + ]. Hence, k1 = k 2.
16. For a first order reaction, A B, k = 5 min1 . In another
first order reaction, C D, only 10% of C decomposes 20. The sidewise graph is shown for
in the time that is required for A to be 50% decomposed. change in concentration of
The rate constant for second reaction is species X and Y for the reaction

conc.
X
(a) 16.61 log10 111
. (b) 16
. log10 111
. X Y , as function of time. The
(c) 10.076 (d) 10 point of intersection of two
curves represents Y
17. 87.5% of a radioactive substance disintegrates in (a) t 1/ 2 (b) t 1/ 4
40 min. What is the half-life of the substance? Time
(c) t 3/ 4 (d) t 2/ 3
(a) 11.21 min (b) 13.21 min (c) 13.32 min (d) 14.21 min
21. The rate law for the reaction A + 2 B Product (P) is
18. What is the value of decay constant of a compound d[P]
given by = K[ A]2 . [B], if A is taken in large excess,
having half-life time as 2.95 days? dt
(a) 2.9 10 5 s 1 (b) 2.9 10 6 s 1 the order of reaction will be
(c) 2.7 10 6 s 1 (d) 3 10 5 s 1 (a) zero (b) 1 (c) 2 (d) 3
0.693
Hint Decay constant, =
t 1/ 2

TEMPERATURE DEPENDENCE OF THE RATE OF A REACTION

AND COLLISION THEORY OF CHEMICAL REACTIONS
Temperature Dependence of the Activated Complex Theory
Rate of a Reaction According to Arrhenius, when a reaction takes place, reactant
molecules first form an unstable intermediate (activated
The rates of most of the chemical reactions increase as the
complex). This intermediate exist for a very short time and
temperature is raised. The rate constant (k), changes with
breaks up to form products.
temperature (T) and it determines the way in which the rate of
A A
reaction varies with temperature. This behaviour is Threshold
summarised by Arrhenius equation k = Ae Ea / RT energy
where, A = Pre-exponential factor or frequency factor B B
Activated complex
Ea = Activation energy, R = Gas constant

Activation Energy
Energy

Ea
It is defined as the minimum amount of energy required by
the reactant molecules to take part in a chemical reaction.
A2+B2 H Enthalpy of reaction
l
Lower the activation energy, faster is the reaction, and Reactants
larger is the value of k. 2AB (Products)
l
Activation energy is always positive, whether the reaction Progress of reaction
is exothermic or endothermic.
l
A positive catalyst decreases Ea value and increases rate of Collision Theory of Chemical Reactions
a reaction, whereas a negative catalyst increases Ea value (Temperature Dependence of Rate of Reaction)
and decreases rate of a reaction.
Note Catalyst neither alter the Gibbs free energy change ( G ) nor Most Probable Kinetic Energy
enthalpy change (H) of the reaction. It provides an Maxwell and Boltzmann used statistics for predicting
alternate pathway by altering the potential energy barrier. behaviour of large number of molecules in a reaction.
According to them most probable kinetic energy is the energy
possessed by large fraction of molecules.

65
 Fraction of molecules
l
For an effective collision, the colliding molecules must
possess threshold energy.
Most probable l
An activation energy is supplied to the molecules for
kinetic energy
attaining the threshold energy. During collisions, this
energy is acquired by the molecules as a result of
interchanges of energies.
Kinetic energy

Often rate of a reaction increases by a factor of two for a 10 K Formulae Related to Activation
rise in temperature. Energy and Collision Theory
E a = Threshold energy average energy of reactants.
Fraction of molecules

T (K)
Additional fraction
Effect of temperature on rate of reaction,
(T+10) K of molecules k Ea 1 1
reacts at (T+10)K log 2 = , (T 2 > T 1 )
k 1 2.303RT T 1 T 2
where, k 1 and k 2 are rate constants at temperatures
T 1 and T 2 respectively.
Kinetic energy
Fraction of molecules
Rate of reaction in terms of collision frequency
reacting at T Rate = Z AB e E a / RT
Collision Theory of Bimolecular Gaseous Reactions where, Z AB = collision frequency of reactants A and B
This theory is based on kinetic theory of gases. e E a / RT = Fraction of molecules having energy either equal
The main postulates of this theory as follows: to or greater than E a .
l
The reaction between the molecules occurs only when
For effective collisions,
they collide with each other in proper orientations. Rate = pZ AB e E a / RT

l
Only those collisions result into chemical reaction in where, p = Steric factor
which the molecules acquire energy greater than the
activation energy.

22. For an endothermic reaction, minimum value of 26. Consider the following graph for the reaction R P.
activation energy (Ea ) will be
Transition state
(a) less than H (b) more than H
Potential energy

(c) H = E a (d) E a = 0 A
B
23. For a first order reaction, energy of activation at 25C
1 C
without using catalyst is 350 kJ mol and with the use
of catalyst is 162 kJ mol 1 . The ratio of rate constants
with the catalyst and to that of without catalyst is Reaction progress
(a) antilog of 23.59 (b) antilog of 23.95 H of the reaction corresponds to the energy
(c) antilog of 32.95 (d) antilog of 32.59
(a) B (b)A
24. Rate constant for the first order decomposition of (c) B A (d) C
H2 O2 is given by the equation,
27. The formation of H2 O2 in the upper atmosphere follow
log k = 14.34 125
. 104 / T , value of activation energy the mechanism:
(Ea ) for this equation is (in kJ /mol)
H2 O + [O] 2 OH H2 O2
(a) 932.43 (c) 239.34 (b) 392.34 (d) 293.43
Ea Given, H = 72 kJ mol , Ea = 77 kJ mol 1
1
Hint Qlog k = log A (i)
2.303RT Ea for backward reaction is (in kJ mol 1 )
1.25 10 4 (a) 149 (b) 149
log k = 14.34 (ii)
T (c) 5 (d) 5
25. With respect to equation, k = Ae Ea / RT of chemical 28. Collision theory is applicable to
kinetics, which one of the following option is correct?
(a) first order reaction (b) zero order reaction
(a) K is equilibrium constant (b) A is adsorption factor
(c) bimolecular reaction (d) intermolecular reaction
(c) E a is energy of activation (d) R is Rydberg constant

66
29. If activation energy (Ea ) for the reaction, (a) E a1 = 2 E a2 (b) E a2 = 2 E a1
2HI (g) H2 (g) + I2 (g) is 209.5 kJ mol 1 at 581K. (c) E a1 = E a2 (d)E a2 = ( E a1 )2
The fraction of molecules of reactant having energy Hint Activation energy does not depend on stoichiometry for a
equal to or greater than activation energy is given reaction. Thus, remains same, it is a characteristic
(a) 4.471 10 29 (b) 1471
. 10 9 property (value) for a particular reaction.
(c) 1.21 10 5 (d) antilog of 19 .1676
Ea 31. A reaction of decomposition is carried out by first order
Hint log x = , where, x = fraction of molecules
2.303 RT reaction. At 300 K, the decomposition completes 50%,
in 20 min. At 350 K, the same substance decomposes
having energy equal to or more than activation energy.
50% in 5 min. The activation energy (Ea )for the
30. Activation energy for the reaction, reaction is (in kJ mol 1 )
N2 O4 - 2NO2 is Ea1 , activation energy Ea2 for the (a) 24.19 (b) 75.79 (c) 50.07 (c) 100.7
reaction, 2N2 O4 4NO2 is
-
Answers
1. (a) 2. (a) 3. (c) 4. (a) 5. (a) 6. (b) 7. (b) 8. (d) 9. (d) 10. (a)
11. (a) 12. (c) 13. (b) 14. (a) 15. (a) 16. (a) 17. (c) 18. (c) 19. (c) 20. (a)
21. (b) 22. (b) 23. (c) 24. (c) 25. (c) 26. (d) 27. (d) 28. (c) 29. (d) 30. (c)
31. (a)

MASTER
1. The activation energies of two reactions are E1 and E2 , Hence, order = 1 +
1
=1
1
(E1 > E2 ). If the temperature changes from T1 to T2 , the 2 2
rate constant of the reactions changes from k1 to k1 in
4. Correct order for first order reaction is
the first reaction and k2 to k2 in the second reaction.
(a) T50 < Tav < T75 (b) Tav < T75 < T50
Predict which of the following expression is correct?
k k k k k k k k (c) T75 < Tav < T50 (d) T50 < T75 < Tav
(a) 1 = 2 (b) 1 > 2 (c) 1 < 2 (d) 1 = 2 = 1 Hint QTav = 144. T50, i.e. T50 = 0.693 Tav and T75 = 15
. T50
k1 k2 k1 k2 k1 k2 k1 k2
Thus, T50 < Tav < T75
2. A gaseous reaction, A B + 2C has specific reaction
rate10 4 , when the reaction was complete, the pressure
5. If I is the intensity of absorbed light and C, is the
concentration of AB for a photochemical reaction,
was 750 mm. Calculate the rate of reaction at the initial
AB + h ( AB)*, the rate of formation of AB* is
stage.
directly proportional to
(a) 1.5 mm s 1 (b) 2.5 mm s 1 (c) 3.5 mm s 1 (d) 0.5 mm s 1
(a) C (b) CI (c) I (d) I 2
Hint Since, 1 mole of a reactant gives 3 moles of product having
Hint Rate of reaction for a photochemical reaction depends on
the pressure of 750 mm, the initial pressure was 750/3 = 250 mm
dp intensity of light ( I ) and concentration of reactant.
A = K p = 10 2 250 = 2.5 mm s 1 Thus, answer is CI.
dt
6. The decomposition of NH3 follows rate expression,
3. For a reaction A2 + B2 2 AB the following k1 [NH3 ]
mechanism is followed. Rate = ,
k1 1 + k2 [NH3 ]
k2
A2 - A + A (fast), A + B2 AB + B (slow) Above expression behaves as first order reaction, when
k concentration of NH3 is
A + B
3
AB (fast)
(a) very high (b) very low
The order of overall reaction is (c) constant (d) can not be predicted
(a) 0 (b) 1
1
(c) 1 (d) 2 Hint At very low concentration of [NH 3 ] 1 + k 2 [NH 3 ] 1
2 Thus, rate = k1[NH 3 ]
[ A ] [ A ]
Hint From A 2 - A + A; k1 = (i) 7. A substance decomposes via two parallel
[ A2 ] k2 B
first order reactions. The rate constants
Q In main reaction [ A ] is not present in products thus to for these reactions are given as A
eleminate [ A ], 4 1 5 1 k1
k1 = 1.26 10 s , k2 = 3.8 10 s C
[ A ]2 = k1[ A 2 ] and [ A ] = k11/ 2 [ A 2 ]1/ 2 [From eq. (i)]
The percentage distribution of B and C are
From slow step, r = k 2[ A ] [B2 ] = k 2k11/ 2 [ A 2 ]1/ 2 [B2 ]
(a) 75% of B and 25% of C (b) 66.66% of B and 33.33% C
Let k 2 k1 = k, r = k [ A 2 ]1/ 2 [B2 ]
(c) 76.83% of B and 23.17% of C (d) 80% of B and 20% of C

67
 Hint For first order decomposition, Which of these mechanism is/are consistent with the
Rate of formation of B 1.26 10 4 12.6 10 5 given rate equation?
= =
Rate of formation of C 3.8 10 5 3.8 10 5 (a) Only I (b) Only II
[B] 12.6 126 (c) I and II (d) None of these
= = and total concentration = 126 + 38 = 164
[C ] 3.8 38 Hint Slowest step will be the rate determining step, thus in
126 case I, rate = r = k [Cl 2 ][H 2S] and
Thus, (i) % of B = 100 = 76.83%
164 in case II, rate = r = k [Cl 2 ][HS ][H + ]
(ii) % of C = 100 76.83 = 23.17% Hence, only mechanism I is consist for the given rate law.

8. The rate law for a reaction is r = k [ A]n[B]m, on doubling 12. For the reaction, 1 A 2 B, rate of disappearance of
the concentration of A and halving the concentration of 2
B, the ratio of new rate to the earlier rate of reaction will A is related to rate of appearance of B by the expression.
d 1d
be (a) [ A] = [ B]
1 dt 2 dt
(a) ( m + n) (b) d d
2m + n (b) [ A ] = 4 [ B]
(c) 2 n m
(d) ( n m) dt dt
d 1d
(c) [ A ] = [ B]
9. In the reaction, xA + yB Products, dt 4 dt
when concentrations of both the reactants A and B are d d
(d) [ A ] = [ B]
doubled, the rate increased by eight times. But when dt dt
concentration of A is doubled keeping concentration of
B constant, the rate of reaction increased by two times. 13. A radioactive element fallen over the floor of a room. Its
half-life period is 30 days. If the initial activity is ten
The order of reaction is
times of the permissible value, after how many days
(a) 0 (b) 1 will it be safe to enter the room?
(c) 2 (d) 3
(a) 1000 days (b) 500 days
10. For the reaction, A(g) + 2 B(g) 2C(g) using the (c) 300 days (d) 100 days
following results. The rate law will be Hint Q Activity N (quantity)
n
N 1
Exp. Initial conc. Initial conc. Initial rate of formation = (Q n = number of half-lifes)
no. of [ A ] mol L1 of [B] mol L1 of [C ], mol L1 N0 2
1. 0.30 0.30 0.10
14. If nt is the number of radioactive atoms present at time
2. 0.30 0.60 0.40
t, then for the first order reaction, which of the
3. 0.60 0.30 0.20
following will be constant?
(a) r = k[ A ]2[B]2 (b) r = k[ A ][B] nt nt
(a) (b) loge
(c) r = k[ A ]2[B] (d) r = k[ A ][B]2 t t
Hint Q Rate [conc. ]n, from exp. no.(1) and (2) d
(c) [loge nt ] (d)nt
rate [B]n (keeping A constant) dt
4 [B]n (n = order of reaction with respect to B) dnt dnt
Hint Q Rate = = nt =
n = 2, i.e. order of of reaction with respect to B = 2. dt nt dt
d
11. For the following reaction, (loge nt ) = (constant)
dt
Cl2 (aq) + H2 S(aq) S(s) + 2H+ (aq) + 2Cl (aq)
15. Variation of rate constant with the temperature is given
the rate equation is r = k[Cl2 ][H2 S] Ea
by log10 k = + constant
The two possible mechanisms of the above reaction are 2.303 RT
H+ + Cl + Cl + + HS
I. (i) Cl2 + H2 S Slow 3153
If for a certain reaction, log10 k = + 11.890
(ii) Cl2 + H + HS
+
H+ + Cl + S
Fast
T
Fast
II. H2 S - H+ + HS The value of activation energy is (in kJ mol 1 )
Cl2 + HS Slow
2Cl + H+ + S (a) 20.48 (b) 40.48 (c) 50.37 (d) 60.37

Answers
1. (b) 2. (b) 3. (c) 4. (a) 5. (b) 6. (b) 7. (c) 8. (c) 9. (d) 10. (d)
11. (a) 12. (c) 13. (d) 14. (c) 15. (d)

68
 Metallurgy
EXTRACTION AND
ISOLATION OF ELEMENTS
Metals occur in two forms in nature
(i) In native state Metals Ore Formula
(ii) In combined state Cu Chalcopyrite CuFeS 2 (copper pyrite)
Less reactive metals (Ag, Au, Pt etc.) are found in native Chalcocite Cu 2S (copper glance)
state (free state) and are not attacked by O 2, H2O and CO2 Cuperite Cu 2O
while reactive metals (Na, Ca, Mg etc.) are found in Azurite 2CuCO 3 Cu (OH)2
combined state in nature and attacked by O2 , H2O and Malachite CuCO 3 Cu(OH)2
CO2 . Ag Argentite Ag 2S (silver glance)
Ore An ore is a complex mixture of a metal-containing Cerargyrite AgCl (horn silver)
mineral and economically worth less material called Pyrargyrite Ag 2S Sb 2S 3 (Ruby silver)
gangue, consisting of sand, clay and other impurities. Fe Haematite Fe 2O 3
Limonite Fe 2O 3 3H 2O
Steps Involving Extraction of Metals Magnetite (lodestone) Fe 3O 4 (magnetic oxide of iron)
Step 1 Concentration of ore and, if necessary, chemical Siderite FeCO 3
treatment prior to the reduction. Iron pyrite FeS 2
Hg Cinnabar HgS
Step 2 Reduction of the mineral to the free metal.
Zn Zinc blende ZnS (black zinc or sphalerite)
Step 3 Refining or purification of metal. Calamine ZnCO 3
Zincite ZnO (red zinc)
Common ores of some important metals
Mn Pyrolusite MnO 2
Metals Ore Formula
Manganite Mn 2O 3 H 2O
Li Spodumene LiAlSi 2O 6 Cr Chromite Cr2O 3 FeO
Lepidolite (Li,Na, K)2 Al 2(SiO 2 )3 F(OH)
Na Common salt
Chile salt petre
NaCl (rock salt)
NaNO 3
Crushing of Ore
Glauberite Na 2SO 4 10H 2O (Glauber's salt) Crushing and grinding of ores are done in order to ease the
Borax Na 2B 4O 7 10H 2O process of concentration of ores. They are crushed into small
Trona Na 2CO 3 NaHCO 3 2H 2O pieces in gyratory crushers followed by grinding.
Soda ash Na 2CO 3
Feldspar NaAlSi 3O 8 Concentration of Ores
K Sylvine KCl
It involves the removal of unwanted materials like sand, clays,
Nitre KNO 3 (saltpeter)
etc., from the ore. The procedure followed depends on physical
Schonite K 2SO 4 MgSO 4 6H 2O
properties of compounds of minerals and impurities present in it.
Mg Magnesite MgCO 3
Some of the important methods involved are:
Dolomite MgCO 3 CaCO 3
Carnallite KCl MgCl 2 6H 2O Gravity Separation or Levigation
Epsom salt MgSO 4 7H 2O
It is based on difference in the density of the ores and the gangue
Ca Gypsum CaSO 4 2H 2O
particles. The powdered ore is washed in a running stream of
Limestone CaCO 3
water. The lighter gangue particles are washed away leaving the
Phosphorite Ca 3 (PO 4 )2
heavier ores. Fe2O3 , Fe3O4 , etc., are concentrated by this method.
Fluorspar CaF2
Al Bauxite Al 2O 3 2H 2O Froth Floatation Method
Diaspore Al 2O 3 H 2O
Sulphide ores of Cu, Ag, Zn, Pb, etc., are concentrated by this
Corundum Al 2O 3
process.
Cryolite Na 3 AlF6 l
A suspension of powdered ore in water is made followed by
Sn Cassiterite SnO 2 (tin stone) the addition of collectors (pine oil, fatty acids, xanthates, etc.)
Pb Galena PbS and froth stabilisers (cresol, aniline, etc.).
Cerussite PbCO 3 l
Ore particles are made wet by oil and come to surface as froth,
Anglesite PbSO 4 whereas gangue particles remain inside with water.

69

Magnetic Separation Method
It is based on difference in magnetic properties of gangue and
Impure Metal
ores. The ore is concentrated by a magnetic separator, that
separates magnetic substances from non-magnetic substances. Refining of Impure Metal The impure metal obtained from the
Magnetite (Fe3O4 ), chromite (FeO Cr2O3 ), pyrolusite (MnO2 ), reduction of metal oxide contains impurities that are refined to get
tungsten ore, etc., are separated by this method. pure metal.

Leaching
In this process, the ore is made soluble in a suitable solvent Pure Metal
leaving the insoluble gangue particles behind. The ore is then
Various processes for reduction of metal oxides to metal are given
recovered from the solution by suitable chemical method. below
Leaching of Bauxite Smelting The concentrated ore is treated with coke and flux and
Conc. NaOH heated at high temperature and the process is called smelting. The
(Al2O3 ) coke reduces metal oxide to metal and flux removes acidic or basic
Bauxite High temperature and pressure
Ore with impurity impurities as slag :
2 CO ( g) 1470 K With Hydrogen M O 3 + 3H 2 M + H 2O (M = Mo or W)
Na[Al(OH)4 ](aq) Al2O3 xH2O(s) Al2O3 (s)
Pure form Goldschmidt Aluminothermic Process Cr and Mn oxides are
Leaching of Ag and Au Ores reduced by this process.
Cr 2O 3 + 2Al Al 2O 3 + 2Cr
Ag and Au ores are concentrated as metal cyanide by treating
3Mn3O 4 + 8Al 4Al 2O 3 + 9Mn
them with dilute NaCN or KCN, from which pure metal is
obtained by replacement reaction.
With Other Metals Highly active metals reduce less active metal
oxides.
EXTRACTION OF CRUDE METAL FROM TiO 2 + 2Mg Ti + 2MgO
CONCENTRATED ORE Self Reduction or Auto-reduction A part of sulphide ore of less
Highly Active Metals (e.g. Na, K, Mg etc.) electropositive metals like Hg, Pb, Cu, etc., are converted to oxide ore.
The sulphide and oxide ores undergo self-reduction to form the metal.

e.g. 2Cu2 S + 3O 2 2Cu2O + 2SO 2 (g )

Electrolytic Reduction The oxides of highly electropositive metals do not Cu2 S + 2Cu2O 6Cu + SO 2 ( g )
reduce easily with coke. Hence, they are extracted by electrolysis of their Note Pyrometallurgy In this process metal is extracted by heating metal
salts in fused sate. Pure metal is obtained at cathode. oxide with a suitable reducing agent.

Hydrometallurgy In this process metal is extracted by dissolving the

ore in a suitable reagent followed by precipitation of metal by a more
electropositive metal.
Less Active Metals
Roasting Sulphide ores are converted to oxide ores by roasting. The ore is Rock Music and Metallurgy
treated in a furnace in regular supply of air at a temperature below the n
Metallurgy plays a big role in rock music, without it rock music as
melting point of the metal. The sulphide ores are converted to metal oxides
we know would not exist.
and the impurities are removed as volatile oxides.
The strings of the guitar being played are the product of complex

technology.
Calcination Hydroxide and carbonate ores do not undergo roasting, hence n
The core of the strings is made of mild steel, varying in hardness
they are heated below melting point in absence of air forming metal and ductility, depending on the type of guitar on which it will be
oxides. used.

n
The core string is wound with fine wrap wire, composed typically
an alloy of copper and zinc for acoustic guitar use, or stainless
Metal Oxide steel for electric guitars.
Reduction of Oxide to Metal Metal oxides are reduced to the
n
Artists can be very passionate about the particular makes and
corresponding metals by various processes based on standard reduction models of strings they use.
potential called pyrometallurgical process and hydrometallurgical process.

1. Which of the following metal has the largest abundance 2. Sulphides ores are common for the metals
in the earth's crust? (a) Ag, Cu and Pb
(a) Aluminium (b) Calcium (b) Ag, Cu and Sn
(c) Magnesium (d) Sodium (c) Ag, Mg and Pb
(d) Al, Cu and Pb

70
 3. Smelting involves reduction of metal oxide with (a) chloride (b) sulphate (c) sulphide (d) nitrite
(a) carbon (b) carbon monoxide Hint (d) Nitrite salt which is least likely to be found in
(c) magnesium (d) aluminium minerals because all nitrates are soluble in water.

4. During smelting, an additional substance is added 8. Which of the following benefication process is used
which combines with impurities to form a fusible mass. for the minerals, Al2O3 2H2O?
The additional substance is called (a) Froth floatation (b) Leaching
(a) flux (b) slag (c) gangue (d) ore (c) Liquation (d) Magnetic separation
5. Which of the following metals are found in native state? Hint (b) Leaching process is used for the minerals
(a) Ag, Pb and Fe (b) Ag, Pt and Mg Al 2O 3 2H 2O.
(c) Au, Pt and Ag (d) Cu, Al and Zn 9. Heating pyrite to remove sulphur is called
6. The ore having two different metal atoms is (a) smelting (b) calcination (c) liquation (d) roasting
(a) haematite (b) galena Hint (d) Heating pyrite to remove sulphur is called roasting.
(c) magnetite (d) copper pyrites
10. In the extraction of metal M from its sulphide ore is
Hint (d) CuFeS 2 (Cu and Fe)
formed by reduction with Cu2O is
7. The salt which is least likely to be found in minerals is (a) Fe (b) Co (c) Cu (d) Zn

THERMODYNAMICS AND ELECTROCHEMICAL

PRINCIPLES OF METALLURGY
Thermodynamics of Metallurgy
+250
For a reaction to be spontaneous, fG value should be 2Ag 2
O
O 2
negative. Hence, during the reduction of metal oxides, a 4Ag+ O
Free energy change, G, kJ mol1

u
reducing agent with a negative value of fG that is sufficient
0 2C
+O 2
2Cu CO+1/2 O2CO2 2Fe
O
to make the over all fG value negative. 2Fe+O 2
O2+CCO2
nO
500 + O 22Z O
2Zn Cr 2 3

Ellingham Diagram 4/3 C

r+O 2
2/3
TiO 2 Al 2O 3 2C+
/3 O2
Ti+O
2
It represents fG versus temperature for the formation of 2 2CO
A l+O 2
oxides of elements. 4 /3
1000 g O
M
2 aO
l
Each plot is a straight line except when a phase change +O 2 2C
2Mg O 2
occurs. +
2Ca
l
There is a point in the curve below which fG is negative 500 1000 1500 2000 2500 3000
Temperature, K
(the oxide is stable) and above this point the metal oxide is
Combined Ellingham diagram for metal and carbon
decomposed to form metal.
l
This diagram is useful in choosing a reducing agent for the Limitations of Ellingham Diagram
reduction of metal oxides.
(i) These do not explain the kinetics of reduction
processes.
The difference in the two fG values after (ii) It is assumed that system is always in the state of
point A determines whether reduction of equilibrium, which is not true.
the oxide of the upper line is feasible by
the element represented by lower line or not. Steeling of Automobiles
n
Steel (many iron alloys are collectively known as steels) is the
-700 A most recycled consumer product, given that about 95% of steel
Al 2O 3
G(kJ mol1 of O2)

-800
2/3 from automobiles is recycled.
l+O 2
-900 4/3A
2MgO n
The steel recycling institute estimates that 14 million tons of steel
-1000 O 2
2Mg+ scrap from automobiles was recycled in the year 2000.
-1100
-1200
n
Approximately 14 10 6 tons of iron (steel) is recycled. Each
10 3 tons iron ore contains 20 tons Fe 3O 4 is which there are
0C 400C 800C 1200C 1600C 2000C
168 tons Fe per 232 tons Fe 3O 4 .
273 K 673 K 1073 K 1473 K 1873 K 2273 K
Temperature
n
About 1 10 9 tons of ore did not have to be mined because of
using recycled steel, saving a substantial amount of material and
the energy needed to process the ore.

71
Furnaces Siemens Martin Open Hearth Furnace
Used in the manufacture of steel. The furnace is lined with CaO
It is a device in which high temperature is produced
and MgO.
either by burning fuel or by using electricity. Several
type of furnaces are used in the metallurgy. Some
l
A mixture of molten cast iron, Fe2O3 and CaCO3 is heated by
important ores among them are: producer gas. The impurities are oxidised and removed.
l
The molten iron is mined with required amount of spiegel (an
Reverberatory Furnace alloy of Fe, C, Mn) to obtain steel of required quality.
This is made up of fire bricks containing fire place,
hearth and chimney. The ore is not directly heated in
Charge Fire brick
this furnace. Basis lining checker
The fuel gas doesnt come in direct contact with the work
material, hence can be used for both oxidation and
reduction. If reduction is required, the ore is mixed with Gas Air
some reducing agent while oxidation is required, hot air
blown in it. It is used for extraction of Cu, Pb, Sn, etc.
Hopper
Hot
Doors for air gases Open hearth process

Advantages of Open Hearth Process

Molten
l
This process is slower and easier to work.
metal
l
Samples can be examined from time to time. Thus, the quality of
Silica
steel can be controlled.
lining
l
Since, heating is done externally, thus, temperature can be
Air controlled more effectively.

Tapping hole Electric Furnaces

Reverberatory furnace
Blast Furnace
This is a steel structure lined with fire bricks. It is
narrow at both the top and bottom, but wider at middle.
There is a hopper at the top through which concentrated
ore, coke and flux are inserted. There are different
temperature zones in the furnace where different
reactions take place. The molten metal is obtained at
the bottom. Fe, Cu, Pb, etc., are purified in the furnace.
In these furnances, electrical energy is converted into heat energy.
Such furnace are largely used where cheap power is available and
very high temperatures are required and also for carrying
electrolytic reduction.
Molten
steel

Steel Charging
Charge Fe2O3
(8 parts) + Coke Double cup and door
(4 parts) + Lime cone arrangement
stone (1 part) Steel plates
Basic
Fire clay lining
bricks Electric furnace process
Hot gases
Essential Transition Metals in Nutrition
Of the ten trace elements known to be essential to human nutrition, seven are
transition metals. For the most part transition metals are present in
biochemical compounds as complex ions, chelated by organic ligand for, e.g.
haemoglobin has such a structure with Fe 2 + as the central ion of the complex.
The Co 3 + ion occupies a similar position in vitamin-B12 , octahedrally
Tuyeres Tuyeres coordinated to organic molecules somewhat similar to those in haemoglobin.
Transition metal cations are frequently found in enzymes. The Zn2 + ion alone is
known to be a component of at least 70 different enzymes.
Molten iron Molten slag Although Zn2 + is essential to human nutrition, compounds of the two
Molten iron Hearth elements below zinc in the periodic table, Cd and Hg are extremely toxic. This
Slag
Metallurgy of Fe : Reactions inside a reflects the fact that Cd and Hg2 + , in contrast to Zn2 + , form very stable
blast furnace complexes with ligands containing sulphur atoms. As a result, these two
cations react with and thereby deactivate enzymes containing SH group.

72
11. According to Ellingham diagram, the oxidation (a) Fe 2O 3 melt (b) FeO (c) Fe 3O 4 (d) metallic iron
reaction of carbon to carbon monoxide may be used to
16. Heating mixture of Cu2O and Cu2S will gave
reduce which one of the following oxides at the lowest
temperature? (a) Cu + SO 2 (b) Cu + SO 3 (c) CuO + CuS (d) Cu2 + SO 3
(a) Al 2O 3 (b) Cu2O (c) MgO (d) ZnO Hint 2Cu2O + Cu2S 6Cu + SO 2
Hint (b) The graph of f G vsT in the Ellingham diagram Auto reduction takes place
shows that Cu Cu2O line is atmost at the top (i.e. much higher
17. G vs T plot in the Ellingham's diagram slopes
than those of Al - Al 2O 3 , Mg-MgO, Zn-ZnO and Fe-FeO) lines.
downwards for the reaction.
Therefore, Cu2O can be reduced to Cu at the lowest
1 1
temperature. (a) Mg + O 2 MgO (b) 2Ag + O 2 Ag 2O
2 2
12. Identify the reaction that does not take place in a blast (c) C +
1
O 2 CO
1
(d) CO + O 2 CO 2
furnace. 2 2
(a) Fe 2O 3 + 3C 2Fe + 3CO
18. Which of the following reactions, taking place in the
(b) CO 2 + C 2CO
blast furnace during extraction of iron is endothermic?
(c) CaCO 3 CaO + CO 2
(a) CaCO 3 CaO + CO 2
(d) FeO + SiO 2 FeSiO 3
(b) 2C + O 2 CO
Hint (d) CaSiO 3 formation takes place in blast furnance (c) C + O 2 CO 2
(FeSiO 3 is not formed). (d) Fe 2O 3 + 3CO 2Fe + 3CO 2
CaO + SiO 2 CaSiO 3
(Slag) 19. Which out of the following reactions, does not indicate
13. Among the metals Cr, Fe, Mn, Ti, Ba and Mg, the one slag formation?
that cannot be obtained by reduction of metal oxide by (a) Fe 2O 3 + P2O 5 2FePO 4
aluminium is (b) PbO + SiO 2 PbSiO 3
(a) Cr (b) Fe (c) Mg (d) Ba (c) 3MgO + P2O 5 Mg 3 (PO 4 )2
Hint (c) Mg metal cannot be obtained by reduction of MgO by (d) None of the above
aluminium because Mg is more reactive than Al. Hint FeO + SiO 2 FeSiO 3
(Slag)
14. Iron obtained from blast furnace is 20. Selection of temperature to carry out a reduction
(a) wrought iron (b) cast iron (c) pig iron (d) steel process depends so as to make
(a) G negative (b) G positive
15. On igniting Fe2O3 at 1400C, the product obtained is
(c) H negative (d) H positive

REFINING OF METALS AND EXTRACTION

SCHEME OF SOME METALS
Metals extracted through any of the methods described in pure crystal of metal leaving impurities in the remaining
topic 1 and 2 are usually contain some impurities. Following part of molten metal. Ge, Si, B, Ga, in are purified by this
methods are used to purify the metals. method.
1. Distillation Method Metals with low boiling point like 5. Vapour Phase Refining Method The impure metal is
Zn, Cd, Hg, etc., are evaporated to collect the pure metal. converted into its volatile compound, which on heating
2. Liquation Method Metals with low melting point like, is decomposed to pure metal.
Sn, Pb, Hg, Bi, etc., are separated from high melting Mond process
impurities by this method. Ni+ CO 330 350 K
Ni(CO)4
3. Electrolysis The impure metal act as anode and Volatile compound
deposited at cathode as pure metal. The electrolysis is 450 470 K
Ni(CO)4 Ni +4CO
carried out in a cell containing aqueous solution of the
van-Arkel Method This method is used to remove
salt of the metal. The more basic impurities remain in
oxygen and nitrogen impurities in metals like Zr, Ti, V,
solution and less basic impurities are deposited as anode
Th, etc., e.g.
mud, e.g. Cu, Zn, Ag, Au, Al, etc.
Ti +2I2 150
250 C
TiI4 (g)
4. Zone-refining Method This is based on the principle Volatile compound
that impurities are more soluble in molten state than in
1400 C
the solid state of metal. The metal obtained is highly TiI4 (g) Ti(s) + 2I2 (g)
Tungsten filament (Pure)
pure. The impure metal on gradual cooling deposit as

73
 6. Hydrometallurgical Process The ore is Copper
Concentrated by froth floatation process
treated with reagents like NaCN or Cl2 in Sulphide ore Concentrated ore
presence of water. The metal forms salt As and S driven off Roasted in a current of air
solution that is recovered in pure form either as volatile oxides in reverberatory furnace
by electrolysis or by replacement reaction in FeS is converted into Fe2+ oxide In silica-lined
which slags off as silicates, while Roasted ore
the solution. Cu2S is converted into molten Cu converter with blow
in the form of Cu matte
7. Amalgamation Process Noble metals like of hot compressed air
i.e. Cu2S and FeS
Ag, Au when come in contact with Hg form On cooling
amalgam, from which pure metal is (Molten Cu) Refined by electrolysis
Blister copper Pure copper
obtained by distillation. Blisters formed due to
using impue Cu anodes and pure Cu
cathodes and CuSO4 as electrolyte
8. Chromatographic Method This is based on liberation of SO2, N2 and O2
the principle that different compounds of a
mixture are differently adsorbed on an Zinc
adsorbent. This method is used when the Concentrated by froth Concentrated Roasted on
Sulphide ore Oxide of metal
impurities are very close in their chemical floatation process ore sintering machine
properties and the metal is present in very
minute quantity. Electrolysis or Pure metal Heated by With clay
Refined metal Briquette
9. Poling Method The impure metal distillation distills off producer gas and coke
containing oxides as impurity can be collected by to 1673 K
purified by this method. The molten impure rapid chilling
metal is stirred with green poles of wood.
Iron
This pole release hydrocarbon gases which Calcination (to remove most H2O)
Purest form of iron
reduce the oxide impurities. This method is Ore
decomposes carbonates,
Calcined ore
Wrought or malleable iron
used specially in case of copper. and oxidise sulphides With limestone
In rever- and coke fed in
10. Cupellation In this process ores or alloyed
beratory with 0.5% blast furnace
metals are treated under very high furnace impurities After pouring With 4% C and
temperatures and have controlled lined with
many other
Molten iron in the lowest
haematite Cast iron
operations to separate noble metals like Ag with 3%
into shapes impurities like
zone called pig iron
and Au, from base metals like Zn, Bi, As etc. of moulds S, P, Si and Mn
carbon
This method is known as cupellation
By any of the following processes.
because impure metal is fused in small boat 1. Bessemers process through
shaped dishes of bone ash or cement called Bessemers converter Mild steel (0.50.5% C)
2. Open hearth process Steel
carpels. Hard steel (0.51.5% C)
3. Oxygen-top blowing process
11. Bessemerisation In this process, the impure 4. Electric arc process
metal is heated in Bessemer converter and a 5. High frequency induction process
blast of compressed air is blown through the
molten mass. The impurities get removed in Silver
the form of volatile oxides. This process is Leaching with
used in making steel from cast iron, in Metal ore Metal cyanide
NaCN solution
purification of Ni etc. [Ag(CN)2]

Extraction Scheme of Some The ppt of metal is collected,

dried and melted with a flux
Pure metal
Zn
[Zn+(CN)4]2
Important Metals (borax or KNO3) to oxidise
Pb and Zn impurities
Aluminium Electrolysis
Bauxite NaOH solution
Refined metal

DIGESTER Mercury
(The bauxite dissolves in NaOH
It is found as 1 10 5 % of earth crust and its most important ore is cinnabar
solution under pressure)
(HgS).
Roasted in air Hg vapour distills over
SETTLING TANK PRECIPITATORS Ore
(Undissolved solids [Al(OH)3 added to above 773 K and condensed
removed from encourage precipitation
Richer ore
the solution) of the solution] Distillation
OR + Metal
quick lime (in iron retorts)
KILN
Al2O3 fed into
Al [Al(OH)3, ppt heated Purification It can be purified by dropping slowly through dil. HNO3 . The
electrolytic cell
at high temperature]
metallic impurities displace Hg from nitrate and go into the solution.
Further purification is carried out by distillation under reduced pressure.

74
21. Calcium is obtained by the 26. Vapour phase refining of nickel is carried out using
(a) roasting of lime stone (a) I 2 (b) Cl 2 (c) HCl (d) CO
(b) electrolysis of solution of calcium chloride in H 2O
(c) electrolysis of molten anhydrous calcium chloride
27. Which of the following refining method and crude
metals are not correctly matched?
(d) reduction of calcium chloride with carbon
(a) Liquation-Tin
22. Blister Cu is about (b) Zone refining-Silicon
(a) 60% Cu (b) 90% Cu (c) 98% Cu (d) 100% Cu (c) Mond process-Aluminium
Hint (c) After bessemerisation of the concentrated ore, Cu (d) Electrolytic refining-Blister copper
obtained is 98 % pure. It is called blister Cu. 28. Which method of purification is represented by the
23. During electrolytic refining of copper, some metals equations?
500 K
present as impurity settle as anode mud. These are Ti + 2I2 TiI4
(a) Sn and Ag (b) Pb and Zn Impure
(c) Ag and Au (d) Fe and Ni 2I2 + Ti
1675 K
Pure
24. Which of the following refining method and crude
metals are not correctly matched? (a) Cupellation (b) Poling
(c) van-Arkel (d) Zone refining
(a) Distillation-Zinc and mercury
(b) Liquation-Tin 29. Which of the following method is used for obtaining
(c) van-Arkel-Zirconium aluminium metal?
(d) Mond process-Lead (a) Electrolysing fused Al 2O 3 and cryolite
25. The process of isolation of metals by dissolving the ore (b) By heating alumina with carbon
in a suitable chemical reagent followed by (c) By heating alumina in muffle furnace
precipitation of the metal by a more electropositive (d) By a process called pyrometallurgy
metal is called 30. Poling process
(a) electrometallurgy (a) reduced SnO 2 to Sn
(b) hydrometallurgy (b) oxidised impurities like iron and removes as scum
(c) electro-refining (c) uses green poles of wood
(d) zone-refining (d) involves all of the above.

Answers
1. (a) 2. (a) 3. (a) 4. (a) 5. (c) 6. (d) 7. (d) 8. (b) 9. (d) 10. (c)
11. (b) 12. (d) 13. (c) 14. (c) 15. (d) 16. (a) 17. (c) 18. (d) 19. (d) 20. (a)
21. (c) 22. (c) 23. (c) 24. (d) 25. (b) 26. (d) 27. (c) 28. (c) 29. (a) 30. (d)

MASTER
1. Which one of the following elements constitutes a 3. Which step is not involved in hydrometallurgical
major impurity in pig iron? process?
(a) Silicon (b) Oxygen (a) Cu2S + 2 Cu2O 6Cu + SO 2
(c) Sulphur (d) Carbon (b) CuSO 4 + Fe Cu + FeSO 4
(c) CuFeS 2 + 2H 2SO 4 CuSO 4 + FeSo 4 +2 H 2S
2. Native silver metal forms a water soluble complex with (d) CuCO 3 + H 2SO 4 CuSO 4 + CO 2 + H 2O
a dilute aqueous solution of NaCN in the presence of 4. Extraction of zinc from zinc blende is achieved by
(a) nitrogen (b) oxygen (a) electrolytic reduction
(c) carbon dioxide (d) argon (b) roasting followed by reduction with carbon
Hint (b) 4Hg + 8NaCN + 2H 2O + O 2 (c) roasting followed by reduction with other metal
4Na[Ag(CN)2 ]+ 4NaOH (d) roasting followed by self reduction
Hint (b) Roasting followed by reduction with carbon.

75
5. By annealing steel 14. Electrolytic reduction of alumina to aluminium by
(a) becomes soft Hall-Heroult process is carried out
(b) becomes liquid (a) in presence of NaCl
(c) becomes hard and brittle (b) in presence of fluorite
(d) is covered with a thin film of Fe 3O 4 (c) in the presence of cryolite which forms a melt with lower
melting temperature
6. In alumino thermite process aluminium acts as (d) in the presence of cryolite which forms a melt with higher
(a) an oxidising agent (b) a flux melting temperature
(c) a reducing agent (d) a solder
15. Ag + Na2CO3 Ag2CO3 X
7. The methods chiefly used for the extraction of lead and
(a) Ag 2O and CO 2 (b) Ag, O 2 and CO 2
tin from their ores are respectively
(c) Ag 2O 2 and CO 2 (d) No effect
(a) self reduction and carbon reduction
Hint (b) X = Ag, O 2 and CO 2
(b) self reduction and electrolytic reduction
(c) carbon reduction and self reduction 16. In the equation,
(d) cynide process and carbon reduction 4 M + 8CN + 2H2O + O2 4 [M(CN)2 ] + 4OH
8. When copper pyrite is roasted in excess of air, a The metal M is
mixture of CuO + FeO is formed. FeO is present as (a) copper (b) iron
impurity. This can be removed as slag during (c) gold (d) zinc
reduction of CuO. The flux added to form slag is Hint (c)
_ _
(a) SiO 2 , which is an acidic flux 4Au + 8CN+ 2H2O + O2
O2
4OH + 4[Au(CN)2]
(b) lime stone, which is basic flux [M=Au]
Gold
(c) SiO 2 , which is the basic flux
(d) CaO, which is a basic flux 17. The auto-reduction process is not used in the
9. Which is chloride ore of Mg? metallurgy of
(a) Kiserite (b) Carnallite (a) Hg (b) Cu
(c) Epsomite (d) Dolomite (c) Pb (d) Fe

10. Corundum is mineral of Al. 18. In the process of extraction of gold,

_ O2
_
(a) silicate (b) oxide Roastedgoldore+CN+H OH+[ X]
2O
(c) double salt (d) sulphate
[X ] + Zn [Y]+ Au
11. Purest form of iron is Identify the complexes [X] and [Y]
(a) cast iron (b) wrought iron (a) X = [Au(CN)2 ] ; Y = [Zn(CN)4 ]2
(c) pig iron (d) None of these (b) X = [Au(CN)4 ]2 ; Y = [Zn(CN)4 ]2
12. Which of the following is not an ore of a metal? (c) X = [Au(CN)2 ] ; Y = [Zn(CN)6 ]4
(a) Malachite (b) Calamine (d) X = [Au(CN)4 ] ; Y = [Zn(CN)4 ]2
(c) Stellite (d) Cerussite 19. Which of the following is used in thermite welding?
13. Black tin is (a) TiO 2 + 4Na Ti + 2Na 2O
(a) an alloy of Sn (b) an allotrope of Sn (b) 2Al + Fe 2O 3 Al 2O 3 + 2Fe
(c) 60 70 % SnO 2 (d) 100 % SnO 2 (c) SnO 2 + 2C Sn + 2CO
(d) Cr2O 3 + 2Al Al 2O 3 + 2Cr
Hint (c) 60-70% SnO 2 called black tin.

Answers
1. (d) 2. (b) 3. (a) 4. (b) 5. (a) 6. (c) 7. (a) 8. (a) 9. (b) 10. (b)
11. (b) 12. (c) 13. (c) 14. (c) 15. (b) 16. (c) 17. (d) 18. (a) 19. (b)

76
 Do you know, our clear visibility is due to rigidity of Do you know, why do molecular orbitals of B2 , C2
double bonds in retinal? and N2 not follow, the same increasing energy order
We see things around us, when light is focused by the lens of our eye as O 2 and F2 ?
onto the retina, the layer of cells lining the interior of the eyeball. The In case of F2 and O 2 , we assume that the interactions between the
retina contains photoreceptor cells called rods and cones. The human s-orbitals and interactions among the p-orbitals are completely
retina contains about 3 million cones and 100 million rods. The rods are independent because of large energy gap between s and p-orbitals.
sensitive to dim light and cones to colours. The tops of the rods and But in case of B 2 , C 2 and N2 energy gap between s and p-orbitals is not
cones contain a molecule called rhodopsin. Rhodopsin consists of a large. Hence, these orbitals interacts with each other and this
protein called opsin, bonded to a reddish-purple pigment called retinal. interaction is known as s-p mixing. Generally, orbitals of same
Our vision depends on the rigidity of double bonds in retinal. symmetry interact together. This means that the 2 g -orbitals, derived
In its normal form, retinal is held rigid by its double bonds. Light entering from the 2 s-orbitals, interact with the 3g -orbitals derived from the
the eye is absorbed by rhodopsin and the energy is used to break the 2 pZ -orbitals. Similarly, the s and p-based u -orbitals interact together,
-bond portion of the circled double bond. The molecule then rotates s- p mixing leads to stabilisation of 2 g and 2 *u -orbitals and
around this bond, changing its geometry. The retinal then separates destabilisation of 3g and 3 *u -orbitals. The destabilisation of the
from the opsin, triggering the reactions that produce a nerve impulse 3g -orbitals is particularly important as they pushes the 3g -orbitals
that the brain interprets as the sensation of vision. It takes as few as five above the 1 u -orbitals in energy level. The -orbitals are not affected by
closely spaced molecules reacting in this fashion to produce the s- p mixing as these are of wrong symmetry to interact with the s-based
sensation of vision. Thus, only five photons of light are necessary to -orbitals.
stimulate the eye.
Do you know, what is the role of HOMOs and LUMOs
H CH3 H
H3 C CH3
in Diels Alder reaction?
C C C H In Diels Alder reaction conjugated diene and dienophile (alkyne or
C C C
alkene) react and form cyclohexene and follow concentrated
H H C H mechanism (bond breaking and bond formation take place
CH3 H3 C C simultaneously). In this reaction, HOMO of electron rich species (diene)
Rhodospin interacts with LUMO of electron deficient
C Opsin
Light H N species (alkyne or alkene). This reaction +
is thermally allowed, provided the
H CH3 H CH3 H orbitals of similar energy.
H3 C CH3
C C C C C Opsin
C C C C N

H H H H
CH3
Do you know, chemical bonds differ only in intensity
of electrostatic force of attraction?
In chemical bonding, we study about different kinds of bonds like, ionic, LUMO LUMO
covalent, coordinate, metallic, hydrogen and van der Waals bonds. All
of these bonds differ from each other only in intensity of electrostatic
force of attraction. This attraction occurs between electrons and
nucleus, either of same species or of two different species. The HOMO
repulsion occurs among electrons, either of same species or of two HOMO
different species. When attraction of force between electron of one
species and nucleus of other species predominates, over repulsive
force, a bond is formed between the two species. In ionic bond, intensity
of force of attraction is found to be maximum. Hence, it is considered as
the strong bond or you may say it requires more energy to be broken into Diene Dienophile
its constituent ions. In case of van der Waals bond intensity of
electrostatic force of attraction is much less. Hence, it is a weak bond or Note If we use a dienophile with electron releasing group and a diene
you may say it requires less amount of energy to be broken into its with an electron withdrawing group then HOMO of dienophile
constituent ions. interacts with LUMO of diene.

77
General Instructions
1. All questions are compulsory.
2. Q. no. 1 to 5 are very short answer questions and carry 1 mark each.
3. Q. no. 6 to 10 are short answer questions and carry 2 marks each.
4. Q. no. 11 to 22 are also short answer questions and carry 3 marks each.
5. Q. no. 23 is a value based question and carry 4 marks.
6. Q. no 24 to 26 are long answer questions and carry 5 marks each.

1 Very Short Answer Type Questions 7. The resistance of a conductivity cell containing
1. Which one out of NH3 and CO2 , will be adsorbed 0.001M KCl solution at 298 K is 1500 . What is the
more readily on the surface of charcoal? Give reason. cell constant, if the conductivity of 0.001M KCl
Hint NH3 , as it has greater intermolecular forces of attraction. solution at 298 K is 0.146 10 3 Sm1 ?
2. Out of benzyl chloride and cyclohexyl chloride, Hint Cell constant = Conductivity ( ) Resistance ( R )
which one would undergo SN 2 reaction faster and 8. Write the IUPAC name of
why? (i) [Pt(NH3 )3 NOCl2 ]Br2
Hint Cyclohexyl chloride would react faster because (ii) [Cr(NH3 )2 Cl4 ]Cl
benzyl chloride is more stable due to + I-effect and resonance.
Hint (i) Triamminedichloridonitrosylplatinum (IV) bromide.
3. Write the IUPAC name of the compound.
(ii) Tetraamminedichloridochromium (III) chloride.
CH3 CH CH2 COOH
9. Describe the following giving the relevant chemical
OH equation in each case:
Hint 3-hydroxybutanoic acid (i) Carbylamine reaction
4. Complete the following chemical equation, (ii) Hofmanns bromamide reaction
P4 +10SO2 Cl2 or
Hint P4 + 10SO 2Cl 2 4PCl 5 + 10SO 2 Draw the structures of major monohalo products in
5. Which point defect in crystals of a solid does not each of the following reactions:
change the density of the solid? PCl5
(i) CH2OH
Hint Frenkel defect

2 Short Answer Type Questions (ii) CH2CH==CH2 +HBr

6. Draw the structure of the following compounds: Hint Br

(i) H2 S2 O8
(i) CH2Cl (ii) CH2CHCH3
(ii) H2 S2 O7

87
 10. Compound A having molecular formula C4 H9 Br (ii) CN ligand produces strong field means splitting of
reacts with aq.KOH solution. The rate of reaction d-orbitals will be large, whereas H2 O ligand produce weak
depends upon the concentration of the compound A field means splitting of d-orbital will be small.
only. When another optically active isomer B of this (iii) Linkage isomerism
compound reacts with aq. KOH solution then rate of 16. (i) Describe Bredigs Arc method briefly.
reaction is found to be dependent on concentrations (ii) Define collodion.
of compound A and KOH both. Write down the (iii) Some reactants give different products using
structural formulae for both compounds A and B. different catalysts. Explain why?
CH3

17. Account for the following.
Optical
Hint CH3 C Br CH3 CH2 C H CH3 (i) Primary amines (R NH2 ) have higher boiling
isomerism
points than tertiary amines (R3 N).
CH3 Br
(ii) Aniline does not undergo Friedel-Crafts reaction.
A B
(iii) (CH3 )2 NH is more basic than (CH3 )3 N in an
3 Short Answer Type Questions aqueous solution.
11. Give reasons for the following: Hint (i) Intermolecular hydrogen bonding is present in primary
(i) (CH3 )3 P ==O exists but (CH3 )3 N==O does not. amines.
(ii) Aniline with AlCl 3 (catalyst) forms salt.
(ii) Oxygen has less electron gain enthalpy with
negative sign than sulphur. (iii) Basic strength depends upon the stabilisation of the
conjugate acids by H-bonding, steric hindrance and
(iii) H3 PO2 is a stronger reducing agent than H3 PO3 . + I-effect.
Hint (i) Nitrogen cannot form d - p multiple bond, while
18. Bring out the following conversions:
phosphorus can form d -p multiple bond.
(i) 1-propanol to 4-hydroxyhexanal.
(ii) Because size of oxygen is smaller than sulphur.
(ii) Bromobenzene to 1-phenylethanol.
(iii) The acids which contain P H bonds, have strong
reducing properties. (iii) Benzene to m-nitroacetophenone.
12. At 25C, the vapour pressures of benzene (C6 H6 ) and 3
Hint (i) CH3CH2CH2OH
CrO
CH3CH2CHO
Aldol
Oxidation condensation
toluene (C7H8 ) are 93.4 torr and 26.9 torr, 1-propanol Propanal
respectively. A solution is made by mixing 35.0 g of
CH3 CH2 CH CH2 CH2 CHO
benzene and 65.0 g of toluene. At what applied |
pressure, in torr, will this solution boil at 25C? OH
4-hydroxy hexanal
Hint pC 6H 5CH 3 = pC 6H 5CH 3 . C 6H 5CH 3
Br MgBr CHCH3
ptotal = pC 6H 6 + pC 6H 5CH 3 = 52.7 torr. Mg (i) CH3CHO
(ii)
13. Find the stability constant of the complex Dry ether (ii) H2O/H+ OH
[Zn(NH3 )4 ]2 + formed in the reaction, Bromobenzene Phenyl 1-phenyl
Zn2+ + 4NH3 [Zn(NH3 )4 ]2 +
- magnesium ethanol
bromide
Given that, E 2 + = 0.76 V
Zn / Zn
and E = 1.03V COCH3 COCH3
2+
[Zn(NH 3 )4 ] / Zn, 4NH 3

0.0591 CH3COCl conc. HNO3

=
Hint Ecell log k; k = 1.371 10 9 (iii)
n AlCl3 conc. H2SO4

14. Explain, why NO2

Benzene Acetophenone m-nitro
(i) Noble gases have very low melting and boiling acetophenone

points? 19. An aromatic compound X (molecular formula,

(ii) Neon is used in illuminating warning signal?
(iii) ICl is more reactive than I2 ?
15. (i) Write the electronic configuration of [Fe(CN)6 ]
4 and sodium hydroxide solution. Compound X
on the basis of crystal field splitting theory.
(ii) Why [ Fe (H2 O)6 ]3 + has magnetic moment value of
5.92 BM, whereas [Fe(CN)6 ]3 has a value of only
1.74 BM?
(iii) What type of isomerism is shown by
[Co(NH3 )3 NO2 ]2 + and [Co(NH3 )3 ONO]2 + ?
Hint (i) t 26g e g0
C8 H8 O) gives positive 2, 4-DNP test. It gives a yellow
precipitate of compound Y on treatment with iodine
does not give Tollens or Fehlings test. On drastic
oxidation with potassium permanganate it forms a
carboxylic acid Z (molecular formula, C7H6 O2 ),
which is also formed alongwith the yellow compound
in the above reaction. Identify X , Y and Z and write all
the reactions involved.

88
 Hint
O CH3 4 Value Based Question
C
NO2 23. Mohan, a class 12th student fainted, while playing
H3 C badminton in his school. Mr. Naveen, the sports
2,4-DNP
C N NH NO2 teacher in his school immediately fetched him a
glass of glucose water and took him to a nearby
X hospital, where he was diagnosed with
[C8H8O]
Acetophenone acute anaemia.The doctor prescribed him, iron and
Acetophenone-2, 4- dinitro multivitamis supplements. Mr. Naveen paid the
phenyl hydrazone medical bills. After sometime Mohan was diagnosed
COONa
to be normal.
(i) I2/NaOH Answer the following questions based on the given
X CHI3 +
(ii) H+ passage:
Y
(Yellow ppt.) Sodium (i) Name the vitamin whose deficiency causes
Iodoform benzoate anaemia.
(ii) Name the protein which is composed of iron and
COOH
is found in blood.
(iii) Why Mr. Naveen immediately fetched glucose
KMnO4
water to Mohan?
[O]
(iv) What are the values associated with Mr. Naveen?
Z
[C7H6O2] Hint (i) Vitamin-B12
Benzoic acid (ii) Haemoglobin
20. (i) Give two examples of macromolecules that are (iii) Glucose provides instant energy, as it does not need to
chosen as drug targets. be digested.
(ii) What are antiseptics? Give an example. (iv) Mr. Naveen is knowledgeable, caring and responsible.
(iii) Why is use of aspartame limited to cold foods and 5 Long Answer Type Questions
soft drinks?
or 24. (i) How many alcohols with molecular formula,
Write the name of atleast one polymer used for C4 H10 O are chiral in nature?
making of following materials, alongwith writing the (ii) How are the following conversions carried out
monomer(s) of them. (a) phenol to acetophenone
(i) Synthetic fibres (ii) Electrical switches (b) ethanol to methanol?
(iii) Paints and lacquers (iii) Write the IUPAC name of the major product
Hint (i) Nucleic acids, proteins. obtained in the following reaction.
OH
(ii) For example - H2O 2
(iii) Aspartame decomposes at baking or cooking H2SO4
temperatures.
Na2CrO7
or
(i) Nylon-6,6 [Monomers: Adipic acid and or
hexamethylenediammine].
(i) Write the mechanism of the reaction of acid
(ii) Bakelite [Monomers: Phenol and formaldehyde].
(H2 SO4 ) with ethene.
(iii) Glyptal [Monomers: Ethylene glycol and phthalic acid].
(ii) Identify A and B in the following reactions:
21. Write the chemical equations for the following CH (CH3)2
reactions:
(i) Stephen reaction O2 H3O+
(a) A B
(ii) Etard reaction
(iii) Hell-Volhard-Zelinsky (HVZ) reaction. Br
22. (i) Write the structural difference between a
nucleoside and a nucleotide. Dinitration PhO Na
(b) A B
(ii) Justify that the two strands of DNA are Ac2O+N2O5
complimentary and not the identical one.
Hint (i) When nucleoside is linked to phosphoric acid at
(iii) Give the structure and the IUPAC name of the
5-position of sugar moiety, we get a nucleotide. major product obtained in the following reaction:
(ii) The two strands of DNA are complementary to each COOH
other because the hydrogen bonds are formed between OH
specific pairs of bases. H+
+(CH3CO)2O

89
 25. (i) Complete the following chemical equations. Calculate the rate law and the rate constant for the
(a) Cr2 O27 +
(aq) + H2 S (g) + H (aq) above reaction.
(b) Cu 2+
(aq) + I (aq) or
(i) For a first order reaction, show that time required
(ii) How would you account for the following? for 99% completion is twice, the time required for
(a) The oxidising power of oxo anions are in the the completion of 90% of reaction.
order: VO+ 2
2 < Cr2 O7 < MnO4

(ii) Consider the following first order gas phase
(b) The third ionisation enthalpy of manganese decomposition reaction
(Z =25) is exceptionally high. X (g) Y(g) + Z(g)
(c) Cr2+ is a stronger reducing agent than Fe2+ .
or The initial pressure of the system was p. After lapse of
(i) Metallic radii of few transition elements are time t total pressure of the system was increased by a
given below. units and became px . Find the rate constant (k) for the
Elements Fe Co Ni Cu reaction.
Metalic radii\ pm 126 125 125 128 Hints
(i)
Arrange these elements in increasing order of
their densities. Slope = k
(ii) Write the reaction involve, when K2 Cr2 O7
solution is added to Sn2+ ion.

conc.
[R]0
(iii) Colour of KMnO4 disappears, when oxalic acid is
added to its solution in acidic mediun.
Hint Time
(i) (a) Cr2O 27 ( aq ) + 3H2S( g ) + 8H+ ( aq ) (ii) Rate = k [ A][ B ]2

2Cr 3+ ( aq ) + 3S( s ) + 7H2O ( l ) Rate constant = 6.0 mol 2 L2 min 1

or
(b) 2Cu 2+ ( aq ) + 4I ( aq ) Cu 2I 2( s ) + I 2( g )
2 .303 Initial concentration
(ii) (a) It is because V in its lower oxidation state is less stable (i) t = log
than Cr which in turn is less stable than Mn. k Final concentration
(b) Because the third electron has to be removed from 2 .303 100 4.606
t 99% = log =
stable half-filled 3d-orbitals. k 1 k
(c) d 4 d 3 transition occurs in Cr 2+ to Cr 3+, while 2 .303 100 2 .303
t 90% = log =
d 6 d 3 transition occurs in Fe 2+ to Fe 3+ . k 10 k
or t 99% : t 90% = 2 : 1
(i) Increasing order of densities of the metals are: 2 .303 pi
(ii) Rate constant, k = log
Fe < Co < Ni < Cu t 2 pi pt
(ii) Oxidation
+
Cr2O72 +14H + 3Sn2+ 2Cr3++3Sn4++7H2O
Reduction
(iii) Due to addition of oxalic acid, Mn 7 + (coloured) reduce to
Mn 2 + (colourless). IPU CET will be on May 8, 2 016
26. (i) Plot the graph between concentration and time Indraprastha University Common Entrance Test
for a zero order reaction.
(ii) The following results have been obtained during (IPU CET) 2016 will be conducted on May 8 (Sunday),
the experiments based on kinetic studies of the 2016 for admissions to various UG engineering
reaction. programmes, says a notification by the conducting
2 A + B C + D authority. According to the notification released by
Guru Gobind Singh Indraprastha University, IPU
Initial rate of formation of CET 2016 will be held between 2 pm to 4.30 pm on
Exp.no [A]/mol L1 [B]/mol L1 D/mol L1 min 1
May 8, 2016 for admissions to B. Tech programmes,
1. 0.1 0.1 6.0 10 3 while the result will be declared latest by May 24,
2. 0.2 0.2 7.2 10 2 2016. Candidates, who fulfill the eligibility criteria
and wish to appear in IPU CET 2016, need to fill up
3. 0.3 0.4 2 .88 10 1
the application form and submit it till March 29,
4. 0.4 0.1 2 .40 10 2 2016 (upto 4 pm).

90
1. What is the covalency of nitrogen in N2 O5 ? 8. Name the reagents used in the following reactions:
Hint Covalency is the number of shared pair of electrons by an
(i) O2N CH3 O2 N COOH
atom in a compound.
2. Write the IUPAC name of the given compound, O
O O
CCl CHO
O (ii) + H2

Hint Propanoyl propanoate Hint (i) KMnO 4 -KOH (ii) Rosenmund reduction
3. Out of BaCl2 and KCl, which one is more effective in 9. A solution prepared by dissolving 8.95 mg of a
causing coagulation of a negatively charged gene fragment in 35.0 mL of water, has an osmotic
colloidal sol? Give reason. pressure of 0.335 torr at 25C. Assuming that the gene
Hint According to Hardy-Schulze rule, greater the valency of fragment is a non-electrolyte, calculate its molar mass.
the flocculating ion added to the colloid, greater is its power to or
cause coagulation.
How much urea (molar mass = 60 g mol 1 ) should be
4. Which of the following is a natural polymer? dissolved in 50 g of water, so that its vapour pressure at
Buna-S, Proteins, PVC. room temperature is reduced by 25%. Calculate the
Hint Proteins. molality of the solution obtained.
wRT
5. A compound contains two types of atoms X and Y. It Hint M 2 = = 14193.3 g mol 1
V
crystallises in a cubic lattice with atoms X at
or
the corners of the unit cell and atom Y at the p p s w 2 / m2 w 1000
body-centred. What is the formula of the compound? = = x 2 and Molality = 2
p w1 / m1 + w 2 / m 2 m 2 w1
Hint The formula of the compound is XY.
10. (i) Write the Nernst equation and compute the emf of
6. What is lanthanoid contraction? What is its effect on the following cell at 298 K.
the chemistry of the elements, which follow the
Sn(s)|Sn2 + (0.05M) H+ (0.02M)H 2 , 1 atmPt
lanthanoids?
Given that E 2 + = 0.14 V
Hint The radii of the members of 3rd transition series is very Sn / Sn
similar to those of 2nd transition series and hence, have same (ii) Calculate the degree of dissociation of acetic acid
physical and chemical properties. at 298 K. Given that
m(CH3 COOH) = 11.70 S cm2 mol 1
7. State Kohlrauschs law of independent migration of m(CH COO ) = 40.90 S cm2 mol 1
ions. Why does the conductivity of a solution m(H + ) = 349.1 S cm2 mol 1
3

decrease with dilution? 0.059 [Sn 2 + ] ~

Hint (i) Ecell = E cell log 0.08V; Ecell = 0.14 V
Hint The conductivity of a solution is related with the number n [H + ]2
of ions present per unit volume of the solution.
(ii) Degree of dissociation, = m = 3.0 10 2

m

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 11. (i) In reference to Freundlich adsorption isotherm, Hint (i) Three geometrical isomers are possible and none will
write the expression for adsorption of gases on exhibit optical isomerism.
solids in the form of an equation. (ii) Its colour becomes lighter on heating.
(ii) Write an important characteristic of lyophilic sols. (iii) Electroplating of metals involves the use of complex
(iii) Based on the type of particles of dispersed phase, salts as electrolytes. K[Ag(CN)2 ] is extensively used in
silver plating.
give one example of each associated colloid and
multimolecular colloid. 16. The resistance of a conductivity cell when filled with
Hint (i) x = Kp1/ n 0.05 M solution of an electrolyte X is 100 at 40C.
m The same conductivity cell filled with 0.01 M
(ii) Lyophilic sols are reversible sols. These are quite solution of electrolyte Y, has a resistance of 50 . The
stable and cannot be coagulated. conductivity of 0.05M solution of electrolyte X is
(iii) Associated colloid e.g. Soap 1.0 10 4 S cm 1 . Calculate
Multimolecular colloid e.g. Gold sol. (i) cell constant
12. (i) How do we separate two sulphide ores by (ii) conductivity of 0.01M Y solution
froth floatation method? Explain with an example. (iii) molar conductivity of 0.01M Y solution.
(ii) Give two requirements for vapour phase refining. Hint (i) Cell constant, G = Resistance (R) Conductivity ()
(iii) How is copper extracted from low grade copper = 10 2 cm 1
ores?
Cell constant (G*)
Hint (ii) Conductivity, = = 2 10 4 S cm 1
Resistance ( R )
(i) In this method, the surface of sulphide ores is preferentially
1000
wetted by oil, while that of gangue is preferentially wetted by (iii) Molar conductivity, m = = 20 S cm 2 mol 1
water. Molarity
(ii) (a) The metal should form a volatile compound with a 17. Explain how the phenomenon of adsorption finds
suitable reagent. application in each of the following processes?
(b) The volatile compound should be easily (i) Production of vacuum
decomposable so that we can get pure metal easily.
(ii) Heterogeneous catalysis
(iii) Leaching.
(iii) Froth floatation process
13. Silver crystallises in fcc lattice, if the edge length of
18. Give reasons.
the unit cell is 4.07 10 8 cm and the density of the
(i) n-butyl bromide has higher boiling point than
crystal is 10.5 g cm 3 , calculate the atomic mass of
t-butyl bromide.
silver. [N A = 6.02 1023 atoms mol 1 ]
ZM (ii) Racemic mixture is optically inactive.
Hint Density, d = M = 106.54 g mol 1 (iii) The presence of nitro group ( NO2 ) at
a 3 NA
o/p positions increases the reactivity of
14. (i) How would you account for the followings? haloarenes towards nucleophilic substitution
(a) E values for Mn, Ni and Zn are more negative reactions.
than expected. Hint (i) Higher the surface area, higher will be the boiling
(b) The halides of transition elements becomes point of a compound.
more covalent with increasing oxidation state (ii) In racemic mixture the two enantiomers rotate the
of the metal. plane-polarised light in opposite directions, the
(ii) Complete the reaction, Cr2 O27 + 8H+ + 3H2 S rotations cancel each other because these
enantiomers are present in equal amounts.
Hint (i)(a) Mn 2+ and Zn 2 + have half-filled and completely filled
(iii) The reactivity of haloarenes can be increased by the
configurations respectively. For, Ni 2+ , E value is
presence of an electron withdrawing group at
related to the highest negative enthalpy of hydration.
o/p positions.
(b) As per Fajans rule, as the size of metal ion
decreases, covalent character of the bond formed 19. Predict the products of the following reactions:
increases
(i) CO, HCl
(ii) Cr2O 27 + 8H+ + 3H2S 2Cr 3+ + 7H2O + 3S (i)
(ii) Anhyd.AlCl3/CuCl
15. (i) Write all the geometrical isomers of complex
[Pt(NH3 )(Cl)(Py)(Br)] and how many of these will (i) O3
(ii)
exhibit optical isomerism? (ii) Zn/H2O
(ii) What happens to the colour of coordination O
compound [Ti(H2 O)6 ]Cl3 when heated gradually?
(iii) Why coordination complexes are preferred in the (i) Me MgBr
(iii)
electrolytic bath for electroplating? (ii) H3O
+

92
 Hint (i) Gattermann-Koch reaction These drugs relieve stress, irritability and anxiety by
inducing a sense of well being. There are also the
CH2CH2CHO essential component of sleeping pills. Now, give the
(ii) (iii) answers of the following questions.
CH2CH2CHO
Me (i) Write the structure of chlorodiazepoxide.
(ii) Why would tranquilisers not been taken regularly
20. How do you convert the followings? for very long period?
(i) Benzene to phenol (iii) Give an example of tranquilisers used to treat
(ii) Ethyl benzene to benzoic acid mood changes and depression.
(iii) Toluene to methyl benzoate (iv) What values are not possessed by Peoples who
Hint (i) Benzene is sulphonated with oleum and then on commit suicides via sleeping pills?
acidification gives phenol. 24. (i) Accounts for the following:
(ii) Oxidation by KMnO 4 and alkaline hydrolysis.
(a) Bi(V) is a stronger oxidising agent than Sb(V).
(iii) Oxidation followed by esterification.
(b) Nitrogen exists as gas whereas phosphorus
or exists as a solid.
(i) Write the mechanism of the following reaction: (c) The NO bond in NO2 is shorter than the N O
CH3 bond in NO3 .
CH3 CH3
CH3CCHCH 3 C C (ii) Draw the structures of the following compounds:.
CH3 H (a) N2 O5 (b) Rhombic sulphur.
H OH
Hint
3-methyl-2-butanol 2-methyl-2-butene (i) (a) Stability of + 3 oxidation state increases down the
group due to inert pair effect.
Hint (i) Step I Formation of protonated alcohol.
(c) Single N N bond is weaker than single P P bond
Step II Formation of carbocation.
due to high interelectronic repulsion of the
Step III Formation of alkene by elimination of a proton. non-bonding electrons, owing to small bond length.
(ii) Write the mechanism involved in the synthesis of or
salicylaldehyde from phenol.
(i) Which allotrope of phosphorus is more reactive
Hint Reimer-Tiemann reaction. and why?
21. (i) Draw the structure of amylopectin. (ii) How are the supersonic jet aeroplanes
(ii) Differentiate between a globular protein and a responsible for the depletion of ozone layers?
fibrous protein. (iii) F2 has lower bond dissociation enthalpy than Cl2 .
(iii) Name the food sources and the deficiency Why?
diseases caused due to lack of vitamins A, C, E (iv) Which noble gas is used in filling balloons for
and K. meteorological observations?
22. (i) Which of the carbon-atoms present in the (v) Complete the equation: XeF2 + PF5
molecule given below are asymmetric. Hint
OH H
HO 4
(i) White phosphorus because it is highly unstable molecule.
1 2
CCCC 3 (ii) NO( g ) + O 3( g ) NO 2( g ) + O 2( g )
H (iii) F-atoms has smaller size, while Cl-atoms has comparatively
H OH larger in size
(ii) Discuss the role of Lewis acid in the preparation (iv) Helium
of aryl bromide and chlorides in the dark. (v) XeF2 + PF5 [XeF] + [PF6 ]
(iii) Why iodoform has appreciable antiseptic property? 25. Compound (X ), containing chlorine, on treatment
Hint (i) If a carbon atom satisfies all of its four valencies with with strong ammonia gives a solid (Y), which is free
four different groups then it is termed as
from chlorine. Composition of (Y), upon analysis is
asymmetric/chiral carbon.
found as : C = 49.31%, H = 9.59% and N = 19.18% and
(ii) Lewis acids are electron deficient species. They are
reacts with Br2 and caustic soda to give a basic
responsible for inducing heterolytic fission in halogen
molecule. compound (Z). (Z) reacts with HNO2 to given ethanol.
(iii) Antiseptic properties of iodoform is due to the Suggest structures for (X ), (Y) and (Z).
libration of I 2 not because of iodoform itself. Hint The molecular formula of Y is CH3CH2CONH2 which
undergoes Hofmann bromamide reaction to give CH3CH2NH2
23. Tranquilisers are the drugs which are used for the (Z).
treatment of stress, mild or even severe mental CH3CH2COCl on reaction with ammonia give CH3CH2CONH2 (Y).
diseases.

93
 or (ii) The decomposition of A into product (P) has a
(i) Give one chemical test to distinguish between value of k as 4.5 103 s 1 at 10C and energy of
the following pairs of compound. activation 60 kJ mol 1 . At what temperature
(a) Ethylamine and aniline would k be 1.5 104 s 1 ?
(b) Aniline and N-methyl aniline Hint
2 .303 [ R ]0
(ii) How will you convert aniline to o-bromoaniline? (i) (a) First order reaction, k = log = 0.016 min 1
t [R]
(iii) Arrange the followings in increasing order of
their basic strength. (b) [N2O 5 ] = 0.078 M
NH2 H NH (c) Rate = k[N2O 5 ] = 6.49 10 3 mol L1 s 1 .
k2 E a T2 T1
N N (ii) log = ; T2 = 297 K
(a) (b) NH3 (c) (d) k1 2 .030 R T1T2
or
Hint (i) (a) Aniline gives azo dye test while ethylamine does (i) The decomposition of phosphine, PH3 proceeds
not give this test. according to the following equation,
(b) Aniline gives carbylamine test but N-methyl aniline 4PH3 (g) P4 (g) + 6H2 (g)
being 2 amine does not give this test. It is found that the reaction follows the following
(ii) Step I Sulphonation, acetylation. rate equation, Rate = k[PH3 ]
Step II Bromination (Br2 /CH3COOH). The half-life of PH3 is 37.9 s at 120C.
Step III Desulphonation. (a) How much time is required for 3/4th of PH3 to
Step IV Hydrolysis. decompose?
26. (i) Dinitrogen pentoxide decomposes according to (b) What fraction of the original sample of PH3
the following equation, remains behind after 1 min?
2N2 O5 (g) 4NO2 (g) + O2 (g) (ii) The rate of a reaction becomes four times when
This first order reaction was allowed to proceed at the temperature changes from 293 K to 313 K.
40C and the data obtained as follows: Calculate the energy of the activation (Ea ) of the
reaction assuming that it does not change with
[N2O5 ] (mol L1 ) Time (min)
temperature (R = 8.314 JK 1 mol 1 , log 4 = 0.6021).
0.400 0.00
Hint
0.289 20.0
(i) (a) For first order reaction,
0.209 40.0 0.693 2 .303 [ R ]0
0.151 60.0 k= ,t = log = 75.76 s
t1 / 2 k [R]
0.109 80.0 2 .303 [ R ]0 [ R ]
(b) k = log , = 0.33
(a) Calculate the rate constant. t [ R ] [ R ]0
(b) What will be the concentration of N2 O5 after k2 E a T2 T1
100 min? (ii) log = ; E a = 52.86 / kJmol 1
k1 2 .303 R T1T2
(c) Calculate the initial rate of reaction.

CBSE CHAPTERWISE
SOLVED PAPERS (2015-2008)
For
CLASS

XII

94
1. If ionisation constant of benzoic acid is 6.46 10-5
and Ksp for silver benzoate is 2.5 10-13 , how many
times is silver benzoate more soluble in a buffer of
pH 3.19 compared to its solubility in pure water?
(a) 3.00 times (b) 3.32 times (c) 2.50 times
2. Which of the following statements is/are correct?
I. In SiCl4 , the central Si-atom has four electrons
but it can expand its covalence beyond four
due to presence of vacant d-orbitals and accept
two more Cl - ions to form [SiCl6 ]2 - .
II. On heating, boric acid loses water in three
different stages at different temperatures and
ultimately give boron trioxide.
4. Drugstores sell 3% aqueous hydrogen peroxide that
is used as an antiseptic. Hydrogen peroxide, H2 O2
decomposes to water and oxygen. Calculate the
volume of oxygen produced if 250 mL of 3%
(d) 2.90 times hydrogen peroxide decomposes fully at 750 mm Hg
and 22C.
(a) 3.5 L (b) 2.0 L (c) 3.0 L (d) 4.0 L
5. In muscle cells under the condition of vigorous
exercise, glucose is converted to lactic acid, by the
chemical reaction given below:
C6 H12 O6 2CH3 CHOHCOOH; DG = - 197 kJ
Glucose Lactic acid

III. Duralumin is used to make aircraft body. If all of the Gibbs free energy from this reaction was
used to convert ADP to ATP, how many moles of
Choose the correct option.
(a) Only I (b) II and III (c) I and II (d) I and III ATP could be produced per mole of glucose?
(a) 6.46 (b) 4.66
3. Which of the following reactions is not correct? (c) 4.30 (d) 6.04

NH2 6. Match the following Columns.

NaNO2/HCl N, N-dimethyl aniline Column I Column II
(a) X (Polymer) (Use)
(0-5C)
CH3 A. Lucite p. Cooking pans coatings
N==N N
CH3 B. Teflon q. Building material insulation
C. Styrofoam r. Indoor-outdoors carpets
NO2 NO2
D. Herculon s. High quality transparent objects
Br2 H2SO4/NaNO2 H3PO2 Codes
(b) X Y
FeBr3 273-278K A B C D
Br Br
(a) p s r q
NH2 (b) s p q r
(c) q r s p
CH2CH2CH3 KOH (d) r q p s
(c) N + C6H5SO2Cl
CH2CH2CH3 H2 O 7. If enthalpy of vaporisation for chlorofluorocarbon
+ (CCl2 F2 ), enthalpy of fusion for solid ice and
NH (CH2CH2CH3)2
specific heat capacity for liquid water are 289 J/g,
CO 6.02 kJ/mol and 4.184 Jg -1 C -1 respectively,
(d) NH + alc.KOH X NO2 what mass of CCl2 F2 substance must evaporate to
CO freeze 2 moles of water initially at 20C?
(i) RX
+ RNH2 (a) 53.8 g (b) 52.7 g
(ii) H+/H2O
Br (c) 51.9 g (d) 50.3 g

95
8. Sodium thiosulphate, Na 2 S2 O3 is used as a fixer in (a) (b)
black and white photography. Assume you have a
(c) (d)
bottle of sodium thiosulphate and want to determine
its purity. The thiosulphate ion can be oxidised with 10. Consider the following reaction,
I2 according to the following reaction,
4 moles of A
2CH4(g) A B
I2 (aq) + 2S2 O23 - (aq) 2I- (aq) + S4 O62 (aq) 1500C +Ni(CN)4
THF (i) NaNH2
If you use 40.21 mL of 0.246 M I2 to completely (ii) C2H5I
react, a 3.232 g sample of impure Na 2 S2 O3 , what is 4 moles of C O3/reduction
C D E
the percentage purity of Na 2 S2 O3 ? Red hot tube
(a) 79.2% (b) 70.3% Find the structure of E.
(c) 69.3% (d) 96.8%
CH3
COOH
9. 27.8 g mixture of alkyne and alkane (both (a) (b) H
containing same number of carbon atoms) is COOH
dissolved in 1000 g of benzene. The solution freezes
at 2.45C. Another 27.8 g mixture requires 0.6 mole CH3 C2H5

of H2 for complete hydrogenation. Calculate the (c) C2H5 (d) H

chemical formula of alkane (Kf for C6 H6 = 4.9).

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